[go: up one dir, main page]

WO2018199159A1 - Procédé pour la production d'une composition de polyester à cristaux liquides et composition de polyester à cristaux liquides - Google Patents

Procédé pour la production d'une composition de polyester à cristaux liquides et composition de polyester à cristaux liquides Download PDF

Info

Publication number
WO2018199159A1
WO2018199159A1 PCT/JP2018/016787 JP2018016787W WO2018199159A1 WO 2018199159 A1 WO2018199159 A1 WO 2018199159A1 JP 2018016787 W JP2018016787 W JP 2018016787W WO 2018199159 A1 WO2018199159 A1 WO 2018199159A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
crystal polyester
polyester composition
less
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/016787
Other languages
English (en)
Japanese (ja)
Inventor
宏充 枌
啓介 山西
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Original Assignee
Sumitomo Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Publication of WO2018199159A1 publication Critical patent/WO2018199159A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/60—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material
    • B29B7/603—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material in measured doses, e.g. proportioning of several materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B29B7/482—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws provided with screw parts in addition to other mixing parts, e.g. paddles, gears, discs
    • B29B7/483—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws provided with screw parts in addition to other mixing parts, e.g. paddles, gears, discs the other mixing parts being discs perpendicular to the screw axis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B29B7/488—Parts, e.g. casings, sealings; Accessories, e.g. flow controlling or throttling devices
    • B29B7/489—Screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/86—Component parts, details or accessories; Auxiliary operations for working at sub- or superatmospheric pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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 method for producing a liquid crystal polyester composition and a liquid crystal polyester composition.
  • Liquid crystal polyester is widely used mainly for electrical and electronic parts because of its excellent heat resistance, fluidity and dimensional stability.
  • a molded body using a liquid crystal polyester composition using liquid crystal polyester and glass fiber having high heat resistance as a forming material has been proposed (for example, Patent Document 1).
  • the present invention has been made in view of such circumstances, and an object thereof is to provide a liquid crystal polyester composition having high heat resistance and high thin-wall fluidity, and a method for producing the same.
  • liquid crystal polyester compositions particularly liquid crystal polyester compositions having a flow start temperature of 330 ° C. or more tend to improve heat resistance.
  • this liquid crystal polyester composition has a problem that the thin wall fluidity is low. The present inventors have found that this problem can be solved by the following aspects, and have completed the present invention.
  • one embodiment of the present invention includes a step of melt-kneading a liquid crystalline polyester and a glass fiber having a number average fiber length of 1 mm or more. However, it melt-kneads until it becomes a glass fiber whose number average fiber length is 30 micrometers or more and 200 micrometers or less, and provides the manufacturing method of the liquid crystal polyester composition whose flow start temperature of a liquid crystal polyester composition is 330 degreeC or more.
  • One embodiment of the present invention is a liquid crystal polyester composition
  • a liquid crystal polyester composition comprising a liquid crystal polyester and glass fibers having a number average fiber length of 30 ⁇ m or more and 200 ⁇ m or less, and the flow start temperature of the liquid crystal polyester composition is 330 ° C. or more, In the case of measuring the melt viscosity at a shear rate of 35 / sec after the liquid crystal polyester composition is left in a furnace of a capillary rheometer set at a temperature 30 ° C. higher than the flow start temperature and then kept at the temperature.
  • the present invention includes the following aspects. [1] including melt-kneading a liquid crystalline polyester and a glass fiber having a number average fiber length of 1 mm or more until the fiber becomes a glass fiber having a number average fiber length of 30 ⁇ m or more and 200 ⁇ m or less, The manufacturing method of the liquid-crystal polyester composition whose flow start temperature is 330 degreeC or more.
  • a liquid crystal polyester composition comprising a liquid crystal polyester and glass fibers having a number average fiber length of 30 ⁇ m or more and 200 ⁇ m or less,
  • the flow start temperature of the liquid crystal polyester composition is 330 ° C. or higher,
  • the liquid crystal polyester composition is allowed to stand for 5 minutes or 1 hour in a capillary rheometer furnace set at a temperature 30 ° C. higher than the flow start temperature, and then held at the temperature to obtain a melt viscosity at a shear rate of 35 / sec.
  • the melt viscosity of the liquid crystal polyester composition measured after being left in the furnace for 5 minutes, and the melt viscosity of the liquid crystal polyester composition measured after being left in the furnace for 1 hour.
  • a liquid crystal polyester composition having a value of 100 ⁇ b / a, where b is 50 or more and 200 or less.
  • liquid crystal polyester composition having high heat resistance and high thin-wall fluidity
  • the liquid crystal polyester composition which is one embodiment of the present invention has high heat resistance and high thin-wall fluidity.
  • the manufacturing method (1st Embodiment) of the liquid-crystalline-polyester composition which is one Embodiment of this invention has the process of melt-kneading liquid crystalline polyester and the glass fibrils whose number average fiber length is 1 mm or more.
  • the melt-kneading step includes melt-kneading until the number average fiber length of the fibrils is 30 ⁇ m or more and 200 ⁇ m or less.
  • the liquid crystal polyester according to the method for producing the liquid crystal polyester composition of the present embodiment exhibits liquid crystallinity in a molten state.
  • the liquid crystalline polyester may be a liquid crystalline polyester amide, a liquid crystalline polyester ether, a liquid crystalline polyester carbonate, or a liquid crystalline polyester imide.
  • the flow start temperature of the liquid crystal polyester according to the production method of the present embodiment is preferably 330 ° C. or higher.
  • the flow initiation temperature of the liquid crystalline polyester is more preferably 330 ° C. or higher and 450 ° C. or lower, still more preferably 330 ° C. or higher and 400 ° C. or lower, and particularly preferably 330 ° C. or higher and 390 ° C. or lower.
  • the flow start temperature may be 340 ° C or higher, 350 ° C or higher, or 360 ° C or higher.
  • the flow start temperature may be 340 ° C. or higher and 450 ° C. or lower, 350 ° C. or higher and 400 ° C. or lower, or 360 ° C. or higher and 390 ° C. or lower.
  • the flow start temperature may be 340 ° C. or higher and 347 ° C. or lower.
  • the flow initiation temperature refers to the use of a capillary rheometer (capillary rheometer) to melt the liquid crystalline polyester while increasing the temperature at a rate of 4 ° C./min under a load of 9.8 MPa (100 kg / cm 2 ). This is the temperature at which a viscosity of 4800 Pa ⁇ s (48000 poise) is exerted when extruding from a nozzle having a length of 1 mm and a length of 10 mm, and is a measure of the molecular weight of the liquid crystalline polyester (“Nanoyuki Koide,“ Liquid Crystal Polymer— “Synthesis / Molding / Application—”, CMC Co., Ltd., June 5, 1987, p. 95).
  • the liquid crystal polyester according to this embodiment is preferably a wholly aromatic liquid crystal polyester in which only an aromatic compound is polymerized as a raw material monomer.
  • Typical examples of the liquid crystal polyester according to the present invention include at least one compound selected from the group consisting of aromatic diols, aromatic hydroxyamines and aromatic diamines, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acids. And at least one compound selected from the group consisting of aromatic hydroxyamines and aromatic diamines, and aromatic dicarboxylic acids Examples include those obtained by polymerizing an acid and an aromatic diol; and those obtained by polymerizing a polyester such as polyethylene terephthalate and an aromatic hydroxycarboxylic acid.
  • aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, the aromatic diol, the aromatic hydroxyamine and the aromatic diamine are each independently replaced with a part or all of their polymerizable derivatives. Also good.
  • Examples of polymerizable derivatives of compounds having a carboxyl group such as aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids include those in which the carboxyl group is substituted with an alkoxycarbonyl group or an aryloxycarbonyl group (ie, esters), Examples include those in which a carboxyl group is substituted with a haloformyl group (that is, an acid halide), and those in which a carboxyl group is substituted with an acyloxycarbonyl group (that is, an acid anhydride).
  • polymerizable derivatives of compounds having hydroxyl groups such as aromatic hydroxycarboxylic acids, aromatic diols and aromatic hydroxyamines, include those wherein the hydroxyl group is acylated and substituted with an acyloxyl group (ie, hydroxyl groups Acylated product).
  • polymerizable derivatives of compounds having amino groups such as aromatic hydroxyamines and aromatic diamines include those in which the amino group is acylated and substituted with an acylamino group (ie, acylated products of amino groups). .
  • the liquid crystalline polyester according to the present invention preferably has a repeating unit represented by the following formula (1) (hereinafter sometimes referred to as “repeating unit (1)”), and the repeating unit (1) and the following formula:
  • the repeating unit represented by (2) hereinafter sometimes referred to as “repeating unit (2)”
  • the repeating unit represented by the following formula (3) hereinafter referred to as “repeating unit (3)” It is more preferable to have.
  • Ar 1 represents a phenylene group, a naphthylene group or a biphenylylene group.
  • Ar 2 and Ar 3 each independently represent a phenylene group, a naphthylene group, a biphenylylene group or a group represented by the following formula (4).
  • X and Y each independently represents an oxygen atom or an imino group (—NH—).
  • the hydrogen atom contained in the group represented by Ar 1 , Ar 2 or Ar 3 may be independently substituted with a halogen atom, an alkyl group or an aryl group.
  • Ar 4 and Ar 5 each independently represent a phenylene group or a naphthylene group.
  • Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group or an alkylidene group.
  • the hydrogen atom contained in the group represented by Ar 4 or Ar 5 may be independently substituted with a halogen atom, an alkyl group or an aryl group.
  • the alkyl group that can be substituted with a hydrogen atom is preferably an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or an s-butyl group.
  • the aryl group that can be substituted with a hydrogen atom may be substituted with at least one hydrogen atom constituting the aryl group, and is preferably an aryl group having 6 to 20 carbon atoms in total including the substituent. , Phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 1-naphthyl group and 2-naphthyl group.
  • the number of substitutions is the group represented by Ar 1 , Ar 2 or Ar 3.
  • Each is independently 2 or less, preferably 1 or less.
  • the alkylidene group is preferably an alkylidene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylidene group, an isopropylidene group, an n-butylidene group, and a 2-ethylhexylidene group.
  • the number of groups substituting the hydrogen atom is Ar 4 or Ar 5
  • it is preferably 2 or less, more preferably 1 independently of each other.
  • the repeating unit (1) is a repeating unit derived from a predetermined aromatic hydroxycarboxylic acid.
  • Ar 1 is a p-phenylene group (for example, a repeating unit derived from p-hydroxybenzoic acid), and Ar 1 is a 2,6-naphthylene group (for example, 6 Preferred is a repeating unit derived from -hydroxy-2-naphthoic acid.
  • the repeating unit (2) is a repeating unit derived from a predetermined aromatic dicarboxylic acid.
  • Ar 2 is a p-phenylene group (for example, a repeating unit derived from terephthalic acid), Ar 2 is an m-phenylene group (for example, a repeating unit derived from isophthalic acid) ), Ar 2 is a 2,6-naphthylene group (for example, a repeating unit derived from 2,6-naphthalenedicarboxylic acid), and Ar 2 is a diphenyl ether-4,4′-diyl group (For example, repeating units derived from diphenyl ether-4,4′-dicarboxylic acid) are preferred.
  • the repeating unit (3) is a repeating unit derived from a predetermined aromatic diol, aromatic hydroxylamine or aromatic diamine.
  • Ar 3 is a p-phenylene group (for example, a repeating unit derived from hydroquinone, p-aminophenol or p-phenylenediamine), and Ar 3 is a 4,4′-biphenylylene group.
  • a p-phenylene group for example, a repeating unit derived from hydroquinone, p-aminophenol or p-phenylenediamine
  • Ar 3 is a 4,4′-biphenylylene group.
  • are preferred for example, repeating units derived from 4,4′-dihydroxybiphenyl, 4-amino-4′-hydroxybiphenyl or 4,4′-diaminobiphenyl.
  • “derived from” means that the chemical structure changes due to polymerization.
  • the content of the repeating unit (1) in the liquid crystal polyester is 30 mol% or more, preferably 30 to 80 mol%, more preferably 40 to 70 mol%, based on the total amount of all the repeating units constituting the liquid crystal polyester. More preferably, it is 45 to 65 mol%.
  • the total amount of all repeating units constituting the liquid crystal polyester is obtained by dividing the mass of each repeating unit constituting the liquid crystal polyester by the formula weight of each repeating unit, and obtaining the substance amount equivalent amount (mole) of each repeating unit. , The sum of them.
  • the mass of each repeating unit constituting the liquid crystal polyester is calculated from the amount of the raw material monomer used, and this is a numerical value assuming that all the raw material monomers react.
  • the content of the repeating unit (2) in the liquid crystal polyester is 35 mol% or less, preferably 10 to 35 mol%, more preferably 15 to 30 mol, based on the total amount of all repeating units constituting the liquid crystal polyester.
  • the mol% is more preferably 17.5 to 27.5 mol%.
  • the content of the repeating unit (3) of the liquid crystal polyester is 35 mol% or less, preferably 10 to 35 mol%, more preferably 15 to 30 mol%, based on the total amount of all repeating units constituting the liquid crystal polyester. More preferably, it is 17.5 to 27.5 mol%.
  • the repeating unit (1) when the liquid crystal polyester includes the repeating unit (1), the repeating unit (2), and the repeating unit (3), the repeating unit (1) with respect to the total amount of all repeating units constituting the liquid crystal polyester.
  • the content of is 30 to 80 mol%, preferably 40 to 70 mol%, more preferably 45 to 65 mol%;
  • the content of the repeating unit (2) is 10 to 35 mol%, preferably 15 to 30 mol%, more preferably 17.5 to 27.5 mol%;
  • content of repeating unit (3) is 10 to 35 mol%, preferably 15 to 30 mol%, more preferably 17.5 to 27.5 mol%.
  • the total content of the repeating unit (1), the repeating unit (2) and the repeating unit (3) does not exceed 100 mol%.
  • the melt fluidity, heat resistance, strength and rigidity are easily improved.
  • the content of the repeating unit (1) is more than 80 mol%, the melting temperature and the melt viscosity tend to be high, and the temperature required for molding tends to be high.
  • the ratio between the content of the repeating unit (2) and the content of the repeating unit (3) is [content of repeating unit (2)] / [content of repeating unit (3)]. It is calculated from the formula represented by [rate] (mol% / mol%).
  • the ratio between the content of the repeating unit (2) and the content of the repeating unit (3) is 0.9 to 1.11, preferably 0.95 to 1.05, more preferably 0.98 to 1.02. It is.
  • the repeating units (1) to (3) possessed by the liquid crystal polyester may be independently derived from one type of raw material monomer or may be derived from two or more types of raw material monomers.
  • the liquid crystalline polyester may have a repeating unit other than the repeating units (1) to (3).
  • the content of repeating units other than the repeating units (1) to (3) is 0 mol% or more and 10 mol% or less, preferably 0 mol% or more and 5 mol based on the total amount of all repeating units constituting the liquid crystal polyester. % Or less.
  • the content of at least one repeating unit selected from the group consisting of the repeating unit (1), the repeating unit (2), and the repeating unit (3) in the liquid crystal polyester according to the present invention is the above-mentioned liquid crystal polyester.
  • it is 90 mol% or more and 100 mol% or less with respect to the total content rate of all the repeating units to comprise, More preferably, it is 95 mol% or more and 100 mol% or less.
  • the liquid crystalline polyester preferably has a repeating unit (3) in which X and Y are each an oxygen atom. That is, it is preferable to have a repeating unit derived from a predetermined aromatic diol because the melt viscosity tends to be low. Further, it is more preferable that the repeating unit (3) has only those in which X and Y are each an oxygen atom.
  • the liquid crystal polyester according to the method for producing the liquid crystal polyester composition of the present embodiment may be commercially available, or may be synthesized from raw material monomers corresponding to the repeating units constituting the liquid crystal polyester. .
  • the liquid crystalline polyester When the liquid crystalline polyester is synthesized, it is preferably produced by melt polymerization of the raw material monomers and solid-phase polymerization of the obtained polymer (hereinafter sometimes referred to as “prepolymer”). Thereby, for example, a liquid crystal polyester having a flow start temperature of 330 ° C. or higher and a high flow start temperature can be produced with good operability.
  • Melt polymerization may be performed in the presence of a catalyst.
  • catalysts that may be used in the melt polymerization include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, and 4- (dimethylamino) pyridine.
  • nitrogen-containing heterocyclic compounds such as 1-methylimidazole, and nitrogen-containing heterocyclic compounds are preferably used.
  • liquid crystalline polyester may have the same repeating unit, and those having different repeating unit contents may be used in combination.
  • the glass fiber according to the method for producing a liquid crystal polyester composition of the present embodiment has a number average fiber length of 1 mm or more. Preferably they are 1 mm or more and 10 mm or less, More preferably, they are 1 mm or more and 6 mm or less.
  • the number average fiber length may be 2 mm or more, or 3 mm or more. As one aspect, the number average fiber length may be 2 mm or more and 10 mm or less, 3 mm or more and 10 mm or less, 2 mm or more and 6 mm or less, or 3 mm or more and 6 mm or less.
  • chopped strands having a narrow fiber length distribution are preferable.
  • the number average fiber diameter of the fibrils according to the method for producing the liquid crystal polyester composition of the present embodiment is not particularly limited, but is preferably 3 ⁇ m or more and 15 ⁇ m or less.
  • the number average fiber diameter of the fibrils is 3 ⁇ m or more, the reinforcing effect of the molded body obtained by molding the obtained liquid crystal polyester composition can be more sufficiently obtained.
  • the number average fiber diameter of the fibrils is 15 ⁇ m or less, the moldability of the obtained liquid crystal polyester composition is improved, and the appearance of the surface of the molded body obtained by molding the liquid crystal polyester composition becomes better.
  • the number average fiber diameter and the number average fiber length of the fibril can be measured by observing with a microscope such as a digital microscope.
  • the surface of the fibril according to this embodiment may be partially or entirely treated with a surface coating agent.
  • a surface coating agent include coupling agents such as titanium coupling agents, resins, and other surface coating agents generally used for surface coating.
  • the fibrils treated with the surface coating agent it is possible to suppress the generation of gas from the molded body obtained by molding the obtained liquid crystal polyester composition. Therefore, the chemical stability of the molded body can be improved. Further, when an electric / electronic device or an optical device is assembled, contamination of peripheral members due to gas generated from the molded body can be reduced.
  • the fibrils according to this embodiment may be treated with an epoxy-based, urethane-based, acrylic-based coating agent or sizing agent.
  • the fibrils according to the method for producing the liquid crystal polyester composition of the present embodiment may be commercially available or may be produced by a known method.
  • the liquid crystal polyester composition obtained by the method for producing a liquid crystal polyester composition according to an embodiment of the present invention may further include other fillers other than glass fibers, additives, or resins other than liquid crystal polyester, if necessary. It may contain at least one component. That is, the method for producing a liquid crystal polyester composition according to an embodiment of the present invention includes a liquid crystal polyester, a glass fibril having a number average fiber length of 1 mm or more, and optionally a filler other than glass fiber, addition Melting and kneading an agent and at least one component selected from the group consisting of resins other than the liquid crystalline polyester.
  • the liquid crystal polyester composition obtained by the production method of the present invention comprises a liquid crystal polyester, the fibrils, and optionally a filler other than the glass fiber, the additive, and a resin other than the liquid crystal polyester. And at least one component selected from the group consisting of:
  • additives include antioxidants, heat stabilizers, ultraviolet absorbers, antistatic agents, surfactants, flame retardants, and colorants.
  • the content of the additive in the liquid crystal polyester composition obtained by the present embodiment is usually 0 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal polyester.
  • resins other than liquid crystal polyesters include polypropylene, polyamide, polyesters other than liquid crystal polyesters, thermoplastic resins other than liquid crystal polyesters such as polysulfone, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene ether, and polyetherimide; and phenol resins And thermosetting resins such as epoxy resins, polyimide resins, and cyanate resins.
  • the content of the resin other than the liquid crystal polyester in the liquid crystal polyester composition obtained by the present embodiment is usually 0 to 20 parts by mass with respect to 100 parts by mass of the liquid crystal polyester.
  • liquid crystal polyester composition of the present embodiment may be commercially available or may be produced by a known method.
  • FIG. 1 is a schematic cross-sectional view showing an example of an extruder used in melt-kneading according to the method for producing a liquid crystal polyester composition of the first embodiment.
  • a liquid crystal polyester composition is manufactured using the extruder shown in FIG. 1 is demonstrated.
  • liquid crystal polyester composition of this embodiment demonstrates as manufacturing liquid crystal polyester composition by melt-kneading liquid crystal polyester and a fibril using the extruder shown in FIG.
  • the extruder 10 shown in FIG. 1 includes a motor 1 housed in a motor box 1a, a cylinder 2 provided adjacent to the motor box 1a, a screw 3 inserted into the cylinder 2 and connected to the motor 1. ,have.
  • An extruder 10 shown in FIG. 1 is a twin-screw extruder in which two screws 3 are inserted into a cylinder 2.
  • the cylinder 2 has a main feed port 5 for supplying liquid crystal polyester and fibrils into the cylinder 2, and a side feed for supplying liquid crystal polyester and fibrils into the cylinder 2 behind the main feed port 5 in the extrusion direction (downstream side).
  • a mouth 7, a first vent portion 4 and a second vent portion 6 for discharging volatile components (gas) generated in the cylinder 2, and a discharge die 9 for molding a melt-kneaded liquid crystal polyester composition are provided.
  • the discharge die 9 is provided with a nozzle hole 9a.
  • the main feed port 5 and the side feed port 7 have a hopper connected to the inside of the cylinder 2 and a supply device for supplying liquid crystal polyester and fibrils (all not shown).
  • the screw 3 includes a transport unit 8 for transporting the liquid crystal polyester composition. Further, the screw 3 includes a first kneading section 11 between the main feed port 5 and the side feed port 7 for plasticizing and kneading the liquid crystalline polyester composition. Further, the screw 3 includes a second kneading part 12 that plasticizes and kneads the liquid crystal polyester composition between the side feed port 7 and the first vent part 4. Furthermore, the screw 3 includes a third kneading portion 13 that kneads the liquid crystal polyester composition between the first vent portion 4 and the second vent portion 6. A fourth kneading part and a fifth kneading part may be further provided between the first vent part 4 and the second vent part 6. At this time, it is preferable to sufficiently control the increase in the cylinder temperature due to shear heat generation.
  • the number average fiber length of the glass fibers contained in the liquid crystal polyester composition is controlled to 30 ⁇ m or more and 200 ⁇ m or less.
  • the temperature condition and shearing force at the time of melt-kneading may be appropriately adjusted.
  • the temperature condition of the melt-kneading is selected from the temperature conditions of [FT-100] ° C. or more and [FT + 80] ° C. or less based on the flow start temperature (sometimes abbreviated as FT) ⁇ 0 (° C.) of the liquid crystal polyester.
  • the shearing force for melt kneading is appropriately adjusted depending on the type and scale of the extruder used. Specifically, the shearing force relating to the melt-kneading can be adjusted by appropriately changing the configuration of the screw and the kneading part in the extruder.
  • the temperature conditions and shearing force of the melt-kneading and the number average fiber length of the glass fibers in the obtained sample are Based on this, the melt-kneading conditions may be appropriately adjusted so that the number average fiber length of the glass fibers in the liquid crystal polyester composition becomes a target value. Thereby, the liquid crystal polyester composition containing the glass fiber which has the target number average fiber length can be obtained.
  • the number average fiber diameter of the glass fibers is considered to have a very low possibility of changing in the melt-kneading process.
  • the liquid crystal polyester to be supplied to the main feed port 5, fibrils, and necessary
  • the supply ratio of the other components blended according to the above is not particularly limited.
  • the supply ratios of the liquid crystal polyester, fibrils, and other components blended as needed are not particularly limited.
  • 30 to 100% of the total amount of liquid crystal polyester may be supplied from the main feed port, and 0 to 70% of the total amount of liquid crystal polyester and the total amount of fibrils may be supplied from the side foot port.
  • the discharge amount of the liquid crystal polyester composition from the discharge die 9 of the extruder 10 is preferably 200 kg / hour to 400 kg / hour. Moreover, it is preferable that the rotation speed of the screw 3 of the extruder 10 shall be 500 rpm to 800 rpm. In addition, it is preferable to adjust these manufacturing conditions so that the torque of the motor 1 which the extruder 10 has becomes 60% or more with respect to the upper limit torque of an extruder.
  • the method for producing a liquid crystal polyester composition may include a step of forming pellets made of the liquid crystal polyester composition after the step of melt-kneading.
  • a molding method of the liquid crystal polyester composition pellets a melt molding method is preferable.
  • the melt molding method include an injection molding method, an extrusion molding method such as a T-die method and an inflation method, a compression molding method, a blow molding method, a vacuum molding method, and a press molding method. Of these, the injection molding method is preferable.
  • the method for producing a liquid crystal polyester composition supplies liquid crystal polyester and glass fibrils having a number average fiber length of 1 mm or more to an extruder; Melt-kneading the liquid crystalline polyester and fibrils supplied to the extruder until the number average fiber length of the fibrils is 30 ⁇ m or more and 200 ⁇ m or less; and the liquid crystal polyester composition obtained by the melt kneading Forming pellets.
  • the melt-kneading is preferably performed at [FT-100] ° C. or more and [FT + 80] ° C. or less with the flow start temperature FT ⁇ 0 (° C.) of the liquid crystal polyester as a base point.
  • the liquid crystal polyester composition pellets are preferably molded by a melt molding method.
  • the extruder according to the method for producing a liquid crystal polyester composition which is one embodiment of the present invention is not limited to the extruder having the configuration shown in FIG.
  • a cylinder, at least one screw disposed in the cylinder, and two or more supply ports (main feed port and side feed port) provided in the cylinder are preferably used.
  • Those provided with one or more vent portions are more preferably used.
  • extruder applicable to one embodiment of the present invention may be a single screw extruder or a twin screw extruder.
  • twin-screw extruders include those with one to three screws rotating in the same direction, parallel shaft types with different directions rotating, oblique shaft types, and incomplete meshing types.
  • the twin screw extruder is preferred. If the number average fiber length of the glass fibers contained in the liquid crystal polyester composition (or pellets) is less than the target value, the liquid crystal polyester composition (or pellets) is again introduced from the supply port of the extruder and melt kneaded. The number average fiber length of the glass fibers can be repeated until the target value is reached. In addition, the measuring method of the number average fiber length of glass fiber is mentioned later.
  • the liquid crystal polyester composition according to one embodiment of the present invention is manufactured. From the above, in the method for producing a liquid crystal polyester composition according to an embodiment of the present invention, the number average fiber length is 1 mm or more, by breaking the fibrils while kneading with the liquid crystal polyester, the number average fibers Melting and kneading can be performed until the glass fiber has a length of 30 ⁇ m to 200 ⁇ m.
  • the liquid crystal polyester is preferably blended in an amount of 40 to 80% by mass with respect to the total mass of the liquid crystal polyester composition to be obtained.
  • the fibrils are preferably blended in an amount of 20 to 60% by mass based on the total mass of the liquid crystal polyester composition to be obtained.
  • liquid crystal polyester composition which is one embodiment of the present invention is produced by the production method described above.
  • the liquid crystal polyester and the fibril are strongly kneaded while the fibril is broken. Therefore, it is considered that the glass fiber is uniformly dispersed in the liquid crystal polyester composition of the present embodiment.
  • the liquid crystal polyester composition of this embodiment it is thought that liquid crystal polyester and glass fiber are interacting strongly. Thereby, it is thought that the liquid crystal polyester composition of this embodiment has high heat resistance and high thin-wall fluidity.
  • the liquid crystal polyester composition according to the second embodiment of the present invention is a liquid crystal polyester composition comprising a liquid crystal polyester and glass fibers having a number average fiber length of 30 ⁇ m or more and 200 ⁇ m or less.
  • the flow start temperature is 330 ° C. or higher, and the liquid crystal polyester composition is left in the capillary rheometer furnace set at a temperature 30 ° C. higher than the flow start temperature for 5 minutes or 1 hour, and then held at the above temperature.
  • the melt viscosity of the liquid crystal polyester composition measured after being left in the furnace for 5 minutes is measured after being left in the furnace for 1 hour.
  • the melt viscosity of the liquid crystal polyester composition is b, the value of 100 ⁇ b / a is 50 or more and 200 or less.
  • the melt viscosity a and the melt viscosity b are measured as follows. First, it is left for a predetermined time (5 minutes or 1 hour) in a furnace of a capillary rheometer set at a temperature 30 ° C. higher than the flow start temperature of the liquid crystal polyester composition of the present embodiment. Thereafter, the melt viscosity at a shear rate of 35 / sec is measured while the temperature is maintained. At this time, the melt viscosity measured with the predetermined time left in the furnace as 5 minutes is defined as a. Further, b is a melt viscosity measured with a predetermined time left in the furnace as 1 hour.
  • the value of 100 ⁇ b / a means the rate of change in melt viscosity when the liquid crystal polyester composition is held at a temperature 30 ° C. higher than its flow start temperature. When this value is less than 50 or more than 200, it can be said that the melt viscosity of the liquid crystal polyester composition tends to change when the liquid crystal polyester composition is held under the above conditions.
  • the value of 100 ⁇ b / a is 50 or more and 200 or less. Therefore, it can be said that when the liquid crystal polyester composition of the present embodiment is held under the above conditions, the melt viscosity of the liquid crystal polyester composition hardly changes.
  • the value of 100 ⁇ b / a is preferably 55 or more. Further, the value of 100 ⁇ b / a is preferably 150 or less, and more preferably 120 or less. As one aspect, the value of 100 ⁇ b / a is preferably 55 or more and 150 or less, more preferably 55 or more and 120 or less, and more preferably 55 or more and 65 or less.
  • liquid crystal polyester composition of the present embodiment When the liquid crystal polyester composition of the present embodiment is held at a high temperature (for example, 360 ° C. or higher) at which a side reaction is likely to occur in the liquid crystal polyester composition, a cross-linking reaction or decomposition between liquid crystal polyester molecules contributing to a change in melt viscosity. It can be said that side reactions such as reactions are unlikely to occur.
  • a high temperature for example, 360 ° C. or higher
  • the interaction between the liquid crystal polyester and the glass fiber constituting the liquid crystal polyester composition of the present embodiment is strong. That is, the liquid crystal polyester composition of the present embodiment is considered to be a composition having a strong interaction between the liquid crystal polyester and the glass fiber.
  • liquid crystal polyester composition satisfying the requirement that the value of 100 ⁇ b / a is 50 or more and 200 or less is excellent in thin-wall fluidity, and completed the present invention.
  • the lower limit of the number average fiber length of the glass fibers contained in the liquid crystal polyester composition is 30 ⁇ m or more, preferably 50 ⁇ m or more, more preferably 70 ⁇ m or more, and further preferably 80 ⁇ m or more.
  • the upper limit of the number average fiber length of the glass fibers contained in the liquid crystal polyester composition is 200 ⁇ m or less, preferably 170 ⁇ m or less, more preferably 150 ⁇ m or less, and further preferably 100 ⁇ m or less.
  • the number average fiber length of the glass fibers contained in the liquid crystal polyester composition is 30 ⁇ m to 200 ⁇ m, preferably 50 ⁇ m to 170 ⁇ m, more preferably 70 ⁇ m to 150 ⁇ m, and even more preferably 80 ⁇ m. It is not less than 100 ⁇ m and particularly preferably not less than 80 ⁇ m and not more than 86 ⁇ m.
  • the number average fiber length of the glass fibers in the liquid crystal polyester composition is measured by the following method. First, a predetermined amount of pellets made of a liquid crystal polyester composition is placed in a crucible and treated in an electric furnace at 600 ° C. for 6 hours for ashing. Next, a micrograph (magnification: 100 times) is taken with the obtained residue dispersed in methanol and developed on a slide glass. The number average fiber length of the glass fibers in the liquid crystal polyester composition is determined by directly reading the length of the glass fibers from the photograph and calculating the average value (for example, the average value when the parameter is 400). In addition, the fiber length here means the maximum length in the fiber.
  • the flow start temperature of the liquid crystal polyester composition of the present embodiment is 330 ° C. or higher and 450 ° C. or lower, which can be said to be sufficiently high.
  • the flow start temperature of the liquid crystal polyester composition of the present embodiment may be 350 ° C. or more and 400 ° C. or less, or 360 ° C. or more and 390 ° C. or less, as one aspect.
  • the flow start temperature may be 340 ° C. or higher and 347 ° C. or lower.
  • liquid crystal polyester composition having a flow start temperature of 330 ° C. or higher can be obtained by using a liquid crystal polyester having a flow start temperature of 330 ° C. or higher and 450 ° C. or lower as a raw material.
  • the flow start temperature of a liquid crystal polyester composition can be measured by the same method as liquid crystal polyester.
  • the high thin-wall fluidity of the liquid crystal polyester composition means that the thin-wall flow length specifically obtained by the following method is long.
  • FIG. 2 is a schematic configuration diagram of a mold for measuring a thin wall flow length in the present embodiment.
  • a thin film flow length measurement mold (0.3 mmt) shown in FIG. 2 is used, and a liquid crystal polyester composition is subjected to a cylinder temperature of 380 ° C. with an injection molding machine (roboshot S2000i-30B manufactured by FANUC). Molding is performed under conditions of a mold temperature of 130 ° C. and an injection speed of 200 mm / second.
  • the thin-wall flow length is determined by measuring the length of the removed molded body.
  • the thin wall flow length is preferably 20 mm or more.
  • the liquid crystal polyester composition of the second embodiment can be produced, for example, by the production method shown in the first embodiment.
  • the content of the liquid crystal polyester is preferably 40 to 80% by mass with respect to the total mass of the liquid crystal polyester composition; glass
  • the fiber content is preferably 20 to 60% by mass relative to the total mass of the liquid crystal polyester composition.
  • molded products can be obtained by molding the liquid crystal polyester composition of the present embodiment.
  • molded products include optical pickup bobbins, transformer bobbins and other bobbins; relay cases, relay bases, relay sprues, relay armatures and other relay parts; RIMM, DDR, CPU socket, S / O, DIMM, Board to Board Connectors, connectors such as FPC connectors, card connectors, etc .; reflectors such as lamp reflectors and LED reflectors; holders such as lamp holders and heater holders; diaphragms such as speaker diaphragms; separation claws for copying machines, separation claws for printers, etc.
  • a liquid crystal polyester composition having high heat resistance and high thin-wall fluidity can be obtained.
  • the liquid crystal polyester composition which is one embodiment of the present invention has high heat resistance and high thin-wall fluidity.
  • the number average fiber length of the fibrils is 30 ⁇ m or more and 200 ⁇ m or less, preferably 50 ⁇ m or more and 170 ⁇ m or less, more preferably 70 ⁇ m or more and 150 ⁇ m or less, more preferably 80 ⁇ m.
  • the liquid crystal polyester is a liquid crystal polyester having a repeating unit represented by the general formulas (1) to (3), preferably a repeating unit derived from p-hydroxybenzoic acid, and 4,4′-dihydroxybiphenyl.
  • a liquid crystalline polyester having a repeating unit, a repeating unit derived from terephthalic acid, and a repeating unit derived from isophthalic acid;
  • the number average fiber length of the fibrils supplied to the extruder is 1 mm or more and 10 mm or less, more preferably 1 mm or more and 6 mm or less;
  • the liquid crystal polyester composition obtained by melt kneading has a flow start temperature of 330 ° C or higher, preferably 350 ° C or higher and 400 ° C or lower, more preferably 360 ° C or higher and 390 ° C or lower, or 340 ° C or higher and 347 ° C or lower.
  • the melt-kneading is preferably performed at [FT-100] ° C. or more and [FT + 80] ° C. or less with the flow start temperature FT ⁇ 0 (° C.) of the liquid crystal polyester as a base point;
  • the manufacturing method may further include forming a pellet of the liquid crystal polyester composition obtained by the melt kneading.
  • a liquid crystal polyester composition comprising liquid crystal polyester, glass fiber, and, if desired, at least one component selected from the group consisting of a filler other than glass fiber, an additive, and a resin other than liquid crystal polyester,
  • the number average fiber length of the glass fibers is 30 ⁇ m or more and 200 ⁇ m or less, preferably 50 ⁇ m or more and 170 ⁇ m or less, more preferably 70 ⁇ m or more and 150 ⁇ m or less, further preferably 80 ⁇ m or more and 100 ⁇ m or less, and particularly preferably 80 ⁇ m or more and 86 ⁇ m or less;
  • the liquid crystal polyester is a liquid crystal polyester having a repeating unit represented by the general formulas (1) to (3), preferably a repeating unit derived from p-hydroxybenzoic acid, and 4,4′-dihydroxybiphenyl.
  • a liquid crystalline polyester having a repeating unit, a repeating unit derived from terephthalic acid, and a repeating unit derived from isophthalic acid;
  • the liquid crystal polyester composition has a flow start temperature of 330 ° C. or higher, preferably 350 ° C. or higher and 400 ° C. or lower, more preferably 360 ° C. or higher and 390 ° C. or lower, or 340 ° C. or higher and 347 ° C. or lower;
  • the liquid crystal polyester composition is allowed to stand for 5 minutes or 1 hour in a capillary rheometer furnace set at a temperature 30 ° C. higher than the flow start temperature, and then held at the temperature to obtain a melt viscosity at a shear rate of 35 / sec.
  • xb / a is 50 or more and 200 or less, preferably 55 or more and 150 or less, more preferably 55 or more and 120 or less, and still more preferably 55 or more and 65 or less;
  • the content of the liquid crystal polyester is 40 to 80% by mass with respect to the total mass of the liquid crystal polyester composition;
  • the glass fiber content is 20 to 60% by mass with respect to the total mass of the liquid crystal polyester composition.
  • the thin-wall fluidity of the liquid crystal polyester composition was evaluated by measuring the thin-wall flow length of the liquid crystal polyester composition by the following method. In this evaluation, it can be said that the longer the thin film flow length of the liquid crystal polyester composition, the better the liquid crystal polyester composition is.
  • the liquid crystal polyester composition was subjected to a cylinder temperature of 380 ° C. and a mold temperature of 130 ° C. using an injection molding machine (roboshot S2000i-30B manufactured by FANUC). Molding was performed under the conditions of an injection speed of 200 mm / sec. Measurement of the length of the cavity portion of the molded body taken out was performed on five molded bodies, and the average value was defined as the thin-wall flow length. At this time, the residence time in the molding machine of the liquid crystalline polyester composition was within 5 minutes.
  • melt viscosity was measured at a shear rate of 35 / sec for the liquid crystal polyester composition held in a capillary rheometer furnace for 1 hour.
  • the melt viscosity obtained here was defined as b.
  • 100 ⁇ b / a was determined.
  • the value of 100 ⁇ b / a means the rate of change in melt viscosity when the liquid crystalline polyester composition stays inside the extruder.
  • the obtained prepolymer was cooled to room temperature and pulverized with a coarse pulverizer to obtain a liquid crystalline polyester powder (particle diameter of about 0.1 mm to about 1 mm). Thereafter, the liquid crystal polyester powder was heated from room temperature to 250 ° C. over 1 hour in a nitrogen atmosphere, heated from 250 ° C. to 300 ° C. over 5 hours, and held at 300 ° C. for 3 hours. The polymerization reaction proceeded at.
  • the flow starting temperature of the obtained liquid crystal polyester was 361 ° C.
  • Fiber A Nitto Boseki Co., Ltd., trade name “CS-3J-260S” (number average fiber length: 3 mm)
  • Fiber B Central Glass Co., Ltd., trade name “Milled Fiber EFH75-01” (number average fiber length: 91 ⁇ m)
  • twin screw extruder manufactured by Toshiba Machine Co., Ltd., model number “TEM-41SS” was used as an extruder.
  • This twin-screw extruder has a configuration in which a fourth kneading portion is added to the first vent portion and a fifth kneading portion is added to the second vent portion to the extruder having the configuration shown in FIG.
  • Example 1 A liquid crystal polyester composition was produced by a twin screw extruder using 45 parts by mass of the fibril A and 55 parts by mass of the liquid crystal polyester obtained in Production Example 1.
  • a screw having the same direction (right rotation) in two axes was used, the screw rotation speed was 650 rpm, and the extrusion rate was 300 kg / hour. Under such conditions, the liquid crystal polyester and the fibril A were melt-kneaded to obtain a liquid crystal polyester composition.
  • the flow starting temperature of the liquid crystal polyester composition obtained in Example 1 was 347 ° C.
  • the number average fiber length of the glass fibers in the liquid crystal polyester composition was 86 ⁇ m.
  • a liquid crystal polyester composition was produced by a twin screw extruder using 45 parts by mass of the basic fiber B and 55 parts by mass of the liquid crystal polyester obtained in Production Example 1. It was manufactured in the same manner as in Example 1 except that the entire amount of liquid crystal polyester was supplied from the main feed port of this twin-screw extruder, the fibril B was supplied from the side feed port, and the processing temperature was uniformly set to 360 ° C.
  • the flow start temperature of the liquid crystal polyester composition obtained in Comparative Example 1 was 347 ° C.
  • the number average fiber length of the glass fibers in the liquid crystal polyester composition was 87 ⁇ m.
  • the flow starting temperature of the liquid crystal polyester composition obtained in Comparative Example 2 was 349 ° C.
  • the number average fiber length of the glass fibers in the liquid crystal polyester composition was 243 ⁇ m.
  • Table 1 summarizes the blending ratios and physical property values of the liquid crystal polyester compositions of Examples and Comparative Examples, and the number average fiber length of the glass fibers in the liquid crystal polyester composition after melt kneading.
  • Example 1 a fibril having a number average fiber length longer than that of the fibril used in Comparative Example 1 was used as a raw material.
  • the number average fiber length of the glass fibers contained in the liquid crystal polyester composition was about the same in Example 1 and Comparative Example 1.
  • the liquid crystal polyester composition of Example 1 showed higher thin-wall fluidity than Comparative Example 1.
  • Example 1 the same fibrils as those in Comparative Example 2 were used as raw materials. However, the number average fiber length of the glass fibers contained in the liquid crystal polyester composition was 200 ⁇ m or less in Example 1, whereas it was longer than 200 ⁇ m in Comparative Example 2. Such a liquid crystal polyester composition of Example 1 showed high thin-wall fluidity as compared with Comparative Example 2.
  • Example 1 Comparative Example 1 and Comparative Example 2
  • the flow start temperature of the liquid crystal polyester used was about the same, 100 ⁇ b / a in Example 1 The value was as low as 200 or less.
  • Such a liquid crystal polyester composition of Example 1 showed high thin-wall fluidity as compared with Comparative Example 1 and Comparative Example 2.
  • the liquid crystal polyester composition having 100 ⁇ b / a of 50 or more and 200 or less has a higher thin-wall flow than the conventional liquid crystal polyester compositions such as Comparative Example 1 and Comparative Example 2. It is considered to indicate the length.
  • the present invention can provide a liquid crystal polyester composition having high heat resistance and high thin-wall fluidity and a method for producing the same, it is extremely useful industrially.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • 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)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé pour la production d'une composition de polyester à cristaux liquides ayant une température de début d'écoulement supérieure ou égale à 330°C, le procédé comprenant le malaxage à l'état fondu d'un polyester à cristaux liquides et de fibrilles constituées de verre ayant une longueur de fibre moyenne en nombre supérieure ou égale à 1 mm jusqu'à ce que les fibrilles deviennent des fibres de verre ayant une longueur de fibre moyenne en nombre de 30 à 200 µm.
PCT/JP2018/016787 2017-04-28 2018-04-25 Procédé pour la production d'une composition de polyester à cristaux liquides et composition de polyester à cristaux liquides Ceased WO2018199159A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-090718 2017-04-28
JP2017090718A JP2018188528A (ja) 2017-04-28 2017-04-28 液晶ポリエステル組成物の製造方法および液晶ポリエステル組成物

Publications (1)

Publication Number Publication Date
WO2018199159A1 true WO2018199159A1 (fr) 2018-11-01

Family

ID=63919680

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/016787 Ceased WO2018199159A1 (fr) 2017-04-28 2018-04-25 Procédé pour la production d'une composition de polyester à cristaux liquides et composition de polyester à cristaux liquides

Country Status (3)

Country Link
JP (1) JP2018188528A (fr)
TW (1) TWI761500B (fr)
WO (1) WO2018199159A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112969750A (zh) * 2018-11-09 2021-06-15 住友化学株式会社 液晶聚酯树脂组合物和成型品

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6675028B1 (ja) 2019-05-17 2020-04-01 住友化学株式会社 液晶ポリエステル樹脂組成物のペレット及び液晶ポリエステル樹脂組成物のペレットの製造方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04103656A (ja) * 1990-08-22 1992-04-06 Toray Ind Inc 液晶ポリエステル樹脂組成物
JP2001288342A (ja) * 2000-04-04 2001-10-16 Sumitomo Chem Co Ltd 液晶ポリエステル樹脂組成物、その製造方法およびその成形体
JP2005089652A (ja) * 2003-09-18 2005-04-07 Nippon Petrochemicals Co Ltd 全芳香族液晶ポリエステル樹脂組成物および光ピックアップ部材
JP2008013600A (ja) * 2006-07-03 2008-01-24 Nippon Oil Corp 全芳香族液晶ポリエステル組成物およびそれを用いた光ピックアップレンズホルダー
WO2012090411A1 (fr) * 2010-12-28 2012-07-05 東レ株式会社 Composition de résine polyester à cristaux liquides, son procédé de fabrication et article moulé fabriqué à partir de celle-ci
JP2012206436A (ja) * 2011-03-30 2012-10-25 Sumitomo Chemical Co Ltd 液晶高分子成形体及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04103656A (ja) * 1990-08-22 1992-04-06 Toray Ind Inc 液晶ポリエステル樹脂組成物
JP2001288342A (ja) * 2000-04-04 2001-10-16 Sumitomo Chem Co Ltd 液晶ポリエステル樹脂組成物、その製造方法およびその成形体
JP2005089652A (ja) * 2003-09-18 2005-04-07 Nippon Petrochemicals Co Ltd 全芳香族液晶ポリエステル樹脂組成物および光ピックアップ部材
JP2008013600A (ja) * 2006-07-03 2008-01-24 Nippon Oil Corp 全芳香族液晶ポリエステル組成物およびそれを用いた光ピックアップレンズホルダー
WO2012090411A1 (fr) * 2010-12-28 2012-07-05 東レ株式会社 Composition de résine polyester à cristaux liquides, son procédé de fabrication et article moulé fabriqué à partir de celle-ci
JP2012206436A (ja) * 2011-03-30 2012-10-25 Sumitomo Chemical Co Ltd 液晶高分子成形体及びその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112969750A (zh) * 2018-11-09 2021-06-15 住友化学株式会社 液晶聚酯树脂组合物和成型品
CN112969750B (zh) * 2018-11-09 2022-07-29 住友化学株式会社 液晶聚酯树脂组合物和成型品

Also Published As

Publication number Publication date
TWI761500B (zh) 2022-04-21
TW201843020A (zh) 2018-12-16
JP2018188528A (ja) 2018-11-29

Similar Documents

Publication Publication Date Title
JP6500140B2 (ja) 液晶ポリエステル組成物
KR101986075B1 (ko) 액정 폴리에스테르 조성물, 액정 폴리에스테르 조성물의 제조 방법 및 성형체
JP5633338B2 (ja) 液晶ポリエステル組成物
KR102173693B1 (ko) 전방향족 액정 폴리에스테르 수지
US9994771B2 (en) Liquid crystal polyester resin composition, connector, and method for producing liquid crystal polyester resin composition
JP5771860B2 (ja) 樹脂組成物の製造方法
JP2018168320A (ja) 液晶ポリエステル組成物および成形体
CN102498171A (zh) 液晶聚酯树脂组合物的成型方法和成型体
CN109863202B (zh) 液晶聚酯树脂组合物
JP2012206296A (ja) 液晶ポリエステル組成物の製造方法
CN104066559A (zh) 树脂组合物的制造方法
TWI754049B (zh) 液晶聚酯組成物
WO2018199159A1 (fr) Procédé pour la production d'une composition de polyester à cristaux liquides et composition de polyester à cristaux liquides
JP2012136625A (ja) 液晶ポリエステル成形材料及びその成形体
TWI883692B (zh) 樹脂組合物以及包含該樹脂組合物之樹脂成形品
JP7359596B2 (ja) 樹脂組成物の製造方法、樹脂成形体の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18791977

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18791977

Country of ref document: EP

Kind code of ref document: A1