WO2009072641A1 - Polyester cristallin liquide, et article moulé - Google Patents

Polyester cristallin liquide, et article moulé Download PDF

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Publication number
WO2009072641A1
WO2009072641A1 PCT/JP2008/072220 JP2008072220W WO2009072641A1 WO 2009072641 A1 WO2009072641 A1 WO 2009072641A1 JP 2008072220 W JP2008072220 W JP 2008072220W WO 2009072641 A1 WO2009072641 A1 WO 2009072641A1
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WIPO (PCT)
Prior art keywords
liquid crystal
group
crystal polyester
temperature
resin composition
Prior art date
Application number
PCT/JP2008/072220
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English (en)
Japanese (ja)
Inventor
Tomoya Hosoda
Tomoko Uehara
Satoshi Okamoto
Original Assignee
Sumitomo Chemical Company, Limited
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Filing date
Publication date
Priority claimed from JP2008090690A external-priority patent/JP2009155623A/ja
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Priority to US12/745,264 priority Critical patent/US8337719B2/en
Priority to CN200880125982.XA priority patent/CN101932654B/zh
Publication of WO2009072641A1 publication Critical patent/WO2009072641A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
    • B29B7/42—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • 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
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to a liquid crystal polyester resin composition containing liquid crystal polyester and a filler made of a high dielectric material, a method for producing the same, and a molded body using the liquid crystal polyester resin composition.
  • antenna base for antenna manufacture
  • a molded body is used.
  • liquid crystal polyester has attracted attention as a thermoplastic resin used in the manufacture of antenna substrates. Liquid crystal polyester has both high heat resistance and heat resistance and low water absorption, so that the durability of the antenna is good as well as the durability of the antenna.
  • the dielectric characteristics required for such an antenna substrate include a high relative dielectric constant (high dielectric property) for electromagnetic waves in a high frequency region and a low dielectric loss tangent. It is important. This is because a high dielectric antenna substrate does not significantly deteriorate the antenna characteristics even with a relatively small antenna, and an antenna gain increases with a low dielectric loss tangent antenna substrate. This is because there is a tendency to do so.
  • a high dielectric material is used as a filler (hereinafter referred to as
  • a method of obtaining an antenna substrate from a resin composition containing the high dielectric material filler and a liquid crystal polyester For example, in Japanese Patent Application Laid-Open No. 2 00 4-1 6 1 9 5 3, a composition containing 25 to 35% by volume of liquid crystal polyester and 65 to 75% by volume of ceramic powder is melt-mixed, Thereafter, a tablet for antenna parts that has been converted into a tablet at room temperature by a tableting machine is disclosed, and it is disclosed that a tablet for antenna parts having excellent shape retention can be obtained by using a wax component together during melt mixing.
  • a resin composition containing a liquid crystal polyester and a filler is prepared by melting and kneading a liquid crystal polyester and a filler in advance before molding the resin composition to obtain a molded body (hereinafter referred to as a pellet-like composition). It is generally practiced to obtain “composition pellets”.
  • a method for producing a composition pellet a liquid crystal polyester and a filler are melted and kneaded, and a molten liquid crystal polyester resin composition is extruded into a string shape to obtain a string composition (strand).
  • a manufacturing method is generally known in which the composition is cooled and solidified and cut to obtain a composition pellets (such a manufacturing method is called a strand method).
  • the composition pellets may not be stably obtained.
  • a production method for tableting with a tableting machine is employed. Such a manufacturing method is relatively complicated and mass production. Is unsuitable and is not suitable for industrial production.
  • the resin composition of the invention of Japanese Patent Application Laid-Open No. 2006-2331 18 is a resin composition capable of obtaining a molded article having excellent dielectric properties even though the filling amount of the high dielectric material filler is small, and the strand tends to be easily obtained. In the direction.
  • the compatibility with the strand method is not necessarily sufficient in order to obtain a composition pellets with industrial stability and good productivity.
  • one of the objects of the present invention is that a resin method using a liquid crystal polyester and a high dielectric material filler can be applied with a strand method suitable for industrial production, and the composition pellets can be stably used.
  • An object of the present invention is to provide a liquid crystal polyester resin composition that can be produced.
  • the present invention comprises a structural unit represented by the following formula ( ⁇ ), a structural unit represented by the formula (ii), and a structural unit represented by the formula (iii), 2, 6-naphthalene diyl group when the total of the divalent aromatic group represented by Ar 2 and the divalent aromatic group represented by Ar 3 is 100 mol%.
  • Liquid crystal polyester (A) 50 to 80% by volume with a melt starting temperature of at least 280 ° C and a melt tension measured at a temperature higher than the flow starting temperature of 1 g or more.
  • Filler made of high dielectric material (B) 20-50% by volume,
  • a liquid crystal polyester resin composition is provided.
  • ⁇ consists of 2, 6-naphthalene diyl group, 1, 4 1-phenylene group, and 4, 4 ′ 1-bif; ⁇ : diene group
  • ⁇ diene group
  • Ar 2 , A r 3 is independently a divalent group selected from the group consisting of 2,6-naphthalenediyl group, 1,4-phenylene group, 1,3-phenylene group, and 4,4′-biphenylene group. Represents an aromatic group.
  • a part of the hydrogen atoms bonded to the aromatic ring are a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. It may be substituted with 20 aryl groups.
  • liquid crystal polyester resin composition of the present invention can be used in various applications that require dielectric properties such as high dielectric properties and low dielectric loss tangents.
  • the present invention further provides a molded body using the liquid crystal polyester resin composition, and an antenna having the molded body and an electrode.
  • a composition pellet can be easily produced by a composition pellet production method such as a strand method, which is widely used in this technical field. Since this composition pellet has good operability, a molded product can be easily obtained by injection molding or the like.
  • the molded body using the liquid crystal polyester resin composition of the present invention is used in various applications where high dielectric properties and low dielectric loss tangents are required, particularly for antennas of information communication equipment to which high frequency electromagnetic waves are applied. Since it can be used suitably, it is very useful industrially.
  • the present invention provides a liquid crystal polyester resin composition containing 50 to 80% by volume of liquid crystal polyester (A) and 20 to 50% by volume of a filler (B) made of a high dielectric material.
  • the liquid crystalline polyester used in the present invention is a polyester that exhibits optical anisotropy when melted and can form an anisotropic melt at a temperature of 45 ° C. or lower. More specifically, the liquid crystalline polyester used in the present invention includes a structural unit represented by the following formula (i), a structural unit represented by the formula (ii), and a structural unit represented by the formula (iii). becomes a divalent aromatic group represented by Alpha eta, the total of divalent aromatic groups represented by divalent aromatic group and a r 3 represented by a r 2 (hereinafter, "total aromatic When the total of the group is “100 mol%”, the aromatic group contains at least 40 mol% of 2,6-naphthalenediyl group.
  • the liquid crystal polyester used in the present invention has a flow start temperature of The melt tension measured at 280 ° C or higher and higher than the flow start temperature is 1 g or higher.
  • ⁇ is a divalent aromatic group selected from the group consisting of 2,6-naphthalenedyl group, 1,4-phenylene group and 4,4′-biphenylene group
  • Ar 2 , A r 3 is each independently a bivalent group selected from the group consisting of 2,6-naphthalenediyl group, 1,4-monophenylene group, 1.3-phenylene group, and 4,4'-biphenylene group. It is an aromatic group.
  • the divalent aromatic group represented by ⁇ , Ar 2 and Ar 3 may have a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms as a substituent. Good.
  • Such a liquid crystal polyester comprises a monomer having a 2,6-naphthalenediyl group and another monomer having an aromatic ring, in which the structural unit having a 2,6-naphthalenediyl group is 40
  • the raw material monomer can be selected and polymerized so as to be at least mol%.
  • a preferable liquid crystal polyester is a liquid crystal polyester in which 2,6-naphthalene diyl group is 50 mol% or more with respect to 100 mol% of total aromatic groups, and more preferably 2,6-naphthalene diyl group is 65 mol%. It is a liquid crystal polyester having a mol% of at least 70, and particularly preferably a liquid crystal polyester having 2,6 mononaphthalenedyl groups of 70 mol% or more.
  • the liquid crystal polyester containing more 2,6-naphthalenediyl groups as the aromatic group can be obtained by setting the melt tension to 1 g or more as will be described later. This makes it possible to produce the composition pellets stably.
  • the liquid crystal polyester containing more 2,6-naphthalenediyl groups also has the advantage that the resulting molded article can be further reduced in dielectric loss tangent.
  • the total aromatic group total is 100 mol%
  • the resulting molded article tends to have a large electrostatic tangent.
  • the total of the structural unit represented by the formula (i), the structural unit represented by the formula (ii) and the structural unit represented by the formula (iii) constituting the liquid crystalline polyester used in the present invention (hereinafter referred to as “the structural unit represented by the formula (i)”)
  • the total of structural units represented by (i) (hereinafter referred to as “structural units (i)”) is 30 to 80 mol%.
  • the total of structural units represented by (ii) (hereinafter referred to as “structural units (ii)”) is 10 to 35 mol%, and the structural units represented by (iii) (hereinafter “structural units”)
  • (iii) J) is preferably 10 to 35 mol%.
  • Liquid crystalline polyesters in which the molar ratio (copolymerization ratio) of the structural unit (i), structural unit (ii), and structural unit (iii) to the total of all structural units is in the above range should exhibit a high degree of liquid crystallinity. In addition to this, it can be melted at a practical temperature, and melt molding becomes easy, which is preferable.
  • the liquid crystalline polyester is preferably a wholly aromatic liquid crystalline polyester in that a higher degree of heat resistance is obtained.
  • the structural unit (i), the structural unit (ii) and the structural unit are preferred.
  • the molar ratio of the total of structural units (ii) to the total of all structural units is substantially equal to the molar ratio of the total of structural units (iii).
  • the molar ratio of the total of the structural units (i) to the total of the structural units is more preferably 40 to 70 mol%, and particularly preferably 45 to 65 mol%.
  • the molar ratio of the total of structural units (ii) and the total molar ratio of structural units (iii) with respect to the total of all structural units is more preferably 15 to 30 mol%, and 17.5 to 27. 5 mol% is particularly preferable.
  • the liquid crystal polyester Tell has the advantage that it can exhibit a higher degree of liquid crystallinity and can be melted at a more practical temperature, facilitating melt molding.
  • the structural unit (i) is a structural unit derived from an aromatic hydroxycarboxylic acid.
  • Examples of the monomer for deriving the structural unit U) include 2-hydroxy-16-naphthoic acid, p-hydroxybenzoic acid, and 4- (4-hydroxyphenyl) benzoic acid. Further, a part of the hydrogen atoms bonded to the benzene ring or naphthalene ring of these monomers are substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Monomers can also be used. Among them, a monomer for deriving a structural unit having a 2,6-naphthalenediyl group is 2-hydroxy 6-naphthoic acid.
  • the structural unit (i i) is a structural unit derived from an aromatic dicarboxylic acid.
  • the monomer for deriving the structural unit (ii) include 2,6-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, and Bif I diluo 4,4'-dicarboxylic acid.
  • a monomer in which a part of hydrogen atoms bonded to the benzene ring or naphthalene ring of these monomers is substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • a monomer for deriving a structural unit having a 2,6 mononaphthalenediyl group is 2,6-naphthalenedicarboxylic acid.
  • the structural unit (iii) is a structural unit derived from an aromatic diol.
  • the monomer for deriving the structural unit (iii) include 2,6-naphthalenediol, hydrated quinone, resorcin, and 4,4′-dihydroxybiphenyl.
  • a monomer in which a part of hydrogen atoms bonded to the benzene ring or naphthalene ring of these monomers is substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • a monomer for deriving a structural unit having a 2,6-naphthalenediyl group is 2,6-naphthalenediol.
  • the structural unit (i), the structural unit (ii), or the structural unit (iii) may have any of the above substituents on the aromatic ring (benzene ring or naphthalene ring).
  • substituents for example, Fluorine atom, chlorine atom, bromine atom, iodine atom are mentioned.
  • alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, etc. These may be linear or branched, and may be alicyclic groups.
  • the aryl group include aryl groups having 6 to 20 carbon atoms represented by phenyl group, naphthyl group and the like.
  • the monomer that derives the structural unit (i), the structural unit (ii), or the structural unit (iii) may be converted into an ester-forming derivative in order to facilitate polymerization in the process of producing the polyester.
  • the ester-forming derivative means a compound having a group that promotes an ester formation reaction.
  • the carboxyl group is represented by an acid halide, an acid li, or the like. It is an ester-forming derivative that has been converted to water, and in the case of a monomer having a hydroxyl group, it is an ester-forming derivative in which the hydroxyl group has been converted to an ester using a lower carboxylic acid.
  • a known method may be adopted as a method for producing the liquid crystal polyester.
  • a preferred production method includes a method of producing a liquid crystal polyester using an ester-forming derivative obtained by converting a hydroxyl group in a monomer molecule into an ester using a lower carboxylic acid as the ester-forming derivative.
  • a production method using an ester-forming derivative obtained by converting (acylating) a hydroxyl group of an aromatic hydroxycarboxylic acid and an aromatic diol into an acyl group is preferable.
  • the acylation can usually be carried out by reacting a monomer having a hydroxyl group (aromatic hydroxycarboxylic acid and aromatic diol) with acetic anhydride.
  • the ester-forming derivative thus obtained can be easily produced into a polyester by polycondensation with an aromatic dicarboxylic acid.
  • the monomer that forms the structural unit (i), the structural unit (ii), and the structural unit (iii) can be derived from a monomer that can derive a structural unit having a 2,6-naphthalenediyl group.
  • the aromatic hydroxycarboxylic acid for deriving the structural unit (i) and the aromatic diol for deriving the structural unit (iii) are converted to ester-forming derivatives after being converted to ester-forming derivatives.
  • ii) is melt-polymerized with the aromatic dicarboxylic acid to form a relatively low molecular weight liquid crystal polyester (hereinafter sometimes referred to as “prepolymer”).
  • prepolymer liquid crystal polyester
  • this prepolymer is used as a powder, and this powder is heated for solid phase polymerization.
  • solid-phase polymerization is used in this manner, the polymerization proceeds more rapidly, and the liquid crystal polyester can be increased in molecular weight, so that the flow start temperature of the obtained liquid crystal polyester can be increased.
  • this solid phase polymerization is also effective for adjusting the melt tension of the liquid crystal polyester.
  • the prepolymer may be cooled and solidified and then pulverized by various known pulverization means.
  • the average particle size of the powder is preferably in the range of about 0.05 mm to about 3 mm, and more preferably in the range of about 0.05 mm to about 1.5 mm. If the particle diameter of the powder is in such a range, it is more preferable because the degree of polymerization of the aromatic liquid crystal polyester is promoted, and if it is in the range of about 0.1 mm to about 1 mm, the sintering between the particles is preferable. This is more preferable because it increases the degree of polymerization of the liquid crystal polyester without causing a ring.
  • Suitable conditions for the heating conditions in the solid phase polymerization are exemplified below.
  • the temperature is raised from room temperature to a temperature that is 20 ° C lower than the flow start temperature of the prepolymer.
  • the temperature raising time at this time is not limited, it is preferably within 1 hour from the viewpoint of shortening the reaction time.
  • the temperature is raised from a temperature 20 ° C. or more lower than the flow start temperature of the prepolymer to a temperature of 28 ° C. or more.
  • the temperature increase is preferably performed at a temperature increase rate of 0.3 ° C. or less, and a temperature increase rate of about 0.1 to 0.15 ° C. is more preferable.
  • the temperature rising rate is 0.3 ° C. or less, sintering between powder particles hardly occurs, and therefore, a liquid crystal polyester having a higher degree of polymerization can be produced relatively easily.
  • the reaction may be carried out at a temperature of 28 ° C. or higher, preferably 30 ° C. to 400 ° C. for 30 minutes or longer. preferable.
  • the reaction is preferably performed at a reaction temperature of 280 to 350 ° C for 30 minutes to 30 hours, and more preferably at a reaction temperature of 285 to 340 ° C for 30 minutes to 20 hours.
  • Such heating conditions can be optimized as appropriate depending on the type of monomer used in the production of the liquid crystalline polyester.
  • the flow start temperature of the liquid crystal polyester can be set to 280 ° C. or higher in a relatively short time.
  • a liquid crystal polyester having such a flow start temperature is obtained according to the present invention.
  • the flow start temperature is a capillary rheometer equipped with a die with an inner diameter of 1 mm and a length of 1 Omm, and a heating rate of 4 ° CZ under a load of 9.8 MPa (100 kg / cm 2 ).
  • the flow start temperature represents the molecular weight of a liquid crystal polyester known in the art Index (see Naoyuki Koide, “Liquid Crystalline Polymer Synthesis / Molding-Application 1”, pages 95-105, CMC, published on June 5, 987.
  • the flow start temperature is As a device to measure, a flow characteristic evaluation device “Flow Tester CFT-500DJ” manufactured by Shimadzu Corporation is used.)
  • an electrode forming process is used.
  • the flow starting temperature of the liquid crystalline polyester is more preferably 290 ° C. or higher, and further preferably 295 ° C. or higher, while the antenna substrate is molded in a practical temperature range. From this point of view, the flow start temperature is preferably 380 ° C or lower, more preferably 350 ° C or lower.
  • the shape of the liquid crystal polyester used as the sample to be measured is not limited to powder, but the liquid crystal polyester may be formed into a pellet shape by a known method.
  • the liquid crystal polyester may be made into a pellet as a sample to be measured for the flow start temperature measurement.
  • the liquid crystal polyester having such a pellet shape can also be used for the melt tension measurement described later.
  • the production method will be briefly described.
  • the extruder to be used include, for example, a single-screw or multi-screw extruder, and a twin-screw extruder, a Banbury type kneader, and a roll-type kneader are preferable.
  • Pellets are obtained by melting liquid crystal polyester in the temperature range from 10 ° C lower than T p to 1 oo ° c higher than T p, starting from its flow start temperature T p [° C]. be able to.
  • the liquid crystalline polyester used in the present invention has a melt tension of 1 g or more measured at a temperature higher than the flow start temperature.
  • a preferred liquid crystal polyester is a liquid crystal polyester having a melt melt of 1.5 g or more, more preferably 2 g or more of a liquid crystal polyester.
  • a liquid crystal polyester having a melt tension of 1 g or more measured at a temperature about 25 ° C. higher than the flow start temperature is a liquid crystal polyester resin composition using a relatively large amount of a highly-inductive material filler as described later.
  • the composition pellets tend to be manufactured stably.
  • the melt tension here refers to a capillograph filled with liquid crystal polyester (pelletized liquid crystal polyester), a cylinder barrel diameter of 1 mm 0, a piston extrusion speed of 5. O mm, and a variable speed winder. It means the tension (g) when the sample is taken up in a filament shape while automatically accelerating and breaks, and several points of melt tension are measured at a temperature higher than the flow start temperature of the liquid crystalline polyester used for measurement. If the melt tension is 1 g or more at one point, it is defined as “liquid crystalline polyester having a melt tension of 1 g or more measured at a temperature higher than the flow start temperature” in the present invention. To do.
  • the liquid crystal polyester may be manufactured by combining the flow start temperatures of 280 ° C or higher.
  • structural unit (i) structural unit derived from p-hydroxybenzoic acid
  • structural unit (ii) structural unit derived from terephthalic acid and Z or isophthalic acid
  • structural unit (iii) As an example, a method for improving the amount of introduction of a structural unit derived from an aromatic diol selected from hydride quinone and resorcin is cited.
  • the amount of structural units having low flexibility is preferred, so that as structural unit (ii), structural units derived from terephthalic acid,
  • the structural unit (iii) is preferably a structural unit derived from hydroquinone.
  • the aromatic ring in these structural units may have a substituent, but in terms of introducing a structural unit having a small molecular volume, the structural unit having no substituent is introduced. Input is preferred.
  • the liquid crystalline polyester used in the present invention needs to contain 2,6-naphthalenediyl groups in an amount of 40 mol% or more based on the total aromatic groups, and has a structure having 2,6-naphthalenediyl groups. It is necessary to control the unit and the structural unit having a monocyclic aromatic group.
  • the structural unit (i-a) derived from 2-hydroxy-16-naphthoic acid is 40 to 75 as the structural unit (i).
  • the total of the structural unit derived from 2,6-naphthalenedicarboxylic acid (ii-a) and the structural unit derived from terephthalic acid (ii 1 b) is 12.5.
  • structural unit (iii) has 12.5 to 30 mol 0 6 structural unit (iii-a) derived from hydroquinone [where structural unit (i-a), (ii a), (ii-1b) and (iii-1a) are 100 mol%], and in structural unit (ii), the molar ratio of (ii-1a) to (ii-1b) is , (Ii—a) / [(ii—a) + (ii-b) ⁇ ⁇ 0.5.
  • More preferred liquid crystalline polyesters are those in which ( ⁇ — a) is 40 to 60 mol% with respect to the sum of the structural units (i 1 a), (i ia), (i i- b) and (i ii— a), (Ii-a) force ⁇ 1 4.5-29. 5 mol%, the sum of (ii-a) and (ii-b) is 15-30 mol%, (iii-a) is 15-5 And (ii) in the structural unit, the molar ratio of the structural unit between (ii—a) and (ii-1b) is (ii—a) /
  • melt polymerization and solid phase polymerization are performed, and the flow start temperature is set to 280 ° C or higher, preferably 295 ° C or higher. This makes it possible to produce liquid crystal polyester that can achieve a tension of 1 g or more.
  • the filler (B) made of a high dielectric material used in the present invention is a known filler applied to a high dielectric composition.
  • a filler as exemplified in JP-A-2004-307607 that is, a titanium dioxide system, a barium titanate system, a barium titanate zirconate system, a titanate stopper Nitium, calcium titanate, bismuth titanate, magnesium titanate, barium neodymium titanate, barium tin titanate, magnesium barium titanate, barium magnesium tantalate, lead titanate , Lead zirconate, lead zirconate titanate, lead niobate, lead magnesium niobate, lead nickel niobate, lead tungstate, calcium tungstate and lead magnesium tungstate Fillers made of high dielectric materials are applicable.
  • titanium ceramic filler is preferable from the viewpoint of obtaining a molded body having a high dielectric constant.
  • the “filler” is a filler made of ceramics having titanium as a constituent element component, and specific examples of the ceramics include titanium oxides and metal titanates.
  • the metal titanate refers to a metal titanate selected from a group consisting of barium, strontium, bismuth, lanthanum, neodymium, samarium, aluminum, calcium and magnesium, or a plurality of metals selected from such a group. There may be mentioned titanates formed by solid solution.
  • the titanium-based ceramic filler used in the present invention mainly contains such titanium-based ceramics, and does not exclude unintentionally contained impurities, and has been subjected to a surface treatment as described later. May be.
  • These high dielectric material fillers may be used in combination of two or more. These high dielectric material fillers may be surface-treated with a surface treatment agent such as a titanate coupling agent, an aluminum coupling agent, or a silane coupling agent.
  • a surface treatment agent such as a titanate coupling agent, an aluminum coupling agent, or a silane coupling agent.
  • the titanium-based ceramics exemplified above can be produced by known means.
  • a metal carbonate selected from the group consisting of barium, strontium, bismuth, lanthanum, neodymium, aluminum, calcium and magnesium, and titanium oxide are mixed and baked, then crushed and crushed as necessary
  • a titanium-based ceramic filler can be manufactured by performing operations such as classification.
  • a titanium-based ceramic filler that can be easily obtained from the market may be used.
  • a filler made of T i 0 2 or Ba T i 0 3 is preferable.
  • a filler made of B a T i 0 3 is ⁇ ⁇ ⁇ ⁇ ⁇ -1 ”manufactured by Fuji Titanium Industry Co., Ltd. wear.
  • a filler consisting of T i 0 2 “CR— 6” manufactured by Ishihara Sangyo Co., Ltd.
  • the titanium-based ceramics may be either single crystal or polycrystalline, and the crystal form is not limited.
  • the shape of the high dielectric material filler is not limited, and may be any of fine powder, fiber, and plate.
  • the liquid crystal polyester resin composition using the filler that can be well dispersed in the heated melt has a high dielectric material filler in the molded product when the molded product is obtained by molding this resin composition. It exists almost uniformly and tends to exhibit good properties related to the filler.
  • the titanium ceramic filler is preferably finely powdered.
  • the fine powdery filler is more preferably an average particle size of 0.01 to 100 ⁇ m, and further preferably 0.1 to 20 / m. Such an average particle diameter is obtained by external observation with an electron microscope when the average particle diameter is 2 O im or less, and when the average particle diameter exceeds 20 m, a laser single diffraction light scattering method is used. Is required.
  • the average particle size of the titanium ceramic filler is 0.23 to 5 jum, and a fine particle size of 0.25 to 1.5 m. More preferably, it is in the form of powder, and more preferably in the form of fine powder of 0.26 to 0.30 jUm. From the viewpoint of improving the mechanical strength such as bending strength, it is preferable to use a fibrous titanium ceramic filler.
  • the number average fiber length is preferably more than 0.5 jum and not more than 1 O im, and the number average fiber diameter is not less than 0.1 / m and not more than 1 jum, Aspect ratio (Number average fiber length Z Number average fiber diameter) More preferably, it is in the form of 2 or more, the number average fiber length is 1 jum or more and 10 m or less, and the number average fiber diameter is 0.1. It is more preferably 0.5 / m or less and a fibrous form with an aspect ratio of 3 or more.
  • Such number-average fiber length and number-average fiber diameter are determined by appearance observation with a scanning electron microscope (SEM).
  • the titanium-based ceramic fillers that can be easily obtained from the above-exemplified market are classified according to their shapes.
  • the fine powdered titanium-based ceramic fillers are “HP BT-1 J”, “CR-60”, “ “CR-58”, “CR-97J”, “SR-1 J” are exemplified, and “Taipaque PF R404” is exemplified as the fibrous titanium ceramic filler.
  • the liquid crystal polyester resin composition of the present invention may contain an additive such as a reinforcing agent depending on necessary properties as long as the object of the present invention is not significantly impaired.
  • additives include fibrous reinforcing agents such as glass fiber, silica alumina fiber, alumina fiber, and carbon fiber; acicular reinforcing agents such as aluminum borate whisker and titanic acid re-wiss whisker; glass Inorganic fillers such as beads, talc, my strength, graph eye candy, wollastonite, dolomite candy; mold release improvers such as fluororesins and metal stones; colorants such as dyes and pigments; antioxidants; thermal stability Agents; ultraviolet absorbers; antistatic agents; surfactants and the like. Two or more of these additives may be used in combination.
  • thermoplastic resins other than liquid crystal polyester for example, polyamide, crystalline polyester, polyethylene sulfide, polyether ketone, polycarbonate, polyphenylene ether and its modified products, polysulfone, Ethersulfone, polyetherimide, etc.
  • thermosetting resins for example, phenol
  • the liquid crystal polyester resin composition used in the present invention is obtained by mixing the liquid crystal polyester (A), the high dielectric material filler (B), and other components such as additives used as necessary.
  • the content ratio of the liquid crystal polyester (A) and the high dielectric material filler (B) is such that the dielectric properties of the high dielectric material filler used are sufficiently expressed, and the melt processability is good. It is determined in consideration of such balance.
  • the high dielectric material filler is preferably 20 to 50% by volume with respect to 100% by volume of the total amount of liquid crystal polyester and high dielectric material filler to be blended. More preferably, the content ratio is 2 2 to 4 5% by volume.
  • the blending means is not particularly limited as long as each raw material component can be melt-kneaded.
  • liquid crystal polyester (A) and high dielectric material filler (B) a method of supplying other components separately added to the melt mixer as needed, these raw material components in a mortar, Henschel mixer And a method of premixing using a ball mill, a ribbon blender, etc., and then feeding to a melt mixer.
  • melt kneading thermo melting
  • the liquid crystal polyester resin composition forms a heated melt.
  • the temperature condition in the melt-kneading can be appropriately optimized based on the flow start temperature T p [° C] of the liquid crystal polyester (A) used.
  • the temperature range is from 10 ° C below T p to 100 ° C above T p, more preferably from 10 ° C below T p to 70 ° C below T p
  • the temperature range is a high temperature, and more preferably, the temperature range is 10 ° C lower than Tp to 50 ° C higher than Tp. If two or more types of liquid crystalline polyester (A) are used, for the mixture of two or more liquid crystal polyesters, the flow start temperature is obtained by the method described above, and the flow start temperature may be used as a base point.
  • the heated melt of the liquid crystalline polyester resin composition obtained by melt-kneading is extruded into a string shape by, for example, a single-screw or multi-screw extruder, preferably a twin-screw extruder, a Banbury set kneader, a roll kneader or the like.
  • the string-like composition (strand) is cooled and solidified, and when it is cut, it can be added to the composition pellets by a series of operations.
  • the Strand method is advantageous in terms of better productivity.
  • the method for preparing the composition pellets using a single screw or twin screw extruder facilitates operability because it can continuously perform from melt-kneading to pelletizing.
  • the pellet method is a known pellet manufacturing means represented by the hot cut method. Can be manufactured stably and with high productivity.
  • the shape of the composition pellets obtained as described above may be cylindrical or prismatic.
  • the cross-sectional shape may be any of a circle, a substantially circle, an ellipse, and a star. In general, it is better to use a columnar composition, Perez®. This cross-sectional shape can be appropriately optimized depending on the shape of the extrusion port of the extruder.
  • the length of the composition pellets is appropriately selected according to the molding method to be described later, but it is preferably 0.1 to 1 O mm on average, and 1 to 5 mm long. More preferable.
  • the ratio of the diameter Z length of the pellets is preferably in the range of 0.1 to 10, more preferably in the range of 0.2 to 3, and particularly preferably in the range of 0.3 to 1.
  • the pellet-like liquid crystal polyester resin composition thus obtained can be applied to various conventional molding methods.
  • the molding method for example, melt molding such as injection molding or press molding is preferable, and injection molding is particularly preferable.
  • injection molding Specific examples include general injection molding, injection compression molding, two-color molding, and sandwich molding. Among these, general injection molding and injection compression molding are preferable.
  • the liquid crystal polyester resin composition of the present invention can be obtained as a composition pellets having excellent operability, so that it can be easily supplied continuously to a molding machine. It is also good in terms of storage.
  • the molded product obtained by using the liquid crystalline polyester resin composition of the present invention is a test method of ASTM D790, although it is relatively filled with a high dielectric material filler.
  • the measured bending strength is 1 OOMPa or more, and it becomes possible to obtain a molded article with extremely high mechanical strength.
  • the molded product obtained using the liquid crystalline polyester resin composition of the present invention has a measured impact strength according to the test method of ASTM D256 (no notch) even though the high dielectric material filler is filled relatively high. However, it is possible to obtain a molded article having an extremely high impact strength.
  • the liquid crystalline polyester (A) used in the present invention contains a specific amount of 2.6-naphthalenediyl group and has a flow start temperature of 280 ° C. or higher and a temperature higher than the flow start temperature. ⁇ The tension is 1 g or more, so it has excellent heat resistance and mechanical strength.
  • the liquid crystal polyester resin composition of the present invention comprises a high dielectric material filler by molding a molded body as a composition pellets
  • the molded product obtained using the resin composition of the present invention exhibits a sufficient dielectric effect, which is related to a high dielectric material filler, particularly a titanium ceramic filler, and has a measurement temperature of 23 ° C. and a frequency of 1 it is also possible to dielectric constant in GH Z expresses six or more.
  • the high-dielectric material filler is substantially uniformly present in the molded body, and the dielectric characteristics partially vary in the molded body. Such inconvenience can be avoided very well.
  • a mold having a desired shape and size can be obtained by appropriately optimizing the mold and the like.
  • the molded body has excellent dielectric properties and high mechanical strength, and further retains the high degree of heat resistance of liquid crystalline polyester, so it is a member for manufacturing antennas, especially for antennas. »Used suitably for the body.
  • the antenna substrate can be manufactured by etching or the like as necessary to form electrodes (radiation electrode, ground electrode).
  • electrodes radiation electrode, ground electrode.
  • known methods such as metal plating, sputtering, ion plating, vacuum evaporation, and soldering are employed.
  • the metal foil processed into the desired electrode shape may be bonded or pressure-bonded with an adhesive or the like. After the metal foil is bonded or pressure-bonded to the surface of the molded body in advance, the desired shape is obtained. A metal foil bonded or pressed may be patterned.
  • the antenna substrate Since the antenna substrate thus obtained has extremely excellent dielectric characteristics and mechanical strength, the antenna substrate is easier to miniaturize than conventional ones.
  • wireless LAN such as Bluetooth
  • mobile phone's PHS or mopile equipment It is particularly suitable for use as an antenna for GPS (Global Positioning System), ETC (Electric Rick! ⁇ One Collection System), and satellite communications.
  • GPS Global Positioning System
  • ETC Electronic Rick! ⁇ One Collection System
  • satellite communications satellite communications.
  • the antenna obtained using the liquid crystal polyester resin composition of the present invention is excellent in durability against the external environment due to high mechanical strength, high heat resistance, etc., and thus can be suitably used as an antenna for outdoor installation. It is.
  • due to the effect of miniaturization due to its excellent dielectric properties due to its excellent dielectric properties, it is extremely excellent as an antenna for automobiles or antennas for portable devices.
  • Capillograph 1 B type manufactured by Toyo Seiki Seisakusho
  • cylinder barrel diameter 1 mm0
  • piston extrusion speed was 5.
  • OmmZ variable speed The sample was taken up into a thread and the tension (g) when it was broken was measured.
  • the cylinder temperature was 350 using an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., PS40E5AS E type).
  • a test piece (sample) having a length of 1 2 7 mm, a width of 1 2.7 mm, and a thickness of 6.4 mm was formed at a mold temperature of 1 ° C. and a mold temperature of 30 ° C. Then, according to the test method of ASTMD790, the bending strength of these samples was measured.
  • the cylinder temperature is 350 ° C using an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., PS40E5ASE type).
  • the temperature was raised from 145 ° C. to 3 10 ° C. over 3 hours and 30 minutes while distilling off distilling by-product acetic acid and unreacted acetic anhydride.
  • a liquid crystal polyester was obtained by incubating at the same temperature for 3 hours.
  • the obtained liquid crystal polyester was cooled to room temperature and pulverized by a pulverizer to obtain a liquid crystal polyester powder (prepolymer 1) having a particle diameter of about 0.1 to 1 mm.
  • the flow initiation temperature of this prepolymer 1 was measured using a flow tester and found to be 267 ° C.
  • Prepolymer 1 obtained in Synthesis Example 1 was heated from 25 ° C to 250 ° C over 1 hour, then heated from the same temperature to 293 ° C over 5 hours, and then at the same temperature for 5 hours The mixture was kept warm and subjected to solid phase polymerization. After solid phase polymerization, the liquid crystal polyester was obtained in the form of powder when cooled. This liquid crystal polyester is designated as L C P 1. The flow initiation temperature of L CP 1 was measured using a flow tester and found to be 317 ° C. Synthesis example 3
  • the prepolymer 1 obtained in Synthesis Example 1 was heated from 25 ° C to 250 ° C over 1 hour, then heated from the same temperature to 310 ° C over 10 hours, and then at the same temperature for 5 hours. The mixture was kept warm and subjected to solid phase polymerization. Upon cooling after solid phase polymerization, liquid crystal polyester was obtained in powder form. This liquid crystal polyester is designated as LCP 2.
  • LC obtained When the flow start temperature was measured for P 2 using a flow tester, 33
  • LCP 1 and LCP 2 obtained in Synthesis Examples 1 to 3 were obtained by calculating the copolymerization mole fraction from the molar ratio of the monomer used.
  • the temperature was raised from 145 ° C. to 3 10 ° C. over 3 hours and 30 minutes while distilling off distilling by-product acetic acid and unreacted acetic anhydride.
  • a liquid crystalline polyester was obtained by incubating at the same temperature for 2 hours.
  • the obtained liquid crystalline polyester is cooled to room temperature and pulverized by a pulverizer to obtain a liquid crystalline polyester powder (prebolimer 2) having a particle size of about 0.1 to 1 mm using a flow tester.
  • the flow starting temperature was measured and found to be 273 ° C.
  • the resulting prepolymer 2 was heated from 25 ° C to 250 ° C over 1 hour, then heated from the same temperature to 300 ° C over 10 hours, and then maintained at the same temperature for 12 hours. Solid state polymerization was carried out by heating. When cooled after solid phase polymerization, liquid crystalline polyester was obtained in powder form. This liquid crystal polyester is designated as LCP 3.
  • the flow initiation temperature of L CP 3 measured using a flow tester was 324 ° C.
  • Synthesis example 5 The temperature of Prevolima 1 obtained in the same manner as in Synthesis Example 4 was raised from 25 ° C to 250 ° C over 1 hour, then from 325 ° C to 325 ° C over 10 hours, and then Solid-state polymerization was carried out at the same temperature for 12 hours. Upon cooling after solid phase polymerization, liquid crystal polyester was obtained in powder form. This liquid crystal polyester is designated as LCP 4. The flow initiation temperature of LCP4 was measured using a flow tester and found to be 34 9 ° C.
  • LCP 3 and LCP4 obtained in Synthesis Examples 4 to 5 are based on the molar ratio of the monomers used, and the copolymerization mole fraction is structural unit (i) : structural unit (ii): structural unit
  • the ratio of (iii) is 52.5 mol%: 23.75 mol%: 23.75 mol% This is expressed in terms of the content ratio of 2,6-naphthalenediyl group to the total of all aromatic groups. 3 mol%.
  • the flow starting temperature of this Prebomer 3 was measured using a flow tester and found to be 257 ° C.
  • Prebomer 3 was heated from 25 ° C to 250 ° C over 1 hour, then heated from the same temperature to 285 ° C over 5 hours, and then kept at that temperature for 3 hours to solidify. Phase polymerized. When cooled after solid state polymerization, liquid crystalline polyester is obtained in powder form. It was. This liquid crystal polyester is designated as LCP 5.
  • the flow initiation temperature of LCP 5 measured using a flow tester was 327 ° C.
  • Prebomer 3 obtained in the same manner as in Synthesis Example 6 was heated from 25 ° C to 250 ° C over 1 hour, then heated from the same temperature to 290 ° C over 5 hours, and then at the same temperature. Incubated for 3 hours for solid phase polymerization. Upon cooling after solid phase polymerization, liquid crystal polyester was obtained in powder form. This liquid crystal polyester is designated as LCP 6.
  • the flow initiation temperature of LCP 6 was measured using a flow tester and found to be 336 ° C.
  • LCP 5 and LCP 6 obtained in Synthesis Examples 6 to 7 can be obtained by calculating the copolymerization mole fraction from the molar ratio of the monomers used.
  • Structural unit (i): Structural unit (ii): Structural unit ( The ratio of iii) is 60 mol%: 20 mol%: 20 mol%. Since the monomer used here does not use a monomer having a 2,6-naphthalenediyl group, the content ratio of the 2,6-naphthalenediyl group to the total aromatic groups is 0 mol%.
  • Prebolimer 1 obtained in Synthesis Example 1 when the measurement temperature was 300 ° C. or less, no land could be formed. In addition, when the measurement temperature was 310 ° C or higher, the resin liquefied rather than formed a strand and melt tension could not be measured. Melt tension measurement was attempted even at a measurement temperature of 300 to 310 ° C, but the melt tension could not be calculated because the obtained strand was easily broken.
  • LCP 1 the melt tension was 1. Og or more at the measurement temperatures of 310 ° C, 320 ° C and 330 ° C.
  • main belt tension was measured at a measurement temperature of 330 ⁇ 360 ° C is was both 1.
  • LCP3 and LCP4 had a melt tension of less than 1. O g at a measurement temperature of 360 ° C or lower, and the melt tension could not be measured in the temperature range higher than that.
  • LCP 5 and LCP 6 had a melt tension of 1.0 g or more at a measurement temperature of 350 ° C.
  • a filler HPBT-1 manufactured by Fuji Titanium Industry Co., Ltd.
  • barium titanate Ba T i 0 3
  • 2 ratio volume ratio
  • the strand can be obtained
  • the number of strand breaks between the starting point and the ending point with the starting point when 0.5 kg of mixed powder is used and the end point when using 3 O kg of mixed powder. By counting (number of strand breaks), the ease of obtaining a strand was determined. The results are shown in Table 2. In this example, no strand break was observed, and it was found that a strand could be stably obtained (number of strand breaks: 0). Examples 2-3
  • Example 2 Using the same high dielectric material filler as that used in LCP 1 obtained in Synthesis Example 2 and Example 1, using the same ratio as shown in Table 2, the same experiment as in Example 1 was performed to break the strand. The number of times was calculated. The results are shown in Table 2. In Example 2, strand breakage was not observed, and it was found that strands were stably obtained (number of strand breaks: 0). On the other hand, in Example 3, a slight strand breakage (strand breakage number: 3 times) was recognized, but there was no problem in practical use.
  • Example 4 Example 4
  • Example 2 Using the same high dielectric material filler as that used in LCP 2 obtained in Synthesis Example 3 and Example 1, and using the proportions shown in Table 2, the same experiment as in Example 1 was performed to break the strand. The number of times was calculated. The results are shown in Table 2. Also in this example, strand breakage was not recognized, and it was found that strands were stably obtained (number of strand breaks: 0).
  • a filler made of titanium oxide (T i 0 2 ) (CR- 60, manufactured by Ishihara Sangyo Co., Ltd., average particle size 0.2 1 ju m) was used.
  • the number of strand breaks was determined by performing the same experiment as in Example 1 except that 1 and the proportions shown in Table 2 were blended. The results are shown in Table 2. Also in this example, no strand break was observed, and it was found that strands could be stably obtained (number of strand breaks: 0).
  • a filler (CR-97 manufactured by Ishihara Sangyo Co., Ltd., average particle size of 0.25 jum) made of titanium oxide ( ⁇ 0 2 ) was used, and LCP 1 obtained in Synthesis Example 2 was used. Except for blending at the ratio shown in Table 2, the same experiment as in Example 1 was performed to determine the number of strand breaks. The results are shown in Table 2. Also in this example, no strand break was observed, and it was found that strands could be stably obtained (number of strand breaks: 0).
  • a filler made of titanium oxide (T i 0 2 ) (SR-1 manufactured by Kayaku Co., Ltd., average particle size 0.26 jum) was used, and L CP 1 obtained in Synthesis Example 2 Except for blending in the proportions shown in Table 2, the same experiment as in Example 1 was performed to determine the number of times the land was cut. The results are shown in Table 2. Also in this example, no strand break was observed, and it was found that a strand could be stably obtained (number of strand breaks: 0).
  • Examples 9 to 1 1 As a high dielectric material filler, a fibrous filler made of titanium oxide (T i 0 2 )
  • LCP 1 obtained in Synthesis Example 2
  • Table 3 The same experiment as in Example 1 was performed to determine the number of strand breaks. The results are shown in Table 3. Also in this example, a slight strand breakage (strand breakage number: 2) was recognized, but there was no problem in practical use. Table 3
  • Prebolimer 1 obtained in Synthesis Example 1 and the same high dielectric material filler used in Example 1 Prebomer 1 is blended to 73% by volume and Filler to 27% by volume ( A total of 4. O kg) and a twin screw extruder (Ikegai Iron Works Co., Ltd. “PCM-30”) tried to pelletize by the strand method with a melting temperature of 295 ° C. could not.
  • PCM-30 twin screw extruder
  • LCP 5 obtained in Synthesis Example 6 and the same high dielectric material filler used in Example 5 were blended in the proportions shown in Table 3 (mixed powder total 4. O kg), twin screw extruder (Ikegai Iron Works Co., Ltd., rpCM-30J) was granulated by the restrand method at a granulation temperature of 340 ° C, causing many strand breaks (strand breaks: 40 times or more). The number of strand breaks was counted up to 40 times, and no more counting was performed.
  • LCP 5 obtained in Synthesis Example 6 and the same high-dielectric material filler used in Example 6 were blended in the proportions shown in Table 3 (mixed powder total 4. O kg), twin screw extruder (Ikegai Iron Works Co., Ltd. “PCM-30”) was granulated by the restructuring method at a granulation temperature of 340 ° C, resulting in frequent strand breaks (strand breaks: 40 times or more). The number of strand breaks was counted up to 40 times, and no more counting was performed.
  • composition pellets obtained in Examples 1 to 3 and Examples 5 to 8 were dried at 120 ° C. for 3 hours, and then injected into an injection molding machine (Nisshin Resin Industry Co., Ltd. 540-5 5 £. JIS K71 1 31 (1) dumbbell (thickness 1.2 mm) sample was molded at a cylinder temperature of 350 ° C and a mold temperature of 1300 ° C. The obtained sample was immersed for 60 seconds in ⁇ 160 solder (60% tin, 40% lead) at 2600 °. After that, the sample was pulled up and checked for foaming and swelling. The results are shown in Table 5. In addition, the composition pellets obtained in Examples 1 to 3 and Examples 5 to 8 were dried at 120 ° C.
  • composition pellets obtained in Examples 1 to 3 and Examples 5 to 8 were dried at 120 ° C. for 3 hours, and then injection molding machine (PS40E5A SE manufactured by Nissin Plastic Industry Co., Ltd.) Mold) at a cylinder temperature of 350 ° C and a mold temperature of 1 30 ° C.
  • a test piece (dielectric property measurement sample) having a thickness of 64 mm, a width of 64 mm, and a thickness of 1 mm was produced.
  • the dielectric properties (dielectric constant, dielectric loss tangent) of these samples at 1 GHz (measurement temperature 23 ° C) were evaluated using an HP impedance analyzer. The results are shown in Table 5.
  • Comparative Example 6 the strands could not be stably drawn. Therefore, the composition extruded from the twin screw extruder was pulverized with a pulverizer to obtain a particulate composition of about 3 mm, and this particulate composition was used. This was the pellet of Comparative Example 6.
  • the presence or absence of foaming by solder, bending strength, and dielectric properties were measured. The results are shown in Table 6.
  • Comparative Example 7 the strand could not be stably drawn. Therefore, the composition extruded from the twin-screw extruder was pulverized with a pulverizer to obtain a particulate composition of about 3 mm. Using this particulate composition, This was designated as Perezka of Comparative Example 7. In the same experiment as in Examples 13 to 19, the presence or absence of foaming by solder, bending strength, and dielectric properties were measured. The results are shown in Table 6.
  • Example 13 The same experiment as in Example 13 was performed, except that the composition pellets obtained in Example 1 were replaced with the composition pellets obtained in Examples 9 to 12. Solder foam tests, flexural strength and dielectric properties (dielectric constant, dielectric loss tangent) were determined for the compacts. The results are shown in Table 7.
  • composition pellets obtained in Examples 5 to 9 were dried at 120 ° C. for 3 hours, and then subjected to a cylinder temperature of 350 ° C. using a injection molding machine (PS40E5ASE manufactured by Nissin Plastic Industry Co., Ltd.). After molding at a mold temperature of 1300C, a molded product with a length of 127mm, a width of 12.7mm, and a thickness of 6.4mm was prepared (a sample for measuring bending strength). This molded product was cut to a length of 64 mm, a width of 12.7 mm, and a thickness of 6.4 mm, and used as a test piece (impact strength measurement sample). The impact strength of these samples (without notches) was measured according to the test method of AS TMD 256. The results are shown in Table 8.
  • composition pellets obtained in Comparative Examples 6 to 7 were dried at 120 ° C for 3 hours, and then the cylinder temperature was 350 ° C using a injection molding machine (PS40 E5ASE type, manufactured by Nissin Plastic Industry Co., Ltd.). After molding at a mold temperature of 1300C, a molded product with a length of 1 27mm, a width of 12.7mm, and a thickness of 6.4mm was prepared (sample for measuring bending strength). This molded product is 64mm long and 1 width? 7 mm. Thickness was cut to 6.4 mm to obtain a test piece (impact strength measurement sample). And ASTMD256 test method
  • liquid crystal polyester resin compositions obtained in Examples 1 to 12 can stably obtain strands, stable composition pellets can be produced by the Strand method.
  • pellet-like liquid crystal polyester resin compositions obtained in Examples 1 to 3 and Examples 5 to 12 were able to obtain molded bodies having extremely excellent solder foam tests, bending strength, and dielectric properties.
  • pellet-like liquid crystal polyester resin compositions obtained in Examples 5 to 9 were able to obtain molded articles having extremely excellent impact strength.
  • the obtained molded article was also inferior in bending strength and dielectric properties.
  • the liquid crystal polyester resin compositions of Comparative Examples 6 to 7 were completely incompatible with the strand method, and the obtained molded articles were inferior in bending strength and impact strength.

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Abstract

La présente invention concerne une composition de résine de polyester cristallin liquide comprenant un polyester cristallin liquide et une charge de matériau hautement diélectrique. La présente invention concerne également un article moulé de la composition de résine de polyester cristallin liquide. La composition de résine de polyester cristallin liquide comprend : de 50 à 80 % en volume d'un polyester cristallin liquide qui contient un groupe 2,6-naphtalènediyle en tant qu'un groupe aromatique en une quantité de 40 % en moles ou plus, qui a une température d'initiation de la fluidification de 280°C ou plus, et qui a une tension de fusion de 1 g ou plus telle que mesurée à une température supérieure à la température d'initiation de la fluidification ; et de 20 à 50 % en volume d'une charge de matériau hautement diélectrique. La composition de résine de polyester cristallin liquide peut être mise sous la forme d'une pastille de composition de manière facile et stable par un procédé de production de ruban ou équivalents. Un article moulé produit à partir de la composition de résine de polyester cristallin liquide présente une excellente résistance en flexion et d'excellentes propriétés diélectriques.
PCT/JP2008/072220 2007-12-03 2008-12-02 Polyester cristallin liquide, et article moulé WO2009072641A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US12/745,264 US8337719B2 (en) 2007-12-03 2008-12-02 Liquid crystalline polyester and molded article thereof
CN200880125982.XA CN101932654B (zh) 2007-12-03 2008-12-02 液晶聚酯及其成型体

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2007-312047 2007-12-03
JP2007312047 2007-12-03
JP2008-090690 2008-03-31
JP2008090690A JP2009155623A (ja) 2007-12-03 2008-03-31 液晶ポリエステル樹脂組成物及びその成形体

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WO2009072641A1 true WO2009072641A1 (fr) 2009-06-11

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US8025814B2 (en) 2008-06-23 2011-09-27 Sumitomo Chemical Company, Limited Resin composition and molded article using the same
EP3315558A4 (fr) * 2015-06-26 2018-12-05 Sumitomo Chemical Company Limited Composition de résine et objet moulé
WO2021085412A1 (fr) * 2019-10-31 2021-05-06 住友化学株式会社 Poudre de polyester à cristaux liquides et procédé pour la production d'une composition de solution de polyester à cristaux liquides
CN114672138A (zh) * 2022-03-16 2022-06-28 张家港大塚化学有限公司 一种低介电损耗液晶复合材料的制备工艺

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US8025814B2 (en) 2008-06-23 2011-09-27 Sumitomo Chemical Company, Limited Resin composition and molded article using the same
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EP3315558A4 (fr) * 2015-06-26 2018-12-05 Sumitomo Chemical Company Limited Composition de résine et objet moulé
WO2021085412A1 (fr) * 2019-10-31 2021-05-06 住友化学株式会社 Poudre de polyester à cristaux liquides et procédé pour la production d'une composition de solution de polyester à cristaux liquides
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CN114672138A (zh) * 2022-03-16 2022-06-28 张家港大塚化学有限公司 一种低介电损耗液晶复合材料的制备工艺

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