WO2019208381A1 - Composition de polyester à cristaux liquides et produit moulé - Google Patents

Composition de polyester à cristaux liquides et produit moulé Download PDF

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Publication number
WO2019208381A1
WO2019208381A1 PCT/JP2019/016615 JP2019016615W WO2019208381A1 WO 2019208381 A1 WO2019208381 A1 WO 2019208381A1 JP 2019016615 W JP2019016615 W JP 2019016615W WO 2019208381 A1 WO2019208381 A1 WO 2019208381A1
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Prior art keywords
liquid crystal
crystal polyester
carbon black
parts
mass
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PCT/JP2019/016615
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English (en)
Japanese (ja)
Inventor
英浩 古▲高▼
Original Assignee
住友化学株式会社
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Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to CN201980026684.3A priority Critical patent/CN111989368B/zh
Priority to JP2020516283A priority patent/JP7269920B2/ja
Publication of WO2019208381A1 publication Critical patent/WO2019208381A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a liquid crystal polyester composition and a molded article.
  • the present application claims priority based on Japanese Patent Application No. 2018-087696 filed in Japan on April 27, 2018, the contents of which are incorporated herein by reference.
  • the electrophotographic system includes five steps of charging, exposure, development, transfer, and fixing. Specifically, first, a uniform charge is applied to the surface of the photoreceptor by corona discharge (charging process). Next, an electrostatic image is formed by light irradiation (exposure process). The obtained electrostatic image is developed with toner (development process). The developed electrostatic image is transferred to copy paper (transfer process). The transferred electrostatic image is fixed by heating / pressure or solvent vapor (fixing step).
  • housing interior parts in such electric and electronic devices including such image forming apparatuses can be manufactured using a thermoplastic resin composition (for example, Patent Document 1).
  • a housing interior part has an insulating property.
  • thermoplastic resin composition In order to suppress an increase in the charge amount of the housing interior part, it is conceivable to add conductivity to the thermoplastic resin composition to be used to impart conductivity to the housing interior part.
  • Carbon black is known as a conductive additive.
  • Patent Document 2 the liquid crystal polyester composition DBP (dibutyl phthalate) absorption amount of carbon black is 60 ⁇ 200cm 3 / 100g is disclosed.
  • liquid crystal polyester composition as in Patent Document 2 cannot always sufficiently suppress the increase in charge amount.
  • the present invention has been made in view of such circumstances, and an object thereof is to provide a molded product capable of suppressing an increase in the amount of charge and a liquid crystal polyester composition from which such a molded product can be obtained.
  • the inventors have found that the increase in the charge amount can be suppressed as a result of adding the first carbon black satisfying the following conditions (A) and (B) to the liquid crystal polyester in order to suppress the increase in the charge amount.
  • the inventors set the upper limit value of the content of the first carbon black and the upper limit value of the content of the carbon black including the first carbon black in order to control the absolute value of the charge amount.
  • the inventors have found that the value can be controlled and have completed the present invention.
  • One embodiment of the present invention includes a liquid crystal polyester and carbon black, the carbon black satisfying the following conditions (A) and (B), conditions (A) and (B) Second carbon black not satisfying at least one of the above, the carbon black content is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the liquid crystalline polyester, and the content W of the first carbon black 1 is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester, and the content of the second carbon black is 0 part by mass or more and 9 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester.
  • a liquid crystal polyester composition is provided.
  • BET specific surface area of the first carbon black may be configured at most 500 meters 2 / g or more 1500 m 2 / g.
  • the filler is a fibrous filler, the content W 2 of the fibrous filler, the liquid crystal polyester 10 parts by mass to 130 parts by weight It is good also as composition which is.
  • the ratio R 12 represented by the following formula (S1) may be greater than 1 ⁇ 10 5 and less than 1 ⁇ 10 11 .
  • [rho 1 represents the volume resistivity of the first carbon black.
  • ⁇ 2 represents the volume resistivity of the fibrous filler.
  • the filler is a plate-like filler, the content W 3 of the plate-like filler, the liquid crystal polyester to 100 parts by mass 80 parts by mass or less at least 5 parts by weight It is good also as composition which is.
  • the ratio R 13 represented by the following formula (S2) may be greater than 1 ⁇ 10 5 and less than 1 ⁇ 10 11 .
  • [rho 1 represents the volume resistivity of the first carbon black.
  • ⁇ 3 represents the volume resistivity of the plate filler.
  • the filler is a fibrous filler and plate-like filler
  • the content W 2 of the fibrous filler, the liquid crystal polyester 10 parts by mass or more or less 130 parts by mass, the content W 3 of the plate-like filler, the liquid crystal polyester 100 parts by weight may be in a configuration to 80 parts by 5 parts by mass or more.
  • the ratio R 123 represented by the following formula (S3) may be greater than 1 ⁇ 10 5 and less than 1 ⁇ 10 11 .
  • [rho 1 represents the volume resistivity of the first carbon black.
  • ⁇ 2 represents the volume resistivity of the fibrous filler.
  • ⁇ 3 represents the volume resistivity of the plate filler.
  • the volume resistivity ⁇ 2 of the fibrous filler may be 1 ⁇ 10 9 ⁇ ⁇ m or more and 1 ⁇ 10 15 ⁇ ⁇ m or less.
  • the volume resistivity ⁇ 3 of the plate filler may be 1 ⁇ 10 9 ⁇ ⁇ m or more and 1 ⁇ 10 15 ⁇ ⁇ m or less.
  • the volume resistivity ⁇ 1 of the first carbon black may be 1 ⁇ 10 2 ⁇ ⁇ m to 1 ⁇ 10 7 ⁇ ⁇ m.
  • the liquid crystal polyester may have a flow start temperature of 280 ° C. or higher and 420 ° C. or lower.
  • the liquid crystalline polyester includes a structural unit (I) derived from an aromatic hydroxycarboxylic acid, a structural unit (II) derived from an aromatic diol, and a structural unit derived from an aromatic dicarboxylic acid (
  • the content of the structural unit (I) is from 30 mol% to 80 mol% with respect to the total of all the structural units of the liquid crystal polyester, and the content of the structural unit (II) is the liquid crystal It is 10 mol% or more and 35 mol% or less with respect to the total of all the structural units of polyester, and the content rate of structural unit (III) is 10 mol% or more and 35 mol% or less with respect to the total of all the structural units of liquid crystal polyester. It is good also as composition which is.
  • the aromatic hydroxycarboxylic acid is p-hydroxybenzoic acid
  • the aromatic diol is at least one of hydroquinone and 4,4′-dihydroxybiphenyl
  • the aromatic dicarboxylic acid is
  • the structure may be at least one selected from the group consisting of terephthalic acid and isophthalic acid.
  • One embodiment of the present invention provides a molded product using the liquid crystal polyester composition as a forming material.
  • a configuration for a case interior part in an electric / electronic device may be used.
  • the “casing interior part” means a part provided inside the casing.
  • the present invention includes the following aspects.
  • the first carbon black is a carbon black that satisfies the following conditions (A) and (B):
  • the second carbon black is a carbon black that does not satisfy at least one of the condition (A) and the condition (B),
  • the content W 1 of the first carbon black, with respect to the liquid crystal polyester to 100 parts by mass, and 10 parts by mass or less 1 part by mass or more
  • the content of the second carbon black is 0 part by mass or more and 9 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester
  • the total content of the first carbon black and the second carbon black is the liquid crystal 1 to 10 parts by mass with respect to 100 parts by mass of polyester, Liquid crystal polyester composition.
  • BET specific surface area of the first carbon black 500m 2 / g or more 1500m
  • a filler is included, The filler is a fibrous filler, The content W 2 of the fibrous filler to the liquid crystal polyester to 100 parts by mass, or less 130 weight parts or more and 10 parts by mass or [1] or a liquid crystal polyester composition according to [2].
  • the filler is a plate filler, The content W 3 of the plate-shaped filler, relative to the liquid crystal polyester to 100 parts by mass, not more than 5 parts by mass or more and 80 parts by mass [1] or a liquid crystal polyester composition according to [2].
  • R 13 represented by the following formula (S2), the ratio The liquid crystal polyester composition according to claim 13, wherein R 13 is greater than 1 ⁇ 10 5 and less than 1 ⁇ 10 11 .
  • ⁇ 1 represents the volume resistivity of the first carbon black.
  • ⁇ 3 represents the volume resistivity of the plate-like filler.
  • W 1 contains the first carbon black with respect to 100 parts by mass of the liquid crystalline polyester.
  • W 3 represents the content of the plate-like filler with respect to 100 parts by mass of the liquid crystalline polyester.
  • a filler is included, The filler is a fibrous filler and a plate filler, The content W 2 of the fibrous filler to the liquid crystal polyester to 100 parts by mass is 10 parts by mass to 130 parts by weight, The content W 3 of the plate-shaped filler, relative to the liquid crystal polyester to 100 parts by mass, not more than 5 parts by mass or more and 80 parts by mass [1] or a liquid crystal polyester composition according to [2].
  • W 1 represents Represents the content of the first carbon black with respect to 100 parts by mass of the liquid crystalline polyester
  • W 2 represents the content of the fibrous filler with respect to 100 parts by mass of the liquid crystalline polyester
  • W 3 represents the content with respect to 100 parts by mass of the liquid crystalline polyester. Represents the content of plate-like filler.
  • the liquid crystalline polyester includes a structural unit (I) derived from an aromatic hydroxycarboxylic acid, a structural unit (II) derived from an aromatic diol, a structural unit (III) derived from an aromatic dicarboxylic acid, Including
  • the content of the structural unit (I) is 30 mol% or more and 80 mol% or less with respect to the total molar amount of all the structural units constituting the liquid crystal polyester,
  • the content of the structural unit (II) is 10 mol% or more and 35 mol% or less with respect to the total molar amount of all the structural units constituting the liquid crystal polyester,
  • the content of the structural unit (III) is any one of [1] to [12], which is 10 mol% or more and 35 mol% or less with respect to the total molar amount of all the structural units constituting the liquid crystal polyester.
  • the aromatic hydroxycarboxylic acid is p-hydroxybenzoic acid,
  • the aromatic diol is at least one of hydroquinone and 4,4′-dihydroxybiphenyl
  • the liquid crystal polyester composition according to [13] wherein the aromatic dicarboxylic acid is at least one selected from the group consisting of terephthalic acid and isophthalic acid.
  • a molded article comprising the liquid crystal polyester composition according to any one of [1] to [14].
  • the molded product according to [15] which is for a housing interior part in an electric / electronic device.
  • a molded product capable of suppressing an increase in charge amount and a liquid crystal polyester composition from which such a molded product is obtained.
  • the liquid crystal polyester composition of the present embodiment includes liquid crystal polyester and carbon black.
  • carbon black means carbon black consisting only of the first carbon black described later, or carbon black consisting only of the first carbon black and second carbon black described later.
  • composition a mixture obtained by mixing liquid crystal polyester and at least carbon black
  • composition a material obtained by forming the obtained mixture into a pellet
  • composition a material obtained by forming the obtained mixture into a pellet
  • the liquid crystal polyester according to the present embodiment is one of thermotropic liquid crystal polymers.
  • the liquid crystal polyester according to this embodiment is a resin that can form a melt exhibiting optical anisotropy at a temperature of 200 ° C. or higher and 450 ° C. or lower.
  • liquid crystal polyester (1) a resin obtained by polymerizing an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid and an aromatic diol; (2) a resin obtained by polymerizing a plurality of types of aromatic hydroxycarboxylic acids, (3) a resin obtained by polymerizing an aromatic dicarboxylic acid and an aromatic diol, (4) A resin obtained by reacting a crystalline polyester such as polyethylene terephthalate with an aromatic hydroxycarboxylic acid, and the like.
  • liquid crystal polyester In the production of the liquid crystal polyester, a part or all of the aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid and aromatic diol used as raw material monomers can be used in advance as an ester-forming derivative. By using such an ester-forming derivative, there is an advantage that the liquid crystal polyester can be produced more easily.
  • ester-forming derivatives are as follows.
  • Examples of ester-forming derivatives of aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids having a carboxyl group in the molecule include the carboxyl group is a haloformyl group (that is, acid halide) or acyloxycarbonyl group (that is, acid anhydride). And the like so that the carboxyl group generates a polyester by a transesterification reaction, such as monohydric alcohols, polyhydric alcohols such as ethylene glycol, phenols, etc. Those formed with an ester may be mentioned.
  • polymerizable derivatives of compounds having a phenolic hydroxyl group such as aromatic hydroxycarboxylic acids and aromatic diols
  • aromatic hydroxycarboxylic acids and aromatic diols include lower carboxylic acids and esters such that the phenolic hydroxyl group forms a polyester by transesterification. Is formed.
  • aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, or aromatic diol described above has a halogen atom such as a chlorine atom or a fluorine atom in its aromatic ring; methyl group, ethyl as long as it does not inhibit ester formation.
  • a halogen atom such as a chlorine atom or a fluorine atom in its aromatic ring
  • methyl group, ethyl as long as it does not inhibit ester formation.
  • An alkyl group having 1 to 10 carbon atoms such as a butyl group or an aryl group having 6 to 20 carbon atoms such as a phenyl group may be substituted.
  • aromatic hydroxycarboxylic acid examples include p-hydroxybenzoic acid (aromatic hydroxycarboxylic acid that induces (A 1 ) described later), m-hydroxybenzoic acid, and 6-hydroxy-2-naphthoic acid (described later ( A 2 ) -derived aromatic hydroxycarboxylic acid), 3-hydroxy-2-naphthoic acid, 5-hydroxy-1-naphthoic acid, 4-hydroxy-4′-carboxydiphenyl ether, and aromatic hydroxycarboxylic acids of these
  • the said aromatic hydroxycarboxylic acid may be used individually by 1 type in manufacture of liquid crystalline polyester, and may be used in combination of 2 or more type.
  • Examples of the structural unit derived from such an aromatic hydroxycarboxylic acid include those shown below.
  • part of the hydrogen atoms in the aromatic ring is substituted with at least one substituent selected from the group consisting of a halogen atom, an alkyl group and an aryl group. May be.
  • derived means that the chemical structure is changed because the raw material monomer is polymerized, and other structural changes are not caused.
  • aromatic dicarboxylic acid examples include terephthalic acid (aromatic dicarboxylic acid that induces (B 1 ) described later), isophthalic acid (aromatic dicarboxylic acid that induces (B 2 ) described later), and biphenyl-4,4.
  • aromatic dicarboxylic acid 2,6-naphthalenediboronic acid (aromatic dicarboxylic acid to derive (B 3 ) described later), diphenyl ether-4,4'-dicarboxylic acid, diphenylthioether-4,4'-dicarboxylic acid, And aromatic dicarboxylic acids in which some of the hydrogen atoms in the aromatic ring of these aromatic dicarboxylic acids are substituted with at least one substituent selected from the group consisting of alkyl groups, aryl groups and halogen atoms. It is done.
  • the said aromatic dicarboxylic acid may be used individually by 1 type in manufacture of liquid crystalline polyester, and may be used in combination of 2 or more type.
  • Examples of the structural unit derived from such an aromatic dicarboxylic acid include those shown below.
  • part of the hydrogen atoms in the aromatic ring is substituted with at least one substituent selected from the group consisting of a halogen atom, an alkyl group and an aryl group. Also good.
  • aromatic diol examples include 4,4′-dihydroxybiphenyl (aromatic diol that induces (C 1 ) described later), hydroquinone (aromatic diol that induces (C 2 ) described later), and resorcin (described later).
  • aromatic diol (C 3 ) -derived aromatic diol), 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenyl ether, bis (4-hydroxyphenyl) methane, 1,2-bis (4-hydroxyphenyl) ethane 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylthioether, 2,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, and some of the hydrogen atoms in the aromatic ring of these aromatic diols , At least one selected from the group consisting of an alkyl group, an aryl group, and a halogen atom Aromatic diol formed by substituted with a substituent can be mentioned.
  • the said aromatic diol may be used individually by 1 type in manufacture of liquid crystalline polyester, and may be used in combination of 2 or more type.
  • Examples of the structural unit derived from such an aromatic diol include those shown below.
  • a part of hydrogen atoms in the aromatic ring may be substituted with at least one substituent selected from the group consisting of a halogen atom, an alkyl group and an aryl group. Good.
  • the structural unit (a structural unit derived from an aromatic hydroxycarboxylic acid, a structural unit derived from an aromatic dicarboxylic acid, or a structural unit derived from an aromatic diol) may optionally have a halogen atom
  • a halogen atom examples include a fluorine atom, a chlorine atom, and a bromine atom
  • the alkyl group is preferably a lower alkyl group having about 1 to 4 carbon atoms, such as a methyl group, an ethyl group, and a butyl group.
  • groups include phenyl groups.
  • the liquid crystalline polyester has a structural unit (A 1 ) derived from p-hydroxybenzoic acid and a structural unit derived from 6-hydroxy-2-naphthoic acid (A 2 ) as structural units (I) derived from aromatic hydroxycarboxylic acid. And at least one of them.
  • the liquid crystalline polyester includes a structural unit (B 1 ) derived from terephthalic acid, a structural unit (B 2 ) derived from isophthalic acid, and 2,6-naphthalenedicarboxylic acid (II) as a structural unit (II) derived from an aromatic dicarboxylic acid. It is preferable to have one selected from the group consisting of structural units derived from B 3 ).
  • the liquid crystal polyester has at least one of a structural unit (C 2 ) derived from hydroquinone and a structural unit (C 1 ) derived from 4,4′-dihydroxybiphenyl as the structural unit (III) derived from an aromatic diol. It is preferable.
  • the content of the structural unit (I) derived from the aromatic hydroxycarboxylic acid is preferably 30 mol% or more and 80 mol% or less with respect to the total molar amount of all the structural units constituting the liquid crystal polyester. Moreover, it is preferable that the content rate of structural unit (II) derived from aromatic diol is 10 to 35 mol% with respect to the total molar amount of all the structural units which comprise liquid crystal polyester. Moreover, it is preferable that the content rate of structural unit (III) derived from aromatic dicarboxylic acid is 10 mol% or more and 35 mol% or less with respect to the total molar amount of all the structural units which comprise liquid crystal polyester. As the liquid crystalline polyester, a resin satisfying all of these is preferable.
  • the content of the structural unit (A 1 ) derived from p-hydroxybenzoic acid is more preferably 30 mol% or more and 80 mol% or less with respect to the total molar amount of all structural units constituting the liquid crystal polyester.
  • the content of at least one of the structural unit (C 2 ) derived from hydroquinone and the structural unit (C 1 ) derived from 4,4′-dihydroxybiphenyl is the total mol of all structural units constituting the liquid crystal polyester. More preferably, it is 10 mol% or more and 35 mol% or less with respect to the amount.
  • At least one content selected from the group consisting of the structural unit (B 1 ) derived from terephthalic acid and the structural unit (B 2 ) derived from isophthalic acid is the total molar amount of all structural units constituting the liquid crystal polyester. More preferably, it is 10 mol% or more and 35 mol% or less. As the liquid crystalline polyester, a resin satisfying all of these is more preferable.
  • the liquid crystal polyester for example, a known method such as a method described in JP-A No. 2002-146003 can be applied. That is, the above-mentioned raw material monomers (aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, or derivatives for forming these esters) are melt polymerized (polycondensation) to produce a relatively low molecular weight aromatic polyester (hereinafter referred to as “polyester”). Abbreviated as “prepolymer”.), And then solid-phase polymerization is carried out by heating the prepolymer to a powder. By solid-phase polymerization in this way, the polymerization proceeds further and a higher molecular weight liquid crystal polyester can be obtained.
  • the raw material monomers aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, or derivatives for forming these esters
  • prepolymer melt polymerized (polycondensation) to produce a relatively low molecular weight aromatic polyester
  • Melt polymerization may be carried out in the presence of a catalyst.
  • a catalyst in this case include metals such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide.
  • metals such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide.
  • nitrogen-containing heterocyclic compounds such as 4- (dimethylamino) pyridine and 1-methylimidazole, and nitrogen-containing heterocyclic compounds are preferably used.
  • the liquid crystal polyester used in the molded product of the present embodiment is preferably a liquid crystal polyester having a flow start temperature determined by the following method of 280 ° C. or higher. As described above, when solid phase polymerization is used in the production of liquid crystal polyester, the flow start temperature of liquid crystal polyester can be set to 280 ° C. or higher in a relatively short time. And the liquid crystal polyester of such a flow start temperature is used as a thermoplastic resin of this embodiment, The molded article obtained will have a high heat resistance.
  • the flow start temperature of the liquid crystalline polyester used in the molded product of the present embodiment is preferably 420 ° C. or lower, and more preferably 390 ° C. or lower.
  • the flow start temperature of the liquid crystal polyester used in the liquid crystal polyester composition of the present embodiment is preferably 280 ° C. or higher and 420 ° C. or lower, and more preferably 280 ° C. or higher and 390 ° C. or lower.
  • the flow start temperature is a liquid crystalline polyester using a capillary rheometer equipped with a die having an inner diameter of 1 mm and a length of 10 mm and a heating rate of 4 ° C./min under a load of 9.8 MPa (100 kg / cm 2 ). Is a temperature at which the melt viscosity shows 4800 Pa ⁇ s (48,000 poise) when the material is extruded from the nozzle.
  • the flow initiation temperature is an index representing the molecular weight of liquid crystal polyesters well known in the art (Naoyuki Koide, “Liquid Crystalline Polymer Synthesis / Molding / Application—”, pages 95 to 105, CMC, June 1987). (See 5th issue).
  • a flow characteristic evaluation apparatus “Flow Tester CFT-500D” manufactured by Shimadzu Corporation can be used.
  • Such a liquid crystal polyester is excellent in heat resistance and fluidity when melted. Therefore, it is preferably used as a forming material for a molded product described later.
  • Liquid crystalline polyester may be used individually by 1 type, and may use 2 or more types together.
  • the content of the liquid crystal polyester in the liquid crystal polyester composition of the present embodiment is preferably 30 to 90% by mass with respect to the total mass of the liquid crystal polyester composition.
  • Carbon black The carbon black according to the liquid crystal polyester composition of the present embodiment has an effect of imparting conductivity to the liquid crystal polyester.
  • the carbon black used in the liquid crystal polyester composition of the present embodiment includes a first carbon black that satisfies the following condition (A) and condition (B).
  • the carbon black according to the liquid crystal polyester composition of the present embodiment is composed only of the first carbon black that satisfies the following conditions (A) and (B).
  • the carbon black according to the liquid crystal polyester composition of the present embodiment is composed of only a first carbon black that satisfies the following conditions (A) and (B) and a second carbon black described later.
  • the primary particle diameter of carbon black employs a value measured by a transmission electron microscope.
  • the DBP oil absorption amount of carbon black employs a value measured according to JIS K 6221 with a dibutyl phthalate absorber meter.
  • the surface resistance value of a molded product molded from the liquid crystal polyester composition can be sufficiently lowered. As a result, an increase in charge amount in the molded product can be suppressed.
  • the primary particle diameter of the first carbon black is 50 nm or less, the first carbon black is easily dispersed in the liquid crystal polyester when a liquid crystal polyester composition or a molded product is produced.
  • the surface resistance value in the surface of the molded product can be easily made uniform. As a result, an increase in the charge amount can be suppressed at any location within the surface of the molded product.
  • the primary particle diameter of the first carbon black is preferably 20 nm or more and 45 nm or less, and more preferably 30 nm or more and 40 nm or less.
  • the molded article molded from the liquid crystal polyester composition When DBP oil absorption of the first carbon black is at 300 cm 3/100 g or more, the molded article molded from the liquid crystal polyester composition, easily passed through enough electricity connection portions of the first carbon black. As a result, the surface resistance value of the molded product can be made sufficiently low. Therefore, an increase in the charge amount in the molded product can be sufficiently suppressed.
  • the DBP oil absorption amount of the first carbon black is too high, there are too many voids near the surface of the first carbon black, and the first carbon blacks are easily caught strongly in the liquid crystal polyester.
  • the viscosity of the mixture increases. As a result, it becomes difficult to granulate the mixture, and it becomes difficult to produce a liquid crystal polyester composition.
  • the liquid crystal polyester When DBP oil absorption of the first carbon black is at most 550 cm 3/100 g, the liquid crystal polyester, an additive to be added by carbon black and optionally the time of melt-kneading, the viscosity of these mixtures is not too high. As a result, it becomes easy to granulate the mixture, and it becomes easy to produce a liquid crystal polyester composition.
  • DBP oil absorption amount of the first carbon black is preferably 325cm at 3/100 g or more 550 cm 3/100 g or less, and more preferably 350 cm 3/100 g or more 525 cm 3/100 g or less.
  • the BET specific surface area of the first carbon black is preferably 500 m 2 / g or more and 1500 m 2 / g or less, more preferably 700 m 2 / g or more and 1350 m 2 / g or less, and more preferably 750 m 2 / g or more and 1300 m 2. / G or less is more preferable.
  • the BET specific surface area of the carbon black is measured by adsorbing nitrogen gas at a liquid nitrogen temperature using a BET specific surface area measuring instrument (for example, AccuSorb 2100E manufactured by Micromeritics), measuring the adsorption amount, The value calculated by the method is adopted.
  • a BET specific surface area measuring instrument for example, AccuSorb 2100E manufactured by Micromeritics
  • the BET specific surface area of particles is affected by the particle diameter.
  • the amount of voids formed in the first carbon black is more dominant. Therefore, the larger the BET specific surface area of the first carbon black, the larger the amount of voids formed in the first carbon black.
  • the first carbon blacks are easily connected in the liquid crystal polyester.
  • the BET specific surface area of the first carbon black is 500 m 2 / g or more
  • a molded product molded from the liquid crystal polyester composition can easily conduct electricity at the connecting portion of the first carbon black.
  • the surface resistance value of the molded product can be made sufficiently low. Therefore, an increase in the charge amount in the molded product can be sufficiently suppressed.
  • the BET specific surface area of the first carbon black is too high, it can be said that the amount of voids formed in the first carbon black is too large.
  • the viscosity of the mixture increases when melt-kneading liquid crystal polyester, carbon black, and an additive that is optionally added. As a result, it becomes difficult to granulate the mixture, and it becomes difficult to produce a liquid crystal polyester composition.
  • the BET specific surface area of the first carbon black is 1500 m 2 / g or less
  • the liquid crystal polyester composition, the molded product, and the liquid crystal polyester, carbon black, and an additive that is optionally added are melt-kneaded,
  • the viscosity of the mixture does not become too high. As a result, it becomes easy to granulate the mixture, and it becomes easy to produce a liquid crystal polyester composition.
  • the volume resistivity ⁇ 1 of the first carbon black is preferably 1 ⁇ 10 2 ⁇ ⁇ m or more and 1 ⁇ 10 7 ⁇ ⁇ m or less, preferably 1 ⁇ 10 3 ⁇ ⁇ m or more and 1 ⁇ 10 6 ⁇ ⁇ m or less. It is more preferable that
  • the volume resistivity [rho 1 of the first carbon black is within the above range, the surface resistance of the molded article molded from the liquid crystal polyester composition can be sufficiently low. Therefore, an increase in the charge amount in the molded product can be suppressed.
  • the volume resistivity of the first carbon black is determined by placing the first carbon black in a silica gel desiccator for 24 hours and then measuring the insulation resistance meter R8340A ULTRA HIGH RESISUTANCE at a measurement temperature of 23 ° C. and a measurement humidity of 50%. A value measured by METER (manufactured by ADC Corporation) is adopted.
  • the carbon black according to the liquid crystal polyester composition of the present embodiment may contain the second carbon black as long as the effects of the present invention are not impaired.
  • the second carbon black does not satisfy at least one of the condition (A) and the condition (B).
  • the second carbon black is inferior to the effect of the first carbon black described above, it has the effect of imparting conductivity to the liquid crystal polyester. Further, the second carbon black can suppress an increase in the viscosity of the liquid crystal polyester mixture when blended with the liquid crystal polyester, as compared with the first carbon black described above. Therefore, in the present embodiment, by using the first carbon black and the second carbon black together, a liquid crystal polyester composition capable of suppressing an increase in charge amount when formed into a molded product while suppressing an increase in viscosity of the liquid crystal polyester mixture. Things are provided.
  • the content W 1 of the first carbon black is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester.
  • the surface resistance value of a molded product molded from the liquid crystal polyester composition can be sufficiently lowered. As a result, an increase in charge amount in the molded product can be suppressed.
  • the first carbon black tends to increase the viscosity of the mixture when melt-kneading the liquid crystal polyester, carbon black, and an additive that is optionally added.
  • the content W 1 of the first carbon black is at most 10 parts by weight, not too high viscosity of the mixture described above. As a result, it becomes easy to granulate the mixture, and it becomes easy to produce a liquid crystal polyester composition.
  • the absolute value of the charge amount can be controlled by setting the content W 1 of the first carbon black within the range of 1 part by mass or more and 10 parts by mass or less.
  • the content W 1 of the first carbon black is preferably 2 parts by mass or more and 9 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester.
  • the carbon black according to the liquid crystal polyester composition of the present embodiment may further contain a second carbon black as long as the effects of the present invention are not impaired.
  • the content of the second carbon black is 0 part by mass or more and 9 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester.
  • the content of the second carbon black may be 0 to 3 parts by mass or 2 to 3 parts by mass with respect to 100 parts by mass of the liquid crystalline polyester. .
  • the total content of the first carbon black and the second carbon black (hereinafter sometimes referred to as carbon black content) is 100 parts by mass of the liquid crystal polyester. 1 part by mass or more and 10 parts by mass or less.
  • the content of the carbon black is 1 part by mass or more, the amount of the first carbon black contained in the carbon black can be sufficiently increased. As a result, the surface resistance value of the molded product molded from the liquid crystal polyester composition can be sufficiently lowered. Therefore, an increase in the charge amount in the molded product can be suppressed.
  • the content of the carbon black is 10 parts by mass or less, it is easy to disperse the first carbon black and the optionally added second carbon black in the liquid crystal polyester when producing a liquid crystal polyester composition or a molded product. .
  • the surface resistance value in the surface of the molded product can be easily made uniform. As a result, an increase in the charge amount can be suppressed at any location within the surface of the molded product.
  • the absolute value of the charge amount can be controlled by setting the carbon black content in the range of 1 part by mass or more and 10 parts by mass or less.
  • the content of the carbon black is preferably 3 parts by mass or more and 9 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester.
  • the liquid crystal polyester composition of the present embodiment preferably further contains a filler in addition to the liquid crystal polyester and the first carbon black. Thereby, the intensity
  • the liquid crystal polyester composition of the present embodiment includes liquid crystal polyester, first carbon black, and a filler.
  • the liquid crystal polyester composition of the present embodiment includes a liquid crystal polyester, a first carbon black, a second carbon black, and a filler.
  • the filler according to the liquid crystal polyester composition of the present embodiment is a fibrous filler or a plate-like filler. Moreover, it is preferable that the liquid crystal polyester composition of this embodiment contains both a fibrous filler and a plate-like filler.
  • fibrous fillers include glass fibers; ceramic fibers such as silica fibers, alumina fibers, silica alumina fibers; and metal fibers such as stainless fibers.
  • whiskers such as potassium titanate whisker, barium titanate whisker, wollastonite whisker, aluminum borate whisker, silicon nitride whisker, and silicon carbide whisker are also included.
  • the number average fiber length of the fibrous filler is preferably 30 ⁇ m to 3 mm, and the number average fiber diameter is preferably 6 to 13 ⁇ m.
  • the content W 2 of the fibrous filler, the liquid crystal polyester 100 parts by weight preferably not more than 10 parts by mass or more 130 parts by mass, 80 parts by mass or more and 10 parts by mass or More preferably, it is more preferably 10 parts by mass or more and 50 parts by mass or less, and particularly preferably 10 parts by mass or more and 45 parts by mass or less.
  • the content of the fibrous filler W 2 may be less than or equal to 45 parts by mass or more 23 parts by weight.
  • the content W 2 of the fibrous filler is at most 130 parts by mass, when the melt-kneading a liquid crystal polyester, carbon black and fibrous fillers, the viscosity of these mixtures is not too high. As a result, the first carbon black is easily dispersed in the liquid crystal polyester.
  • the surface resistance value in the surface of the molded product can be easily made uniform. As a result, an increase in the charge amount can be suppressed at any location within the surface of the molded product.
  • Plate filler examples include talc, mica, graphite, wollastonite, barium sulfate and calcium carbonate. Mica may be muscovite, phlogopite, fluorine phlogopite, or tetrasilicon mica.
  • the content W 3 of the plate-like filler, the liquid crystal polyester 100 parts by weight preferably not more than 80 parts by mass 5 parts by mass or more, at least 5 parts by weight 50 parts by weight More preferably, it is more preferably 5 parts by mass or more and 30 parts by mass or less, and particularly preferably 10 parts by mass or more and 25 parts by mass or less.
  • the content W 3 of the plate-like filler may be less than or equal 23 parts by 17 parts by mass or more.
  • the content W 3 of the plate-like filler is at least 5 parts by weight, the dimensional stability and strength of the molded article molded from the liquid crystal polyester composition high enough.
  • the content W 3 of the plate-like filler is at most 80 parts by mass, when the melt-kneading a liquid crystal polyester, carbon black and the plate filler, the viscosity of these mixtures is not too high. As a result, the first carbon black is easily dispersed in the liquid crystal polyester.
  • the surface resistance value in the surface of the molded product can be easily made uniform. As a result, an increase in the charge amount can be suppressed at any location within the surface of the molded product.
  • the volume resistivity ⁇ 2 of the fibrous filler is preferably 1 ⁇ 10 9 ⁇ ⁇ m or more and 1 ⁇ 10 15 ⁇ ⁇ m or less, preferably 1 ⁇ 10 10 ⁇ ⁇ m or more and 1 ⁇ 10 13 ⁇ ⁇ m or less. More preferably.
  • the volume resistivity ⁇ 2 of the fibrous filler is within the above range, the surface resistance value of a molded product molded from the liquid crystal polyester composition can be sufficiently lowered. Therefore, an increase in the charge amount in the molded product can be suppressed.
  • the volume resistivity ⁇ 3 of the plate-like filler is preferably 1 ⁇ 10 9 ⁇ ⁇ m or more and 1 ⁇ 10 15 ⁇ ⁇ m or less, preferably 1 ⁇ 10 10 ⁇ ⁇ m or more and 1 ⁇ 10 13 ⁇ ⁇ m or less. More preferably.
  • the volume resistivity ⁇ 3 of the plate-like filler is within the above range, the surface resistance value of a molded product molded from the liquid crystal polyester composition can be sufficiently lowered. Therefore, an increase in the charge amount in the molded product can be suppressed.
  • the measuring method of the volume resistivity of the fibrous filler and the plate-like filler is the same as the measuring method of the volume resistivity of the first carbon black.
  • the liquid crystal polyester composition of the present embodiment when containing only a fibrous filler as a filler, is that the ratio R 12 represented by the following formula (S1) exceeds 1 ⁇ 10 5, less than 1 ⁇ 10 11 It is preferably 1 ⁇ 10 6 or more and 1 ⁇ 10 10 or less, more preferably 1 ⁇ 10 7 or more and 1 ⁇ 10 9 or less.
  • ⁇ 1 represents the volume resistivity of the first carbon black.
  • ⁇ 2 represents the volume resistivity of the fibrous filler.
  • W 1 represents the content of the first carbon black to the liquid crystal polyester 100 parts by (parts by weight).
  • W 2 represents the content of the fibrous filler to the liquid crystal polyester 100 parts by (parts by weight).
  • the ratio R 13 represented by the following formula (S2) is more than 1 ⁇ 10 5 and less than 1 ⁇ 10 11.
  • it is 1 ⁇ 10 5 or more and 1 ⁇ 10 9 or less, more preferably 5 ⁇ 10 5 or more and 1 ⁇ 10 8 or less.
  • ⁇ 3 represents the volume resistivity of the plate filler.
  • W 3 being represented content of the plate-like filler to the liquid crystal polyester 100 parts by (parts by weight).
  • the ratio R 123 represented by the following formula (S3) is more than 1 ⁇ 10 5 and less than 1 ⁇ 10 11 .
  • it is 1 ⁇ 10 6 or more and 1 ⁇ 10 10 or less, more preferably 1.1 ⁇ 10 7 or more and 1 ⁇ 10 9 or less.
  • the ratio R 12 , the ratio R 13 , and the ratio R 123 defined in the present embodiment are the volume resistivity ⁇ 1 , ⁇ 2, and ⁇ 3 of the carbon black and the filler that can affect the charge amount, and the content W 1 , It is represented by as a function of both the W 2 and W 3.
  • ratio R 12 , ratio R 13 , and ratio R 123 satisfy a desired range, the balance between volume resistivity and content can be controlled, and the absolute value of the charge amount can be controlled.
  • liquid crystal polyester composition of the present embodiment may further contain components other than the filler as long as the effects of the present invention are not impaired.
  • mold release agents such as fluororesins and metal soaps
  • colorants such as dyes and pigments
  • antioxidants heat stabilizers
  • ultraviolet absorbers antistatic agents
  • the additive generally used for the forming material of a molded article is mentioned.
  • Examples of the above components include those having an external lubricant effect such as higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, and fluorocarbon surfactants.
  • thermosetting resins such as phenol resin, epoxy resin, and polyimide resin.
  • the liquid crystal polyester composition having the above-described configuration, a molded product that can control the absolute value of the charge amount can be obtained.
  • the content of the above components is preferably 0 to 10% by mass with respect to the total mass of the liquid crystal polyester composition.
  • the molded product of this embodiment contains the liquid crystal polyester composition described above as a forming material.
  • the molded product of the present embodiment is a molded product for a housing interior part in an electric / electronic device.
  • the electric / electronic device include a camera, a personal computer, a mobile phone, a smartphone, a tablet, a printer, and a projector.
  • housing interior parts in such electric / electronic devices include connectors, camera modules, blower fans, and fixing parts for printers.
  • the thickness of the molded product of this embodiment is 0.1 mm or more, preferably 0.2 mm or more, more preferably 0.5 mm or more, and further preferably 1 mm or more. Further, the thickness of the molded product is preferably 20 mm or less. As one aspect, the thickness of the molded product of the present embodiment is 0.1 mm or more and 20 mm or less, preferably 0.2 mm or more and 20 mm or less, more preferably 0.5 mm or more and 20 mm or less, and still more preferably. Is from 1 mm to 20 mm.
  • the thickness of the molded product means the thickness (shortest distance) from one surface of the molded product to the other surface.
  • the thickness of the thinnest portion may be 0.1 mm, preferably 0.2 mm or more, more preferably 0.8 mm. It is 5 mm or more, more preferably 1 mm or more. Further, the thickness of the thickest part is preferably 20 mm or less.
  • the thickness of the molded product is the average of the measured values when the thickness of the molded product is measured at three random locations using a micrometer or a non-contact three-dimensional measuring instrument (“QuickVisionPRO” manufactured by Mitutoyo Corporation). It is. Note that the thickness of the molded product can be quantitatively obtained when either the micrometer or the non-contact two-dimensional measuring device is selected.
  • the surface of fixing parts for printers is flat so that copy paper can be transported without any delay.
  • static electricity may be generated when the fixing component and the copy paper are rubbed. Since the toner adheres to the copy paper due to static electricity from the transfer process to the fixing process in image formation, the position of the transferred electrostatic image may be shifted when the charge amount of the fixing component increases.
  • the surface resistance value of the surface on the side where the copy paper to which the toner adheres is in contact is 10 12 ⁇ or more and less than 10 15 ⁇ , preferably 10 13 ⁇ or more and 10 15 ⁇ . Is less than.
  • the surface resistance value of the fixing component is 10 12 ⁇ or more, the charge amount after the molded product and the copy paper come into contact with each other does not become too low, and problems such as the toner adhering to the copy paper coming off hardly occur.
  • the surface resistance value of the fixing component is less than 10 15 ⁇ , the amount of charge after the molded product and the copy paper come into contact with each other does not become too high, and problems such as the toner adhering to the copy paper coming off hardly occur. .
  • the value measured using the well-known measuring apparatus based on “ASTM D257” was employ
  • the surface resistance value of the molded product should be measured, for example, under resistance measurement conditions (using a digital super insulation / microammeter “DSM-8104” manufactured by Toa DKK Corporation, measuring temperature 23 ° C.) in accordance with “ASTM D257”. Can do.
  • a melt molding method is preferable.
  • 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, a blow molding method, and a vacuum molding method. And press molding.
  • the injection molding method is preferable.
  • an injection molding method is used will be described as an example of a method for manufacturing a molded product according to the present embodiment.
  • the liquid crystal polyester composition is melted using an injection molding machine (for example, “hydraulic horizontal molding machine PS40E5ASE type” manufactured by Nissei Plastic Industry Co., Ltd.), and the melted liquid crystal polyester composition is appropriately used. It can be performed by heating to a suitable temperature and injecting it into the mold.
  • an injection molding machine for example, “hydraulic horizontal molding machine PS40E5ASE type” manufactured by Nissei Plastic Industry Co., Ltd.
  • the temperature at which the liquid crystal polyester composition is heated and melted for injection is preferably [Tp + 10] ° C. or more and [Tp + 50] ° C. or less based on the flow start temperature Tp ° C. of the liquid crystal polyester composition to be used.
  • the temperature of the mold is preferably selected from 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 composition.
  • the absolute value of the charge amount can be controlled.
  • the molded product is a fixing part for a printer, it is possible to suppress the displacement of the position of the transferred electrostatic image and to suppress the disturbance of the resulting image.
  • the molded product is a camera module
  • the liquid crystal polyester composition according to one embodiment of the present invention is: Liquid crystal polyester, First carbon black, A second carbon black, if desired, A filler;
  • the liquid crystalline polyester is a structural unit derived from p-hydroxybenzoic acid (30 mol% to 80 mol% based on the total molar amount of all structural units constituting the liquid crystalline polyester), 4,4′-dihydroxybiphenyl.
  • the first carbon black is Primary particle size is at 30nm or more 40nm or less and a DBP oil absorption of not more than 350 cm 3/100 g or more 525 cm 3/100 g, the second carbon black, DBP oil absorption amount not satisfy the 300 cm 3/100 g or more 550 cm 3/100 g the following conditions;
  • the filler is a fibrous filler (preferably glass fiber) and a plate filler (preferably talc);
  • the content of the liquid crystal polyester is 30 to 90%
  • the ratio R 123 when representing the relationship with the ratio R 123 represented by the formula (S3), the ratio R 123 is greater than 4 ⁇ 10 7, it is less than 5.8 ⁇ 10 8, It is a liquid crystal polyester composition. Furthermore, the liquid crystalline polyester is The BET specific surface area of the first carbon black may be 750 m 2 / g or more and 1300 m 2 / g or less, The volume resistivity ⁇ 1 of the first carbon black may be 1 ⁇ 10 2 ⁇ ⁇ m or more and 1 ⁇ 10 7 ⁇ ⁇ m or less, The volume resistivity ⁇ 2 of the fibrous filler may be 1 ⁇ 10 9 ⁇ ⁇ m or more and 1 ⁇ 10 15 ⁇ ⁇ m or less, The plate-like filler may have a volume resistivity ⁇ 3 of 1 ⁇ 10 9 ⁇ ⁇ m or more and 1 ⁇ 10 15 ⁇ ⁇ m or less.
  • a method for controlling the charge amount of a housing interior part The method Producing a housing interior part from the liquid crystalline polyester composition, and providing the housing interior part in the housing;
  • the liquid crystal polyester composition is Liquid crystal polyester, First carbon black, Optionally containing a second carbon black,
  • the first carbon black is a carbon black that satisfies the following conditions (A) and (B):
  • the second carbon black is a carbon black that does not satisfy at least one of the condition (A) and the condition (B),
  • the content of the second carbon black is 0 part by mass or more and 9 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester, and the total content of the first carbon black and the second carbon black is the liquid crystal 1 to 10 parts by mass with respect to 100 parts by mass of polyester,
  • the surface resistance value of the molded product was measured at 23 ° C. under resistance measurement conditions (using a digital super insulation / microammeter “DSM-8104” manufactured by Toa DKK Co., Ltd.) in accordance with “ASTM D257”.
  • volume resistivity of the first carbon black, fibrous filler, and talc filler is determined by measuring the temperature at 23 ° C. and the measurement humidity after leaving the first carbon black, fibrous filler, or talc filler in a silica gel desiccator for 24 hours. Measurement was performed with an insulation resistance meter R8340A ULTRA HIGH RESISUTANCE METER (manufactured by ADC Corporation) at 50% (relative humidity).
  • this prepolymer was pulverized using a pulverizer, and the obtained pulverized product was heated from room temperature to 250 ° C. over 1 hour in a nitrogen atmosphere, and then heated from 250 ° C. to 295 ° C. over 5 hours.
  • Solid-state polymerization was performed by maintaining at 295 ° C. for 3 hours.
  • the obtained solid phase polymer was cooled to room temperature to obtain a powdered liquid crystal polyester (1).
  • the flow starting temperature of the obtained liquid crystal polyester (1) was 327 ° C.
  • this prepolymer was pulverized using a pulverizer, and the resulting pulverized product was heated from room temperature to 220 ° C. over 1 hour in a nitrogen atmosphere, and then heated from 220 ° C. to 240 ° C. over 30 minutes.
  • the solid phase polymerization was carried out by holding at 240 ° C. for 10 hours.
  • the obtained solid phase polymer was cooled to room temperature to obtain a powdered liquid crystal polyester (2).
  • the flow starting temperature of the obtained liquid crystal polyester (2) was 286 ° C.
  • carbon black and filler The following materials were used as carbon black and filler.
  • the physical properties of carbon black and filler are manufacturer's nominal values.
  • First carbon black Ketjen Black EC300J (Lion Specialty Chemicals Co., Ltd., primary particle diameter 39.5 nm, DBP oil absorption of 360 cm 3/100 g, BET specific surface area 800 m 2 / g, a volume resistivity of 2.51 ⁇ 10 4 ⁇ ⁇ m)
  • Second carbon black CB # 960 (Mitsubishi Chemical Co., primary particle diameter 16 nm, DBP oil absorption of 69cm 3/100 g, BET specific surface area of 260 meters 2 / g, a volume resistivity of 4.96 ⁇ 10 5 ⁇ ⁇ m)
  • Glass fiber (2) EFH75-01 (manufactured by Central Glass Fiber Co., Ltd., number average fiber length 30 ⁇ m, number average fiber diameter 11 ⁇ m, volume resistivity 3.43 ⁇ 10 11 ⁇ ⁇ m)
  • Tables 1 and 2 show the ratio R 123 of the filler used, which is represented by the following formula (S3).
  • Comparative Examples 1 to 4 Liquid crystalline polyester, carbon black and components added as required are melted at a cylinder temperature of 340 ° C. using a twin-screw extruder (“PCM-30” manufactured by Ikekai Tekko Co., Ltd.) in the proportions shown in Tables 1 and 2. The mixture was kneaded to obtain a pellet-shaped liquid crystal polyester composition. In addition, the unit of the ratio shown in Table 1 and Table 2 is a mass part.
  • the liquid crystalline polyester composition was molded at a molding temperature of 350 ° C., a mold temperature of 130 ° C., an injection speed of 100 mm / second, 64 mm long and 64 mm wide. A flat test piece having a thickness of 1 mm was formed.
  • Tables 3 and 4 show the overall evaluation of the examples and comparative examples.
  • the comprehensive evaluation of the examples and comparative examples was performed according to the following criteria using the granulation properties and the absolute values of the charge amount of the test piece and the copy paper after the test.
  • the case where the liquid crystal polyester composition could be granulated was designated as “A”
  • the case where granulation was impossible was designated as “B”.
  • the absolute value of the charge amount of the test piece is 30 V or more and 200 V or less
  • the absolute value of the charge amount of the copy paper is 0 V or more and 5 V or less
  • B Other than the above
  • test pieces of Examples 1 to 6 to which the present invention was applied had higher surface resistance values than the test piece of Comparative Example 3.
  • the absolute value of the charge amount of the test piece after the test was larger than that in Comparative Example 3.
  • the present invention sets the surface resistance value of the test piece to 10 12 ⁇ by setting the content of the first carbon black and the total content of the first carbon black and the second carbon black within a specific range.
  • the adjustment within the range of less than 10 15 ⁇ was able to moderately suppress the increase in the charge amount of both the test piece and the copy paper after the test.
  • the present invention can provide a molded product capable of suppressing an increase in charge amount and a liquid crystal polyester composition from which such a molded product can be obtained, it is extremely useful industrially.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Liquid Crystal Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne une composition de polyester à cristaux liquides comprenant un polyester à cristaux liquides, un premier noir de carbone et, comme souhaité, un second noir de carbone : le premier noir de carbone satisfaisant aux conditions (A) et (B) suivantes ; le second noir de carbone ne satisfaisant pas à ladite condition (A) et/ou à ladite condition (B) ; la teneur W1 en premier noir de carbone étant de 1 à 10 parties en masse pour 100 parties en masse du polyester à cristaux liquides ; la teneur en second noir de carbone étant de 0 à 9 parties en masse pour 100 parties en masse du polyester à cristaux liquides ; et la teneur totale en premier noir de carbone et en second noir de carbone étant de 1 à 10 parties en masse pour 100 parties en masse du polyester à cristaux liquides. (A) : le diamètre de particule primaire est situé dans la plage allant de 10 à 50 nm (B) : la quantité d'absorption d'huile DBP est située dans la plage allant de 300 cm3/100 g à 550 cm3/100 g.
PCT/JP2019/016615 2018-04-27 2019-04-18 Composition de polyester à cristaux liquides et produit moulé WO2019208381A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116438245A (zh) * 2020-10-29 2023-07-14 大塚化学株式会社 液晶聚合物组合物、液晶聚合物成型体和电气电子设备

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06207083A (ja) * 1992-06-02 1994-07-26 Sumitomo Chem Co Ltd 液晶ポリエステル樹脂組成物、電子部品用キャリヤーおよびｉｃ用耐熱トレー
JPH06340799A (ja) * 1993-06-02 1994-12-13 Teijin Ltd 導電性樹脂組成物
JP2000017179A (ja) * 1998-06-30 2000-01-18 Nichias Corp 導電性樹脂組成物、燃料電池用セパレータ及びシール材料
JP2002322366A (ja) * 2001-04-23 2002-11-08 Riken Technos Corp 導電性熱可塑性樹脂組成物
JP2008247985A (ja) * 2007-03-29 2008-10-16 Nippon Oil Corp 導電性樹脂組成物
JP2011157422A (ja) * 2010-01-29 2011-08-18 Sumitomo Chemical Co Ltd 液晶ポリエステル組成物、その製造方法及びコネクター

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW401454B (en) * 1992-06-02 2000-08-11 Sumitomo Chemical Co Liquid crystal polyester resin composition and molded article
JP2001279066A (ja) * 2000-03-31 2001-10-10 Sumitomo Chem Co Ltd 液晶ポリエステル樹脂組成物
JP2006045298A (ja) * 2004-08-03 2006-02-16 Ntn Corp 液晶ポリエステル樹脂組成物
JP5486889B2 (ja) * 2009-09-28 2014-05-07 Ｊｘ日鉱日石エネルギー株式会社 液晶ポリエステル樹脂組成物
JP5206903B2 (ja) * 2011-03-25 2013-06-12 東レ株式会社 熱可塑性樹脂組成物およびそれを用いた成形品

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06207083A (ja) * 1992-06-02 1994-07-26 Sumitomo Chem Co Ltd 液晶ポリエステル樹脂組成物、電子部品用キャリヤーおよびｉｃ用耐熱トレー
JPH06340799A (ja) * 1993-06-02 1994-12-13 Teijin Ltd 導電性樹脂組成物
JP2000017179A (ja) * 1998-06-30 2000-01-18 Nichias Corp 導電性樹脂組成物、燃料電池用セパレータ及びシール材料
JP2002322366A (ja) * 2001-04-23 2002-11-08 Riken Technos Corp 導電性熱可塑性樹脂組成物
JP2008247985A (ja) * 2007-03-29 2008-10-16 Nippon Oil Corp 導電性樹脂組成物
JP2011157422A (ja) * 2010-01-29 2011-08-18 Sumitomo Chemical Co Ltd 液晶ポリエステル組成物、その製造方法及びコネクター

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116438245A (zh) * 2020-10-29 2023-07-14 大塚化学株式会社 液晶聚合物组合物、液晶聚合物成型体和电气电子设备

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