Resin composition, pellet, and molded article

Abstract

A resin composition contains a liquid crystal polyester and a styrene resin, the liquid crystal polyester containing a first monomer unit having a fused aromatic ring and a second monomer unit having a benzene ring. The dielectric loss tangent of the styrene resin at 10 GHz is 0.001 or less, the content of the styrene resin is 0.5-20 parts by mass per 100 parts by mass of the total of the liquid crystal polyester and the styrene resin, and the content of an inorganic filler is 20 mass % or less.

Description

Resin compositions, pellets and molded products

[0001] The present disclosure relates to a resin composition and a molded article thereof.

[0002] Liquid crystal polyesters are used in a variety of applications due to their high fluidity, heat resistance and dimensional accuracy.

[0003] Liquid crystal polyesters are sometimes used as liquid crystal polyester compositions containing fillers, etc. For example, Patent Document 1 describes a liquid crystal polymer composition containing 20% ​​by mass or more of specific flat glass fibers and specific plate-like fillers.

[0004] Japanese Patent Application Laid-Open No. 2003-268252

[0005] However, resin compositions containing a large amount of inorganic filler may impose limitations on the shape of molded articles, and the exposure of the inorganic filler on the surface of the molded article may affect the surface properties, appearance, etc.

[0006] An object of the present disclosure is to provide a resin composition containing a sufficiently small amount of inorganic filler, which has good fluidity when melted, and which provides a molded article with good electrical properties and flexibility. Another object of the present disclosure is to provide a molded article formed from a resin composition containing a sufficiently small amount of inorganic filler and which has excellent moldability, and which has good electrical properties and flexibility.

[0007] The present disclosure provides, for example, the following: [1] A resin composition comprising a liquid crystal polyester and a styrene-based resin, wherein the liquid crystal polyester contains a first monomer unit having a condensed aromatic ring and a second monomer unit having a benzene ring, wherein the styrene-based resin has a dielectric dissipation factor of 0.001 or less at 10 GHz, wherein the content of the styrene-based resin is 0.5 to 20 parts by mass relative to 100 parts by mass of the total of the liquid crystal polyester and the styrene-based resin, and wherein the content of an inorganic filler is 20% by mass or less. [2] The resin composition according to [1], wherein the styrene-based resin is polystyrene. [3] The resin composition according to [1] or [2], wherein the condensed aromatic ring is a naphthalene ring. [4] The resin composition according to any one of [1] to [3], wherein the content of the first monomer unit is 50 mol% or more relative to the total of all monomer units constituting the liquid crystal polyester. [5] The resin composition according to any one of [1] to [4], which has a dielectric loss tangent of 0.001 or less at 10 GHz. [6] A pellet comprising the resin composition according to any one of [1] to [5]. [7] A molded article comprising the resin composition according to any one of [1] to [5], the molded article being a connector, a socket, a relay part, a coil bobbin, an optical pickup, an oscillator, a semiconductor package, an IC tray, a wafer carrier, a household electrical appliance part, a lighting fixture part, an audio product part, a ferrule for an optical cable, a telephone part, a facsimile part, a modem part, a separation claw, a heater holder, an impeller, a fan gear, a gear, a bearing, a motor part, a motor case, an engine part, an engine room part, an electrical component, an automobile interior part, a microwave cooking pot, a heat-resistant tableware, a flooring material, a wall material, a beam, a pillar, a roofing material, an aircraft part, a spacecraft part, a space equipment part, a nuclear reactor, a marine facility member, a cleaning tool, an optical equipment part, a valve, a pipe, a nozzle, a filter, a membrane, a medical equipment part, a medical material, a sensor part, a sanitary fixture, a sporting goods, or a leisure goods.

[0008] According to the present disclosure, it is possible to provide a resin composition containing a sufficiently small amount of inorganic filler, which has good fluidity when melted, good electrical properties of a molded article, and good flexibility of the molded article. Furthermore, according to the present disclosure, it is possible to provide a molded article which is formed from a resin composition containing a sufficiently small amount of inorganic filler and has excellent moldability, and which has good electrical properties and good flexibility.

[0009] Preferred embodiments of the present disclosure will be described in detail below.

[0010] The resin composition of this embodiment (hereinafter also simply referred to as "resin composition") contains a liquid crystal polyester and a styrene-based resin. The liquid crystal polyester contains a first monomer unit having a condensed aromatic ring and a second monomer unit having a benzene ring. The dielectric dissipation factor of the styrene-based resin at 10 GHz is 0.001 or less. The content of the styrene-based resin is 0.5 to 20 parts by mass per 100 parts by mass of the total of the liquid crystal polyester and the styrene-based resin. In this embodiment, the resin composition may or may not contain an inorganic filler, but the content of the inorganic filler is 20% by mass or less.

[0011] The resin composition of the present embodiment is a resin composition containing a sufficiently small amount of inorganic filler, yet has good fluidity when melted, and good electrical properties and flexibility of the molded article.

[0012] In this embodiment, the liquid crystal polyester and the styrene-based resin have similar structures in that they both contain many aromatic rings. Furthermore, the liquid crystal polyester has a small dielectric loss tangent due to the presence of condensed aromatic rings. Therefore, the liquid crystal polyester and the styrene-based resin have similar molecular chain mobility in that they both have small dielectric loss tangents. From these perspectives, in this embodiment, it is believed that the dispersion and interaction between the liquid crystal polyester and the styrene-based resin are favorable, resulting in high flexibility. Furthermore, the liquid crystal polyester forms liquid crystal domains due to its liquid crystallinity. The liquid crystal polyester and the liquid crystal domains tend to align in the flow direction, but the liquid crystal domains do not extend much in the direction perpendicular to the flow direction, resulting in low interaction in the direction perpendicular to the flow direction. On the other hand, the styrene-based resin's molecular chains tend to extend in the direction perpendicular to the flow direction, resulting in high interaction in the direction perpendicular to the flow direction. This facilitates interaction between the liquid crystal polyesters and between the liquid crystal domains in the direction perpendicular to the flow direction via a small amount of the styrene-based resin, which is believed to facilitate orientation of the liquid crystal polyester and further enhance fluidity.

[0013] In this embodiment, it is believed that the styrene-based resin content of 20 parts by mass or less can achieve the above-mentioned effects without impairing the good mechanical properties of the liquid crystal polyester. Also, in this embodiment, it is believed that the content of the inorganic filler of 20 mass% or less can prevent the interaction between the liquid crystal polyester and the styrene-based resin and the alignment of the liquid crystal polyester molecules via a small amount of the styrene-based resin from being inhibited, thereby achieving the above-mentioned effects significantly.

[0014] The liquid crystal polyester may be any polyester that exhibits liquid crystallinity in a molten state. The resin composition may contain only one type of liquid crystal polyester, or may contain two or more types of liquid crystal polyester.

[0015] The flow initiation temperature of the liquid crystal polyester may be, for example, 250° C. or higher, or 270° C. or higher. The flow initiation temperature of the liquid crystal polyester may be, for example, 400° C. or lower, 360° C. or lower, or 340° C. or lower. That is, the flow initiation temperature of the liquid crystal polyester may be, for example, 250° C. or higher and 400° C. or lower, 250° C. or higher and 360° C. or lower, 250° C. or higher and 340° C. or lower, 270° C. or higher and 400° C. or lower, 270° C. or higher and 360° C. or lower, or 270° C. or higher and 340° C. or lower.

[0016] In this specification, the flow initiation temperature of the liquid crystal polyester is measured using a flow tester, and the liquid crystal polyester is subjected to a pressure of 9.8 MPa (100 kg / cm ２ The liquid crystalline polyester is melted while being heated at a rate of 4°C / min under a load of 1000 kJ / min, and the molten liquid crystalline polyester is extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm, and the temperature is the temperature at which the viscosity of the extruded liquid crystalline polyester is 4800 Pa·s (48,000 poise).

[0017] The liquid crystal polyester has constituent units (also referred to as monomer units) derived from raw material monomers. The liquid crystal polyester may have a main monomer unit (for example, 90 mol% or more, 95 mol% or more, or 99 mol% or more of the monomer units relative to the total of all monomer units, preferably all monomer units) derived from an aromatic compound. A liquid crystal polyester in which all monomer units are derived from an aromatic compound is also referred to as a wholly aromatic liquid crystal polyester.

[0018] The liquid crystal polyester has a first monomer unit having a condensed aromatic ring and a monomer unit having a benzene ring. The liquid crystal polyester may have one or more types of first monomer units. The liquid crystal polyester may also have one or more types of second monomer units. The second monomer unit may be a monomer unit having a benzene ring but not having a condensed aromatic ring.

[0019] The first monomer unit may be a monomer unit derived from an aromatic compound (1) having a fused aromatic ring, and the second monomer unit may be a monomer unit derived from an aromatic compound (2) having a benzene ring.

[0020] In this specification, "derived" means that in the monomer units of the liquid crystal polyester formed by polymerization of the raw material monomers, the chemical structure of the functional group that contributes to polymerization of the raw material monomers has changed, but other structural changes have not occurred. Here, "derived" is a concept that also includes cases where the monomer unit is derived from a polymerizable derivative of the raw material monomer (for example, a compound obtained by converting the functional group that contributes to polymerization of the raw material monomers into another polymerizable group).

[0021] Examples of the first monomer unit include a monomer unit derived from an aromatic hydroxycarboxylic acid (1-1) having a fused aromatic ring (hereinafter also referred to as a monomer unit (1-1)), a monomer unit derived from an aromatic dicarboxylic acid (1-2) having a fused aromatic ring (hereinafter also referred to as a monomer unit (1-2)), and a monomer unit derived from an aromatic diol (1-3) having a fused aromatic ring (hereinafter also referred to as a monomer unit (1-3)).

[0022] Examples of the second monomer unit include a monomer unit derived from an aromatic hydroxycarboxylic acid (2-1) (hereinafter also referred to as a monomer unit (2-1)), a monomer unit derived from an aromatic dicarboxylic acid (2-2) (hereinafter also referred to as a monomer unit (2-2)), and a monomer unit derived from an aromatic diol (2-3) (hereinafter also referred to as a monomer unit (2-3)).

[0023] Examples of the fused aromatic ring contained in the first monomer unit include a naphthalene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a pyrene ring, a triphenylene ring, a perylene ring, and a fluorene ring. Of these, a naphthalene ring is preferred from the viewpoints of availability and cost.

[0024] Examples of the monomer unit contained in the liquid crystal polyester include a monomer unit represented by the following formula (I) (hereinafter also referred to as monomer unit (I)), a monomer unit represented by the following formula (II) (hereinafter also referred to as monomer unit (II)), and a monomer unit represented by the following formula (III) (hereinafter also referred to as monomer unit (III)). １ -CO- (I) -CO-Ar ２ -CO- (II) -X-Ar３ -Y- (III) [wherein, Ar １ , Ar ２ and Ar ３ each independently represents a phenylene group, a biphenylene group, a condensed polycyclic aromatic hydrocarbon group, or a group represented by formula (IV). １ , Ar ２ and Ar ３ Some or all of the hydrogen atoms in -Ar may be substituted with halogen atoms, alkyl groups, or aryl groups. X and Y each independently represent an oxygen atom or an imino group (—NH—). ４ -Z-Ar ５ - (IV) [wherein, Ar ４ and Ar ５ each independently represents a phenylene group or a condensed polycyclic aromatic hydrocarbon group; Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkanediyl group.

[0025] The phenylene group may be a 1,4-phenylene group or a 1,3-phenylene group, and is preferably a 1,4-phenylene group.

[0026] The biphenylene group may be a 4,4'-biphenylylene group.

[0027] The condensed polycyclic aromatic hydrocarbon group is a group in which two hydrogen atoms have been removed from a condensed polycyclic aromatic hydrocarbon. Examples of the condensed polycyclic aromatic hydrocarbon include naphthalene, anthracene, phenanthrene, tetracene, pyrene, triphenylene, perylene, and fluorene. Among these, naphthalene is preferred from the viewpoints of availability and cost.

[0028] The condensed polycyclic aromatic hydrocarbon group may be a naphthylene group. The naphthylene group may be a 2,6-naphthylene group or a 2,7-naphthylene group, and is preferably a 2,6-naphthylene group.

[0029] Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0030] The alkyl group as a substituent may be linear, branched, or cyclic. The alkyl group may be, for example, an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-hexyl group, a 2-ethylhexyl group, an n-octyl group, and an n-decyl group.

[0031] The aryl group as a substituent may be a monocyclic ring or a fused ring. The aryl group may be, for example, an aryl group having 6 to 20 carbon atoms. Examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group, and a 2-naphthyl group. The aryl group may be a group in which a hydrogen atom of an aromatic ring is substituted with an alkyl group, such as a tolyl group.

[0032] Ar １ , Ar ２ and Ar ３ The number of substituents that the has may be, for example, 0 to 2, or may be 0 or 1, or may be 0.

[0033] X and Y are preferably oxygen atoms.

[0034] The alkanediyl group in Z may be linear or branched. The alkanediyl group may be an alkanediyl group having 1 to 10 carbon atoms. Examples of the alkanediyl group include a methylene group, an ethanediyl group, a propanediyl group (e.g., a propane-2,2-diyl group), a butanediyl group, and an octanediyl group (e.g., an octane-3,3-diyl group).

[0035] Z is preferably an oxygen atom, a sulfur atom, a methylene group, an ethanediyl group, or a propanediyl group, and more preferably an oxygen atom.

[0036] The first monomer unit is a monomer unit represented by formula (I) (Ar １ is a condensed polycyclic aromatic hydrocarbon group, or Ar ４ and Ar ５ and a monomer unit represented by formula (II) (Ar２ is a condensed polycyclic aromatic hydrocarbon group, or Ar ４ and Ar ５ and a monomer unit represented by formula (III) (Ar ２ is a condensed polycyclic aromatic hydrocarbon group, or Ar ４ and Ar ５ and at least one of which is a condensed polycyclic aromatic hydrocarbon group, may be a group represented by formula (IV).

[0037] The first monomer unit may be a monomer unit derived from an aromatic compound (1) having a fused aromatic ring. Examples of the aromatic compound (1) include 2-hydroxy-6-naphthoic acid, 2,6-naphthalenedicarboxylic acid, 2,6-dihydroxynaphthalene, 2-hydroxy-3-naphthoic acid, 1-hydroxy-5-naphthoic acid, and 2,7-naphthalenediol.

[0038] The second monomer unit is a monomer unit represented by formula (I) (Ar １ is a phenylene group, a biphenylene group, or Ar ４ and Ar ５ is a phenylene group), and the monomer unit represented by formula (II) (Ar ２ is a phenylene group, a biphenylene group, or Ar ４ and Ar ５ is a phenylene group), and the monomer unit represented by formula (III) (Ar ３ is a phenylene group, a biphenylene group, or Ar ４ and Ar ５ is a phenylene group).

[0039] The second monomer unit may be a monomer unit derived from an aromatic compound (2) that does not have a fused aromatic ring but has a benzene ring. Examples of the aromatic compound (2) include p-hydroxybenzoic acid, terephthalic acid, hydroquinone, isophthalic acid, and 4,4'-biphenol.

[0040] In the liquid crystal polyester, the content of the first monomer unit may be, for example, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol% or more, based on the total of all monomer units constituting the liquid crystal polyester. A high content of the first monomer unit tends to further improve dielectric properties. Furthermore, the content of the first monomer unit may be, for example, 90 mol% or less, 85 mol% or less, or even 80 mol% or less, based on the total of all monomer units constituting the liquid crystal polyester. This tends to improve moldability and processability at low temperatures. That is, the content of the first monomer unit, relative to the total of all monomer units constituting the liquid crystal polyester, may be, for example, 20 mol% to 90 mol%, 20 mol% to 85 mol%, 20 mol% to 80 mol%, 30 mol% to 90 mol%, 30 mol% to 85 mol%, 30 mol% to 80 mol%, 40 mol% to 40 mol%, 40 mol% to 85 mol%, 40 mol% to 80 mol%, 50 mol% to 90 mol%, 50 mol% to 85 mol%, 50 mol% to 80 mol%, 60 mol% to 90 mol%, 60 mol% to 85 mol%, 60 mol% to 80 mol%, 70 mol% to 90 mol%, 70 mol% to 85 mol%, or 70 mol% to 80 mol%.

[0041] In the liquid crystal polyester, the content of the second monomer unit may be, for example, 10 mol% or more, 15 mol% or more, or 20 mol% or more, relative to the sum of all monomer units constituting the liquid crystal polyester. Also, the content of the second monomer unit may be, for example, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, or 30 mol% or less, relative to the sum of all monomer units constituting the liquid crystal polyester. That is, the content of the second monomer unit may be, for example, 10 mol% or more and 80 mol% or less, 10 mol% or more and 70 mol% or less, 10 mol% or more and 60 mol% or less, 10 mol% or more and 50 mol% or less, 10 mol% or more and 40 mol% or less, 10 mol% or more and 30 mol% or less, 15 mol% or more and 80 mol% or less, 15 mol% or more and 70 mol% or less, 15 mol% or more and 60 mol% or less, 15 mol% or more and 50 mol% or less, 15 mol% or more and 40 mol% or less, 15 mol% or more and 30 mol% or less, 20 mol% or more and 80 mol% or less, 20 mol% or more and 70 mol% or less, 20 mol% or more and 60 mol% or less, 20 mol% or more and 50 mol% or less, 20 mol% or more and 40 mol% or less, or 20 mol% or more and 30 mol% or less.

[0042] In the liquid crystal polyester, the total amount of the first monomer unit and the second monomer unit may be, for example, 90 mol% or more, 95 mol% or more, 99 mol% or more, or 100 mol% relative to the total of all monomer units constituting the liquid crystal polyester.

[0043] The liquid crystal polyester may be a polymer having two or more types of monomer unit (I), or may be a polymer having monomer unit (I), monomer unit (II) and monomer unit (III).

[0044] When the liquid crystal polyester has the monomer unit (I), the monomer unit (II) and the monomer unit (III), the content of the monomer unit (I) may be, for example, 30 mol% or more, 40 mol% or more, 45 mol% or more, 50 mol% or more, or 55 mol% or more, based on the total of all the monomer units of the liquid crystal polyester. Also, when the liquid crystal polyester has the monomer unit (I), the monomer unit (II) and the monomer unit (III), the content of the monomer unit (I) may be, for example, 80% or less, or 70% or less, based on the total of all the monomer units of the liquid crystal polyester. That is, when the liquid crystal polyester has the monomer unit (I), the monomer unit (II), and the monomer unit (III), the content of the monomer unit (I) may be, for example, 30 mol% or more and 80 mol% or less, 30 mol% or more and 70 mol% or less, 40 mol% or more and 80 mol% or less, 40 mol% or more and 70 mol% or less, 45 mol% or more and 80 mol% or less, 45 mol% or more and 70 mol% or less, 50 mol% or more and 80 mol% or less, 50 mol% or more and 70 mol% or less, 55 mol% or more and 80 mol% or less, or 55 mol% or more and 70 mol% or less, based on the total of all the monomer units of the liquid crystal polyester.

[0045] When the liquid crystal polyester has the monomer unit (I), the monomer unit (II), and the monomer unit (III), the content of the monomer unit (II) and the content of the monomer unit (III) may be, for example, 35 mol% or less, or 30 mol% or less, based on the total of all the monomer units of the liquid crystal polyester. When the liquid crystal polyester has the monomer unit (I), the monomer unit (II), and the monomer unit (III), the content of the monomer unit (II) and the content of the monomer unit (III) may be, for example, 5 mol% or more, 10 mol% or more, or 15 mol% or more, based on the total of all the monomer units of the liquid crystal polyester. That is, when the liquid crystal polyester has the monomer unit (I), the monomer unit (II), and the monomer unit (III), the content of the monomer unit (II) and the content of the monomer unit (III) may be, for example, 5 mol% or more and 35 mol% or less, 5 mol% or more and 30 mol% or less, 10 mol% or more and 35 mol% or less, 10 mol% or more and 30 mol% or less, 15 mol% or more and 35 mol% or less, or 15 mol% or more and 30 mol% or less, relative to the total of all the monomer units of the liquid crystal polyester.

[0046] The liquid crystal polyester may have monomer units other than the monomer unit (I), the monomer unit (II) and the monomer unit (III), and the number of such monomer units may be 10 mol % or less, 5 mol % or less, 2 mol % or less, 1 mol % or less, or even 0 mol % or less, relative to the total of all monomer units of the liquid crystal polyester.

[0047] In this specification, the number of each monomer unit contained in the liquid crystal polyester is determined by the analytical method described in JP 2000-19168 A. Specifically, the liquid crystal polyester is depolymerized by reacting it with a lower alcohol in a supercritical state, and the depolymerization product (monomers that derive each monomer unit) is quantified by liquid chromatography, whereby the number of each monomer unit relative to the total monomer units can be calculated.

[0048] The liquid crystal polyester can be produced by polymerizing raw material monomers corresponding to the monomer units that constitute the polyester, for example, according to the method described in Japanese Patent No. 6439027.

[0049] The liquid crystal polyester may have a dielectric loss tangent at 10 GHz of, for example, 0.002 or less, preferably 0.0015 or less, and more preferably 0.001 or less, which makes it easier to obtain a resin composition having a suitable dielectric loss tangent as described below.

[0050] The liquid crystal polyester may have a relative dielectric constant at 10 GHz of, for example, 4.0 or less, or 3.8 or less. The liquid crystal polyester may have a relative dielectric constant at 10 GHz of, for example, 2.8 or more, or 3.0 or more.

[0051] In this specification, the dielectric loss tangent and relative permittivity of the liquid crystal polyester at 10 GHz are measured by the following method. Using an injection molding machine (ROBOSHOT S-2000i 30B, manufactured by FANUC Corporation), a cylinder temperature of 330°C, a mold temperature of 130°C, and an injection speed of 100 mm / s, a test piece having a width of 50 mm, a length of 50 mm, and a thickness of 0.5 mm is obtained using a liquid crystal polyester pellet as the molding material. The relative permittivity and dielectric loss tangent of the obtained test piece at 10 GHz are measured using a vector network analyzer (N5290A, manufactured by Keysight Technologies Inc.) and a split cylinder resonator (CR710, manufactured by EM Lab Co., Ltd.). The measurement environment is 23°C and 50% RH.

[0052] The styrene-based resin is a polymer having a monomer unit derived from styrene.

[0053] The styrene-based resin may contain monomer units derived from a monomer other than styrene, such as acrylonitrile, butadiene, and ethylene.

[0054] The styrene-based resin may be, for example, polystyrene, modified polystyrene, etc., and polystyrene is preferred from the viewpoint of obtaining the above-mentioned effects more remarkably.

[0055] The polystyrene may be isotactic polystyrene, syndiotactic polystyrene or atactic polystyrene.

[0056] The dielectric loss tangent of the styrene-based resin at 10 GHz is 0.001 or less, and may be 0.0008 or less.

[0057] The relative dielectric constant of the styrene-based resin at 10 GHz may be, for example, 3 or less, or may be 2.6 or less. The relative dielectric constant of the styrene-based resin at 10 GHz may be, for example, 2 or more, or may be 2.2 or more.

[0058] In this specification, the dielectric loss tangent and relative permittivity of styrene-based resins at 10 GHz are measured by the following method. Using an injection molding machine (ROBOSHOT S-2000i 30B, manufactured by FANUC Corporation), a cylinder temperature of 290°C (Xarek 300ZC) or 300°C (Xarek 90ZC), a mold temperature of 130°C, and an injection speed of 100 mm / s, a test piece measuring 50 mm in width, 50 mm in length, and 0.5 mm in thickness is obtained using styrene-based resin pellets as the molding material. The cylinder temperature is set to a temperature at which the resin to be measured is sufficiently plasticized and does not significantly decompose. The resulting test piece is measured for its relative permittivity and dielectric loss tangent at 10 GHz using a vector network analyzer (N5290A, manufactured by Keysight Technologies Inc.) and a split cylinder resonator (CR710, manufactured by EM Lab Co., Ltd.). The measurement environment is 23°C and 50% RH.

[0059] The number average molecular weight (Mn) of the styrene-based resin may be, for example, 10,000 or more, 20,000 or more, 30,000 or more, or 40,000 or more. The number average molecular weight (Mn) of the styrene-based resin may be, for example, 200,000 or less, 150,000 or less, 130,000 or less, or 100,000 or less.

[0060] The weight average molecular weight (Mw) of the styrene-based resin may be, for example, 20,000 or more, 40,000 or more, 60,000 or more, or 800,000 or more. The weight average molecular weight (Mw) of the styrene-based resin may be, for example, 400,000 or less, 300,000 or less, 250,000 or less, or 200,000 or less.

[0061] The molecular weight distribution (Mw / Mn) of the styrene-based resin may be, for example, 1.3 or more, 1.6 or more, 1.8 or more, or 2 or more. The molecular weight distribution (Mw / Mn) of the styrene-based resin may be, for example, 8 or less, 7 or less, 6 or less, or 5 or less.

[0062] In this specification, the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the styrene-based resin are values ​​measured by gel permeation chromatography at 135°C using 1,2,4-trichlorobenzene as a solvent.

[0063] The content of the styrene-based resin in the resin composition is 0.5 parts by mass or more, 1 part by mass or more, or 2 parts by mass or more, relative to 100 parts by mass of the total of the liquid crystal polyester and the styrene-based resin. This tends to further improve the fluidity of the resin composition when melted and the flexibility of the molded article. The content of the styrene-based resin in the resin composition may be 20 parts by mass or less, 17 parts by mass or less, 15 parts by mass or less, 13 parts by mass or less, or 10 parts by mass or less, relative to 100 parts by mass of the total of the liquid crystal polyester and the styrene-based resin. This tends to further improve the flexibility and heat resistance of the molded article. The content of the styrene-based resin in the resin composition is 0.5 parts by mass or more and 20 parts by mass or less, 1 part by mass or more and 17 parts by mass or less, 1 part by mass or more and 15 parts by mass or less, 1 part by mass or more and 13 parts by mass or less, or 2 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the total of the liquid crystal polyester and the styrene-based resin.

[0064] In the resin composition, the total amount of the liquid crystal polyester and the styrene-based resin may be, for example, 80% by mass or more, 85% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, or 99% by mass or more, or may be 100% by mass.

[0065] The resin composition may further contain other components in addition to the liquid crystal polyester and the styrene-based resin.

[0066] For example, the resin composition may contain one or more resins other than the liquid crystal polyester and the styrene-based resin, such as polyolefin, cyclic polyolefin, polyvinyl chloride, polysulfone, (meth)acrylic resin, polyphenylene ether resin, polyacetal resin, polyamide resin, imide resin, cellulose resin, polyether ether ketone resin, fluororesin, polycarbonate resin, and thermosetting resin.

[0067] The resin composition may further contain an inorganic filler, a colorant, a dispersant, a plasticizer, an antioxidant, a curing agent, a flame retardant, a heat stabilizer, an ultraviolet absorber, an antistatic agent, a surfactant, a lubricant, a mold release agent, etc.

[0068] However, the content of the inorganic filler in the resin composition is 20% by mass or less, based on the total amount of the resin composition. The content of the inorganic filler in the resin composition may be 17% by mass or less, 15% by mass or less, 10% by mass or less, 5% by mass or less, or 2% by mass or less, based on the total amount of the resin composition, or may be 0% by mass or more, or 0.1% by mass or more. The content of the inorganic filler in the resin composition may be, for example, 0.1% by mass or more to 20% by mass or less, 0.1% by mass or more to 17% by mass or less, 0.1% by mass or more to 15% by mass or less, 0.1% by mass or more to 10% by mass or less, 0.1% by mass or more to 5% by mass or less, or 0.1% by mass or more to 2% by mass or less, based on the total amount of the resin composition.

[0069] The resin composition of the present embodiment has excellent fluidity when melted, and therefore can be suitably used as a molding material. The resin composition may be used, for example, in the form of pellets.

[0070] The molded article of this embodiment includes the resin composition described above. The molded article of this embodiment may be a connector, a socket, a relay part, a coil bobbin, an optical pickup, an oscillator, a semiconductor package, an IC tray, a wafer carrier, a household electrical appliance part, a lighting fixture part, an audio product part, a ferrule for an optical cable, a telephone part, a facsimile part, a modem part, a separation claw, a heater holder, an impeller, a fan gear, a gear, a bearing, a motor part, a motor case, an engine part, an engine room part, an electrical component, an automobile interior part, a microwave cooking pot, a heat-resistant tableware, a floor material, a wall material, a beam, a pillar, a roof material, an aircraft part, a spacecraft part, a space equipment part, a nuclear reactor, a marine facility member, a cleaning tool, an optical equipment part, a valve, a pipe, a nozzle, a filter, a membrane, a medical equipment part, a medical material, a sensor part, a sanitary fixture, a sporting goods, or a leisure goods.

[0071] The molded article of this embodiment can be obtained, for example, by molding the above-described resin composition into a desired shape and subjecting it to processing treatment as necessary.

[0072] The molding method for the molded article is preferably melt molding, and examples of the melt molding method include injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, and press molding.

[0073] Although the preferred embodiments of the present disclosure have been described above, the present disclosure is not limited to the above embodiments.

[0074] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Hereinafter, percentages and parts representing the content or amount used are based on mass unless otherwise specified.

[0075] (Example 1-1) (1) Production of Liquid Crystal Polyester (LCP1) A reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser was charged with 1035.0 g (5.5 mol) of 2-hydroxy-6-naphthoic acid, 378.3 g (1.75 mol) of 2,6-naphthalenedicarboxylic acid (Ueno Pharmaceutical Co., Ltd.), 83.1 g (0.5 mol) of terephthalic acid, 255.2 g of hydroquinone, 1226.87 g (12 mol) of acetic anhydride, and 0.17 g of 1-methylimidazole as a catalyst. After thoroughly purging the reactor with nitrogen gas, the temperature was raised to 140°C over 1 hour under a nitrogen gas stream, and the temperature was maintained while refluxing for 1 hour. Thereafter, the temperature was raised to 310°C over 4 hours and 35 minutes while distilling off the by-product acetic acid. The reaction was considered to be complete when an increase in torque was observed, and the contents were removed. The flow initiation temperature of the obtained solid content was 270° C. The obtained solid content was cooled to room temperature and pulverized in a coarse pulverizer, and then heated in a nitrogen atmosphere from room temperature to 250° C. over 1 hour, then from 250° C. to 283° C. over 5 hours and 30 minutes, and maintained at 283° C. for 6 hours, allowing a polymerization reaction to proceed in the solid phase to obtain a liquid crystal polyester (LCP1).

[0076] The flow initiation temperature of the liquid crystal polyester (LCP1) was measured by the following method and found to be 306° C. <Measurement of Flow Initiation Temperature> Using a flow tester (Shimadzu Corporation, CFT-500 model), about 2 g of liquid crystal polyester pellets were filled into a cylinder equipped with a die having a nozzle with an inner diameter of 1 mm and a length of 10 mm, and the temperature was raised to 9.8 MPa (100 kg / cm ２ The liquid crystalline polyester was melted and extruded from a nozzle while increasing the temperature at a rate of 4°C / min under a load of 1000 kJ / min, and the temperature (FT) at which the viscosity reached 4800 Pa s (48000 P) was measured, and this temperature was defined as the flow initiation temperature. "About 2 g" can be estimated as 2 g ± 0.1 g.

[0077] The liquid crystal polyester (LCP1) had a relative dielectric constant of 3.6 and a dielectric loss tangent of 0.00091 at 10 GHz.

[0078] (2) Preparation of styrene-based resin (S1) As the styrene-based resin (S1), syndiotactic polystyrene (manufactured by Idemitsu Kosan Co., Ltd., "XAREC 300ZC", weight average molecular weight (Mw) 140,000) was prepared. The styrene-based resin (S1) had a relative dielectric constant of 2.6 and a dielectric dissipation factor of 0.00038 at 10 GHz.

[0079] (3) Production of Resin Composition and Pellets A resin composition was obtained by mixing a liquid crystal polyester (LCP1) and a styrene-based resin (S1) in a mass ratio of 93:7. The resin composition was then granulated at a cylinder temperature of 320°C using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) to obtain pellets of the resin composition.

[0080] (4) Evaluation of Resin Composition and Molded Article The melt viscosity, tensile elongation, relative dielectric constant, and dielectric loss tangent were determined by the following methods. The results are shown in Table 1. <Evaluation of Fluidity During Melt> Using a capillary rheometer (Capillograph 1D, manufactured by Toyo Seiki Seisaku-sho, Ltd.), a capillary with an inner diameter of 0.5 mm and a length of 10 mm was attached to the tip of the cylinder, and pellets of the resin composition were melted in the cylinder heated to 340°C and extruded from the nozzle. The viscosity of the extruded resin composition at a shear rate of 1000 / sec was measured, and this viscosity was evaluated as the melt viscosity of the resin composition.

[0081] <Evaluation of Flexibility> Using an injection molding machine (PNX-40-5A, manufactured by Nissei Plastic Industrial Co., Ltd.), ASTM D638 dumbbell-shaped test pieces Type IV (thickness 2.5 mm) were injection molded using pellets of the resin composition as the molding material under conditions of a cylinder temperature of 340°C, a mold temperature of 130°C, and an injection speed of 75 mm / s. Five samples of the resulting dumbbell test pieces were subjected to a tensile test using a tensile tester (Tensilon RTG-1310, manufactured by A&D Co., Ltd.) at a chuck distance of 50 mm, a crosshead speed of 10 mm / min, and a test temperature of 23°C. The elongation at this time was measured, and the average tensile elongation (%) at break for the five samples was calculated. The tensile elongation was calculated using the following formula: Tensile elongation (%) = (L - Lo) / Lo x 100, where Lo is the chuck distance before the test (mm), L is the chuck distance at break (mm).

[0082] <Evaluation of Dielectric Properties> Using an injection molding machine (ROBOSHOT S-2000i 30B, manufactured by FANUC Corporation), test pieces having a width of 50 mm, a length of 50 mm, and a thickness of 0.5 mm were obtained using pellets of the resin composition as the molding material under conditions of a cylinder temperature of 330°C, a mold temperature of 130°C, and an injection speed of 50 mm / s. The relative permittivity and dielectric loss tangent at 10 GHz of the obtained test pieces were measured using a vector network analyzer (N5290A, manufactured by Keysight Technologies Inc.) and a split cylinder resonator (CR710, manufactured by EM Lab Co., Ltd.). Measurement environment: 23°C, 50% RH

[0083] (Example 1-2) A resin composition and pellets were produced in the same manner as in Example 1-1, except that the ratio of the liquid crystal polyester (LCP1) to the styrene-based resin (S1) was changed from 93: 7 to 85: 15. The obtained pellets were evaluated in the same manner as in Example 1-1, and the results are shown in Table 1.

[0084] Comparative Example 1-1 A resin composition and pellets were produced in the same manner as in Example 1-1, except that the styrene-based resin (S1) was not blended and only the liquid crystal polyester (LCP1) was used. The obtained pellets were evaluated in the same manner as in Example 1-1, and the results are shown in Table 1. The molding temperature for the ASTM dumbbell was 320°C, and the molding temperature for the test piece for evaluating the dielectric properties was 320°C.

[0085] Comparative Example 1-2 A resin composition and pellets were produced in the same manner as in Example 1-1, except that the ratio of liquid crystal polyester (LCP1) to styrene-based resin (S1) was changed from 93:7 to 70:30. The obtained pellets were evaluated in the same manner as in Example 1-1, and the results are shown in Table 1. The molding temperature for the ASTM dumbbell was 320°C, and the molding temperature for the test piece for evaluating the dielectric properties was 320°C.

[0086] (Comparative Example 1-3) Pellets of a styrene-based resin (S1) were used without blending the liquid crystal polyester (LCP1). Using these pellets, the same evaluation as in Example 1-1 was performed, and the results are shown in Table 1. The conditions for preparing the ASTM dumbbells were a temperature of 290°C, a mold temperature of 135°C, and an injection speed of 50 mm / s. The conditions for preparing test pieces for evaluating dielectric properties were a temperature of 290°C, a mold temperature of 135°C, and an injection speed of 50 mm / s.

[0087]

[0088] (Example 2-1) (1) Production of Liquid Crystal Polyester (LCP2) 1035.0 g (5.5 mol) of 2-hydroxy-6-naphthoic acid, 378.3 g (1.75 mol) of 2,6-naphthalenedicarboxylic acid, 83.1 g (0.5 mol) of terephthalic acid, 255.2 g of hydroquinone, 1226.87 g (12 mol) of acetic anhydride, and 0.17 g of 1-methylimidazole as a catalyst were placed in a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser. After thoroughly purging the reactor with nitrogen gas, the temperature was raised to 140°C over 1 hour under a nitrogen gas stream, and the temperature was maintained while refluxing for 1 hour. Thereafter, the temperature was raised to 310°C over 4 hours and 35 minutes while distilling off the by-product acetic acid. The reaction was considered complete when an increase in torque was observed, and the contents were removed. The flow initiation temperature of the resulting solid content was 270°C. The obtained solid content was cooled to room temperature and pulverized in a coarse pulverizer. The temperature was then raised from room temperature to 250°C over 1 hour under a nitrogen atmosphere, then from 250°C to 286°C over 7 hours and 40 minutes, and the temperature was maintained at 286°C for 6 hours, allowing a polymerization reaction to proceed in the solid phase to obtain a liquid crystal polyester (LCP2).

[0089] The flow initiation temperature of the liquid crystal polyester (LCP2) was measured by the above method and was found to be 311° C. The liquid crystal polyester (LCP2) had a relative dielectric constant of 3.5 and a dielectric loss tangent of 0.00080 at 10 GHz.

[0090] (2) Production and Evaluation of Resin Composition and Pellets A resin composition was obtained by mixing a liquid crystal polyester (LCP2) and a styrene-based resin (S1) in a mass ratio of 96:4. Next, the resin composition was granulated using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) at a cylinder temperature of 340°C to obtain pellets of the resin composition. Using the obtained pellets, evaluations similar to those in Example 1-1 were carried out, and the results are shown in Table 2. The molding temperature for the ASTM dumbbell was 340°C, and the molding temperature for the test specimens for evaluating dielectric properties was 325°C.

[0091] Example 2-2 A resin composition and pellets were produced in the same manner as in Example 2-1, except that the ratio of liquid crystal polyester (LCP2) to styrene-based resin (S1) was changed from 96:4 to 93:7 (however, the cylinder temperature was set to 320°C). The obtained pellets were evaluated in the same manner as in Example 1-1, and the results are shown in Table 2. The molding temperature for the ASTM dumbbell was 340°C, and the molding temperature for the test piece for evaluating dielectric properties was 325°C.

[0092] Comparative Example 2-1 A resin composition and pellets were produced in the same manner as in Example 2-1, except that the styrene resin (S1) was not blended and only the liquid crystal polyester (LCP2) was used (however, the cylinder temperature was set to 330°C). The obtained pellets were used to carry out the same evaluations as in Example 1-1, and the results are shown in Table 1. The molding temperature for the ASTM dumbbell was 340°C, and the molding temperature for the test piece for evaluating the dielectric properties was 325°C.

[0093]

[0094] (Example 3-1) (1) Preparation of styrene-based resin (S2) As the styrene-based resin (S2), syndiotactic polystyrene (manufactured by Idemitsu Kosan Co., Ltd., "XAREC 90ZC", weight average molecular weight (Mw) 200,000) was prepared. The styrene-based resin (S2) had a relative dielectric constant of 2.6 and a dielectric dissipation factor of 0.00037 at 10 GHz.

[0095] (2) Production and Evaluation of Resin Composition and Pellets A resin composition was obtained by mixing a liquid crystal polyester (LCP2) and a styrene-based resin (S2) in a mass ratio of 99:1. Next, the resin composition was granulated at a cylinder temperature of 330°C using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) to obtain pellets of the resin composition. Using the obtained pellets, evaluations similar to those in Example 1-1 were carried out, and the results are shown in Table 3. The molding temperature for the ASTM dumbbells was 340°C, and the molding temperature for the test pieces for evaluating the dielectric properties was 325°C.

[0096] Example 3-2 A resin composition and pellets were produced in the same manner as in Example 3-1, except that the ratio of liquid crystal polyester (LCP2) to styrene-based resin (S2) was changed from 99:1 to 96:4 (cylinder temperature: 330°C). The obtained pellets were used to carry out the same evaluations as in Example 1-1, and the results are shown in Table 3. The molding temperature for the ASTM dumbbell was 340°C, and the molding temperature for the test specimens for dielectric property evaluation was 325°C.

[0097] Example 3-3 A resin composition and pellets were produced in the same manner as in Example 3-1, except that the ratio of liquid crystal polyester (LCP2) to styrene-based resin (S2) was changed from 99:1 to 93:7 (cylinder temperature: 330°C). The obtained pellets were used to carry out evaluations similar to those in Example 1-1, and the results are shown in Table 3. The molding temperature for the ASTM dumbbell was 340°C, and the molding temperature for the test specimens for dielectric property evaluation was 325°C.

[0098] (Comparative Example 3-1) Pellets of a styrene-based resin (S2) were used without blending liquid crystal polyester (LCP2). Using these pellets, the same evaluation as in Example 1-1 was performed, and the results are shown in Table 3. The conditions for preparing ASTM dumbbells were a temperature of 290°C, a mold temperature of 135°C, and an injection speed of 50 mm / s. The conditions for preparing test pieces for evaluating dielectric properties were a temperature of 300°C, a mold temperature of 135°C, and an injection speed of 50 mm / s.

[0099]

[0100] Example 4-1 A resin composition was obtained by mixing a liquid crystal polyester (LCP2), a styrene-based resin (S1), and glass fiber (SC3J260S, manufactured by Nitto Boseki Co., Ltd.) in a mass ratio of 88.6:6.7:4.7. The resin composition was then granulated at a cylinder temperature of 330°C to obtain pellets of the resin composition. The obtained pellets were evaluated in the same manner as in Example 1-1, and the results are shown in Table 4. The molding temperature for the ASTM dumbbell was 340°C, and the molding temperature for the test specimens for dielectric property evaluation was 325°C.

[0101] Comparative Example 4-1 A resin composition and pellets were produced in the same manner as in Example 4-1, except that the ratio of liquid crystal polyester (LCP2), styrene-based resin (S1), and glass fiber was changed to 71.5:5.4:23.1. The obtained pellets were used to carry out evaluations in the same manner as in Example 1-1, and the results are shown in Table 4. The molding temperature for the ASTM dumbbell was 340°C, and the molding temperature for the test specimens for evaluating dielectric properties was 325°C.

[0102]

[0103] (Comparative Example 5-1) (1) Production of Liquid Crystal Polyester (LCP3) A reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser was charged with 994.5 g (7.2 mol) of 4-hydroxybenzoic acid, 446.9 g (2.4 mol) of 4,4'-dihydroxybiphenyl, 299.0 g (1.8 mol) of terephthalic acid, 99.7 g (0.6 mol) of isophthalic acid, and 1347.6 g (13.2 mol) of acetic anhydride, and 0.19 g of 1-methylimidazole was added as a catalyst. After thoroughly replacing the atmosphere in the reactor with nitrogen gas, the temperature was raised to 140°C over 30 minutes under a nitrogen gas stream, and the temperature was maintained and refluxed for 1 hour. Next, 0.92 g of 1-methylimidazole was added. The temperature was then raised to 300°C over 4 hours and 20 minutes while distilling off the by-product acetic acid. The reaction was considered complete when an increase in torque was observed, and the contents were removed. The flow initiation temperature of the resulting solid was 245°C. The resulting solid was cooled to room temperature and pulverized using a coarse pulverizer. Under a nitrogen atmosphere, the temperature was raised from room temperature to 240°C over 1 hour, then from 240°C to 284°C over 5 hours and 40 minutes, and maintained at 284°C for 5 hours. Polymerization proceeded in the solid phase, yielding a liquid crystal polyester (LCP3). The flow initiation temperature of the resulting liquid crystal polyester (LCP3) was 330°C.

[0104] (2) Production and Evaluation of Resin Composition and Pellets Pellets were produced in the same manner as in Example 1-1 using only liquid crystal polyester (LCP3). The resulting pellets were evaluated in the same manner as in Example 1-1 (except that the cylinder temperature was 330°C), and the results are shown in Table 5. The molding temperature for the ASTM dumbbell was 340°C, and the molding temperature for the test pieces for evaluating the dielectric properties was 340°C.

[0105] (Comparative Example 5-2) Liquid crystal polystyrene (LCP3) and styrene-based resin (S1) were mixed in a mass ratio of 93:7 to obtain a resin composition. Next, pellets were produced in the same manner as in Example 1-1. The obtained pellets were evaluated in the same manner as in Example 1-1, and the results are shown in Table 5. The molding temperature for the ASTM dumbbell was 340°C, and the molding temperature for the test piece for evaluating the dielectric properties was 340°C.

[0106]

[0107] (Example 6-1) (1) Preparation of styrene-based resin (S3) Atactic polystyrene (Toyo Styrene GP HRM10N, manufactured by Toyo Styrene Co., Ltd.) was prepared as the styrene-based resin (S3). The relative dielectric constant of the styrene-based resin (S3) was 2.5 and the dielectric dissipation factor was 0.00041 at 10 GHz.

[0108] (2) Production and Evaluation of Resin Composition and Pellets A resin composition was obtained by mixing a liquid crystal polyester (LCP2) and a styrene-based resin (S3) in a mass ratio of 96:4. The resin composition was then granulated using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) at a cylinder temperature of 330°C to obtain pellets of the resin composition. Using the resulting pellets, evaluations similar to those in Example 1-1 were performed, and the results are shown in Table 6. The molding temperature for the ASTM dumbbells was 340°C, and the molding temperature for the test pieces for dielectric property evaluation was 325°C. Table 6 compares Example 6-1 with Comparative Example 2-1.

[0109]

Claims

1. A resin composition comprising a liquid crystal polyester and a styrene-based resin, wherein the liquid crystal polyester contains a first monomer unit having a condensed aromatic ring and a second monomer unit having a benzene ring, the styrene-based resin has a dielectric tangent of 0.001 or less at 10 GHz, the content of the styrene-based resin is 0.5 to 20 parts by mass per 100 parts by mass of the total of the liquid crystal polyester and the styrene-based resin, and the content of an inorganic filler is 20% by mass or less.

2. The resin composition according to claim 1, wherein the styrene-based resin is polystyrene.

3. The resin composition according to claim 1, wherein the condensed aromatic ring is a naphthalene ring.

4. The resin composition according to claim 1, wherein the content of the first monomer unit is 50 mol % or more based on the total of all monomer units constituting the liquid crystal polyester.

5. The resin composition according to claim 1, having a dielectric loss tangent at 10 GHz of 0.001 or less.

6. A pellet comprising the resin composition according to any one of claims 1 to 5.

7. A molded article comprising the resin composition according to any one of claims 1 to 5, the molded article being any one of connectors, sockets, relay parts, coil bobbins, optical pickups, oscillators, semiconductor packages, IC trays, wafer carriers, household electrical appliance parts, lighting equipment parts, audio product parts, ferrules for optical cables, telephone parts, facsimile parts, modem parts, separation claws, heater holders, impellers, fan gears, gears, bearings, motor parts, motor cases, engine parts, engine room parts, electrical parts, automotive interior parts, microwave cooking pots, heat-resistant tableware, flooring materials, wall materials, beams, columns, roofing materials, aircraft parts, spacecraft parts, space equipment parts, nuclear reactors, marine facility members, cleaning jigs, optical equipment parts, valves, pipes, nozzles, filters, membranes, medical equipment parts, medical materials, sensor parts, sanitary equipment, sporting goods, and leisure goods.

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