WO2021029271A1 - Pastille de résine de polyester à cristaux liquides, et article moulé en résine de polyester à cristaux liquides et procédé de fabrication d'un article moulé en résine de polyester à cristaux liquides - Google Patents

Pastille de résine de polyester à cristaux liquides, et article moulé en résine de polyester à cristaux liquides et procédé de fabrication d'un article moulé en résine de polyester à cristaux liquides Download PDF

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Publication number
WO2021029271A1
WO2021029271A1 PCT/JP2020/029768 JP2020029768W WO2021029271A1 WO 2021029271 A1 WO2021029271 A1 WO 2021029271A1 JP 2020029768 W JP2020029768 W JP 2020029768W WO 2021029271 A1 WO2021029271 A1 WO 2021029271A1
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liquid crystal
crystal polyester
polyester resin
pitch
based carbon
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PCT/JP2020/029768
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English (en)
Japanese (ja)
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翼 田村
貴之 杉山
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住友化学株式会社
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    • 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
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • B29B7/002—Methods
    • B29B7/007—Methods for continuous mixing
    • 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
    • B29B7/72—Measuring, controlling or regulating
    • B29B7/726—Measuring properties of mixture, e.g. temperature or density
    • 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
    • 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
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • 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
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • 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
    • C08J3/12—Powdering or granulating
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • 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
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • 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
    • 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
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0079—Liquid crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • B29K2105/10—Cords, strands or rovings, e.g. oriented cords, strands or rovings
    • B29K2105/101—Oriented
    • B29K2105/105—Oriented uni directionally
    • B29K2105/106—Oriented uni directionally longitudinally
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2307/00—Use of elements other than metals as reinforcement
    • B29K2307/04—Carbon

Definitions

  • the present invention relates to a liquid crystal polyester resin pellet, a liquid crystal polyester resin molded product, and a method for producing the liquid crystal polyester resin molded product.
  • the present application claims priority based on Japanese Patent Application No. 2019-148157 filed in Japan on August 9, 2019, the contents of which are incorporated herein by reference.
  • Liquid crystal polyester is known to have high fluidity, heat resistance and dimensional accuracy. Liquid crystal polyesters are rarely used alone, and are used as liquid crystal polyester resin compositions containing a filler in order to satisfy the required characteristics (for example, bending characteristics and impact resistance) in various applications. It is known that a molded product made from such a liquid crystal polyester resin composition is lightweight and has high strength.
  • the molded product obtained from the above-mentioned liquid crystal polyester resin composition has a problem that the mechanical properties are lower than those of the molded product obtained from the metal material.
  • the present invention has been made in view of the above circumstances, and is a liquid crystal polyester resin pellet capable of producing a molded product having an excellent flexural modulus, and a liquid crystal polyester resin molding having an excellent flexural modulus. It is an object of the present invention to provide a body and a method for producing the liquid crystal polyester resin molded product.
  • the present invention has the following aspects.
  • the density of the pitch-based carbon fibers is 2.10 g / cm 3 or more, and A liquid crystal polyester resin pellet having a length-weighted average fiber length of 4 mm or more and less than 50 mm of the pitch-based carbon fibers.
  • the liquid crystal polyester contains a repeating unit represented by the following formula (1), (2) or (3).
  • the content of the repeating unit represented by the following formula (1) with respect to the total amount of the repeating units represented by the following formulas (1), (2) and (3) is 30 mol% or more and 100 mol% or less.
  • the content of the repeating unit represented by the following formula (2) with respect to the total amount of the repeating units represented by the following formulas (1), (2) and (3) is 0 mol% or more and 35 mol% or less.
  • the content of the repeating unit represented by the following formula (3) is 0 mol% or more and 35 mol% or less with respect to the total amount of the repeating units represented by the following formulas (1), (2) and (3).
  • Ar 1 represents a phenylene group, a naphthylene group or a biphenylylene group
  • Ar 2 and Ar 3 are independently a phenylene group, a naphthylene group, a biphenylene group or the following formula (4).
  • X and Y each independently represent an oxygen atom or an imino group.
  • the hydrogen atom in the group represented by Ar 1 , Ar 2 and Ar 3 independently represents a halogen.
  • a method for producing a liquid crystal polyester resin molded product which comprises a step of molding using the liquid crystal polyester resin pellet according to any one of the above [1] to [4].
  • a liquid crystal polyester resin molded product containing liquid crystal polyester and pitch-based carbon fibers A liquid crystal polyester resin molded body in which the density of the pitch-based carbon fibers is 2.10 g / cm 3 or more, and the length-weighted average fiber length of the pitch-based carbon fibers is 170 ⁇ m or more and 500 ⁇ m or less.
  • a liquid crystal polyester resin pellet capable of producing a molded product having an excellent flexural modulus, a liquid crystal polyester resin molded product having an excellent flexural modulus, and a method for producing the liquid crystal polyester resin molded product. Can be provided.
  • the liquid crystal polyester resin pellet of the present embodiment contains liquid crystal polyester and pitch-based carbon fibers.
  • liquid crystal polyester resin composition a composition containing a thermoplastic resin containing a liquid crystal polyester and a pitch-based carbon fiber is referred to as a “liquid crystal polyester resin composition”.
  • the molding material for producing a molded product obtained by granulating the liquid crystal polyester resin composition is referred to as "liquid crystal polyester resin pellets”.
  • a molded product obtained from a liquid crystal polyester resin composition or a liquid crystal polyester resin pellet is referred to as a “liquid crystal polyester resin molded product”.
  • Examples of the shape of the liquid crystal polyester resin pellet include, and are not limited to, columnar, disk-shaped, elliptical columnar, elliptical, gostone, spherical, and indefinite. Cylindrical is more preferable from the viewpoint of productivity and handling at the time of molding.
  • the density of the pitch-based carbon fibers is 2.10 g / cm 3 or more, and the length-weighted average fiber length of the pitch-based carbon fibers is 4 mm or more and less than 50 mm.
  • the liquid crystal polyester resin pellet of this embodiment is suitably used as a molding material for a molded product described later.
  • the liquid crystal polyester resin pellet of the present embodiment contains a liquid crystal polyester.
  • the liquid crystal polyester used in the liquid crystal polyester resin pellets of the present embodiment preferably exhibits liquid crystal properties in a molten state, and the thermoplastic resin containing the liquid crystal polyester also exhibits liquid crystal properties in a molten state, and melts at a temperature of 450 ° C. or lower. It is preferable that the liquid crystal is used.
  • the liquid crystal polyester used in the present embodiment may be a liquid crystal polyester amide, a liquid crystal polyester ether, a liquid crystal polyester carbonate, or a liquid crystal polyester imide.
  • the liquid crystal polyester used in the present embodiment is preferably a fully aromatic liquid crystal polyester using only an aromatic compound as a raw material monomer.
  • a typical example of the liquid crystal polyester used in the present embodiment is at least one compound selected from the group consisting of aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine and aromatic diamine.
  • examples thereof include those obtained by polymerizing at least one compound, 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 independently used in place of a part or all of them, and a polymerizable derivative thereof is used. May be good.
  • Examples of polymerizable derivatives of compounds having a carboxyl group are those obtained by converting a carboxyl group into an alkoxycarbonyl group or an aryloxycarbonyl group (ester), carboxyl. Examples thereof include those obtained by converting a group into a haloformyl group (acid halide) and those obtained by converting a carboxyl group into an acyloxycarbonyl group (acid anhydride).
  • Examples of polymerizable derivatives of compounds having a hydroxyl group such as aromatic hydroxycarboxylic acids, aromatic diols and aromatic hydroxyamines, are those obtained by acylating a hydroxyl group into an acyloxyl group (acylated product).
  • the liquid crystal polyester used in the present embodiment preferably has a repeating unit represented by the following formula (1) (hereinafter, may be referred to as “repetition unit (1)”), and the repeating unit (1) and A repeating unit represented by the following formula (2) (hereinafter, may be referred to as “repetition unit (2)”) and a repeating unit represented by the following formula (3) (hereinafter, "repetition unit (3)"”. It is more preferable to have (may be).
  • Ar 1 represents a phenylene group, a naphthylene group or a biphenylylene group
  • Ar 2 and Ar 3 are independently a phenylene group, a naphthylene group, a biphenylene group or the following formula (4).
  • X and Y each independently represent an oxygen atom or an imino group.
  • the hydrogen atom in the group represented by Ar 1 , Ar 2 and Ar 3 independently represents a halogen. It may be substituted with an atom, an alkyl group or an aryl group.
  • Ar 4 and Ar 5 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.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-hexyl group and 2-ethylhexyl group.
  • examples thereof include an n-octyl group and an n-decyl group, and the number of carbon atoms thereof is preferably 1 to 10.
  • aryl group examples include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group and a 2-naphthyl group, and the number of carbon atoms thereof is preferably 6 to 20.
  • the number is preferably 2 or less, more preferably 1 or less, independently for each of the groups represented by Ar 1 , Ar 2 or Ar 3. preferable.
  • alkylidene group examples include a methylene group, an ethylidene group, an isopropylidene group, an n-butylidene group and a 2-ethylhexylidene group, and the carbon number thereof is preferably 1 to 10.
  • the repeating unit (1) is a repeating unit derived from a predetermined aromatic hydroxycarboxylic acid.
  • Ar 1 is a p-phenylene group (repeating unit derived from p-hydroxybenzoic acid), and Ar 1 is a 2,6-naphthylene group (6-hydroxy-2). -A repeating unit derived from naphthoic acid) is preferable.
  • the term "origin” means that the chemical structure of the functional group that contributes to the polymerization changes due to the polymerization of the raw material monomer, and no other structural change occurs.
  • the repeating unit (2) is a repeating unit derived from a predetermined aromatic dicarboxylic acid.
  • Ar 2 is a p-phenylene group (repeating unit derived from terephthalic acid)
  • Ar 2 is an m-phenylene group (repeating unit derived from isophthalic acid)
  • Ar 2 Is a 2,6-naphthylene group (repetitive unit derived from 2,6-naphthalenedicarboxylic acid)
  • Ar 2 is a diphenyl ether-4,4'-diyl group (diphenyl ether-).
  • a repeating unit derived from 4,4'-dicarboxylic acid) is 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 (a repeating unit derived from hydroquinone, p-aminophenol or p-phenylenediamine), and Ar 3 is a 4,4'-biphenylylene group. (Repeat units derived from 4,4'-dihydroxybiphenyl, 4-amino-4'-hydroxybiphenyl or 4,4'-diaminobiphenyl) are preferred.
  • the content of the repeating unit (1) is the total amount of all repeating units (by dividing the mass of each repeating unit constituting the liquid crystal polyester resin by the formula amount of each repeating unit, the amount equivalent to the amount of substance of each repeating unit ( Mol) is determined, and the total value thereof) is preferably 30 mol% or more and 100 mol% or less, more preferably 30 mol% or more and 90 mol% or less, and further preferably 40 mol% or more and 80 mol% or less. Especially preferably 50 mol% or more and 70 mol% or less.
  • the content of the repeating unit (2) is preferably 0 mol% or more and 35 mol% or less, more preferably 10 mol% or more and 35 mol% or less, and 15 mol% or more and 30 mol% with respect to the total amount of all repeating units.
  • the following is more preferable, and 17.5 mol% or more and 27.5 mol% or less are particularly preferable.
  • the content of the repeating unit (3) is preferably 0 mol% or more and 35 mol% or less, more preferably 10 mol% or more and 35 mol% or less, and 15 mol% or more and 30 mol% with respect to the total amount of all repeating units.
  • the following is more preferable, and 17.5 mol% or more and 27.5 mol% or less are particularly preferable.
  • the total amount of the repeating units (1), (2) and (3) does not exceed 100 mol%.
  • the ratio between the content of the repeating unit (2) and the content of the repeating unit (3) is expressed by [content of repeating unit (2)] / [content of repeating unit (3)] (mol / mol). Therefore, 0.9 / 1 to 1 / 0.9 is preferable, 0.95 / 1 to 1 / 0.95 is more preferable, and 0.98 / 1 to 1 / 0.98 is even more preferable.
  • the liquid crystal polyester used in the present embodiment may have two or more repeating units (1) to (3) independently of each other. Further, the liquid crystal polyester may have a repeating unit other than the repeating units (1) to (3), but the content thereof is preferably 10 mol% or less with respect to the total amount of all repeating units. More preferably, it is mol% or less.
  • the liquid crystal polyester used in the present embodiment has a repeating unit (3) in which X and Y are oxygen atoms, respectively, that is, it has a repeating unit derived from a predetermined aromatic diol. Is likely to be low, so it is preferable to have only those in which X and Y are oxygen atoms, respectively, as the repeating unit (3).
  • the liquid crystal polyester used in the present embodiment is obtained by melt-polymerizing a raw material monomer corresponding to a repeating unit constituting the liquid crystal polyester, and solid-phase polymerizing the obtained polymer (hereinafter, may be referred to as “prepolymer”). It is preferable to manufacture the product. As a result, a high molecular weight liquid crystal polyester having high heat resistance, strength and rigidity can be produced with good operability.
  • the melt polymerization may be carried out in the presence of a catalyst, and examples of this catalyst include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate and antimony trioxide. , 4- (Dimethylamino) pyridine, 1-methylimidazole and the like, and the nitrogen-containing heterocyclic compound is mentioned, and the nitrogen-containing heterocyclic compound is preferably used.
  • the flow start temperature of the liquid crystal polyester used in the present embodiment is preferably 280 ° C. or higher, more preferably 280 ° C. or higher and 400 ° C. or lower, and further preferably 280 ° C. or higher and 380 ° C. or lower.
  • the higher the flow start temperature of the liquid crystal polyester used in the present embodiment the more the heat resistance, strength and rigidity of the liquid crystal polyester tend to improve.
  • the flow start temperature of the liquid crystal polyester exceeds 400 ° C., the melting temperature and the melting viscosity of the liquid crystal polyester tend to increase. Therefore, the temperature required for molding the liquid crystal polyester tends to increase.
  • the flow start temperature of the liquid crystal polyester is also referred to as a flow temperature or a flow temperature, and is a temperature that serves as a guideline for the molecular weight of the liquid crystal polyester (edited by Naoyuki Koide, "Liquid Crystal Polymer-Synthesis / Molding / Application-”. , CMC Co., Ltd., June 5, 1987, p.95).
  • the flow start temperature is such that the liquid crystal polyester is melted while raising the temperature at a rate of 4 ° C./min under a load of 9.8 MPa (100 kg / cm 2 ) using a capillary rheometer, and from a nozzle having an inner diameter of 1 mm and a length of 10 mm. It is a temperature showing a viscosity of 4800 Pa ⁇ s (48000 poisons) when extruded.
  • the content ratio of the liquid crystal polyester with respect to 100% by mass of the thermoplastic resin is preferably 80% by mass or more and 100% by mass or less, more preferably 85% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass. It is particularly preferable that it is mass% or less.
  • the content ratio of the liquid crystal polyester is at least the above lower limit value, there is an effect that the flexural modulus of the test piece produced by using the liquid crystal polyester resin pellet of the present embodiment can be improved.
  • the content ratio of the liquid crystal polyester is preferably 30 to 90.9% by mass, more preferably 32 to 87% by mass, further preferably 36 to 83% by mass, and 40 by mass, based on 100% by mass of the liquid crystal polyester resin pellets. -80% by mass is particularly preferable.
  • the liquid crystal polyester resin pellet of the present embodiment contains pitch-based carbon fibers.
  • the density of the pitch-based carbon fibers in the liquid crystal polyester resin pellet of the present embodiment is 2.10 g / cm 3 or more.
  • the density of the pitch-based carbon fiber is 2.11 g / cm 3 or more, more preferably 2.12 g / cm 3 or more, particularly preferably 2.13 g / cm 3 or more.
  • the density of the pitch-based carbon fibers is less than 2.25 g / cm 3, more preferably 2.22 g / cm 3 or less, particularly preferably 2.20 g / cm 3 or less.
  • the density of the pitch-based carbon fibers is less than 2.11 g / cm 3 or more 2.25 g / cm 3, more preferably 2.12 g / cm 3 or more 2.22 g / cm 3 or less, it is especially preferred 2.13 g / cm 3 or more 2.20 g / cm 3 or less.
  • the pitch-based carbon fibers in the liquid crystal polyester resin pellet of the present embodiment have a length-weighted average fiber length of 4 mm or more and less than 50 mm.
  • the length-weighted average fiber length of the pitch-based carbon fibers in the liquid crystal polyester resin pellet is preferably 4.5 mm or more, and more preferably 6 mm or more.
  • the length-weighted average fiber length of the pitch-based carbon fibers in the liquid crystal polyester resin pellet is less than 50 mm, preferably 40 mm or less, and more preferably 20 mm or less.
  • the length-weighted average fiber length of the pitch-based carbon fibers in the liquid crystal polyester resin pellet is preferably 4.5 mm or more and 40 mm or less, and more preferably 6 mm or more and 20 mm or less.
  • the length-weighted average fiber length of the pitch-based carbon fibers in the liquid crystal polyester resin pellet of the present embodiment is 95 to 105% of the length in the longitudinal direction of the liquid crystal polyester resin pellet, and is preferably 4 mm or more. , 4.5 mm or more is more preferable, and 6 mm or more is further preferable.
  • the length-weighted average fiber length of the pitch-based carbon fibers in the liquid crystal polyester resin pellet is 95 to 105% of the length in the longitudinal direction of the liquid crystal polyester resin pellet, preferably less than 50 mm, and preferably 40 mm or less. More preferably, it is more preferably 20 mm or less.
  • the length-weighted average fiber length of the pitch-based carbon fibers in the liquid crystal polyester resin pellet is 95 to 105% of the length in the longitudinal direction of the liquid crystal polyester resin pellet, and is preferably 4 mm or more and less than 50 mm. It is more preferably 5.5 mm or more and 40 mm or less, and further preferably 6 mm or more and 20 mm or less.
  • the liquid crystal polyester resin pellet of the present embodiment By setting the density of the pitch-based carbon fibers in the liquid crystal polyester resin pellet of the present embodiment to 2.10 g / cm 3 or more and the length-weighted average fiber length to be 4 mm or more and less than 50 mm, the liquid crystal polyester resin pellets It becomes easy to improve the flexural modulus of the obtained molded product.
  • the density of the pitch-based carbon fibers in the liquid crystal polyester resin pellets is determined by dissolving the liquid crystal polyester in the liquid crystal polyester resin pellets with, for example, a mixed solution of triethylene glycol and monoethanolamine at a ratio of 4: 1. After collecting the sample of, it can be measured using a specific gravity bottle.
  • the tensile strength of the pitch-based carbon fiber is preferably 2000 MPa or more, more preferably 2500 MPa or more, and further preferably 3000 MPa or more. Further, by using the pitch-based carbon fiber having high tensile strength, the fiber breakage during the processing process up to the production of the molded product is suppressed, and the fiber can be left for a long time, so that the effect of the invention can be easily obtained.
  • the tensile strength of the pitch-based carbon fiber means a value measured in accordance with JIS R 7606: 2000.
  • Pitch-based carbon fibers can be mainly classified into mesophase pitch-based carbon fibers using mesophase pitch as a starting material and isotropic pitch-based carbon fibers using isotropic pitch as a starting material. From the viewpoint of obtaining high mechanical properties, mesophase pitch carbon fibers are preferably used.
  • the tensile elastic modulus of the pitch-based carbon fiber is preferably 200 GPa or more, more preferably 250 GPa or more, further preferably 500 GPa or more, and particularly preferably 650 GPa or more.
  • the tensile elastic modulus of the pitch-based carbon fiber means a value measured in accordance with JIS R 7606: 2000.
  • pitch-based carbon fibers examples include “Dialed (registered trademark)” manufactured by Mitsubishi Chemical Corporation, “GRANOC (registered trademark)” manufactured by Nippon Graphite Fiber Co., Ltd., and “Donna Carbo (registered trademark)” manufactured by Osaka Gas Chemical Corporation. , “Kureka (registered trademark)” manufactured by Kureha Co., Ltd., etc.
  • mesophase pitch carbon fiber examples include “Dialed (registered trademark)” manufactured by Mitsubishi Chemical Corporation and “GRANOC (registered trademark)” manufactured by Nippon Graphite Fiber Co., Ltd. It is preferable to use the mesophase pitch carbon fiber because the mechanical properties of the molded product can be improved.
  • the number average fiber diameter of the pitch-based carbon fibers in the liquid crystal polyester resin pellet of the present embodiment is not particularly limited, but is preferably 1 to 40 ⁇ m, preferably 3 to 35 ⁇ m, and 1 to 25 ⁇ m. It is preferably 3 to 20 ⁇ m, more preferably 5 to 15 ⁇ m.
  • the number average fiber diameter of the pitch-based carbon fibers is the number average value obtained by observing the pitch-based carbon fibers with a microscope (500 times) and measuring the fiber diameters of 500 randomly selected pitch-based carbon fibers. Is adopted.
  • the number average fiber diameter of the pitch-based carbon fibers is at least the lower limit of the above-mentioned preferable range, the pitch-based carbon fibers are likely to be dispersed in the liquid crystal polyester resin pellets.
  • the number average fiber diameter of the pitch-based carbon fibers is at least the lower limit of the above-mentioned preferable range, the pitch-based carbon fibers can be easily handled during the production of the liquid crystal polyester resin pellets.
  • the liquid crystal polyester is efficiently strengthened by the pitch-based carbon fibers. Therefore, an excellent flexural modulus can be imparted to the molded product obtained by molding the liquid crystal polyester resin pellets of the present embodiment.
  • Pitch-based carbon fibers may be treated with a sizing agent. Pitch-based carbon fibers that have been appropriately sized are superior in productivity and quality stability during pellet production, and can reduce variations in physical properties in the molded product.
  • the sizing agent in the present invention is not particularly limited, and examples thereof include nylon-based polymers, polyether-based polymers, epoxy-based polymers, ester-based polymers, urethane-based polymers, mixed polymers thereof, and modified polymers thereof. Further, a so-called silane coupling agent such as aminosilane or epoxysilane, or a known coupling agent such as a titanium coupling agent can also be used.
  • the single fibers do not necessarily have to be arranged in one direction, but from the viewpoint of productivity in the process of manufacturing the molding material, the single fibers are on one side. It is preferable that the fibers are arranged and the fiber bundles are continuous in the length direction of the fibers.
  • the number of single yarns in the pitch carbon fiber is preferably 10,000 or more and 100,000 or less, more preferably 10,000 or more and 50,000 or less, and further preferably 10,000 or more and 30,000 or less.
  • the content ratio of the pitch-based carbon fibers in the liquid crystal polyester resin pellet of the present embodiment is preferably 10 to 230 parts by mass, more preferably 15 to 210 parts by mass, and 20 to 210 parts by mass with respect to 100 parts by mass of the liquid crystal polyester. 180 parts by mass is more preferable, and 25 to 150 parts by mass is particularly preferable.
  • the content ratio of the pitch-based carbon fibers is preferably 9.1 to 70% by mass, more preferably 13 to 68% by mass, still more preferably 17 to 64% by mass, based on 100% by mass of the liquid crystal polyester resin pellets. , 20-60% by mass is particularly preferable.
  • the content ratio of the pitch-based carbon fibers is equal to or higher than the lower limit of the above-mentioned preferable range, the effect of improving the flexural modulus by the pitch-based carbon fibers is likely to be enhanced.
  • the value is not more than the upper limit of the above-mentioned preferable range, the pitch-based carbon fibers can be easily opened, which is suitable for producing resin pellets.
  • the liquid crystal polyester resin pellet of the present embodiment contains, as a raw material, other components such as the above-mentioned liquid crystal polyester and pitch-based carbon fiber, and if necessary, a thermoplastic resin other than the liquid crystal polyester, a filler, and an additive. It may contain more than seeds.
  • resins other than liquid crystal polyester contained in liquid crystal polyester resin pellets include polyolefin resins such as polypropylene, polybutadiene, and polymethylpentene, vinyl resins such as vinyl chloride, vinylidene chloride acetate, and polyvinyl alcohol, polystyrene, and acrylonitrile-styrene.
  • Polyamide resin such as resin (AS resin), acrylonitrile-butadiene-styrene resin (ABS resin), polyamide 6 (nylon 6), polyamide 66 (nylon 66), polyamide 11 (nylon 11), polyamide 12 (nylon 12), Polyamide 46 (Nylon 46), Polyamide 610 (Nylon 610), Polytetramethylene terephthalamide (Nylon 4T), Polyhexamethylene terephthalamide (Nylon 6T), Polymethoxylylen adipamide (Nylon MXD6), Polynonamethylene terephthalamide Polyamide resin such as (nylon 9T), polydecamethylene terephthalamide (nylon 10T), polyester resin other than liquid crystal polyester such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polytrimethylene terephthalate, modified polysulfone, polyether Polysulfone-based resins such as sulfone, polysulfone, and polyphenyl
  • the filler may be a plate-shaped filler, a spherical filler, or other granular filler. Further, the filler may be an inorganic filler or an organic filler.
  • plate-like inorganic fillers examples include talc, mica, graphite, wollastonite, glass flakes, barium sulfate, and calcium carbonate.
  • the mica may be muscovite, phlogopite, fluorine phlogopite, or tetrasilicon mica.
  • Examples of granular inorganic fillers include silica, alumina, titanium oxide, glass beads, glass balloons, boron nitride, silicon carbide, and calcium carbonate.
  • additives include flame retardants, conductivity-imparting agents, crystal nucleating agents, UV absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, anticoloring agents, heat stabilizers, and release agents.
  • examples include molds, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, viscosity modifiers and surfactants.
  • the liquid crystal polyester resin pellets of the present embodiment are excluded from those in which fullerenes are present near the interface between the carbon fiber bundle and the liquid crystal polyester resin.
  • the density of the pitch-based carbon fibers in the liquid crystal polyester resin pellet of the present embodiment is 2.10 g / cm 3 or more, and the length-weighted average fiber length of the pitch-based carbon fibers is 4 mm or more and less than 50 mm. Density of the pitch-based carbon fiber of the liquid crystal polyester resin pellets of the present embodiment is less 2.11 g / cm 3 or more 2.25 g / cm 3, the length weighted average fiber length of the pitch-based carbon fibers or 4mm It is preferably 40 mm or less.
  • Density of the pitch-based carbon fiber of the liquid crystal polyester resin pellets of the present embodiment is less 2.11 g / cm 3 or more 2.25 g / cm 3, the length weighted average fiber length of the pitch-based carbon fibers 4. More preferably, it is 5 mm or more and 40 mm or less. Density of the pitch-based carbon fiber of the liquid crystal polyester resin pellets of the present embodiment is less 2.12 g / cm 3 or more 2.22 g / cm 3, the length weighted average fiber length of the pitch-based carbon fibers 4. More preferably, it is 5 mm or more and 40 mm or less.
  • Density of the pitch-based carbon fiber of the liquid crystal polyester resin pellets of the present embodiment is less 2.13 g / cm 3 or more 2.20 g / cm 3, the length weighted average fiber length of the pitch-based carbon fibers or 6mm It is particularly preferably 20 mm or less. Density of the pitch-based carbon fiber of the liquid crystal polyester resin pellets of the present embodiment is less 2.12 g / cm 3 or more 2.15 g / cm 3, the length weighted average fiber length of the pitch-based carbon fibers or 4mm It may be 40 mm or less.
  • the flexural modulus of the test piece obtained by injection molding the liquid crystal polyester resin pellet of the present embodiment is preferably 28 GPa or more, more preferably 30 GPa or more, still more preferably 34 GPa or more, and particularly preferably 43 GPa or more. That is all.
  • the flexural modulus can be measured by injection molding the liquid crystal polyester resin pellet under the following injection molding conditions and measuring the following test piece obtained under the following bending test measurement conditions.
  • the bending strength of the test piece obtained by injection molding the liquid crystal polyester resin pellet of the present embodiment is preferably 165 MPa or more, more preferably 170 MPa or more, and further preferably 175 MPa or more.
  • the bending strength can be measured by injection molding a liquid crystal polyester resin pellet under the injection molding conditions and measuring the test piece obtained under the measurement conditions of the bending test.
  • the tensile strength of the test piece obtained by injection molding the liquid crystal polyester resin pellet of the present embodiment is preferably 90 MPa or more, more preferably 95 MPa or more, still more preferably 100 MPa or more, and particularly preferably 110 MPa or more. Is.
  • the tensile strength strain of the test piece obtained by injection molding the liquid crystal polyester resin pellet of the present embodiment is preferably 0.5% or more, more preferably 1.0% or more, still more preferably 1.4%. That is all.
  • the tensile strength and the tensile strength strain can be measured by injection molding the liquid crystal polyester resin pellet under the injection molding conditions on the following test piece under the measurement conditions of the following tensile test.
  • the liquid crystal polyester resin pellet of the present invention has the following aspects. "1" A liquid crystal polyester resin pellet containing liquid crystal polyester and pitch-based carbon fibers. The density of the pitch-based carbon fibers is 2.10 g / cm 3 or more, and A liquid crystal polyester resin pellet having a length-weighted average fiber length of 4 mm or more and less than 50 mm of the pitch-based carbon fibers.
  • the density of the pitch-based carbon fibers is 2.10 g / cm 3 or more
  • the following test piece obtained by injection molding the liquid crystal polyester resin pellet under the following injection molding conditions has a flexural modulus of 28 GPa or more measured under the measurement conditions of the following bending test.
  • the content ratio of the pitch-based carbon fiber is 10 to 230 parts by mass, preferably 15 to 210 parts by mass, and more preferably 2 to 180 parts by mass with respect to 100 parts by mass of the liquid crystal polyester.
  • the liquid crystal polyester contains a repeating unit represented by the following formula (1), (2) or (3).
  • the content of the repeating unit represented by the following formula (1) with respect to the total amount of the repeating units represented by the following formulas (1), (2) and (3) is 30 mol% or more and 100 mol% or less.
  • the content of the repeating unit represented by the following formula (2) with respect to the total amount of the repeating units represented by the following formulas (1), (2) and (3) is 0 mol% or more and 35 mol% or less. It is preferably 10 mol% or more and 35 mol% or less, more preferably 15 mol% or more and 30 mol% or less, and further preferably 17.5 mol% or more and 27.5 mol% or less.
  • the content of the repeating unit represented by the following formula (3) with respect to the total amount of the repeating units represented by the following formulas (1), (2) and (3) is 0 mol% or more and 35 mol% or less.
  • the total amount of the repeating units represented by the formulas (1), (2) and (3) does not exceed 100 mol%.
  • Ar 1 represents a phenylene group, a naphthylene group or a biphenylylene group
  • Ar 2 and Ar 3 are independently a phenylene group, a naphthylene group, a biphenylene group or the following formula (4).
  • X and Y each independently represent an oxygen atom or an imino group.
  • the hydrogen atom in the group represented by Ar 1 , Ar 2 and Ar 3 independently represents a halogen.
  • the content of the repeating unit represented by the formula (2) is 10 mol% or more and 35 mol% or less with respect to the total amount of the repeating units represented by the formulas (1), (2) and (3).
  • the content of the repeating unit represented by the formula (3) is 10 mol% or more and 35 mol% or less with respect to the total amount of the repeating units represented by the formulas (1), (2) and (3). 7 ”.
  • the liquid crystal polyester resin pellet However, the total amount of the repeating units represented by the formulas (1), (2) and (3) does not exceed 100 mol%. "9”
  • a "10" Density of the pitch-based carbon fiber is 2.11 g / cm 3 or higher, preferably 2.12 g / cm 3 or more, preferably 2.14 g / cm 3 or more, wherein "1" to The liquid crystal polyester resin pellet according to any one of "9".
  • the length-weighted average fiber length of the pitch-based carbon fibers is 4.5 mm or more and 40 mm or less, preferably 6 mm or more and 20 mm or less, according to any one of "1” to "10”.
  • "12” A liquid crystal polyester resin pellet containing liquid crystal polyester and pitch-based carbon fibers.
  • the content ratio of the liquid crystal polyester with respect to 100% by mass of the thermoplastic resin is 80% by mass or more and 100% by mass or less, preferably 85% by mass or more and 100% by mass or less, and more preferably 90% by mass or more and 100% by mass or less.
  • the liquid crystal polyester resin pellet according to any one of "1" to "11" below.
  • the method for producing the liquid crystal polyester resin pellet of the present embodiment is obtained by melt-kneading the liquid crystal polyester and other components, if necessary, while feeding out a pitch-based carbon fiber bundle in which a plurality of pitch-based carbon fibers are converged.
  • FIG. 1 is a schematic view showing an example of the liquid crystal polyester resin pellet manufacturing apparatus of this embodiment.
  • a liquid crystal polyester resin pellet 15 is obtained by using a pitch-based carbon fiber roving 10 in which a pitch-based carbon fiber bundle 11 in which a plurality of pitch-based carbon fibers are converged is wound into a roll shape. Will be explained.
  • the manufacturing apparatus 100 includes a preheating unit 121, an impregnation unit 123, a cooling unit 125, a take-up unit 127, a cutting unit 129, and transfer rolls 101 to 109.
  • the extruder 120 is connected to the impregnation unit 123.
  • FIG. 1 shows how the pitch-based carbon fiber bundle 11 with a converging agent is continuously fed out from the pitch-based carbon fiber roving 10.
  • the liquid crystal polyester resin pellets are produced while the pitch-based carbon fiber bundle 11 with a converging agent unwound from the pitch-based carbon fiber roving 10 is transported in the longitudinal direction by the transport rolls 101 to 109.
  • the fineness of the pitch-based carbon fiber roving 10 used in the production of the liquid crystal polyester resin pellet of the present embodiment is not particularly limited, but is preferably 100 g / 1000 m or more, and more preferably 1000 g / 1000 m or more.
  • the fineness of the pitch-based carbon fiber roving 10 is preferably 3000 g / 1000 m or less, and more preferably 2500 g / 1000 m or less.
  • the fineness of the carbon fiber roving 10 is 3000 g / 1000 m or less, the liquid crystal polyester resin is easily impregnated, and the effect of the invention can be stably obtained.
  • the fineness of the carbon fiber roving 10 is 3000 g / 1000 m or less, pitch-based carbon fibers can be easily handled during the production of the liquid crystal polyester resin pellets. That is, the fineness of the pitch-based carbon fiber roving 10 is preferably 100 g / 1000 m or more and 3050 g / 1000 m or less, and more preferably 1000 g / 1000 m or more and 3000 g / 1000 m or less.
  • the pitch-based carbon fiber bundle 11 unwound from the pitch-based carbon fiber roving 10 is preheated and dried.
  • the heating temperature at that time is not particularly limited, but is, for example, 100 to 200 ° C.
  • the heating time in the preheating unit 121 is not particularly limited, but is, for example, 10 seconds to 5 minutes.
  • the resin material M (liquid crystal polyester, other components blended if necessary) is impregnated into the pitch-based carbon fiber bundle 11.
  • the resin material M may be charged from the supply port 123a and heated in the impregnated portion 123 to impregnate the pitch-based carbon fiber bundle 11, or the molten resin material M may be impregnated in the extruder 120.
  • the pitch-based carbon fiber bundle 11 may be impregnated by feeding from the supply port 123a.
  • the resin structure 13 in which the pitch-based carbon fiber bundle 11 is impregnated and coated with the melt is obtained.
  • the resin structure 13 is cut to obtain a liquid crystal polyester resin pellet 15 containing a thermoplastic resin containing liquid crystal polyester and pitch-based carbon fibers.
  • the heating temperature in the impregnated portion 123 is appropriately determined according to the type of the liquid crystal polyester, and is preferably set to a temperature 10 to 80 ° C. higher than the flow start temperature of the liquid crystal polyester used, for example, 300 to 400 ° C.
  • the impregnated portion 123 1 to 120 parts by mass, preferably 30 to 120 parts by mass, more preferably 30 to 120 parts by mass of pitch-based carbon fibers with respect to 100 parts by mass of the liquid crystal polyester, depending on the characteristics required for the liquid crystal polyester resin pellets and the like. Impregnate 80 to 120 parts by mass.
  • the pitch-based carbon fiber bundle is sufficiently impregnated with the liquid crystal polyester, and liquid crystal polyester resin pellets having a good shape can be obtained, and the moldability can be obtained. Is improved.
  • the carbon fibers can be easily opened, liquid polyester resin pellets having good impregnation property can be obtained, and the molded product produced using the resin pellets can be obtained.
  • the variation in flexural modulus can be reduced.
  • the cooling unit 125 cools the resin structure 13 (the resin structure 13 in which the pitch-based carbon fiber bundle is impregnated and coated with the melt) heated by the impregnation unit 123 to, for example, 50 to 150 ° C.
  • the cooling time is not particularly limited, but is, for example, 3 to 30 seconds.
  • the take-up section 127 continuously picks up the resin structure 13 cooled by the cooling section 125 and feeds it to the next cutting section 129.
  • the cooled resin structure 13 is cut to a desired length to prepare a liquid crystal polyester resin pellet 15.
  • the cutting portion 129 includes, for example, a rotary blade.
  • pellets in which pitch-based carbon fibers are hardened with a thermoplastic resin containing the liquid crystal polyester are manufactured as follows. ..
  • the preheating section 121 heats and dries the pitch-based carbon fiber bundle 11 while continuously feeding out the pitch-based carbon fiber bundle 11 in which a plurality of pitch-based carbon fibers are converged from the pitch-based carbon fiber roving 10. ..
  • the molding material M melt-kneaded by the extruder 120 is charged from the supply port 123a and melted into the pitch-based carbon fiber bundle 11.
  • the molding material M in the state is impregnated.
  • the resin structure 13 in which the pitch-based carbon fiber bundle is impregnated and coated with the melt is obtained.
  • the resin structure 13 heated by the impregnated portion 123 is cooled by the cooling portion 125.
  • the pitch-based carbon fibers are arranged substantially parallel to the longitudinal direction of the resin structure 13.
  • the carbon fibers are arranged substantially parallel to the longitudinal direction of the resin structure means that the angle formed by the longitudinal direction of the carbon fibers and the longitudinal direction of the resin structure is approximately 0 °. Specifically, carbon It shows a state in which the angle formed by each of the fiber and the resin structure in the longitudinal direction is -5 ° to 5 °.
  • the cooled resin structure 13 is taken up in a strand shape by the taking-up portion 127 and fed out to the cutting portion 129.
  • the strand-shaped resin structure 13 is cut to a predetermined length in the longitudinal direction thereof to obtain pellets 15.
  • the predetermined length of the pellet 15 referred to here is the length of the pellet 15 set according to the required performance of the molded product using the pellet 15 as a material.
  • the length of the pellet 15 and the length of the pitch-based carbon fibers arranged in the pellet 15 are substantially the same length.
  • the length of the pellet and the length of the carbon fiber are substantially the same means that the length-weighted average fiber length of the carbon fibers arranged in the pellet is 95, which is the length in the longitudinal direction of the pellet. It shows that it is ⁇ 105%.
  • pitch-based carbon fibers are hardened with a thermoplastic resin containing liquid crystal polyester, and the pitch-based carbon fibers are arranged substantially parallel to the longitudinal direction of the pellet, that is, the said. Pitch carbon fibers are lined up in one direction. Further, the length-weighted average fiber length of the pitch-based carbon fibers arranged in the liquid crystal polyester resin pellet 15 is substantially the same as the length of the liquid crystal polyester resin pellet 15.
  • the length of the liquid crystal polyester resin pellet 15 produced in the present embodiment is 4 mm or more and less than 50 mm from the viewpoint that the molded product using the liquid crystal polyester resin pellet 15 as a molding material has an excellent flexural modulus. It may be .5-48 mm or 5-46 mm.
  • the pitch-based carbon fibers are arranged substantially parallel to the longitudinal direction of the liquid crystal polyester resin pellet 15, the pitch-based carbon fibers are arranged in one direction, and the length-weighted average fiber length of the pitch-based carbon fibers is determined. Since the length is substantially the same as the length of the liquid crystal polyester resin pellets, the flexural modulus of the molded product is improved.
  • the liquid crystal polyester resin molded body of the present embodiment is a liquid crystal polyester resin molded body containing liquid crystal polyester and pitch-based carbon fibers, and the density of the pitch-based carbon fibers is 2.10 g / cm 3 or more.
  • the length-weighted average fiber length of the pitch-based carbon fibers is 170 ⁇ m or more and 500 ⁇ m or less, more preferably 190 ⁇ m or more and less than 500 ⁇ m, still more preferably 200 ⁇ m or more and less than 500 ⁇ m, and particularly preferably 200 ⁇ m or more and 400 ⁇ m or less.
  • the length-weighted average fiber length of the pitch-based carbon fiber is at least the above lower limit value, the flexural modulus is excellent.
  • the molded product of the present embodiment can be produced by using the liquid crystal polyester resin pellets.
  • the density of the pitch-based carbon fibers in the liquid crystal polyester resin molded product of the present embodiment is 2.10 g / cm 3 or more, and the details are the same as the density of the pitch-based carbon fibers in the liquid crystal polyester resin pellets. is there.
  • the density of the pitch-based carbon fibers in the liquid crystal polyester resin molded body obtained through the step of molding using the liquid crystal polyester resin pellets shall not change from the density of the pitch-based carbon fibers in the liquid crystal polyester resin pellets. be able to.
  • the density of pitch-based carbon fibers in the liquid crystal polyester resin molded body is determined by, for example, dissolving the liquid crystal polyester in the liquid crystal polyester resin molded body with a mixed solution of triethylene glycol and monoethanolamine at a ratio of 4: 1 to obtain a pitch system. After collecting the carbon fiber sample, it can be measured using a specific gravity bottle.
  • the length-weighted average fiber length of the pitch-based carbon fibers in the liquid crystal polyester resin molded body obtained through the step of molding using the liquid crystal polyester resin pellets is the length weighted of the pitch-based carbon fibers in the liquid crystal polyester resin pellets.
  • the average fiber length is 4 mm or more and less than 50 mm, it can be 170 ⁇ m or more and 500 ⁇ m or less, and can be excellent in mechanical strength such as flexural modulus.
  • the length-weighted average fiber length of the fibrous filler in the liquid crystal polyester resin molded body can be obtained by the same method as the length-weighted average fiber length of the fibrous filler in the liquid crystal polyester resin pellets.
  • the flexural modulus of the liquid crystal polyester resin molded product is preferably 28 GPa or more, more preferably 30 GPa or more, further preferably 34 GPa or more, and particularly preferably 43 GPa or more.
  • the bending strength of the liquid crystal polyester resin molded product is preferably 165 MPa or more, more preferably 170 MPa or more, and further preferably 175 MPa or more.
  • the tensile strength of the liquid crystal polyester resin molded product is preferably 90 MPa or more, more preferably 95 MPa or more, still more preferably 100 MPa or more, and particularly preferably 110 MPa or more.
  • the tensile strength strain of the liquid crystal polyester resin molded product is preferably 0.5% or more, more preferably 1.0% or more, still more preferably 1.4% or more.
  • the liquid crystal polyester resin molded product of the present invention has the following aspects. "21" A liquid crystal polyester resin molded product containing liquid crystal polyester and pitch-based carbon fibers. A liquid crystal polyester resin molded body in which the density of the pitch-based carbon fibers is 2.10 g / cm 3 or more, and the length-weighted average fiber length of the pitch-based carbon fibers is 170 ⁇ m or more and 500 ⁇ m or less.
  • the liquid crystal polyester contains a repeating unit represented by the following formula (1), (2) or (3).
  • the content of the repeating unit represented by the following formula (1) with respect to the total amount of the repeating units represented by the following formulas (1), (2) and (3) is 30 mol% or more and 100 mol% or less.
  • the content of the repeating unit represented by the following formula (2) with respect to the total amount of the repeating units represented by the following formulas (1), (2) and (3) is 0 mol% or more and 35 mol% or less.
  • the content of the repeating unit represented by the following formula (3) is 0 mol% or more and 35 mol% or less with respect to the total amount of the repeating units represented by the following formulas (1), (2) and (3).
  • Ar 1 represents a phenylene group, a naphthylene group or a biphenylylene group
  • Ar 2 and Ar 3 are independently a phenylene group, a naphthylene group, a biphenylene group or the following formula (4).
  • X and Y each independently represent an oxygen atom or an imino group.
  • the hydrogen atom in the group represented by Ar 1 , Ar 2 and Ar 3 independently represents a halogen. It may be substituted with an atom, an alkyl group or an aryl group.
  • (4) -Ar 4- Z-Ar 5- In the formula (4), Ar 4 and Ar 5 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 method for producing a liquid crystal polyester resin molded product of the present embodiment includes a step of molding using the liquid crystal polyester resin pellets.
  • the liquid crystal polyester resin pellet can be molded by a known molding method.
  • a melt molding method is preferable, and examples thereof include an injection molding method, an extrusion molding method such as a T-die method and an inflation method, a compression molding method, and a blow molding method. Vacuum forming method and press molding can be mentioned. Of these, the injection molding method is preferable.
  • the liquid crystal polyester resin pellet when used as a molding material and molded by an injection molding method, the liquid crystal polyester resin pellet is melted by using a known injection molding machine, and the melted liquid crystal polyester resin composition is placed in a mold. It is molded by injecting into.
  • known injection molding machines include TR450EH3 manufactured by Sodick Co., Ltd. and PS40E5ASE type hydraulic horizontal molding machine manufactured by Nissei Resin Industry Co., Ltd.
  • Examples of the type of injection molding machine include an in-line type in which the pellet plasticizing part and the injection part are integrated, and a pre-plastic type injection molding machine in which the pellet plasticizing part and the injection part are independent. A pre-plastic injection molding machine is preferable because there is no check valve and the injection pressure can be reduced.
  • the pre-plastic injection molding machine include TR450EH3 manufactured by Sodick Co., Ltd.
  • the cylinder temperature (that is, molding temperature) of the injection molding machine is appropriately determined according to the type of the liquid crystal polyester, and is preferably set to a temperature 10 to 80 ° C. higher than the flow start temperature of the liquid crystal polyester used, for example, 300 to 400. °C.
  • the temperature of the mold is preferably set in the range of room temperature (for example, 23 ° C.) to 180 ° C. from the viewpoint of the cooling rate and productivity of the liquid crystal polyester resin composition.
  • the molded product obtained by the manufacturing method of the present embodiment uses the liquid crystal polyester resin pellet to which the present invention is applied, the rigidity of the molded product is increased, and a molded product that is not easily bent by external stress is manufactured. be able to.
  • the method for producing a liquid crystal polyester resin molded product of the present invention has the following aspects.
  • “31” A method for producing a liquid crystal polyester resin molded product, which comprises a step of molding using the liquid crystal polyester resin pellet according to any one of "1" to "10".
  • the molded product obtained by the manufacturing method of the present embodiment described above can be generally applied to all applications to which the liquid crystal polyester resin can be applied, and is particularly suitable for applications in the automobile field.
  • Applications in the automobile field include, for example, injection molded products for automobile interior materials, injection molded products for ceiling materials, injection molded products for wheel house covers, injection molded products for trunk room lining, injection molded products for instrument panel skin materials, and handles.
  • Injection molded product for cover injection molded product for armrest, injection molded product for headrest, injection molded product for seat belt cover, injection molded product for shift lever boot, injection molded product for console box, injection molded product for horn pad, for knob Injection molding, injection molding for airbag cover, injection molding for various trims, injection molding for various pillars, injection molding for door lock bezel, injection molding for grab box, injection molding for defroster nozzle, for scuff plate
  • Examples thereof include an injection molded product, an injection molded product for a steering wheel, and an injection molded product for a steering column cover.
  • an injection molded body for an automobile exterior material for example, as an injection molded body for an automobile exterior material, an injection molded body for a bumper, an injection molded body for a spoiler, an injection molded body for a mudguard, an injection molded body for a side molding, and an injection molded body for a radiator grill.
  • Body injection molding for wheel cover, injection molding for wheel cap, injection molding for cowl belt grill, injection molding for air outlet louver, injection molding for air scoop, injection molding for hood bulge, for fender Examples thereof include injection molded products and injection molded products for back doors.
  • Injection moldings for cylinders and head covers injection moldings for engine mounts, injection moldings for air intake manifolds, injection moldings for throttle bodies, injection moldings for air intake pipes, radiator tanks as parts in the engine room for automobiles.
  • Injection moldings for radiator support injection moldings for water pumps and inlets, injection moldings for water pumps and outlets, injection moldings for thermostat housings, injection moldings for cooling fans, injection moldings for fan shrouds Body, injection molded body for oil pan, injection molded body for oil filter housing, injection molded body for oil filler cap, injection molded body for oil level gauge, injection molded body for timing belt, injection for timing belt cover Examples include molded parts and injection molded parts for engine covers.
  • Automotive fuel components include fuel caps, fuel filler tubes, automotive fuel tanks, fuel sender modules, fuel cutoff valves, quick connectors, canisters, fuel delivery pipes, fuel filler necks and the like.
  • Examples of automobile drive system components include shift lever housings and propeller shafts.
  • Examples of chassis parts for automobiles include stabilizers and linkage rods.
  • injection molded products for automobile parts include injection molded products for automobile head lamps, injection molded products for glass run channels, injection molded products for weather strips, injection molded products for drain hoses, and injection molded products for window washer tubes. Examples thereof include injection molded products for tubes, injection molded products for tubes, injection molded products for rack and pinion boots, and injection molded products for gaskets. Above all, it can be preferably used for members that require rigidity.
  • the molded body of the present embodiment includes a sensor, an LED lamp, a connector, a socket, a resistor, a relay case, a switch, a coil bobbin, a capacitor, a variable condenser case, an optical pickup, an oscillator, various terminal boards, and a metamorphic device.
  • Plugs printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystal displays, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, microwave parts, It can also be applied to applications such as audio / audio equipment parts, lighting parts, air conditioner parts, office computer-related parts, telephone / FAX-related parts, and copying machine-related parts.
  • the liquid crystal polyester 1 contains 60 mol% of the repeating unit (1) in which Ar 1 is a 1,4-phenylene group and Ar 2 is a repeating unit having a 1,3-phenylene group, based on the total amount of all repeating units.
  • (2) is 8.0 mol%
  • Ar 2 is a repeating unit (2) having a 1,4-phenylene group is 12 mol%
  • Ar 3 is a repeating unit (3) having a 4,4'-biphenylene group. It had 20 mol%, and its flow starting temperature was 291 ° C.
  • the liquid crystal polyester 2 based on the total amount of all repeating units, Ar @ 1 is repeating unit (1) 55 mole% 2,6-naphthylene group, repeating unit Ar 2 is a 2,6-naphthylene group ( 2) is 17.5 mol%, Ar 2 is a repeating unit (2) having a 1,4-phenylene group of 5 mol%, and Ar 3 is a repeating unit (3) having a 1,4-phenylene group. It had 5 mol%, and its flow starting temperature was 333 ° C.
  • the obtained solid material is pulverized with a pulverizer to a particle size of about 0.1 to 1 mm, heated from room temperature to 250 ° C. over 1 hour under a nitrogen atmosphere, and then raised from 250 ° C. to 285 ° C. over 5 hours.
  • Solid phase polymerization was carried out by warming and holding at 285 ° C. for 3 hours. After solid-phase polymerization, it was cooled to obtain a powdery liquid crystal polyester 3.
  • the liquid crystal polyester 3 contains 60 mol% of the repeating unit (1) in which Ar 1 is a 1,4-phenylene group and Ar 2 is a repeating unit having a 1,3-phenylene group, based on the total amount of all repeating units.
  • the obtained prepolymer had a size of about 3 to 5 cm square, pulverized to an average particle size of 1 mm or less using a pulverizer, and then the flow start temperature was measured and found to be 239 ° C. This prepolymer exhibited optical anisotropy when melted.
  • the liquid crystal polyester 4 based on the total amount of all repeating units, the repeating units (1) to 73 mol% Ar 1 is 1,4-phenylene group, the recurring units Ar 1 is a 2,6-naphthylene group It had 27 mol% of (1), and its flow start temperature was 287 ° C.
  • the length-weighted average fiber lengths of carbon fibers such as pitch-based carbon fibers and PAN-based carbon fibers in the resin pellets and in the multipurpose test piece (that is, the molded body) were measured by the following measuring methods.
  • a width 10 mm ⁇ a length 20 mm ⁇ a thickness 4 mm is cut out from the central portion of a multipurpose test piece (type A1) conforming to JIS K 7139. Also, select about 5 resin pellets.
  • These test samples are sintered in a muffle furnace to remove the resin component. However, the firing conditions are 500 ° C. and 3 hours.
  • a carbon fiber dispersion is prepared by dispersing the carbon fiber alone in 500 mL of an aqueous solution containing 0.05% by volume of a surfactant (NICRO90 manufactured by INTERRNATIONAL PRODUCTS CORPORATION).
  • NICRO90 manufactured by INTERRNATIONAL PRODUCTS CORPORATION
  • a part of the dispersion liquid was taken out and the carbon fibers were observed with a microscope.
  • a microscope manufactured by KEYENCE CORPORATION, VH-Z25
  • a microscope manufactured by KEYENCE CORPORATION, VH-ZST
  • VH-ZST a microscope (manufactured by KEYENCE CORPORATION, VH-ZST) is used to photograph the fibers at a magnification of 100 times.
  • liquid crystal polyester resin pellets were obtained as follows.
  • a GTS-40 type extruder manufactured by Plastic Engineering Laboratory Co., Ltd.
  • EBD-1500A manufactured by Imex Co., Ltd.
  • the carbon fiber roving 10 is converted into a pitch-based carbon fiber bundle 11 and the pitch-based carbon fiber 1 (manufactured by Mitsubishi Chemical Corporation, Dialead) (Registered Trademark) Grade: K13916, density 2.15 g / cm 3 , fiber diameter 11 ⁇ m, tensile elastic modulus 760 GPa, tensile strength 3000 MPa) was continuously fed at a take-up speed of 10 m / min, and first, the preheating section 121 was used. It was heated to 200 ° C. and dried.
  • the liquid crystal polyester 1 obtained in the above ⁇ Production of liquid crystal polyester 1> was heated to 360 ° C. to prepare a molten state.
  • the liquid crystal polyester 1 in a molten state is supplied from the extruder 120.
  • (Resin material M) was charged from the supply port 123a.
  • the liquid crystal polyester 1 (resin material M) was melted at 360 ° C. in the die (impregnated portion 123), and the pitch-based carbon fiber 1 was impregnated.
  • the impregnation amount of the liquid crystal polyester 1 was adjusted by changing the size of the hole diameter at the outlet of the impregnation die.
  • a resin structure 13 having 82 parts by mass of pitch-based carbon fibers 1 (pitch-based carbon fiber bundles 11) with respect to 100 parts by mass of liquid crystal polyester 1 was obtained.
  • the pitch-based carbon fibers 1 were arranged substantially parallel to the longitudinal direction of the liquid crystal polyester layer. After that, the resin structure 13 in a heated state in the die (impregnated portion 123) was cooled to 150 ° C. or lower by the cooling portion 125.
  • the cooled resin structure 13 is taken up in a strand shape by the belt-type take-up machine (take-up portion 127) and fed out to a pelletizer (cutting portion 129) to pull out the strand (resin structure 13).
  • the liquid crystal polyester resin pellet 15 of Example 1 having a cylindrical shape was obtained by cutting it in the longitudinal direction with a length of 12 mm.
  • the length-weighted average fiber length of the pitch-based carbon fibers 1 in the pellet was 12 mm (Example 1), and the number average fiber diameter was 11 ⁇ m (Example 1).
  • the density of carbon fibers recovered from the liquid crystal polyester resin pellets of Example 1 was measured by the following procedure. (1) The density of 1-butanol at 23 ° C. was measured with an Anton Pearl density measuring device. (2) After weighing the sufficiently dried specific gravity bottle in advance, 1-butanol was filled up to the marked line at 23 ° C. ⁇ 0.5 ° C. and the mass was weighed. (3) Next, the specific gravity bottle was emptied and dried, and 10 mg to 20 mg of a carbon fiber sample was added and weighed. 1-Butanol was added thereto, and the mixture was placed in a vacuum desiccator for 20 minutes or more to remove air bubbles.
  • the density of the pitch-based carbon fibers recovered from the liquid crystal polyester resin pellets of Example 1 was 2.14 g / cm 3 . From this, the density of the pitch-based carbon fibers recovered from the liquid crystal polyester resin pellets did not change from the density of the pitch-based carbon fibers as the raw material.
  • Examples 2 to 3 The same as in Example 1 except that the cutting of the strand (resin structure 13) having a length of 12 mm in the longitudinal direction was changed to the cutting of the length of each liquid crystal polyester resin pellet shown in Table 1. , The liquid crystal polyester resin pellets 15 of Examples 2 to 3 having a columnar shape having a predetermined length were obtained. The length-weighted average fiber lengths of the pitch-based carbon fibers 1 in the pellets were 40 mm (Example 2) and 4 mm (Example 3), and the number average fiber diameter was 11 ⁇ m (Examples 2 and 3).
  • Example 4 Except that the liquid crystal polyester 1 obtained in the ⁇ manufacturing of the liquid crystal polyester 1> in Example 1 was changed to the liquid crystal polyester 2 obtained in the ⁇ manufacturing of the liquid crystal polyester 2>, and the melting temperature was changed to 380 ° C. Obtained a liquid crystal polyester resin pellet 15 of Example 4 having a cylindrical shape (length 12 mm) in the same manner as in Example 1. The length-weighted average fiber length of the pitch-based carbon fibers 1 in the pellet was 12 mm (Example 4), and the number average fiber diameter was 11 ⁇ m (Example 4).
  • Example 5 By changing the size of the hole diameter at the outlet of the impregnated die, 82 parts by mass of the pitch-based carbon fiber 1 is made into 100 parts by mass of the liquid crystal polyester 2 with respect to 100 parts by mass of the liquid crystal polyester 2 in Example 4.
  • the liquid crystal polyester resin pellet 15 of Example 5 having a columnar shape having a predetermined length was obtained in the same manner as in Example 4 except that the pitch-based carbon fiber 1 was changed to 120 parts by mass.
  • the length-weighted average fiber length of the pitch-based carbon fibers 1 in the pellet was 12 mm (Example 5), and the number average fiber diameter was 11 ⁇ m (Example 5).
  • Example 6 Except that the liquid crystal polyester 1 obtained in the ⁇ manufacturing of the liquid crystal polyester 1> in Example 1 was changed to the liquid crystal polyester 3 obtained in the ⁇ manufacturing of the liquid crystal polyester 3>, and the melting temperature was changed to 380 ° C. Obtained a liquid crystal polyester resin pellet 15 of Example 6 having a columnar shape (length 12 mm) in the same manner as in Example 1. The length-weighted average fiber length of the pitch-based carbon fibers 1 in the pellet was 12 mm, and the number average fiber diameter was 11 ⁇ m (Example 6).
  • Example 7 Except that the liquid crystal polyester 1 obtained in the ⁇ manufacturing of the liquid crystal polyester 1> in Example 1 was changed to the liquid crystal polyester 4 obtained in the ⁇ manufacturing of the liquid crystal polyester 4>, and the melting temperature was changed to 340 ° C. Obtained a liquid crystal polyester resin pellet 15 of Example 7 having a columnar shape (length 12 mm) in the same manner as in Example 1. The length-weighted average fiber length of the pitch-based carbon fibers 1 in the pellet was 12 mm, and the number average fiber diameter was 11 ⁇ m (Example 7).
  • Example 8 Pitch-based carbon fiber 1 (manufactured by Mitsubishi Chemical Corporation, Dialead (registered trademark) grade: K13916, density 2.15 g / cm 3 , fiber diameter 11 ⁇ m, tensile elastic modulus 760 GPa, tensile strength 3000 MPa) in Example 1 was used.
  • pitch carbon fiber 2 manufactured by Nippon Graphite Fiber Co., Ltd., GRANOC (registered trademark), grade: YSH-60A-A2s, density 2.12 g / cm 3 , fiber diameter 7 ⁇ m, tensile modulus 630 GPa, tensile strength 3600 MPa
  • GRANOC registered trademark
  • the liquid crystal polyester resin pellet 15 of Example 8 having a columnar shape (length 12 mm) was obtained in the same manner as in Example 1 except that the carbon fiber 2 (density 2.12 g / cm 3 ) was changed.
  • the length-weighted average fiber length of the pitch-based carbon fibers 2 in the pellet was 12 mm, and the number average fiber diameter was 7 ⁇ m (Example 8).
  • Example 1 In the same manner as in Example 1, a cylindrical shape having a predetermined length is formed in the same manner as in Example 1 except that the cutting having a length of 12 mm in the longitudinal direction of the strand (resin structure 13) is changed to a cutting having a length of 50 mm. , The liquid crystal polyester resin pellet 15 of Comparative Example 1 was obtained. The length-weighted average fiber length of the pitch-based carbon fibers 1 in the pellet was 50 mm (Comparative Example 1), and the number average fiber diameter was 11 ⁇ m (Comparative Example 1).
  • Example 2 The liquid crystal polyester 1 obtained in the above ⁇ Production of liquid crystal polyester 1> in Example 1 was changed to PEEK resin (polyetheretherketone resin manufactured by Victrex, grade: 90 G, melting point 350 ° C.), and the melting temperature was 400.
  • a resin pellet of Comparative Example 2 having a cylindrical shape (length 12 mm) was obtained in the same manner as in Example 1 except that the temperature was changed to ° C.
  • the length-weighted average fiber length of the pitch-based carbon fibers 1 in the pellet was 12 mm, and the number average fiber diameter was 11 ⁇ m (Comparative Example 2).
  • Example 3 Pitch-based carbon fiber 1 (manufactured by Mitsubishi Chemical Corporation, Dialead (registered trademark) grade: K13916, density 2.15 g / cm 3 , fiber diameter 11 ⁇ m, tensile elastic modulus 760 GPa, tensile strength 3000 MPa) in Example 1 was used.
  • PAN-based carbon fiber 1 manufactured by Mitsubishi Chemical Co., Ltd., Pyrofil (registered trademark) CF toe, grade: TR50S15L, density 1.82 g / cm 3 , fiber diameter 7 ⁇ m, tensile modulus 235 GPa, tensile strength 4900 MPa
  • the liquid crystal polyester resin pellet 15 of Comparative Example 3 having a cylindrical shape (length 12 mm) was obtained in the same manner as in Example 1.
  • the length-weighted average fiber length of the PAN-based carbon fiber 1 in the pellet was 12 mm, and the number average fiber diameter was 7 ⁇ m (Comparative Example 3).
  • Example 4 An attempt was made to produce pellets having a pellet length of 3 mm or less by adjusting the rotation speed of the rotary blade of the pelletizer (cutting portion 129) in Example 1, but the pellets did not become cylindrical, the size was uneven, and there was a lot of floss. One was obtained and the desired pellet could not be obtained. The length-weighted average fiber length of the pitch-based carbon fibers 1 in the obtained pellets was less than 3 mm.
  • Comparative Example 5 100 parts by mass of the liquid crystal polyester 1 and 82 parts by mass of pitch-based carbon fiber 3 (manufactured by Mitsubishi Chemical Corporation, Dialead (registered trademark) grade: K6371T, cut length 6 mm, density 2.10 g / cm 3 , fiber A diameter of 11 ⁇ m, a tensile elastic modulus of 640 GPa, and a tensile strength of 2600 MPa) were mixed using a tumbler, and then using a twin-screw extruder (manufactured by Ikekai Iron Works Co., Ltd., PCM-30) at a cylinder temperature of 310 ° C.
  • pitch-based carbon fiber 3 manufactured by Mitsubishi Chemical Corporation, Dialead (registered trademark) grade: K6371T, cut length 6 mm, density 2.10 g / cm 3 , fiber A diameter of 11 ⁇ m, a tensile elastic modulus of 640 GPa, and a tensile strength of 2600 MPa
  • a liquid crystal polyester resin pellet 15 of Comparative Example 5 having a length of 3 mm) was obtained.
  • the length-weighted average fiber length of the pitch-based carbon fibers 3 in the pellet was 0.20 mm, and the number average fiber diameter was 11 ⁇ m (Comparative Example 5).
  • Example 6 Pitch-based carbon fiber 1 (manufactured by Mitsubishi Chemical Corporation, Dialead (registered trademark) grade: K13916, density 2.15 g / cm 3 , fiber diameter 11 ⁇ m, tensile elastic modulus 760 GPa, tensile strength 3000 MPa) in Example 1 was used.
  • Pitch-based carbon fiber 4 manufactured by Nippon Graphite Fiber Co., Ltd., GRANOC (registered trademark), grade: XN-15-30S, density 1.82 g / cm 3 , fiber diameter 10 ⁇ m, tensile modulus 155 GPa, tensile strength 2400 MPa, tensile elongation
  • the liquid crystal polyester resin pellet 15 of Comparative Example 6 having a cylindrical shape (length 12 mm) was obtained in the same manner as in Example 1 except that the value was changed to 1.5%).
  • the length-weighted average fiber length of the pitch-based carbon fibers 4 in the pellet was 12 mm, and the number average fiber diameter was 10 ⁇ m (Comparative Example 6).
  • Comparative Example 7 100 parts by mass of the liquid crystal polyester 1 and 33 parts by mass of pitch-based carbon fiber 3 (manufactured by Mitsubishi Chemical Corporation, Dialead (registered trademark) grade: K6371T, cut length 6 mm, density 2.10 g / cm 3 , fiber A diameter of 11 ⁇ m, a tensile elastic modulus of 640 GPa, and a tensile strength of 2600 MPa) were mixed using a tumbler, and then using a twin-screw extruder (manufactured by Ikekai Iron Works Co., Ltd., PCM-30) at a cylinder temperature of 310 ° C.
  • pitch-based carbon fiber 3 manufactured by Mitsubishi Chemical Corporation, Dialead (registered trademark) grade: K6371T, cut length 6 mm, density 2.10 g / cm 3 , fiber A diameter of 11 ⁇ m, a tensile elastic modulus of 640 GPa, and a tensile strength of 2600 MPa
  • a liquid crystal polyester resin pellet 15 of Comparative Example 7 having a length of 3 mm) was obtained.
  • the length-weighted average fiber length of the pitch-based carbon fibers 3 in the pellet was 0.25 mm, and the number average fiber diameter was 11 ⁇ m (Comparative Example 7).
  • the densities of the carbon fibers contained in the liquid crystal polyester resin pellets 15 obtained in Examples 2 to 8 and Comparative Examples 1 to 7 were measured by the above method, the density of the carbon fibers used as the raw material was measured. No change was observed.
  • the liquid crystal polyester resin pellets of Examples 4 and 5 were put into an injection molding machine TR450EH3 (manufactured by Sodick Co., Ltd.) having a molding temperature of 380 ° C., and into a mold having a mold temperature of 100 ° C.
  • a multipurpose test piece (type A1) conforming to JIS K 7139 was produced by injecting at several 100 rpm, a holding pressure of 100 MPa, and a back pressure of 0 MPa.
  • the liquid crystal polyester resin pellet of Example 6 was put into an injection molding machine TR450EH3 (manufactured by Sodick Co., Ltd.) having a molding temperature of 320 ° C., and the injection speed was 20 mm / s and the screw rotation speed was 100 rpm into a mold having a mold temperature of 100 ° C.
  • a multipurpose test piece (type A1) conforming to JIS K 7139 was produced by injecting at a holding pressure of 100 MPa and a back pressure of 0 MPa.
  • the liquid crystal polyester resin pellet of Example 7 was put into an injection molding machine TR450EH3 (manufactured by Sodick Co., Ltd.) having a molding temperature of 360 ° C., and the injection speed was 20 mm / s and the screw rotation speed was 100 rpm into a mold having a mold temperature of 100 ° C.
  • a multipurpose test piece (type A1) conforming to JIS K 7139 was produced by injecting at a holding pressure of 100 MPa and a back pressure of 0 MPa.
  • the liquid crystal polyester resin pellet of Example 8 was put into an injection molding machine TR450EH3 (manufactured by Sodick Co., Ltd.) having a molding temperature of 400 ° C., and the injection speed was 20 mm / s and the screw rotation speed was 100 rpm into a mold having a mold temperature of 100 ° C.
  • a multipurpose test piece (type A1) conforming to JIS K 7139 was produced by injecting at a holding pressure of 100 MPa and a back pressure of 0 MPa.
  • the polyetheretherketone resin pellets of Comparative Example 2 were put into an injection molding machine TR450EH3 (manufactured by Sodick Co., Ltd.) having a molding temperature of 400 ° C., and into a mold having a mold temperature of 150 ° C.
  • a multipurpose test piece (type A1) conforming to JIS K 7139 was prepared by injecting at several 100 rpm, holding pressure 100 MPa, and back pressure 0 MPa.
  • the liquid crystal polyester resin pellet of Comparative Example 3 was put into an injection molding machine TR450EH3 (manufactured by Sodick Co., Ltd.) having a molding temperature of 360 ° C., and the injection speed was 20 mm / s and the screw rotation speed was 100 rpm into a mold having a mold temperature of 100 ° C. , A multipurpose test piece (type A1) conforming to JIS K 7139 was produced by injection at a holding pressure of 100 MPa and a back pressure of 0 MPa.
  • the liquid crystal polyester resin pellets of Comparative Examples 5, 6 and 7 were put into an injection molding machine TR450EH3 (manufactured by Sodick Co., Ltd.) having a molding temperature of 360 ° C., and injected into a mold having a mold temperature of 100 ° C.
  • a multipurpose test piece (type A1) conforming to JIS K7139 was produced by injecting at a screw rotation speed of 100 rpm, a holding pressure of 100 MPa, and a back pressure of 0 MPa.
  • ⁇ Density of carbon fibers in liquid crystal polyester resin molded product A width 10 mm x length 20 mm x thickness 4 mm was cut out from the center of a JIS K 7139 compliant multipurpose test piece (type A1) obtained from the liquid crystal polyester resin pellet of Example 1, and a Teflon (registered trademark) inner cylinder was cut out.
  • the density of the pitch-based carbon fibers in the liquid crystal polyester resin molded product obtained from the liquid crystal polyester resin pellets of Example 1 was 2.15 g / cm 3 .
  • the density of the pitch-based carbon fibers in the liquid crystal polyester resin molded product obtained from the liquid crystal polyester resin pellets did not change from the density of the pitch-based carbon fibers as the raw material.
  • the density of the carbon fibers in the liquid crystal polyester resin molded product obtained from the liquid crystal polyester resin pellets of Examples 2 to 8 and Comparative Examples 2, 3, 5 to 7 is the same as the density of the carbon fibers used as the raw material. On the other hand, no change was observed.
  • the obtained multipurpose test pieces (type A1) conforming to JIS K 7139 of each example were cut into test pieces having a width of 10 mm, a thickness of 4 mm, and a length of 80 mm.
  • a Tencilon universal material tester RTG-1250 manufactured by A & D Co., Ltd.
  • the test speed was 2 mm / min, in accordance with JIS K 7171 (Plastic-How to determine bending characteristics) and ISO178.
  • a three-point bending test was performed five times with a distance between fulcrums of 64 mm and an indenter radius of 5 mm, and the bending strength and flexural modulus were determined from the average values. The results are shown in Tables 1 and 2.
  • the injection-molded test pieces (that is, molded bodies) produced by using the liquid crystal polyester resin pellets of Examples 1 to 7 were the liquid crystal polyester resin pellets of Comparative Examples 3, 5 and 6. It was confirmed that the flexural modulus was higher than that of the injection-molded test piece (that is, the molded product) produced by using.
  • injection-molded test pieces (that is, molded bodies) produced by using the liquid crystal polyester resin pellets of Examples 1 to 7 to which the present invention is applied have conventionally been known to have excellent flexural modulus. It was confirmed that the flexural modulus was higher than that of the injection-molded test piece (that is, the molded product) produced by using the pellets of the reinforced PEEK resin (polyetheretherketone resin).
  • the injection-molded test pieces (that is, molded bodies) produced by using the liquid crystal polyester resin pellets of Example 8 contain the same amount of pitch-based carbon fibers. It was confirmed that the flexural modulus was higher than that of the injection-molded test piece (that is, the molded product) produced by using the resin pellet of Example 7.
  • liquid crystal polyester resin pellets of Examples 1 to 8 in which the density of the pitch-based carbon fibers is 2.10 g / cm 3 or more and the length-weighted average fiber length of the pitch-based carbon fibers is 4 mm or more and less than 50 mm are used. It was shown that the liquid crystal polyester resin molded body having a length-weighted average fiber length of 170 ⁇ m or more and 500 ⁇ m or less produced from the pitch-based carbon fibers has a high flexural modulus and the rigidity of the molded product is enhanced.

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Abstract

La présente invention concerne une pastille de résine de polyester à cristaux liquides contenant un polyester à cristaux liquides et des fibres de carbone à base de brai, la densité des fibres de carbone à base de brai étant de 2,10 g/g/cm3 ou plus, et la longueur de fibre moyenne pondérée en longueur des fibres de carbone à base de brai n'est pas inférieure à 4 mm mais inférieure à 50 mm.
PCT/JP2020/029768 2019-08-09 2020-08-04 Pastille de résine de polyester à cristaux liquides, et article moulé en résine de polyester à cristaux liquides et procédé de fabrication d'un article moulé en résine de polyester à cristaux liquides WO2021029271A1 (fr)

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