Liquid composition, method for producing the liquid composition, method for producing a liquid crystal polyester film, and method for producing a laminate

Abstract

To provide an aqueous composition having excellent dispersibility into a medium of liquid crystal polyester powder.SOLUTION: An aqueous composition comprises liquid crystal polyester powder having an average particle size of 30 μm or smaller and a medium, in which a specific gravity measured based on JIS Z8804 with reference to water of the medium as reference material of 0.90 or larger. The aqueous composition is preferably such that the liquid crystal polyester powder is insoluble in the medium, and the liquid crystal polyester powder is a dispersion liquid dispersed in the medium of liquid.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid composition, a method for producing a liquid composition, a method for producing a liquid crystal polyester film, and a method for producing a laminate. [Background technology]

[0002] Liquid crystal polyester film is attracting attention as an electronics substrate material due to its excellent high-frequency properties and low water absorption.

[0003] In the manufacture of liquid crystal polyester films, compositions containing liquid crystal polyester may be used. Patent Document 1 discloses a paste comprising a dispersion medium and a specific fibrillated liquid crystal polymer powder dispersed in the dispersion medium. Examples of the dispersion medium include ethanol, terpineol, butyl lactone, and isopropyl alcohol. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2014 / 188830 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The inventors first discovered that a liquid crystal polyester film having suitable quality for use as an electronic component film can be manufactured by applying a liquid composition containing liquid crystal polyester powder and a dispersion medium onto a support and then heat-treating it. To manufacture high-quality liquid crystal polyester films, it is preferable that the liquid crystal polyester powder is more uniformly dispersed in the medium. However, in the pastes and the like described in Patent Document 1, there is still room for improvement in terms of the dispersibility of the liquid crystal polyester powder in the liquid composition.

[0006] The present invention was made to solve the above-mentioned problems, and aims to provide a liquid composition comprising liquid crystal polyester powder and a medium, wherein the liquid crystal polyester powder has good dispersibility in the medium, and a method for producing the liquid composition. Furthermore, the present invention aims to provide a method for manufacturing a liquid crystal polyester film using the liquid composition, and a method for manufacturing a laminate. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the present inventors have found that by mixing liquid crystal polyester powder having a specific average particle size with a medium having a specific specific gravity, it is possible to provide a liquid composition with good dispersibility of liquid crystal polyester powder, and have completed the present invention. In other words, the present invention has the following aspects.

[0008] <1> A liquid crystal polyester powder containing liquid crystal polyester with an average particle size of 30 μm or less, Including the medium, A liquid composition wherein the medium has a specific gravity of 0.90 or higher, as measured in accordance with JIS Z 8804 with water as the reference substance. <2> The liquid crystal polyester powder is insoluble in the medium, The liquid crystal polyester powder is dispersed in the liquid medium, <1> The liquid composition described above. <3> The difference in specific gravity between the specific gravity of the liquid crystal polyester powder measured according to JIS K 7112 (Method A) and the specific gravity of the medium water measured according to JIS Z 8804 is within 0.48. <1> or <2> The liquid composition described above. <4> The specific gravity of the aforementioned medium, measured in accordance with JIS Z 8804 with water as the reference substance, is 0.95 or higher. <1> ~ <3> A liquid composition according to any one of the following. <5> The liquid composition according to any one of <1> to <4>, wherein the medium is at least one selected from the group consisting of propylene glycol, ethylene glycol, butanediol, N-methyl-2-pyrrolidone, butyl lactate, di-(2-chloroethyl) ether, dichloromethane, and sulfolane. <6> The liquid composition according to any one of <1> to <4>, wherein the medium is at least one selected from the group consisting of propylene glycol, ethylene glycol, butanediol, dichloromethane, and sulfolane. <7> The liquid composition according to any one of <1> to <6>, wherein the specific gravity measured in accordance with JIS Z 8804 using water as a reference substance for the medium is 1.03 or more. <8> The liquid composition according to any one of <1> to <7>, wherein the viscosity measured at 20 to 25 °C for the medium is 10 mPa·s or more. <9> The liquid composition according to any one of <1> to <8>, wherein the specific gravity measured by JIS K 7112 (Method A) for the liquid crystal polyester powder is 1.35 or more and 1.40 or less. <10> The liquid composition according to any one of <1> to <9>, wherein the liquid crystal polyester contains a structural unit represented by the following formula (1). (1)-O-Ar1-CO- (Ar1 represents a divalent aromatic hydrocarbon group, One or more hydrogen atoms in the group represented by Ar1 may be independently substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.) <11> The liquid composition according to any one of <1> to <10>, wherein the liquid crystal polyester contains a structural unit containing a naphthalene structure. <12> The liquid composition according to <11>, wherein the liquid crystal polyester contains a structural unit represented by the following formula (1) in an amount of 40 mol% or more based on the total amount of all structural units in the liquid crystal polyester. (1)-O-Ar1-CO- (Ar1 represents a 2,6-naphthylene group, One or more hydrogen atoms in the group represented by Ar1 may be independently substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. <13> A step of mixing a liquid crystal polyester powder containing a liquid crystal polyester and having an average particle diameter of 30 μm or less with a medium, The method for producing a liquid composition according to any one of <1> to <12>, wherein the specific gravity of the medium measured in accordance with JIS Z 8804 using water as a reference substance is 0.90 or more. <14> A method for producing a liquid crystal polyester film, including applying the liquid composition according to any one of <1> to <12> on a support and performing heat treatment to obtain a liquid crystal polyester film containing a liquid crystal polyester. <15> A method for producing a laminate, including applying the liquid composition according to any one of <1> to <12> on a support and performing heat treatment to form a liquid crystal polyester film containing a liquid crystal polyester, thereby obtaining a laminate including the support and the liquid crystal polyester film.

Advantages of the Invention

[0009] According to the present invention, it is possible to provide a liquid composition in which the liquid crystal polyester powder has good dispersibility in a medium, and a method for producing the liquid composition. Moreover, according to the present invention, it is possible to provide a method for producing a liquid crystal polyester film using the liquid composition, and a method for producing a laminate.

Brief Description of the Drawings

[0010] [Figure 1] It is a schematic diagram showing the manufacturing process of the liquid crystal polyester film and the laminate of one embodiment of the present invention. [Figure 2] It is a schematic diagram showing the configuration of the liquid crystal polyester film of one embodiment of the present invention. [Figure 3] It is a schematic diagram showing the configuration of the laminate of one embodiment of the present invention. <00001This image shows the liquid composition (dispersion medium: cyclohexanone) of Example 5. [Figure 5] This image shows the liquid composition (dispersion medium: ethylene glycol) of Example 10. [Figure 6] These are images showing the liquid compositions of Examples 17-21. [Figure 7] These are images showing the liquid compositions of Examples 22-26. [Figure 8] These are images showing the liquid compositions of Examples 27-31. [Figure 9] These are images showing the liquid compositions of Examples 32-36. [Figure 10] These are images showing the liquid compositions of Examples 37-41. [Figure 11] These are images showing the liquid compositions of Examples 42-46. [Modes for carrying out the invention]

[0011] The following describes embodiments of the liquid composition, the method for producing the liquid composition, the method for producing a liquid crystal polyester film, and the method for producing a laminate of the present invention.

[0012] <Liquid Composition> The liquid composition of the embodiment comprises a liquid crystal polyester powder having an average particle size of 30 μm or less and a medium, wherein the specific gravity measured in accordance with JIS Z 8804 with water in the medium as the reference substance is 0.90 or higher. The liquid composition of the embodiment has good dispersibility of liquid crystal polyester powder in a medium. In the liquid composition of the embodiment, a state in which the liquid crystal polyester powder has good dispersibility in the medium means a state in which the distribution of liquid crystal polyester powder in the composition can be confirmed to be uniform by visual inspection. The liquid composition containing the liquid crystal polyester powder of the embodiment is suitable as a raw material for the method of manufacturing a liquid crystal polyester film or laminate according to the embodiment.

[0013] <Liquid crystal polyester powder> The liquid crystal polyester powder according to this embodiment contains liquid crystal polyester and has an average particle size of 30 μm or less. Using liquid crystal polyester powder that meets the above specifications, it is possible to manufacture liquid crystal polyester films with suitable quality for use as films for electronic components. One of the quality criteria is the isotropy of the film. Details of the liquid crystal polyester film will be described later.

[0014] In this specification, "average particle size" refers to the particle diameter at the point where the cumulative volume reaches 50% in a volume-based cumulative particle size distribution curve measured by laser diffraction scattering (50% cumulative volume particle size D). 50 ) Furthermore, the particle size at which the cumulative volume percentage from the small particle side becomes 10% is D 10 , the particle size that makes up 90% is D 90 Let's assume that.

[0015] Average particle size of liquid crystal polyester powder (D 50 The average particle size of the liquid crystal polyester powder is 30 μm or less, preferably 20 μm or less, more preferably 18 μm or less, even more preferably 15 μm or less, and particularly preferably 10 μm or less. If the average particle size of the liquid crystal polyester powder exceeds 30 μm, it becomes difficult to obtain a liquid composition with good dispersion of the liquid crystal polyester powder. Furthermore, if the average particle size of the liquid crystal polyester is 20 μm or less, it is possible to manufacture a liquid crystal polyester film with a suitable thickness for electronic components (e.g., 50 μm or less) and good surface smoothness. Furthermore, from the perspective of ease of handling the powder, the average particle size (D) of the liquid crystal polyester powder is considered. 50 The particle size is preferably 0.5 μm or larger, more preferably 3 μm or larger, and even more preferably 5 μm or larger. The average particle size (D) of the above liquid crystal polyester powder 50The upper limit value and the lower limit value of the value of ) can be freely combined. As an example of the numerical range of the value of the average particle diameter of the liquid crystal polyester powder described above, it may be 0.5 μm or more and 30 μm or less, 0.5 μm or more and 20 μm or less, 3 μm or more and 18 μm or less, 5 μm or more and 15 μm or less, 5 μm or more and 12 μm or less, or 5 μm or more and 10 μm or less.

[0016] The particle diameter (D 10 ) of the liquid crystal polyester powder is preferably 1 μm or more and 20 μm or less, more preferably 2 μm or more and 18 μm or less, and even more preferably 3 μm or more and 15 μm or less. When the value of D 10 is within the above range, the liquid crystal polyester powder is preferable because its dispersibility in the medium is improved.

[0017] The particle diameter (D 90 ) of the liquid crystal polyester powder is preferably 5 μm or more and 100 μm or less, more preferably 10 μm or more and 80 μm or less, and even more preferably 15 μm or more and 60 μm or less. When the value of D 90 is within the above range, the liquid crystal polyester powder is preferable because its dispersibility in the medium is improved.

[0018] The liquid crystal polyester powder according to the embodiment can be obtained, for example, by pulverizing the powder of the liquid crystal polyester produced by the production method of the liquid crystal polyester described later using a jet mill or the like so that its average particle diameter becomes 30 μm or less.

[0019] As a method for controlling the particle diameter within the above range, for example, there is a method of pulverizing the liquid crystal polyester using a jet mill. In that case, the particle diameter can be controlled by changing the rotational speed of the classification rotor, the pressure of the pulverizing nozzle, the processing speed, etc. Further, an operation of classifying the particles using a sieve having a mesh size corresponding to the desired particle diameter may be performed.

[0020] The liquid composition of the embodiment may be a dispersion liquid in which the liquid crystal polyester powder is insoluble in the medium and the liquid crystal polyester powder is dispersed in the liquid medium.

[0021] Here, whether or not the liquid crystal polyester powder is insoluble in the medium can be confirmed by performing the following test.

[0022] • Test method Liquid crystal polyester powder (5 parts by mass) is stirred in a medium (95 parts by mass) at 180°C for 6 hours using an anchor blade at 200 rpm, and then cooled to room temperature (23°C). Next, the mixture is filtered using a 5 μm mesh membrane filter and a pressurized filter, and the residue on the membrane filter is checked. If no solid material is found, the mixture is considered soluble in the medium. If solid material is found, the mixture is considered insoluble in the medium. Solid material can be identified by microscopic observation.

[0023] Because the liquid crystal polyester powder is insoluble in the medium, in the manufacturing methods for the liquid crystal polyester film or laminate according to the embodiments described later, it is not necessary to dissolve the liquid crystal polyester powder in a solvent, and thus liquid crystal polyester powder with excellent dielectric properties can be used as a raw material. From liquid crystal polyester powder with excellent dielectric properties, it is possible to manufacture liquid crystal polyester films with excellent dielectric properties. In this specification, "dielectric properties" refers to properties relating to relative permittivity and dielectric loss tangent.

[0024] The liquid crystal polyester powder according to the embodiment preferably has a relative permittivity of 3 or less at a frequency of 1 GHz, preferably 2.9 or less, preferably 2.8 or less, more preferably less than 2.8, even more preferably 2.78 or less, and particularly preferably 2.76 or less. Furthermore, the relative permittivity of the liquid crystal polyester powder may be 2.5 or more, 2.6 or more, or 2.7 or more. The upper and lower limits of the relative permittivity value of the liquid crystal polyester powder can be freely combined. An example of the numerical range for the relative permittivity value of the liquid crystal polyester powder is that it may be 2.5 or more and 3 or less, 2.6 or more and 2.78 or less, or 2.7 or more and 2.76 or less.

[0025] The liquid crystal polyester powder according to the embodiment preferably has a dielectric loss tangent of 0.005 or less, preferably 0.004 or less, more preferably 0.003 or less, even more preferably 0.0025 or less, and particularly preferably 0.002 or less at a frequency of 1 GHz. The dielectric loss tangent of the liquid crystal polyester powder may also be 0.0003 or more, 0.0005 or more, or 0.001 or more. An example of the numerical range for the dielectric loss tangent value of the above liquid crystal polyester powder is that it may be 0.0003 or more and 0.005 or less, 0.0005 or more and 0.004 or less, 0.001 or more and 0.003 or less, 0.001 or more and 0.0025 or less, or 0.001 or more and 0.002 or less.

[0026] Furthermore, the relative permittivity and dielectric loss tangent of liquid crystal polyester powder at a frequency of 1 GHz can be measured using the capacitance method with an impedance analyzer under the following conditions. A tablet with a diameter of 1 cm and a thickness of 0.5 cm is prepared by melting liquid crystal polyester fine particle powder at a temperature 5°C higher than the melting point measured using a flow tester, and then cooling and solidifying it. The relative permittivity and dielectric loss tangent of the obtained tablet are measured at 1 GHz under the following conditions. ·Measurement method: Capacitive method ·Electrode model: 16453A • Measurement environment: 23℃, 50%RH • Applied voltage: 1V

[0027] Note that the dielectric constant and dielectric loss tangent of the liquid crystal polyester powder according to this embodiment may differ from those of a liquid crystal polyester film manufactured using the powder as a raw material. This is thought to be due to differences in the molecular weight of the liquid crystal polyester contained.

[0028] The liquid crystal polyester content relative to 100% by mass of liquid crystal polyester powder according to the embodiment may be 80 to 100% by mass, or 90 to 98% by mass.

[0029] Furthermore, acetic acid derived from acetic anhydride used in the production of liquid crystal polyester may remain in the liquid crystal polyester powder according to the embodiment. However, the amount of residual acetic acid that may be contained in 100% by mass of the liquid crystal polyester powder according to the embodiment is preferably 1% by mass or less, more preferably 500 ppm by mass or less, and even more preferably 300 ppm by mass or less, from the viewpoint of mechanical properties after processing into a film. Furthermore, the amount of residual acetic acid contained in 100% by mass of the liquid crystal polyester powder according to the embodiment is preferably 30 ppm by mass or more, more preferably 50 ppm by mass or more, and even more preferably 100 ppm by mass or more, from the viewpoint of pulverability. An example of the numerical range for the amount of residual acetic acid that may be contained in 100% by mass of the above-mentioned liquid crystal polyester powder is that it may be 30 ppm by mass or more and 1% by mass or less, 50 ppm by mass or more and 500 ppm by mass or less, or 100 ppm by mass or more and 300 ppm by mass or less.

[0030] The liquid crystal polyester powder according to the embodiment may be a liquid crystal polyester powder having an average particle size of 30 μm or less (however, excluding liquid crystal polyesters consisting of structural units derived from 2-hydroxy-6-naphthoic acid, structural units derived from 2,6-naphthalenedicarboxylic acid, structural units derived from terephthalic acid, and structural units derived from hydroquinone, with a volume average particle size of 9 μm).

[0031] The liquid crystal polyester powder according to the embodiment may be a liquid crystal polyester powder containing a liquid crystal polyester and having an average particle size of 30 μm or less (however, this excludes liquid crystal polyester powder consisting of a polymer obtained by reacting a mixture of 2-hydroxy-6-naphthoic acid (5.5 mol), 2,6-naphthalenedicarboxylic acid (1.75 mol), terephthalic acid (0.5 mol), hydroquinone (2.475 mol), acetic anhydride (12 mol), and 1-methylimidazole as a catalyst, with a volume average particle size of 9 μm).

[0032] The liquid crystal polyester powder according to the embodiment may be a liquid crystal polyester powder containing a liquid crystal polyester and having an average particle size of 30 μm or less (however, this excludes a liquid crystal polyester powder with a volume average particle size of 9 μm obtained by grinding a liquid crystal polyester with a flow start temperature of 265°C, which consists of structural units derived from 2-hydroxy-6-naphthoic acid, structural units derived from 2,6-naphthalenedicarboxylic acid, structural units derived from terephthalic acid, and structural units derived from hydroquinone).

[0033] The liquid crystal polyester powder according to the embodiment may be a liquid crystal polyester powder having an average particle size of 30 μm or less (however, excluding liquid crystal polyester powder that contains structural units derived from 2-hydroxy-6-naphthoic acid, structural units derived from 2,6-naphthalenedicarboxylic acid, structural units derived from terephthalic acid, and structural units derived from hydroquinone, and has a volume average particle size of 9 μm).

[0034] The liquid crystal polyester powder according to the embodiment may contain liquid crystal polyester and have an average particle size of 30 μm or less (however, this excludes liquid crystal polyester powder that is a polymer obtained by reacting a mixture of 2-hydroxy-6-naphthoic acid (5.5 mol), 2,6-naphthalenedicarboxylic acid (1.75 mol), terephthalic acid (0.5 mol), hydroquinone (2.475 mol), acetic anhydride (12 mol), and 1-methylimidazole as a catalyst, and has a volume average particle size of 9 μm).

[0035] The liquid crystal polyester powder according to the embodiment may be a liquid crystal polyester powder containing a liquid crystal polyester and having an average particle size of 30 μm or less (however, this excludes a liquid crystal polyester powder with a volume average particle size of 9 μm obtained by grinding a liquid crystal polyester containing structural units derived from 2-hydroxy-6-naphthoic acid, structural units derived from 2,6-naphthalenedicarboxylic acid, structural units derived from terephthalic acid, and structural units derived from hydroquinone, and having a flow start temperature of 265°C).

[0036] The liquid crystal polyester powder according to the embodiment may be a liquid crystal polyester powder having an average particle size of 30 μm or less (however, this excludes a liquid crystal polyester powder having a volume average particle size of 9 μm obtained by pulverizing a polymer obtained by reacting a mixture of 2-hydroxy-6-naphthoic acid (5.5 mol), 2,6-naphthalenedicarboxylic acid (1.75 mol), terephthalic acid (0.5 mol), hydroquinone (2.475 mol), acetic anhydride (12 mol), and 1-methylimidazole as a catalyst, the polymer having a flow start temperature of 265°C).

[0037] Here, "volume-average particle size" refers to the particle size at the point where the cumulative volume reaches 50% (50% cumulative volume particle size) in a volume-based cumulative particle size distribution curve measured by a scattering particle size distribution analyzer (for example, HORIBA's "LA-950V2"), using a refractive index of 1.333 for pure water. 50 )

[0038] (Liquid crystal polyester) The following describes one embodiment of the liquid crystal polyester used in this embodiment.

[0039] The liquid crystal polyester according to this embodiment is a polyester that exhibits liquid crystal properties in a molten state, and is preferably melted at a temperature of 450°C or lower. The liquid crystal polyester may be a liquid crystal polyester amide, a liquid crystal polyester ether, a liquid crystal polyester carbonate, or a liquid crystal polyester imide. The liquid crystal polyester is preferably a fully aromatic liquid crystal polyester having only structural units derived from aromatic compounds as raw material monomers.

[0040] Typical examples of liquid crystal polyesters include polymers obtained by polycondensation (condensation) of aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, and at least one compound selected from the group consisting of aromatic diol, aromatic hydroxyamine, and aromatic diamine; polymers obtained by polymerizing multiple types of aromatic hydroxycarboxylic acid; polymers obtained by polymerizing aromatic dicarboxylic acid and at least one compound selected from the group consisting of aromatic diol, aromatic hydroxyamine, and aromatic diamine; and polymers obtained by polymerizing polyester such as polyethylene terephthalate with aromatic hydroxycarboxylic acid.

[0041] In particular, among the liquid crystal polyesters, polymers obtained by polycondensation (condensation) of aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, and at least one compound selected from the group consisting of aromatic diol, aromatic hydroxyamine, and aromatic diamine are preferred.

[0042] Here, aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic hydroxyamines, and aromatic diamines may be independently replaced by their polymerizable ester-forming derivatives in whole or in part.

[0043] Examples of polymerizable derivatives of compounds having a carboxyl group, such as aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids, include esters, acid halides, and acid anhydrides. Examples of esters include compounds obtained by converting the carboxyl group to an alkoxycarbonyl group or an aryloxycarbonyl group. Examples of acid halides include compounds obtained by converting the carboxyl group to a haloformyl group. Examples of acid anhydrides include compounds obtained by converting the carboxyl group to an acyloxycarbonyl group.

[0044] Examples of polymerizable derivatives of compounds having a hydroxyl group, such as aromatic hydroxycarboxylic acids, aromatic diols, and aromatic hydroxyamines, include those obtained by acyling the hydroxyl group to convert it into an acyloxy group (acylated compounds). Examples of polymerizable derivatives of compounds having an amino group, such as aromatic hydroxyamines and aromatic diamines, include compounds (acylated compounds) obtained by acyling the amino group to convert it into an acylamino group.

[0045] Among the examples of polymerizable derivatives exemplified, acylated products obtained by acyling aromatic hydroxycarboxylic acids and aromatic diols are preferred as raw material monomers for liquid crystal polyesters.

[0046] The liquid crystal polyester according to this embodiment preferably has a structural unit represented by the following formula (1) (hereinafter sometimes referred to as "structural unit (1)"). (1)-O-Ar1-CO- (Ar1 represents a divalent aromatic hydrocarbon group, One or more hydrogen atoms in the group represented by Ar1 may be independently substituted with halogen atoms, C1-C10 alkyl groups, or C6-C20 aryl groups.

[0047] In the embodiment, the liquid crystal polyester preferably has a structural unit represented by the following formula (1), in which Ar1 represents a phenylene group, a naphthylene group, or a biphenylylene group. More preferably, the liquid crystal polyester according to the embodiment has structural unit (1), a structural unit represented by the following formula (2) (hereinafter sometimes referred to as "structural unit (2)"), and a structural unit represented by the following formula (3) (hereinafter sometimes referred to as "structural unit (3)").

[0048] (1)-O-Ar1-CO- (2) New CO-Ar2-CO- (3)-X-Ar3-Y-

[0049] [In formulas (1) to (3), Ar1 represents a phenylene group, a naphthylene group, or a biphenylylene group. Ar2 and Ar3 independently represent a phenylene group, a naphthylene group, a biphenylylene group, or a group represented by the following formula (4). X and Y independently represent an oxygen atom or an imino group (-NH-). One or more hydrogen atoms in the group represented by Ar1, Ar2, or Ar3 may be independently substituted with a halogen atom, a C1-C10 alkyl group, or a C6-C20 aryl group.

[0050] (4)-Ar4-Z-Ar5-

[0051] [In formula (4), Ar4 and Ar5 independently represent a phenylene group or a naphthylene group. Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylidene group having 1 to 10 carbon atoms. One or more hydrogen atoms in the group represented by Ar4 or Ar5 may be independently substituted with a halogen atom, a C1-C10 alkyl group, or a C6-C20 aryl group.

[0052] Because liquid crystal polyester powder tends to be insoluble in the medium, it is preferable that X and Y in structural unit (3) are oxygen atoms.

[0053] Examples of halogen atoms that can be substituted for hydrogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0054] Examples of C1-C10 alkyl groups that can be substituted for hydrogen atoms include methyl, ethyl, 1-propyl, isopropyl, 1-butyl, isobutyl, sec-butyl, tert-butyl, 1-hexyl, 2-ethylhexyl, 1-octyl, and 1-decyl groups.

[0055] Examples of aryl groups having 6 to 20 carbon atoms that can be substituted with a hydrogen atom include monocyclic aromatic groups such as phenyl, orthotolyl, metatolyl, and paratolyl groups, as well as fused aromatic groups such as 1-naphthyl and 2-naphthyl groups.

[0056] When one or more hydrogen atoms in the group represented by Ar1, Ar2, Ar3, Ar4, or Ar5 are substituted with the halogen atom, the C1-C10 alkyl group, or the C6-C20 aryl group, the number of groups substituting the hydrogen atoms is preferably one or two, and more preferably one, for each group represented by Ar1, Ar2, Ar3, Ar4, or Ar5, independently of each other.

[0057] Examples of alkylidene groups having 1 to 10 carbon atoms include methylene group, ethylidene group, isopropylidene group, 1-butylidene group, and 2-ethylhexylidene group.

[0058] The liquid crystal polyester according to the embodiment preferably contains structural units including a naphthalene structure. Liquid crystal polyester containing structural units including a naphthalene structure tends to have excellent dielectric properties.

[0059] In liquid crystal polyester, the content of structural units containing naphthalene structures is preferably 40 mol% or more, more preferably 50 mol% or more, more preferably 55 mol% or more, and even more preferably 60 mol% or more, relative to the total amount of structural units in the liquid crystal polyester (calculated by dividing the mass of each structural unit constituting the liquid crystal polyester by the formula weight of that structural unit to obtain the equivalent amount of substance (moles) of each structural unit, and then summing them up). By having a content of structural units containing naphthalene structures above the above lower limit, it is possible to further reduce the dielectric constant of the liquid crystal polyester. In liquid crystal polyester, the content of structural units containing naphthalene structures is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less, based on the total amount of all structural units in the liquid crystal polyester (100 mol%). By keeping the content of structural units containing naphthalene structures below the above upper limit, reaction stability during the production of liquid crystal polyester can be ensured. Examples of numerical ranges for the content of structural units containing the naphthalene structure described above include 40 mol% to 90 mol%, 50 mol% to 85 mol%, 55 mol% to 85 mol%, and 60 mol% to 80 mol%.

[0060] In a liquid crystal polyester having a structural unit containing a divalent naphthalene structure, the above structural unit (1), the following structural unit (2), and the following structural unit (3) are preferably such that at least one of the multiple Ar1, Ar2, Ar3, Ar4, and Ar5 is a naphthylene group.

[0061] In the embodiment, the liquid crystal polyester preferably has Ar1 as a 2,6-naphthylene group. Here, it is preferable that the liquid crystal polyester in which Ar1 is a 2,6-naphthylene group has the above structural unit (1), the following structural unit (2), and the following structural unit (3). The liquid crystal polyester according to this embodiment may contain 40 mol% or more of structural units in which Ar1 is a 2,6-naphthylene group, relative to the total amount of all structural units in the liquid crystal polyester, or it may contain 40 mol% to 90 mol%, 50 mol% to 85 mol%, 55 mol% to 85 mol%, or 60 mol% to 80 mol%. ru.

[0062] Structural unit (1) is a structural unit derived from an aromatic hydroxycarboxylic acid. Examples of the aromatic hydroxycarboxylic acid include parahydroxybenzoic acid, metahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-3-naphthoic acid, 1-hydroxy-5-naphthoic acid, 4-hydroxy-4'-carboxydiphenyl ether, and aromatic hydroxycarboxylic acids obtained by substituting some of the hydrogen atoms in the aromatic ring of these aromatic hydroxycarboxylic acids with substituents selected from the group consisting of alkyl groups, aryl groups, and halogen atoms. The aromatic hydroxycarboxylic acid may be used alone or in combination of two or more in the production of liquid crystal polyester. The structural unit (1) is preferably one in which Ar1 is a 1,4-phenylene group (for example, a structural unit derived from 4-hydroxybenzoic acid) and one in which Ar1 is a 2,6-naphthylene group (for example, a structural unit derived from 6-hydroxy-2-naphthoic acid).

[0063] Structural unit (2) is a structural unit derived from an aromatic dicarboxylic acid. Examples of the aforementioned aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, biphenyl-4,4'-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylthioether-4,4'-dicarboxylic acid, and aromatic dicarboxylic acids in which some of the hydrogen atoms in the aromatic ring of these aromatic dicarboxylic acids are substituted with substituents selected from the group consisting of alkyl groups, aryl groups, and halogen atoms. The aforementioned aromatic dicarboxylic acids may be used alone or in combination of two or more in the production of liquid crystal polyesters. The structural unit (2) is preferably one in which Ar2 is a 1,4-phenylene group (for example, a structural unit derived from terephthalic acid), one in which Ar2 is a 1,3-phenylene group (for example, a structural unit derived from isophthalic acid), one in which Ar2 is a 2,6-naphthylene group (for example, a structural unit derived from 2,6-naphthalenedicarboxylic acid), and one in which Ar2 is a diphenyl ether-4,4'-diyl group (for example, a structural unit derived from diphenyl ether-4,4'-dicarboxylic acid).

[0064] Structural unit (3) is a structural unit derived from an aromatic diol, aromatic hydroxyamine, or aromatic diamine. Examples of aromatic diols, aromatic hydroxyamines, or aromatic diamines include 4,4'-dihydroxybiphenyl, hydroquinone, methylhydroquinone, resorcinol, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, bis(4-hydroxyphenyl)methane, 1,2-bis(4-hydroxyphenyl)ethane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl thioether, 2,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 4-aminophenol, 1,4-phenylenediamine, 4-amino-4'-hydroxybiphenyl, and 4,4'-diaminobiphenyl. The aforementioned aromatic diol, aromatic hydroxyamine, or aromatic diamine may be used alone or in combination of two or more in the production of liquid crystal polyester. As structural unit (3), those in which Ar3 is a 1,4-phenylene group (for example, structural units derived from hydroquinone, 4-aminophenol, or 1,4-phenylenediamine) and those in which Ar3 is a 4,4'-biphenylylene group (for example, structural units derived from 4,4'-dihydroxybiphenyl, 4-amino-4'-hydroxybiphenyl, or 4,4'-diaminobiphenyl) are preferred.

[0065] In this specification, "derived from" means that the chemical structure of the raw material monomer changes due to polymerization, but no other structural changes occur.

[0066] Furthermore, if the liquid crystal polyester film obtained from the liquid composition of the embodiment requires particularly good heat resistance, it is preferable to have fewer substituents, and it is especially preferable that it does not have substituents such as alkyl groups.

[0067] Next, examples of liquid crystal polyesters particularly suitable for application to the liquid composition of the embodiment are given below. Specific examples of preferred liquid crystal polyesters include copolymers composed of structural units derived from monomers in the following combinations.

[0068] 1) 4-Hydroxybenzoic acid / 2-Hydroxy-6-Naphthoic acid copolymer 2) 4-Hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer 3) 4-Hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4,4'-dihydroxybiphenyl copolymer 4) 4-Hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4,4'-dihydroxybiphenyl / hydroquinone copolymer 5) 4-Hydroxybenzoic acid / terephthalic acid / hydroquinone copolymer 6) 2-Hydroxy-6-Naphthoic Acid / Terephthalic Acid / Hydroquinone Copolymer 7) 2-Hydroxy-6-naphthoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 8) 4-Hydroxybenzoic acid / 2-Hydroxy-6-Naphthoic acid / Terephthalic acid copolymer 9) 4-Hydroxybenzoic acid / 2-Hydroxy-6-naphthoic acid / Isophthalic acid copolymer 10) 4-Hydroxybenzoic acid / 2-Hydroxy-6-Naphthoic acid / Terephthalic acid / 4,4'-Dihydroxybiphenyl copolymer 11) 4-Hydroxybenzoic acid / 2-Hydroxy-6-Naphthoic acid / Isophthalic acid / 4,4'-Dihydroxybiphenyl copolymer 12) 4-Hydroxybenzoic acid / 2-Hydroxy-6-Naphthoic acid / Terephthalic acid / 2,6-Naphthalenedicarboxylic acid / 4,4'-Dihydroxybiphenyl copolymer 13) 4-Hydroxybenzoic acid / 2-Hydroxy-6-Naphthoic acid / Terephthalic acid / 4,4'-Dihydroxybiphenyl / Methylhydroquinone copolymer 14) 2-Hydroxy-6-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer 15) 2-Hydroxy-6-Naphthoic Acid / Terephthalic Acid / Isophthalic Acid / 4,4'-Dihydroxybiphenyl Copolymer 16) 2-Hydroxy-6-naphthoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / 4,4'-dihydroxybiphenyl copolymer 17) 2-Hydroxy-6-naphthoic acid / terephthalic acid / isophthalic acid / 2,6-naphthalenedicarboxylic acid / 4,4'-dihydroxybiphenyl copolymer 18) 4-Hydroxybenzoic acid / 2-Hydroxy-6-Naphthoic acid / Terephthalic acid / Hydroquinone copolymer 19) 4-Hydroxybenzoic acid / 2-Hydroxy-6-naphthoic acid / Terephthalic acid / 3,3'-Dimethyl-1,1'-biphenyl-4,4'-diol copolymer 20) 4-Hydroxybenzoic acid / 2-Hydroxy-6-Naphthoic acid / Terephthalic acid / Hydroquinone / 4,4'-Dihydroxybiphenyl copolymer 21) 4-Hydroxybenzoic acid / 2,6-Naphthalenedicarboxylic acid / 4,4'-Dihydroxybiphenyl copolymer 22) 4-Hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 23) 4-Hydroxybenzoic acid / 2,6-Naphthalenedicarboxylic acid / Hydroquinone copolymer 24) 4-Hydroxybenzoic acid / 2-Hydroxy-6-naphthoic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 25) 4-Hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone / 4,4'-dihydroxybiphenyl copolymer 26) 4-Hydroxybenzoic acid / terephthalic acid / 4-aminophenol copolymer 27) 2-Hydroxy-6-Naphthoic Acid / Terephthalic Acid / 4-Aminophenol Copolymer 28) 4-Hydroxybenzoic acid / 2-Hydroxy-6-Naphthoic acid / Terephthalic acid / 4-Aminophenol copolymer 29) 4-Hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / 4-aminophenol copolymer 30) 4-Hydroxybenzoic acid / terephthalic acid / ethylene glycol copolymer 31) 4-Hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / ethylene glycol copolymer 32) 4-Hydroxybenzoic acid / 2-Hydroxy-6-naphthoic acid / Terephthalic acid / Ethylene glycol copolymer 33) 4-Hydroxybenzoic acid / 2-Hydroxy-6-naphthoic acid / Terephthalic acid / 4,4'-Dihydroxybiphenyl / Ethylene glycol copolymer 34) 4-Hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / 4,4'-dihydroxybiphenyl copolymer.

[0069] The content of the liquid crystal polyester structural unit (1) is preferably 30 mol% or more, more preferably 30 to 90 mol%, more preferably 30 to 85 mol%, even more preferably 40 to 75 mol%, particularly preferably 50 to 70 mol%, and especially preferably 55 to 70 mol%, relative to the total amount of all structural units constituting the liquid crystal polyester (the amount of substance equivalent (moles) of each structural unit obtained by dividing the mass of each structural unit constituting the liquid crystal polyester by the formula weight of each structural unit, and then summing them up). When the content of structural unit (1) of the liquid crystal polyester is 30 mol% or more, the heat resistance and hardness of the molded article obtained using the liquid composition of this embodiment tend to improve. Furthermore, when the content of structural unit (1) is 80 mol% or less, the melt viscosity can be lowered. As a result, the temperature required for molding the liquid crystal polyester tends to be lower.

[0070] The content of the liquid crystal polyester structural units (2) is preferably 35 mol% or less, more preferably 10 to 35 mol%, even more preferably 15 to 35 mol%, and particularly preferably 17.5 to 32.5 mol%, relative to the total amount of all structural units constituting the liquid crystal polyester.

[0071] The content of the liquid crystal polyester structural units (3) is preferably 35 mol% or less, more preferably 10 to 35 mol%, even more preferably 15 to 35 mol%, and particularly preferably 17.5 to 32.5 mol%, relative to the total amount of all structural units constituting the liquid crystal polyester.

[0072] In liquid crystal polyester, the ratio of the content of structural unit (2) to the content of structural unit (3) is expressed as [content of structural unit (2)] / [content of structural unit (3)] (moles / moles), and is preferably 0.9 to 1.1, more preferably 0.95 to 1.05, and even more preferably 0.98 to 1.02.

[0073] In liquid crystal polyester, the ratio of the content of structural unit (3) to the content of structural unit (1) is expressed as [content of structural unit (3)] / [content of structural unit (1)] (moles / moles), and is preferably 0.2 to 1.0, more preferably 0.25 to 0.85, and even more preferably 0.3 to 0.75.

[0074] The liquid crystal polyester may have only one type of structural unit (1) to (3), or two or more types, independently. Furthermore, the liquid crystal polyester may have one or more structural units other than structural units (1) to (3), but their content is preferably 10 mol% or less, more preferably 5 mol% or less, relative to the total amount of all structural units of the liquid crystal polyester.

[0075] In this embodiment, it is also possible to use a liquid crystal polyester mixture in which multiple types of liquid crystal polyesters are mixed. Here, a liquid crystal polyester resin mixture is a mixture of liquid crystal polyester resins having different flow initiation temperatures. In the liquid crystal polyester resin mixture, the one with the highest flow initiation temperature is designated as the first liquid crystal polyester resin, and the one with the lowest flow initiation temperature is designated as the second liquid crystal polyester resin. A liquid crystal polyester resin mixture consisting substantially of the first liquid crystal polyester and the second liquid crystal polyester is preferred.

[0076] Furthermore, in the liquid crystal polyester mixture, the content of the second liquid crystal polyester is preferably 10 to 150 parts by mass, more preferably 30 to 120 parts by mass, and even more preferably 50 to 100 parts by mass, per 100 parts by mass of the first liquid crystal polyester.

[0077] (Method of manufacturing liquid crystal polyester) Next, an example of a method for manufacturing liquid crystal polyester according to this embodiment will be described.

[0078] The liquid crystal polyester of this embodiment is preferably manufactured by the following acylation and polymerization steps.

[0079] The acylation process is a process in which an acylated product is obtained by acyling the phenolic hydroxyl group of a raw material monomer with a fatty acid anhydride (for example, acetic anhydride).

[0080] In the polymerization step, it is preferable to obtain a liquid crystal polyester by polymerizing the acyl group of the acylated product obtained in the acylation step with the carboxyl group of the acylated product of aromatic dicarboxylic acid and aromatic hydroxycarboxylic acid in a manner that involves transesterification.

[0081] The acylation step and polymerization step may be carried out in the presence of a heterocyclic organic base compound represented by the following formula (5).

[0082] [ka]

[0083] In equation (5) above, R 1 ~R 4 Each of these independently represents a hydrogen atom, a C1-C4 alkyl group, a hydroxymethyl group, a cyano group, a cyanoalkyl group with C1-C4 alkyl groups, a cyanoalkoxy group with C1-C4 alkoxy groups, a carboxyl group, an amino group, an aminoalkyl group with C1-C4, an aminoalkoxy group with C1-C4, a phenyl group, a benzyl group, a phenylpropyl group, or a formyl group.

[0084] The heterocyclic organic base compound in formula (5) above is R 1 is an alkyl group having 1 to 4 carbon atoms, and R 2 ~R 4 Preferably, each of these is an imidazole derivative in which each atom is a hydrogen atom. This can further improve the reactivity of the acylation reaction in the acylation step and the transesterification reaction in the polymerization step. Furthermore, it is possible to improve the color tone of the liquid crystal polyester film obtained using the liquid composition of this embodiment.

[0085] Among heterocyclic organic base compounds, 1-methylimidazole and 1-ethylimidazole, or both, are particularly preferred due to their availability.

[0086] Furthermore, it is preferable that the amount of heterocyclic organic base compound used be 0.005 to 1 part by mass when the total amount of raw material monomers for the liquid crystal polyester (i.e., aromatic dicarboxylic acid, aromatic diol, and aromatic hydroxycarboxylic acid) is 100 parts by mass. Moreover, from the viewpoint of the color tone of the molded article and productivity, it is more preferable that the amount be 0.05 to 0.5 parts by mass per 100 parts by mass of raw material monomers.

[0087] The heterocyclic organic base compound only needs to be present at some point during the acylation and transesterification reactions. Its addition may occur immediately before the start of the acylation reaction, during the acylation reaction, or between the acylation and transesterification reactions. The resulting liquid crystal polyester has very high melt fluidity and excellent thermal stability.

[0088] The amount of fatty acid anhydride (e.g., acetic anhydride) used should be determined considering the amount of aromatic diol and aromatic hydroxycarboxylic acid used as raw material monomers. Specifically, it is preferable to use an amount of 1.0 to 1.2 equivalents relative to the total amount of phenolic hydroxy groups contained in these raw material monomers, more preferably 1.0 to 1.15 equivalents, even more preferably 1.03 to 1.12 equivalents, and particularly preferably 1.05 to 1.1 equivalents.

[0089] When the amount of fatty acid anhydride used is 1.0 equivalent or more relative to the total amount of phenolic hydroxyl groups in the raw material monomers, the acylation reaction proceeds easily, less unreacted raw material monomers remain in the subsequent polymerization step, and as a result, polymerization proceeds efficiently. Furthermore, when the acylation reaction proceeds sufficiently in this way, there is less possibility that unacylated raw material monomers will sublimate and clog the fractional distiller used during polymerization. On the other hand, when the amount of fatty acid anhydride used is 1.2 equivalent or less, the resulting liquid crystal polyester is less likely to be colored.

[0090] The acylation reaction in the acylation step described above is preferably carried out at a temperature range of 130°C to 180°C for 30 minutes to 20 hours, and more preferably at 140°C to 160°C for 1 to 5 hours.

[0091] The aromatic dicarboxylic acid used in the polymerization step described above may be present in the reaction system during the acylation step. That is, the aromatic diol, aromatic hydroxycarboxylic acid, and aromatic dicarboxylic acid may be present in the same reaction system during the acylation step. This is because the carboxyl group and optionally substituted substituents on the aromatic dicarboxylic acid are not affected in any way by the fatty acid anhydride.

[0092] Therefore, the process may involve sequentially carrying out the acylation and polymerization steps after charging the aromatic diol, aromatic hydroxycarboxylic acid, and aromatic dicarboxylic acid into a reactor, or it may involve charging the aromatic diol and aromatic dicarboxylic acid into a reactor, carrying out the acylation step, and then further charging the aromatic dicarboxylic acid into the reactor to carry out the polymerization step. From the viewpoint of simplifying the manufacturing process, the former method is preferred.

[0093] The transesterification reaction in the polymerization step described above is preferably carried out while increasing the temperature from 130°C to 400°C at a heating rate of 0.1 to 50°C / min, and more preferably while increasing the temperature from 150°C to 350°C at a heating rate of 0.3 to 5°C / min.

[0094] Furthermore, when carrying out the transesterification reaction in the polymerization process, it is preferable to evaporate and distill off by-product fatty acids (e.g., acetic acid) and unreacted fatty acid anhydrides (e.g., acetic anhydride) to shift the equilibrium. At this time, by refluxing a portion of the distilled fatty acids and returning them to the reactor, it is also possible to condense or backsublimate the raw material monomers that evaporate or sublimate along with the fatty acids and return them to the reactor.

[0095] In the acylation reaction of the acylation step and the transesterification reaction of the polymerization step, either a batch reactor or a continuous reactor may be used. Regardless of which reactor is used, a liquid crystal polyester suitable for use in this embodiment can be obtained.

[0096] The desired fine powder can be obtained by grinding after the polymerization process described above. While it is possible to increase the molecular weight of the liquid crystal polyester resin obtained in this polymerization process by performing heat treatment or other processes after the polymerization process, it is preferable to avoid processes that increase molecular weight, such as heat treatment, considering the pulverability of the liquid crystal polyester before grinding.

[0097] The liquid crystal polyester with the above-mentioned preferred flow initiation temperature can be easily obtained by appropriately optimizing the structural units constituting the liquid crystal polyester. In other words, improving the linearity of the molecular chains of the liquid crystal polyester tends to increase its flow initiation temperature.

[0098] For example, structural units derived from terephthalic acid improve the linearity of liquid crystal polyester molecular chains. On the other hand, structural units derived from isophthalic acid improve the flexibility (decreasing linearity) of liquid crystal polyester molecular chains. Therefore, by controlling the copolymerization ratio of terephthalic acid and isophthalic acid, it is possible to obtain liquid crystal polyester with a desired flow initiation temperature.

[0099] When using the above-mentioned liquid crystal polyester mixture, it is preferable that at least one of the liquid crystal polyesters is a polymer obtained by polymerizing raw material monomers containing an aromatic hydroxycarboxylic acid in the presence of an imidazole compound. The liquid crystal polyester obtained in this way has very high fluidity when melted and excellent thermal stability.

[0100] Furthermore, in the liquid crystal polyester used in this embodiment, it is preferable to optimize the copolymerization ratio of terephthalic acid and isophthalic acid. This allows control of the linearity of the molecular chains of the liquid crystal polyester, as described above. As a result, multiple types of liquid crystal polyesters with different flow initiation temperatures can be produced.

[0101] In the embodiment, the number-average molecular weight of the liquid crystal polyester in the liquid crystal polyester powder is preferably 10,000 or less, more preferably 3,000 to 10,000, even more preferably 4,000 to 8,000, and particularly preferably 5,000 to 7,000. When the number-average molecular weight of the liquid crystal polyester in the liquid crystal polyester powder is 10,000 or less, it is easy to process it into a film with excellent isotropy. Furthermore, the smaller the number-average molecular weight of the liquid crystal polyester, the more likely it is that the thermal conductivity in the thickness direction of the film after heat treatment will improve, which is preferable. When the number-average molecular weight of the liquid crystal polyester is above the lower limit mentioned above, the heat resistance, strength, and rigidity of the film after heat treatment are good.

[0102] In this specification, "number-average molecular weight" refers to the absolute value measured using a gel permeation chromatograph-multi-angle light scattering photometer.

[0103] In the liquid crystal polyester powder according to this embodiment, the liquid crystal polyester has a flow initiation temperature of preferably 240°C or higher, more preferably 250°C to 350°C, and even more preferably 260°C to 330°C. The higher the flow initiation temperature of the liquid crystal polyester, the easier it is to improve heat resistance, strength, and rigidity, but if it is too high, the pulverability deteriorates and it becomes difficult to obtain powder of the target particle size.

[0104] The flow start temperature, also called the flow temperature or fluid temperature, is measured using a capillary rheometer at 9.8 MPa (100 kg / cm²). 2This temperature, when liquid crystal polyester is melted under a load and heated at a rate of 4°C / min, and extruded from a nozzle with an inner diameter of 1 mm and a length of 10 mm, exhibits a viscosity of 4800 Pa·s (48000 poise), and serves as an indicator of the molecular weight of the liquid crystal polyester (see Naoyuki Koide (ed.), "Liquid Crystal Polymers - Synthesis, Molding, and Applications," CMC Corporation, June 5, 1987, p. 95).

[0105] <medium> The liquid composition of the embodiment includes a medium. The "medium" included in the liquid composition of the embodiment refers to a substance that is in a liquid state at 1 atm and 25°C. In this specification, a composition in which the medium is in a liquid state is referred to as a "liquid composition". The medium is preferably a volatile component that is a substance that can be volatile during the film formation of a liquid crystal polyester film.

[0106] The medium is preferably a dispersion medium in which the liquid crystal polyester powder is insoluble and which disperses the liquid crystal polyester powder. In the embodiment, the liquid composition is preferably a dispersion in which the liquid crystal polyester powder is insoluble in the medium and dispersed in the liquid medium.

[0107] Here, "dispersion" refers to a state in which the liquid crystal polyester powder is suspended or floating in the dispersion medium, and is a term used to distinguish it from a state in which the liquid crystal polyester powder is dissolved (excluding the state in which the liquid crystal polyester powder is completely dissolved in the liquid composition). There may be non-uniform areas in the distribution of the liquid crystal polyester powder in the composition. The state of the liquid crystal polyester powder in the composition is sufficient to allow the liquid composition to be applied to the support in the liquid crystal polyester film manufacturing method described later.

[0108] Examples of media include aliphatic polyhydric alcohols such as glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butanediol, hexylene glycol, polyethylene glycol, and polypropylene glycol; halogenated hydrocarbons such as dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, 1-chlorobutane, chlorobenzene, and o-dichlorobenzene; halogenated phenols such as p-chlorophenol, pentachlorophenol, and pentafluorophenol; ethers such as diethyl ether, di-(2-chloroethyl) ether, tetrahydrofuran, and 1,4-dioxane; and Examples include ketones such as cetone, cyclohexanone, and isophorone; esters such as ethyl acetate, butyl lactate, and γ-butyrolactone; carbonates such as ethylene carbonate and propylene carbonate; amines such as triethylamine; nitrogen-containing heterocyclic aromatic compounds such as pyridine; nitriles such as acetonitrile and succinonitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, and urea compounds such as tetramethylurea; nitro compounds such as nitromethane and nitrobenzene; sulfur compounds such as dimethyl sulfoxide and sulfolane; and phosphorus compounds such as hexamethylphosphate and tri-n-butyl phosphate. Two or more of these may be used.

[0109] The liquid composition of the embodiment includes a medium with a specific gravity of 0.90 or higher as a medium with excellent dispersibility for liquid crystal polyester powder. In this specification, the "specific gravity" of a medium refers to the measurement taken using water as the reference substance in accordance with JIS Z 8804:2012 (hydrometer). Here, specific gravity is defined as the density of the sample liquid divided by the density of water at a pressure of 101325 Pa (1 atmosphere). The liquid composition of the embodiment contains a medium with a specific gravity of 0.90 or higher, preferably a medium with a specific gravity of 0.95 or higher, more preferably a medium with a specific gravity of 1.03 or higher, even more preferably a medium with a specific gravity of 1.1 or higher, and particularly preferably a medium with a specific gravity of 1.3 or higher. When the specific gravity of the medium is above the above lower limit, the dispersibility of the liquid crystal polyester powder is excellent. The upper limit of the specific gravity mentioned above may be, for example, 1.84 or less. The liquid composition of the embodiment may contain a medium with a specific gravity of 1.84 or less, a medium with a specific gravity of 1.68 or less, a medium with a specific gravity of 1.58 or less, or a medium with a specific gravity of 1.48 or less. If the specific gravity of the medium is below the upper limit mentioned above, it prevents the liquid crystal polyester powder from floating on the surface of the medium, which would make dispersion difficult. The upper and lower limits of the specific gravity values ​​of the above-mentioned media can be freely combined. As an example of the numerical range of the specific gravity values ​​of the above-mentioned media, the liquid composition of the embodiment may contain media with a specific gravity of 0.90 or more and 1.84 or less, media with a specific gravity of 0.95 or more and 1.68 or less, media with a specific gravity of 1.03 or more and 1.58 or less, and media with a specific gravity of 1.1 or more and 1.48 or less.

[0110] As described above, the improvement in the dispersibility of liquid crystal polyester powder is largely due to the specific gravity of the medium, but in addition, the affinity at the interface between the liquid crystal polyester and the medium (the property of easily achieving a uniform mixed state) is also a favorable factor. As shown in the examples described later, the inventors found that propylene glycol, ethylene glycol, butanediol, N-methyl-2-pyrrolidone, butyl lactate, di-(2-chloroethyl) ether, dichloromethane, sulfolane, cyclohexanone, and isophorone are media that exhibit excellent affinity with liquid crystal polyester powder. This finding does not necessarily match the trend in solubility parameters, and the media exhibiting excellent affinity with liquid crystal polyester powder were difficult to predict. That is, the liquid composition of the embodiment preferably contains at least one medium selected from the group consisting of propylene glycol, ethylene glycol, butanediol, N-methyl-2-pyrrolidone, butyl lactate, di-(2-chloroethyl) ether, dichloromethane, sulfolane, cyclohexanone, and isophorone. The specific gravity of these mediums is 0.90 or higher. A medium that has excellent affinity for liquid crystal polyester powder exhibits excellent dispersibility of the liquid crystal polyester powder.

[0111] The liquid composition of the embodiment comprises at least one copolymer selected from the group consisting of 1) to 34) listed above as specific examples of preferred liquid crystal polyesters, Preferably, the medium includes at least one medium selected from the group consisting of propylene glycol, ethylene glycol, butanediol, N-methyl-2-pyrrolidone, butyl lactate, di-(2-chloroethyl) ether, dichloromethane, sulfolane, cyclohexanone, and isophorone.

[0112] From the viewpoint of having excellent dispersibility for liquid crystal polyester and also having excellent effect in suppressing the sedimentation of liquid crystal polyester powder, the liquid composition of the embodiment preferably contains at least one medium selected from the group consisting of propylene glycol, ethylene glycol, butanediol, N-methyl-2-pyrrolidone, butyl lactate, di-(2-chloroethyl) ether, dichloromethane, and sulfolane, among the media exemplified above.

[0113] From the viewpoint of having excellent dispersibility of liquid crystal polyester and being more effective in suppressing the sedimentation of liquid crystal polyester powder, the liquid composition of the embodiment preferably contains at least one medium selected from the group consisting of propylene glycol, ethylene glycol, butanediol, dichloromethane, and sulfolane among the media exemplified above.

[0114] From the viewpoint of having excellent dispersibility for liquid crystal polyester and a superior effect in suppressing sedimentation of liquid crystal polyester powder, it is preferable that the viscosity of the medium measured at 20-25°C is 10 mPa·s or higher. Examples of the medium that satisfy this requirement include propylene glycol, ethylene glycol, butanediol, and sulfolane.

[0115] Similarly, the liquid composition of the embodiment preferably contains a medium with a viscosity of 10 mPa·s to 200 mPa·s as measured at 20 to 25°C, more preferably a medium with a viscosity of 10 mPa·s to 150 mPa·s, even more preferably a medium with a viscosity of 12 mPa·s to 100 mPa·s, and even more preferably a medium with a viscosity of 15 mPa·s to 80 mPa·s.

[0116] The viscosity of the medium shall be measured at 20-25°C in accordance with the method specified in JIS Z 8803.

[0117] As a medium, a medium mainly composed of a compound with a boiling point of 220°C or less at 1 atmosphere is preferred because it is easy to remove during film formation. The proportion of the compound with a boiling point of 220°C or less at 1 atmosphere in the total medium is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 90 to 100% by mass.

[0118] In the embodiment, the liquid composition preferably has a specific gravity difference of 0.48 or less between the specific gravity of the liquid crystal polyester powder measured according to JIS K 7112 (Method A) and the specific gravity of the medium water measured according to JIS Z 8804. A smaller specific gravity difference between the liquid crystal polyester powder and the medium tends to improve the dispersibility of the liquid crystal polyester. The above specific gravity difference is preferably 0.48 or less, preferably 0.46 or less, more preferably 0.4 or less, even more preferably 0.36 or less, and particularly preferably 0.15 or less.

[0119] For measurement of liquid crystal polyester powder according to JIS K 7112 (Method A), the sample used shall be liquid crystal polyester powder molded as described below. The liquid crystal polyester powder to be measured for specific gravity (however, the particle size of the powder may differ from that of the liquid composition as long as the specific gravity can be measured) is subjected to heat treatment by heating under a nitrogen atmosphere. The heat treatment temperature is set to 260-300°C, the temperature at which solid-phase polymerization of the liquid crystal polyester occurs, in order to improve the moldability for preparing the measurement sample. Next, using a twin-screw extruder (e.g., PCM-30 manufactured by Ikegai Iron Works Co., Ltd.), melt kneading is performed at a die head temperature of 300-345°C and a screw rotation speed of 150 rpm to obtain liquid crystal polyester pellets. Subsequently, using an injection molding machine (e.g., PNX40 manufactured by Nissei Plastic Industrial Co., Ltd.), injection molding is performed at a cylinder temperature of 310-350°C and a mold temperature of 130°C to form a plate shape of 64 mm × 64 mm × 3 mm, which is used as the measurement sample.

[0120] Note that the specific gravity of either the liquid crystal polyester powder or the medium may be greater. The specific gravity difference may be either "specific gravity of liquid crystal polyester powder - specific gravity of medium (where the specific gravity of liquid crystal polyester powder ≥ specific gravity of medium)" or "specific gravity of medium - specific gravity of liquid crystal polyester powder (where the specific gravity of medium ≥ specific gravity of liquid crystal polyester powder)". From the viewpoint of ease of preparation of the liquid composition, it is preferable that the specific gravity of the liquid crystal polyester powder is greater than that of the medium. When the specific gravity of the liquid crystal polyester powder is greater than that of the medium, it prevents the liquid crystal polyester powder from floating on the surface of the medium and becoming difficult to disperse.

[0121] The specific gravity of the liquid crystal polyester powder according to the embodiment, as measured by JIS K 7112 (Method A), can be exemplified as being between 1.35 and 1.40.

[0122] The ratio of the media content to the total mass of the liquid composition in the embodiment is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and even more preferably 70 to 90% by mass.

[0123] The proportion of the medium in the embodiment that satisfies the above-described requirements for specific gravity, specific gravity difference, and viscosity, relative to the total mass of the medium contained in the liquid composition of the embodiment, is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 90 to 100% by mass.

[0124] The proportion of at least one medium selected from the group consisting of propylene glycol, ethylene glycol, butanediol, N-methyl-2-pyrrolidone, butyl lactate, di-(2-chloroethyl) ether, dichloromethane, sulfolane, cyclohexanone, and isophorone, relative to the total mass of the medium contained in the liquid composition of the embodiment, is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 90 to 100% by mass.

[0125] The liquid composition of the embodiment may contain liquid components other than the medium. The proportion of the medium according to the embodiment that satisfies the above-described requirements such as specific gravity, specific gravity difference, and viscosity, relative to the total mass of the liquid components, is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass.

[0126] The ratio of liquid crystal polyester powder to the total amount of solids contained in the liquid composition may, for example, be 50 to 100% by mass, 70 to 100% by mass, or 90 to 100% by mass. The "solid content" in the liquid composition of the embodiment refers to non-volatile components excluding substances that can volatilize during the formation of liquid crystal polyester films, etc.

[0127] The proportion of liquid crystal polyester powder contained in the liquid composition is preferably 0.1 to 60 parts by mass, more preferably 1 to 50 parts by mass, even more preferably 3 to 40 parts by mass, and particularly preferably 5 to 30 parts by mass, based on 100 parts by mass of the total amount of liquid crystal polyester powder and medium.

[0128] The liquid composition may contain one or more other components, such as fillers, additives, and resins other than liquid crystal polyester.

[0129] However, it is preferable that the liquid composition does not contain a thickening agent. In this specification, "thickening agent" refers to a substance that, when added to a liquid composition, increases the viscosity of the medium. The medium is not included in the thickening agent. Furthermore, it is preferable that the liquid composition does not contain an emulsifier.

[0130] Examples of fillers include inorganic fillers such as silica, alumina, titanium oxide, barium titanate, strontium titanate, aluminum hydroxide, and calcium carbonate; and organic fillers such as cured epoxy resin, crosslinked benzoguanamine resin, and crosslinked acrylic resin. The content of these fillers may be 0 parts by mass or less, and is preferably 100 parts by mass or less, per 100 parts by mass of liquid crystal polyester.

[0131] Examples of additives include leveling agents, defoaming agents, antioxidants, ultraviolet absorbers, flame retardants, and colorants. The amount of these additives may be 0, and preferably 5 parts by mass or less, per 100 parts by mass of liquid crystal polyester.

[0132] Examples of resins other than liquid crystal polyester include thermoplastic resins other than liquid crystal polyester such as polypropylene, polyamide, polyesters other than liquid crystal polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether and its modified products, and polyetherimide; elastomers such as copolymers of glycidyl methacrylate and polyethylene; and thermosetting resins such as phenolic resins, epoxy resins, polyimide resins, and cyanate resins. The content of these resins may be 0, and preferably 20 parts by mass or less, per 100 parts by mass of liquid crystal polyester.

[0133] The liquid composition of the embodiment may contain more than 70% by mass and 100% by mass or 80 to 100% by mass of the liquid crystal polyester of the embodiment, based on 100% by mass of the total amount of liquid crystal polyesters contained. The liquid crystal polyester may be those exemplified in the liquid crystal polyester powder of the embodiment, and may be liquid crystal polyesters that do not fall under component (X) below, among the liquid crystal polyesters described in the (liquid crystal polyester) section of the embodiment above, for example, those having a structural unit represented by formula (1), or liquid crystal polyesters having a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3). At least one copolymer selected from the group consisting of 1) to 34) listed as specific examples of the preferred liquid crystal polyester can also be exemplified.

[0134] The liquid composition of the embodiment may contain a medium and liquid crystal polyester powder (provided that the content of liquid crystal polyester soluble in the medium is less than 5% by mass, relative to 100% by mass of the total liquid crystal polyester).

[0135] The liquid composition of the embodiment may contain a medium and liquid crystal polyester powder (except for those containing liquid crystal polyester soluble in the medium).

[0136] The liquid composition of the embodiment may contain a medium and liquid crystal polyester powder (provided that the content of liquid crystal polyester soluble in an aprotic solvent (medium) is less than 5% by mass, relative to 100% by mass of the total liquid crystal polyester).

[0137] The liquid composition of the embodiment may contain a medium and liquid crystal polyester powder (however, if the resin powder contains liquid crystal polyester powder, it may not contain liquid crystal polyester that is soluble in an aprotic solvent (medium)).

[0138] The liquid crystal polyester soluble in aprotic solvents may be a liquid crystal polyester containing structural units derived from acetaminophen. The liquid crystal polyester soluble in aprotic solvents may be a liquid crystal polyester composed of structural units derived from 6-hydroxy-2-naphthoic acid, structural units derived from acetaminophen, and structural units derived from isophthalic acid. The liquid crystal polyester soluble in aprotic solvent may be a polymer obtained by reacting a mixture of 6-hydroxy-2-naphthoic acid (5.0 mol), acetaminophen (2.5 mol), isophthalic acid (2.5 mol), and acetic anhydride (8.4 mol).

[0139] The following describes liquid crystal polyesters that are soluble in aprotic solvents.

[0140] ≪(X) component≫ Component (X) is a liquid crystalline polyester soluble in aprotic solvents. Here, "soluble in aprotic solvents" can be confirmed by performing the following test.

[0141] • Test method The liquid crystalline polyester is stirred in an aprotic solvent at a temperature of 120°C to 180°C for 1 to 6 hours, and then cooled to room temperature (23°C). Next, it is filtered using a 5 μm membrane filter and a pressurized filter, and the residue on the membrane filter is checked. If no solid material is found, it is determined to be soluble in the aprotic solvent. More specifically, 1 part by mass of liquid crystalline polyester is stirred in 99 parts by mass of an aprotic solvent at 140°C for 4 hours, and then cooled to 23°C. Next, the mixture is filtered using a 5 μm membrane filter and a pressurized filter, and the residue on the membrane filter is checked. If no solid material is found at this stage, the mixture is considered soluble in the aprotic solvent.

[0142] The liquid crystalline polyester (X) preferably contains structural units represented by the following formulas (X1), (X2), and (X3).

[0143] As one aspect, the content of the structural unit represented by formula (X1) is 30-80 mol% of the total content of all structural units constituting component (X), the content of the structural unit represented by formula (X2) is 35-10 mol%, and the content of the structural unit represented by formula (X3) is 35-10 mol%. However, the total content of the structural units represented by formula (X1), formula (X2), and formula (X3) shall not exceed 100 mol%. (X1) -O-Ar1'-CO- (X2) -CO-Ar2'-CO- (X3) ―X-Ar3'-Y- (In X1-X3, Ar1' represents a 1,4-phenylene group, a 2,6-naphthylene group, or a 4,4'-biphenylene group. Ar2' represents a 1,4-phenylene group, a 1,3-phenylene group, or a 2,6-naphthylene group. Ar3' represents a 1,4-phenylene group or a 1,3-phenylene group. X is -NH-, and Y is -O- or NH-.)

[0144] Structural unit (X1) is a structural unit derived from an aromatic hydroxycarboxylic acid, structural unit (X2) is a structural unit derived from an aromatic dicarboxylic acid, and structural unit (X3) is a structural unit derived from an aromatic diamine or an aromatic amine having a phenolic hydroxyl group. Component (X) may use esters or amide-forming derivatives of the above-mentioned structural units instead of the above-mentioned structural units.

[0145] In this embodiment, it is preferable that Ar1' is a 2,6-naphthylene group, Ar2' is a 1,3-phenylene group, Ar3' is a 1,4-phenylene group, and Y is -O-.

[0146] Examples of ester-forming derivatives of carboxylic acids include those in which the carboxyl group is a highly reactive derivative such as an acid chloride or acid anhydride that promotes the reaction of producing polyester, and those in which the carboxyl group forms esters with alcohols or ethylene glycol, etc., that produce polyester through transesterification reactions. Examples of ester-forming derivatives of phenolic hydroxyl groups include those in which the phenolic hydroxyl group forms an ester with carboxylic acids. Examples of amide-forming derivatives of amino groups include those in which the amino group forms an amide with carboxylic acids.

[0147] Examples of structural units of component (X) used in this embodiment include, but are not limited to, the following.

[0148] Examples of structural units represented by formula (X1) include those derived from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, or 4'-hydroxy-4-biphenylcarboxylic acid, and two or more of these structural units may be included in the total structural units. Among these structural units, it is preferable to use component (X) which contains a structural unit derived from 6-hydroxy-2-naphthoic acid. The content of structural unit (X1) is 30 mol% to 80 mol%, preferably 40 mol% to 70 mol%, and more preferably 45 mol% to 65 mol%, relative to the total content of structural units constituting component (X). A high concentration of structural units (X1) tends to significantly reduce solubility in the solvent, while too little tends to result in a lack of liquid crystalline properties. In other words, when the content of structural units (X1) is within the above range, solubility in the solvent is good, and liquid crystalline properties are easily observed.

[0149] Examples of structural units represented by formula (X2) include structural units derived from terephthalic acid, isophthalic acid, or 2,6-naphthalenedicarboxylic acid, and two or more of these structural units may be included in the total number of structural units. Among these structural units, it is preferable to use a liquid crystalline polyester containing structural units derived from isophthalic acid from the viewpoint of solubility in solvents. The content of structural unit (X2) is preferably 10 mol% to 35 mol%, more preferably 15 mol% to 30 mol%, and particularly preferably 17.5 mol% to 27.5 mol%, relative to the total content of structural units constituting component (X). Too much structural unit (X2) tends to reduce liquid crystalline properties, while too little tends to reduce solubility in the solvent. In other words, when the content of structural unit (X2) is within the above range, both liquid crystalline properties and solubility in the solvent are good.

[0150] Examples of structural units represented by formula (X3) include structural units derived from 3-aminophenol, 4-aminophenol, 1,4-phenylenediamine, or 1,3-phenylenediamine, and two or more of these structural units may be included in the total number of structural units. Among these structural units, it is preferable to use a liquid crystalline polyester containing structural units derived from 4-aminophenol from the viewpoint of reactivity.

[0151] The content of structural unit (X3) is preferably 10 mol% to 35 mol%, more preferably 15 mol% to 30 mol%, and particularly preferably 17.5 mol% to 27.5 mol%, relative to the total content of structural units constituting component (X). Too much structural unit (3) tends to reduce liquid crystalline properties, while too little tends to reduce solubility in the solvent. In other words, when the content of structural unit (X3) is within the above range, both liquid crystalline properties and solubility in the solvent are good.

[0152] It is preferable that structural unit (X3) is used in substantially equal amounts to structural unit (X2), but the degree of polymerization of the liquid crystalline polyester can also be controlled by setting the content of structural unit (X3) to -10 to +10 mol% relative to the content of structural unit (X2).

[0153] Liquid crystal polyester can be manufactured using, for example, batch processing equipment, continuous processing equipment, etc. When the liquid crystalline polyester (X) is in powder form, it is preferable that the volume-average particle size is 100 to 2000 μm. The volume-average particle size of the powdered liquid crystalline polyester (X) can be measured by a dry sieving method (for example, RPS-105 manufactured by Seishin Corporation).

[0154] One aspect is that the content of component (X) is preferably 5 to 10% by mass relative to the total mass of the liquid crystalline polyester composition.

[0155] [Example of manufacturing liquid crystalline polyester (X)] In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser, 940.9 g (5.0 mol) of 6-hydroxy-2-naphthoic acid, 377.9 g (2.5 mol) of acetaminophen, 415.3 g (2.5 mol) of isophthalic acid, and 867.8 g (8.4 mol) of acetic anhydride were added. After replacing the gas in the reactor with nitrogen gas, the temperature was raised from room temperature (23°C) to 140°C over 60 minutes while stirring under a nitrogen gas stream, and then refluxed at 140°C for 3 hours. Next, while distilling off the by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 150°C to 300°C over 5 hours, and held at 300°C for 30 minutes. After that, the contents were removed from the reactor and cooled to room temperature (23°C). The resulting solid was pulverized to obtain powdered liquid crystalline polyester (X-1). The flow initiation temperature for this liquid crystalline polyester (X-1) may be 193.3°C.

[0156] Liquid crystalline polyester (X-1) can be solid-phase polymerized by raising its temperature from room temperature (23°C) to 160°C over 2 hours and 20 minutes under a nitrogen atmosphere, then raising its temperature from 160°C to 180°C over 3 hours and 20 minutes, and holding it at 180°C for 5 hours. After this, it is cooled to 23°C and then pulverized with a pulverizer to obtain powdered liquid crystalline polyester (X-2). The flow initiation temperature of this liquid crystalline polyester (X-2) may be 220°C.

[0157] Liquid crystalline polyester (X-2) is heated in a nitrogen atmosphere from room temperature to 180°C over 1 hour and 25 minutes, then heated from 180°C to 255°C over 6 hours and 40 minutes, and held at 255°C for 5 hours to undergo solid-phase polymerization. After cooling to 23°C, powdery liquid crystalline polyester (X) with a volume-average particle size of 871 μm can be obtained. The volume-average particle size of liquid crystalline polyester (X) is measured using an RPS-105 manufactured by Seishin Corporation. The flow initiation temperature of liquid crystalline polyester (X) may be 302°C.

[0158] A liquid crystalline polyester solution (X') can be prepared by adding 92 parts by mass of N-methylpyrrolidone (boiling point (1 atm) 204°C) to 8 parts by mass of liquid crystalline polyester (X) and stirring at 140°C for 4 hours under a nitrogen atmosphere. The viscosity of this liquid crystalline polyester solution (X') may be 955 mPa·s.

[0159] According to the liquid composition containing the liquid crystal polyester powder of the embodiment, it is possible to manufacture a liquid crystal polyester film having suitable quality for use as a film for electronic components. The quality criteria include the isotropy and thickness of the film.

[0160] According to the liquid composition containing the liquid crystal polyester powder of the embodiment, it is possible to manufacture a liquid crystal polyester film with excellent isotropy. Conventionally, liquid crystal polyester films are generally manufactured by melt molding or casting methods, which involve melting liquid crystal polyester. The melt molding method is a method of forming a film by extruding a mixture from an extruder. However, in films produced by the melt molding method, the liquid crystal polyester molecules tend to be oriented in the film formation direction (also called the extrusion direction, Machine Direction (MD)) rather than in the transverse direction relative to the extrusion direction (perpendicular to the extrusion direction and the thickness direction of the film, Transverse Direction (TD)), making it difficult to obtain a liquid crystal polyester film with excellent isotropy. The liquid crystal polyester powder according to this embodiment is suitable as a raw material for the liquid crystal polyester film manufacturing method described later. By applying this method, a liquid crystal polyester film with excellent isotropy can be easily manufactured without the need for the extrusion molding operation described above. Here, "excellent isotropy" of a liquid crystal polyester film means that the molecular orientation degree (MOR) of the liquid crystal polyester film is in the range of 1 to 1.3.

[0161] In the embodiment, if the liquid composition is a dispersion in which the liquid crystal polyester powder is insoluble in the medium and the liquid crystal polyester powder is dispersed in the liquid medium, it is possible to manufacture a liquid crystal polyester film that achieves both dielectric properties and isotropy. The solution casting method has a limitation: it requires the use of liquid crystal polyesters that are soluble in solvents. Liquid crystal polyesters with increased solubility in solvents may have reduced dielectric properties, for example, due to increased polarity. In contrast, the liquid composition containing the liquid crystal polyester powder of the embodiment does not require the dissolution of the liquid crystal polyester powder in a solvent, and it is possible to manufacture a liquid crystal polyester film that achieves both dielectric properties and isotropy.

[0162] <Method for producing a liquid composition> The liquid composition of the embodiment can be obtained by mixing the medium, liquid crystal polyester powder, and other components used as needed, either all at once or in an appropriate order.

[0163] Examples of the medium and liquid crystal polyester powder can be found in the section on "Liquid Compositions" above.

[0164] As one embodiment, a method for producing a liquid composition is provided, comprising the step of mixing liquid crystal polyester powder containing liquid crystal polyester and having an average particle size of 30 μm or less with a medium, wherein the specific gravity of the medium, measured in accordance with JIS Z 8804 with water as the reference substance, is 0.90 or higher.

[0165] ≪Method for manufacturing liquid crystal polyester film≫ The method for manufacturing a liquid crystal polyester film according to the embodiment includes applying a liquid composition according to the embodiment onto a support and heat-treating it to obtain a liquid crystal polyester film containing liquid crystal polyester.

[0166] Examples of liquid compositions include those described in the section above titled "Liquid Compositions."

[0167] The manufacturing method may include the following steps: A step (coating step) in which a liquid composition according to the embodiment is applied to a support to form a precursor of a liquid crystal polyester film on the support. A step of obtaining a liquid crystal polyester film by heat-treating the precursor of the liquid crystal polyester film (heat treatment step).

[0168] In the method for manufacturing a liquid crystal polyester film, the coating step may include a step of coating a liquid composition according to the embodiment onto a support, and then removing the medium from the coated liquid composition (drying step). In other words, the method for manufacturing the liquid crystal polyester film of the embodiment may include applying the liquid composition according to the embodiment onto a support, removing the medium from the applied liquid composition, and heat-treating it to obtain a liquid crystal polyester film containing liquid crystal polyester.

[0169] Furthermore, the method for manufacturing a liquid crystal polyester film may also include a step of separating the support from the laminate in which the support and the liquid crystal polyester film are laminated (separation step). However, since the liquid crystal polyester film can be suitably used as a film for electronic components even when formed on the support as a laminate, the separation step is not an essential step in the manufacturing process of the liquid crystal polyester film.

[0170] An example of a method for manufacturing a liquid crystal polyester film according to an embodiment will be described below with reference to the drawings.

[0171] Figure 1 is a schematic diagram showing an example of the manufacturing process of a liquid crystal polyester film and laminate according to the embodiment. First, the liquid composition 30 is applied onto the support 12 (Figure 1(a) Application process). The liquid composition 30 contains liquid crystal polyester powder 1 and a medium 3. The liquid crystal polyester liquid composition can be applied to the support by methods such as roller coating, dip coating, spray coating, spinner coating, curtain coating, slot coating, and screen printing, and a method that allows for a smooth and uniform application on the support can be appropriately selected. In addition, to ensure a uniform distribution of the liquid crystal polyester powder, the liquid composition may be stirred before application.

[0172] The support 12 is preferably in the shape of a plate, sheet, or film, and examples include a glass plate, a resin film, or a metal foil. Among these, a resin film or a metal foil is preferred, and copper foil is particularly preferred because it has excellent heat resistance, is easy to apply the liquid composition to, and is easy to remove from the liquid crystal polyester film. Examples of resin films include polyimide (PI) films. Examples of commercially available products include Ube Industries, Ltd.'s "Yupirex S" and "Yupirex R", Toray DuPont Co., Ltd.'s "Kapton", and SKC Kolon PI's "IF30", "IF70", and "LV300". The thickness of the resin film is preferably 25 μm to 75 μm, more preferably 50 μm to 75 μm. The thickness of the metal foil is preferably 3 μm to 75 μm, more preferably 5 μm to 30 μm, and even more preferably 10 μm to 25 μm.

[0173] Next, the medium 3 is removed from the liquid composition 30 coated on the support 12 (Figure 1(b) drying step) to obtain the liquid crystal polyester film precursor 40 to be heat-treated. Note that the medium 3 does not need to be completely removed from the liquid composition; some of the medium contained in the liquid composition may be removed, or all of the medium may be removed. The proportion of the medium contained in the liquid crystal polyester film precursor 40 is preferably 50% by mass or less, more preferably 3% by mass or more and 12% by mass or less, and even more preferably 5% by mass or more and 10% by mass or less, based on the total mass of the liquid crystal polyester film precursor. By having a medium content in the liquid crystal polyester film precursor above the lower limit, the risk of a decrease in the thermal conductivity of the liquid crystal polyester film is reduced. Furthermore, by having a medium content in the liquid crystal polyester film precursor below the upper limit, the risk of a decrease in the appearance of the liquid crystal polyester film due to foaming during heat treatment is reduced.

[0174] The removal of the medium is preferably carried out by evaporation, and methods for this include heating, reduced pressure, and ventilation, which may be combined. The removal of the medium may be carried out in a continuous or single-wafer manner. From the viewpoint of productivity and operability, the removal of the medium is preferably carried out by continuous heating, and more preferably by continuous heating with ventilation. The removal temperature of the medium is preferably below the melting point of the liquid crystal polyester powder, for example, 40°C to 200°C, and preferably 60°C to 200°C. The time for removal of the medium is, for example, 0.2 hours to 12 hours, and preferably 0.5 hours to 8 hours.

[0175] The laminate precursor 22, which thus has the support 12 and the liquid crystal polyester film precursor 40, is heat-treated to obtain a laminate 20 having the support 12 and the liquid crystal polyester film 10 (a film formed by heat-treating the liquid crystal polyester film precursor 40) (Figure 1(c) Heat treatment step). At this time, a liquid crystal polyester film 10 formed on the support is obtained. Heat treatment may further advance the polymerization reaction (solid-phase polymerization) of the liquid crystal polyester contained in the liquid crystal polyester film precursor. Heat treatment conditions include, for example, raising the temperature from -50°C (the boiling point of the medium) to the heat treatment temperature, and then performing heat treatment at a temperature above the melting point of the liquid crystal polyester. During this heating process, the polymerization reaction of the liquid crystal polyester may proceed due to heating. However, by increasing the heating rate until the heat treatment temperature is reached, the increase in the molecular weight of the liquid crystal polyester in the liquid crystal polyester powder can be suppressed to some extent, resulting in better melting of the liquid crystal polyester powder and easy acquisition of high-quality films. The heating rate from the boiling point of the solvent, -50°C, to the heat treatment temperature is preferably 3°C / min or more, and more preferably 5°C / min or more. The heat treatment temperature is preferably above the melting point of the liquid crystal polyester, more preferably higher than the melting point of the liquid crystal polyester, and even more preferably 5°C or higher than the melting point of the liquid crystal polyester. The heat treatment temperature can be appropriately determined depending on the type of liquid crystal polyester, but as an example, 230°C to 400°C is preferred, 300°C to 380°C is more preferred, and 320°C to 350°C is even more preferred. By performing heat treatment at a temperature higher than the melting point of the liquid crystal polyester, the liquid crystal polyester powder melts well, and a high-quality liquid crystal polyester film can be formed. The melting of the liquid crystal polyester powder can be confirmed by the transparency of the liquid crystal polyester film precursor 40. The boiling point of the medium referred to here is the boiling point at the pressure during heating. Furthermore, if heating of the laminate precursor 22 is started below -50°C (the boiling point of the medium), the heating rate should be determined within the range from when it reaches -50°C (the boiling point of the medium) to when it reaches the heat treatment temperature. The time it takes to reach -50°C (the boiling point of the medium) is arbitrary. The time after reaching the heat treatment temperature should be considered as the heat treatment time. The heat treatment time may be, for example, 0.5 hours or more, 1 hour to 24 hours or less, or 3 hours to 12 hours or less.

[0176] The heat treatment, like the removal of the media, may be carried out in a continuous or single-wafer manner. However, from the standpoint of productivity and ease of operation, it is preferable to carry it out in a continuous manner, and it is even more preferable to carry it out in a continuous manner immediately following the removal of the media.

[0177] Next, the liquid crystal polyester film 10 can be obtained as a single-layer film by separating it from the laminate 20 having the support 12 and the liquid crystal polyester film 10 (Figure 1(d) Separation process). When a glass plate is used as the support 12, the liquid crystal polyester film 10 is preferably separated from the laminate 20 by peeling it off. When a resin film is used as the support 12, the separation is preferably done by peeling the resin film or the liquid crystal polyester film 10 off the laminate 20. When a metal foil is used as the support 12, the separation is preferably done by etching and removing the metal foil from the laminate 20. When a resin film, especially a polyimide film, is used as the support, the polyimide film or liquid crystal polyester film is easily peeled off from the laminate 20, and a liquid crystal polyester film with a good appearance can be obtained. When a metal foil is used as the support, the laminate 20 may be used as a metal-clad laminate for printed circuit boards without separating the liquid crystal polyester film from the laminate 20.

[0178] According to the method for manufacturing a liquid crystal polyester film of this embodiment, it is possible to manufacture a liquid crystal polyester film with excellent isotropy. Conventional melt molding methods produce thin films of liquid crystal polyester by forming molten liquid crystal polyester into a film. In contrast, the manufacturing method described in this embodiment differs significantly from conventional film manufacturing methods in that a thin layer of liquid crystal polyester powder is first placed on a support before being melted. In the method for manufacturing a liquid crystal polyester film or laminate of the embodiment, liquid crystal polyester powder is first thinly arranged on a support and then formed into a film. As a result, no physical forces that cause bias in molecular orientation, such as those used in extrusion molding, are applied, making it possible to manufacture a liquid crystal polyester film with excellent isotropy. Furthermore, if the number-average molecular weight of the liquid crystal polyester in the liquid crystal polyester powder is 10,000 or less, the liquid composition will have properties suitable for coating, and the melting state of the liquid crystal polyester film during heat treatment will be good, making it possible to manufacture a high-quality liquid crystal polyester film with excellent isotropy that is suitable for use as a film for electronic components. Furthermore, by using liquid crystal polyester powder with an average particle size of 30 μm or less as a raw material, it is possible to easily manufacture high-quality polyester films with a thinness suitable for use in electronic component films. Furthermore, since there is no restriction that the liquid composition must be soluble in the medium, a liquid crystal polyester with excellent dielectric properties can be used, and a liquid crystal polyester film with excellent dielectric properties and isotropy can be easily obtained.

[0179] ≪Method for manufacturing laminates≫ The method for manufacturing the laminate of the embodiment includes applying the liquid composition according to the embodiment onto a support, heat-treating it to form a liquid crystal polyester film containing liquid crystal polyester, thereby obtaining a laminate comprising the support and the liquid crystal polyester film.

[0180] The manufacturing method may include the following steps: A step (coating step) in which a liquid composition according to the embodiment is applied to a support to form a liquid crystal polyester film precursor on the support. A step of heat-treating the liquid crystal polyester film precursor to obtain a laminate comprising the support and the liquid crystal polyester film (heat treatment step).

[0181] Similar to the method for manufacturing the liquid crystal polyester film described above, the coating step in the method for manufacturing the laminate may include a step of coating the liquid composition according to the embodiment onto a support, and then removing the medium from the coated liquid composition (drying step). In other words, the method for manufacturing the laminate of the embodiment may include applying the liquid composition according to the embodiment onto a support, removing the medium from the applied liquid composition, and heat-treating it to form a liquid crystal polyester film containing liquid crystal polyester, thereby obtaining a laminate comprising the support and the liquid crystal polyester film.

[0182] Figure 1 is a schematic diagram showing an example of the manufacturing process of the liquid crystal polyester film and laminate according to the embodiment. The manufacturing method of the laminate illustrated in Figure 1 is the same as described in the above-mentioned "Method for Manufacturing Liquid Crystal Polyester Film," except that the separation step (Figure 1(d)) is not performed, so the explanation is omitted.

[0183] According to the manufacturing method of the embodiment, it is possible to manufacture a laminate having the liquid crystal polyester film of the embodiment.

[0184] ≪Liquid crystal polyester film≫ Figure 2 is a schematic diagram showing the configuration of the liquid crystal polyester film 11 of the embodiment.

[0185] The liquid crystal polyester film of the embodiment (hereinafter sometimes simply referred to as "film") contains liquid crystal polyester, has a relative permittivity of 3 or less at a frequency of 1 GHz, a dielectric loss tangent of 0.005 or less at a frequency of 1 GHz, and a molecular orientation (MOR) value measured by a microwave orientation meter in the range of 1 to 1.3. Films that meet the above specifications have suitable quality for use as films for electronic components. The quality criteria include the relative permittivity, dielectric loss tangent, and molecular orientation (isotropy of the film), as well as other factors such as thickness and appearance (presence or absence of holes or through-holes). For example, the relative permittivity and dielectric loss tangent values ​​of a film can be controlled by the type of liquid crystal polyester used. Also, for example, the degree of isotropy of a film can be controlled by the film manufacturing method.

[0186] The film of the embodiment has a relative permittivity of 3 or less at a frequency of 1 GHz, preferably 2.9 or less, more preferably 2.8 or less, even more preferably 2.7 or less, and particularly preferably 2.6 or less. The relative permittivity of the film may also be 2.3 or more, 2.4 or more, or 2.5 or more. Examples of the numerical range for the relative permittivity of the above film include 2.3 to 3, 2.4 to 2.9, 2.5 to 2.8, 2.5 to 2.7, and 2.5 to 2.6.

[0187] The film of the embodiment has a dielectric loss tangent of 0.005 or less at a frequency of 1 GHz, preferably 0.004 or less, more preferably 0.003 or less, even more preferably 0.002 or less, and particularly preferably 0.001 or less. The dielectric loss tangent of the liquid crystal polyester film may be 0.0003 or more, 0.0005 or more, or 0.0007 or more. An example of the numerical range for the dielectric loss tangent value of the above film is that it may be 0.0003 or more and 0.005 or less, 0.0005 or more and 0.004 or less, 0.0007 or more and 0.003 or less, 0.0007 or more and 0.002 or less, or 0.0007 or more and 0.001 or less. Furthermore, the relative permittivity and dielectric loss tangent of the film at a frequency of 1 GHz can be measured using the capacitance method with an impedance analyzer under the following conditions. A tablet with a diameter of 1 cm and a thickness of 0.5 cm is prepared by melting the film at 350°C using a flow tester and then cooling and solidifying it. The relative permittivity and dielectric loss tangent of the obtained tablet are measured at 1 GHz under the following conditions. ·Measurement method: Capacitive method ·Electrode model: 16453A • Measurement environment: 23℃, 50%RH • Applied voltage: 1V

[0188] The film of the embodiment has a molecular orientation degree (MOR) value measured by a microwave orientation meter that is in the range of 1 to 1.3, preferably in the range of 1 to 1.1, preferably in the range of 1 to 1.08, more preferably in the range of 1 to 1.06, and even more preferably in the range of 1 to 1.04.

[0189] The degree of molecular orientation (MOR) is measured using a microwave molecular orientometer (e.g., MOA-5012A, manufactured by Oji Instruments Co., Ltd.). A microwave molecular orientometer is a device that utilizes the fact that the transmission intensity of microwaves differs depending on the orientation of the molecules, with the transmission intensity differing in the direction perpendicular to the orientation. Specifically, while rotating the sample, microwaves with a constant frequency (12 GHz is used) are irradiated, and the intensity of the transmitted microwaves, which changes according to the molecular orientation, is measured. The ratio of the maximum value to the minimum value is defined as the MOR. The interaction between the microwave electric field with a constant frequency and the dipoles that make up the molecules is related to the dot product of their vectors. Due to the anisotropy of the dielectric constant of the sample, the microwave intensity changes depending on the angle at which the sample is positioned, making it possible to determine the degree of orientation.

[0190] The linear expansion coefficient of the film in the embodiment is preferably 85 ppm / °C or less, more preferably 50 ppm / °C or less, even more preferably 40 ppm / °C or less, and particularly preferably 30 ppm / °C or less, as determined in a temperature range of 50 to 100°C under a heating rate of 5°C / min. The lower limit of the linear expansion coefficient is not particularly limited, but for example, it is 0 ppm / °C or higher. Furthermore, for example, when copper foil and film are laminated, since the linear expansion coefficient of copper foil is 18 ppm / °C, it is preferable that the linear expansion coefficient of the film in the embodiment be close to that value. In other words, the linear expansion coefficient of the film in the embodiment is preferably 0 ppm / °C or more and 50 ppm / °C or less, more preferably 10 ppm / °C or more and 40 ppm / °C or less, and even more preferably 20 ppm / °C or more and 30 ppm / °C or less. If the linear expansion coefficient differs depending on the direction or part of the film, the higher value shall be adopted as the linear expansion coefficient of the film. The coefficient of linear expansion of the film can be measured using a thermomechanical analyzer (for example, Rigaku Corporation, model: TMA8310). Films of embodiments that satisfy the above numerical range have a low coefficient of linear expansion and high dimensional stability.

[0191] A film with excellent isotropy exhibits a small difference in the coefficient of linear expansion depending on the measurement direction. In the embodiment, the film preferably has a linear expansion coefficient of 2 ppm / °C or less, and more preferably 1 ppm / °C or less, where the difference between the linear expansion coefficient of MD and the linear expansion coefficient of TD (MD-TD if MD > TD, and TD-MD if TD > MD) is 2 ppm / °C or less. In a film manufactured by the casting method, MD refers to the coating direction of the dispersion. As shown in the calculation of the difference in linear expansion coefficients above, in practice, it is sufficient to know the linear expansion coefficients in different directions. Therefore, if the MD and TD of the film are unknown, the direction should be set such that the difference in linear expansion coefficients in each direction is maximized when any direction of the film is designated as MD and the direction intersecting it at 90° is designated as TD. The film of the embodiment that satisfies the above numerical range exhibits excellent isotropy in linear expansion and high dimensional stability in the longitudinal and transverse directions.

[0192] The film of the embodiment preferably has no holes or through-holes, as this gives it a suitable appearance for use as a film for electronic components. If it has holes or through-holes, there is a possibility that the plating solution may seep into the holes or through-holes during the plating process. The liquid crystal polyester film manufactured using the liquid crystal polyester powder according to the embodiment is of high quality, having a suitable thickness for use as a film for electronic components while suppressing the occurrence of holes or through-holes.

[0193] The thickness of the film in the embodiment is not particularly limited, but a suitable thickness for an electronic component film is preferably 5 to 50 μm, more preferably 7 to 40 μm, even more preferably 10 to 33 μm, and particularly preferably 15 to 20 μm. In this specification, "thickness" refers to the average value obtained by measuring the thickness at 10 randomly selected locations in accordance with the JIS standard (K7130-1992).

[0194] By selecting a raw material with excellent dielectric properties from among any liquid crystal polyester, a film with excellent dielectric properties can be obtained. The liquid crystal polyester content relative to 100% of the total mass of the film in the embodiment may be 50 to 100% by mass, or 80 to 95% by mass.

[0195] The liquid crystal polyester of the embodiment may be contained in an amount of 70% to 100% by mass, or 80 to 100% by mass, relative to 100% by mass of the total amount of liquid crystal polyester contained in the film of the embodiment. The liquid crystal polyester is exemplified by the liquid crystal polyester powder of the embodiment described above, and is, for example, a liquid crystal polyester having a structural unit represented by formula (1), a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3). At least one copolymer selected from the group consisting of 1) to 34) listed above as specific examples of preferred liquid crystal polyester can also be exemplified.

[0196] The film of the embodiment may be a film containing liquid crystal polyester, having a relative permittivity of 3 or less at a frequency of 1 GHz, a dielectric loss tangent of 0.005 or less at a frequency of 1 GHz, and a molecular orientation (MOR) value measured by a microwave orientation meter in the range of 1 to 1.3 (provided that the content of liquid crystal polyester soluble in aprotic solvent is less than 5% by mass with respect to 100% by mass of the total liquid crystal polyester).

[0197] The film of the embodiment may be a film containing liquid crystal polyester, having a relative permittivity of 3 or less at a frequency of 1 GHz, a dielectric loss tangent of 0.005 or less at a frequency of 1 GHz, and a molecular orientation (MOR) value measured by a microwave orientation meter in the range of 1 to 1.3 (provided that the content of liquid crystal polyester soluble in the medium relating to the liquid composition of the embodiment is less than 5% by mass, relative to 100% by mass of the total amount of liquid crystal polyester).

[0198] The film of the embodiment may be a film containing liquid crystal polyester, having a relative permittivity of 3 or less at a frequency of 1 GHz, a dielectric loss tangent of 0.005 or less at a frequency of 1 GHz, and a molecular orientation (MOR) value measured by a microwave orientation meter in the range of 1 to 1.3 (excluding films containing liquid crystal polyester soluble in aprotic solvents).

[0199] The film of the embodiment may be a film containing liquid crystal polyester, having a relative permittivity of 3 or less at a frequency of 1 GHz, a dielectric loss tangent of 0.005 or less at a frequency of 1 GHz, and a molecular orientation (MOR) value measured by a microwave orientation meter in the range of 1 to 1.3 (excluding films containing liquid crystal polyester soluble in the medium relating to the liquid composition of the embodiment).

[0200] Here, examples of liquid crystal polyesters soluble in aprotic solvents and media include the liquid crystal polyester powders according to the embodiment.

[0201] The method for manufacturing the film of the embodiment is not particularly limited, but the film of the embodiment can be manufactured by the method described above in "Method for Manufacturing Crystalline Polyester Film".

[0202] The film of this embodiment can be suitably used as a film for electronic components such as printed circuit boards. The film of this embodiment can be provided as a substrate (e.g., a flexible substrate), a laminate (e.g., a flexible copper-clad laminate), a printed circuit board, a printed wiring board, a printed circuit board, etc., which incorporate the film as an insulating material.

[0203] ≪Laminated structure≫ The laminate of the embodiment comprises a metal layer and a film according to the embodiment laminated on the metal layer. Figure 3 is a schematic diagram showing the configuration of a laminate 21 according to one embodiment of the present invention. The laminate 21 comprises a metal layer 13 and a film 11 laminated on the metal layer 13. The films incorporated into the laminate are exemplified above, and their explanation will be omitted. The metal layer of the laminate can be exemplified as a support in the above-mentioned "Method for Manufacturing Liquid Crystal Polyester Film" and "Method for Manufacturing a Laminate," with metal foil being preferred. Copper is preferred as the metal constituting the metal layer from the viewpoint of conductivity and cost, and copper foil is preferred as the metal foil.

[0204] The thickness of the laminate in the embodiment is not particularly limited, but is preferably 5 to 130 μm, more preferably 10 to 70 μm, and even more preferably 15 to 60 μm.

[0205] The method for manufacturing the laminate of the embodiment is not particularly limited, but the laminate of the embodiment can be manufactured by the above-described "Method for Manufacturing Laminate".

[0206] The laminate of this embodiment can be suitably used as a film for electronic components such as printed circuit boards. [Examples]

[0207] Next, examples will be shown to explain the present invention in more detail. However, the present invention is not limited to the following examples.

[0208] ≪Liquid Crystal Polyester Fine Particle Powder≫ <Measurement Method> [Measurement of the Flow Initiation Temperature of Liquid Crystal Polyester] Using a flow tester ("CFT-500 type" manufactured by Shimadzu Corporation), approximately 2 g of liquid crystal polyester was filled into a cylinder equipped with a die having a nozzle with an inner diameter of 1 mm and a length of 10 mm. Under a load of 9.8 MPa (100 kg / cm 2 ), while raising the temperature at a rate of 4 °C / min, the liquid crystal polyester was melted, extruded from the nozzle, and the temperature (FT) at which a viscosity of 4800 Pa·s (48000 P) was exhibited was measured.

[0209] [Measurement of the Melting Point of Liquid Crystal Polyester] Using a differential scanning calorimeter ("DSC-50" manufactured by Shimadzu Corporation), the temperature was raised at a rate of 10 °C / min, the position of the endothermic peak was confirmed, and the temperature at the peak position of the endothermic peak was measured as the melting point of the liquid crystal polyester.

[0210] [Measurement of the Particle Size of Liquid Crystal Polyester Fine Particle Powder] Weighed 0.01 g of liquid crystal polyester fine particle powder and dispersed it in approximately 10 g of pure water. The prepared dispersion of liquid crystal polyester fine particle powder was dispersed by ultrasonic waves for 5 minutes. Using a laser diffraction / scattering particle size distribution measuring device ("LA-950V2" manufactured by HORIBA, Ltd.), assuming the refractive index of pure water is 1.333, the volume-based cumulative particle size distribution of the liquid crystal polyester fine particle powder was measured, and the particle size (μm) at which the cumulative volume ratio from the small particle side is 10% was D 10 , the particle size (μm) at which it is 50% was the average particle size (D 50 ), and the particle size (μm) at which it is 90% was D 90 and calculated as such.

[0211] [Measurement of the Specific Gravity of Liquid Crystal Polyester Fine Particle Powder] In accordance with the method specified in (Method A) of JIS K 7112, the specific gravity at a temperature of 23°C and a pressure of 1 atm was measured using water as the immersion liquid. The measurement samples were prepared by processing the liquid crystal polyester powders produced in the following production examples by the methods shown below.

[0212] <Measurement sample of the specific gravity of the powder of liquid crystal polyester (A)> The powder of liquid crystal polyester (A) obtained in the following production example was heated from room temperature to 215°C over 50 minutes in a nitrogen atmosphere, then heated from 215°C to 230°C over 1 hour, heated from 230°C to 295°C over 15 hours and 30 minutes, and after reaching 295°C, a heat treatment of heating at the same temperature for 6 hours was performed. As a result of measuring the flow start temperature of the heat-treated liquid crystal polyester (A), it was 322°C. Next, using a twin-screw extruder (manufactured by Ikegai Tekko Co., Ltd., PCM-30), melt-kneading was performed at a die head temperature of 335°C and a screw rotation speed of 150 rpm to granulate, and after obtaining pellets of the liquid crystal polyester, using an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., PNX40), injection molding was performed at a cylinder temperature of 340°C and a mold temperature of 130°C to form into a plate shape of 64 mm × 64 mm × 3 mm, and this was used as the measurement sample.

[0213] <Measurement sample of the specific gravity of the powder of liquid crystal polyester (B)> The powder of liquid crystal polyester (B) obtained in the following production example was heated from room temperature to 230°C over 1 hour in a nitrogen atmosphere, then heated from 230°C to 240°C over 10 minutes, heated from 240°C to 287°C over 6 hours, and after reaching 287°C, a heat treatment of heating at the same temperature for 5 hours was performed. As a result of measuring the flow start temperature of the heat-treated liquid crystal polyester (B), it was 331°C. Next, using a twin-screw extruder (manufactured by Ikegai Tekko Co., Ltd., PCM-30), melt-kneading was performed at a die head temperature of 345°C and a screw rotation speed of 150 rpm to granulate, and after obtaining pellets of the liquid crystal polyester, using an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., PNX40), injection molding was performed at a cylinder temperature of 350°C and a mold temperature of 130°C to form into a plate shape of 64 mm × 64 mm × 3 mm, and this was used as the measurement sample.

[0214] <Measurement sample of specific gravity of liquid crystal polyester (C) powder> The liquid crystal polyester (C) powder obtained in the manufacturing example below was subjected to a heat treatment under a nitrogen atmosphere, where it was heated from room temperature to 215°C over 49 minutes, then from 215°C to 225°C over 8 minutes, then from 225°C to 260°C over 2 hours and 55 minutes, and after reaching 260°C, it was heated at the same temperature for 5 hours. The flow initiation temperature of the resulting heat-treated liquid crystal polyester (C) was measured to be 302°C. Next, using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.), the liquid crystal polyester was melt-kneaded and granulated at a die head temperature of 300°C and a screw rotation speed of 150 rpm to obtain liquid crystal polyester pellets. These pellets were then injection-molded using an injection molding machine (PNX40, manufactured by Nissei Plastic Industrial Co., Ltd.) at a cylinder temperature of 320°C and a mold temperature of 130°C to form a 64mm x 64mm x 3mm plate, which was used as the measurement sample.

[0215] <Measurement sample of specific gravity of liquid crystal polyester (D) powder> The liquid crystal polyester (D) powder obtained in the manufacturing example below was subjected to a heat treatment under a nitrogen atmosphere, where it was heated from room temperature to 215°C over 49 minutes, then from 215°C to 225°C over 8 minutes, then from 225°C to 275°C over 4 hours and 10 minutes, and after reaching 275°C, it was heated at the same temperature for 5 hours. The flow initiation temperature of the resulting heat-treated liquid crystal polyester (D) was measured to be 304°C. Next, using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.), the liquid crystal polyester was melt-kneaded and granulated at a die head temperature of 300°C and a screw rotation speed of 150 rpm to obtain liquid crystal polyester pellets. These pellets were then injection-molded using an injection molding machine (PNX40, manufactured by Nissei Plastic Industrial Co., Ltd.) at a cylinder temperature of 320°C and a mold temperature of 130°C to form a 64mm x 64mm x 3mm plate, which was used as the measurement sample.

[0216] <Measurement sample of specific gravity of liquid crystal polyester (E) powder> The liquid crystal polyester (E) powder obtained in the manufacturing example below was subjected to a heat treatment under a nitrogen atmosphere, where it was heated from room temperature to 215°C over 49 minutes, then from 215°C to 225°C over 8 minutes, then from 225°C to 260°C over 2 hours and 55 minutes, and after reaching 260°C, it was heated at the same temperature for 5 hours. The flow initiation temperature of the resulting heat-treated liquid crystal polyester (E) was measured to be 304°C. Next, using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.), the liquid crystal polyester was melt-kneaded and granulated at a die head temperature of 300°C and a screw rotation speed of 150 rpm to obtain liquid crystal polyester pellets. These pellets were then injection-molded using an injection molding machine (PNX40, manufactured by Nissei Plastic Industrial Co., Ltd.) at a cylinder temperature of 320°C and a mold temperature of 130°C to form a 64mm x 64mm x 3mm plate, which was used as the measurement sample.

[0217] <Measurement sample of specific gravity of liquid crystal polyester (F) powder> The liquid crystal polyester (F) powder obtained in the manufacturing example below was subjected to a heat treatment under a nitrogen atmosphere, where it was heated from room temperature to 215°C over 49 minutes, then from 215°C to 225°C over 8 minutes, then from 225°C to 260°C over 2 hours and 55 minutes, and after reaching 260°C, it was heated at the same temperature for 5 hours. The flow initiation temperature of the resulting heat-treated liquid crystal polyester (F) was measured to be 298°C. Next, using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.), the liquid crystal polyester was melt-kneaded and granulated at a die head temperature of 300°C and a screw rotation speed of 150 rpm to obtain liquid crystal polyester pellets. These pellets were then injection-molded using an injection molding machine (PNX40, manufactured by Nissei Plastic Industrial Co., Ltd.) at a cylinder temperature of 310°C and a mold temperature of 130°C to form a 64mm x 64mm x 3mm plate, which was used as the measurement sample.

[0218] <Measurement sample of specific gravity of liquid crystal polyester (G) powder> The liquid crystal polyester (G) powder obtained in the manufacturing example below was subjected to a heat treatment under a nitrogen atmosphere, where it was heated from room temperature to 215°C over 49 minutes, then from 215°C to 225°C over 8 minutes, and from 225°C to 290°C over 5 hours and 25 minutes. After reaching 290°C, it was heated at the same temperature for 5 hours. The flow initiation temperature of the resulting heat-treated liquid crystal polyester (G) was measured and found to be 290°C. Next, using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.), the liquid crystal polyester was melt-kneaded and granulated at a die head temperature of 300°C and a screw rotation speed of 150 rpm to obtain liquid crystal polyester pellets. These pellets were then injection-molded using an injection molding machine (PNX40, manufactured by Nissei Plastic Industrial Co., Ltd.) at a cylinder temperature of 310°C and a mold temperature of 130°C to form a 64mm x 64mm x 3mm plate, which was used as the measurement sample.

[0219] <Measurement sample of specific gravity of liquid crystal polyester (H) powder> The liquid crystal polyester (H) powder obtained in the manufacturing example below was subjected to a heat treatment under a nitrogen atmosphere, where it was heated from room temperature to 215°C over 49 minutes, then from 215°C to 225°C over 8 minutes, and from 225°C to 290°C over 5 hours and 25 minutes. After reaching 290°C, it was heated at the same temperature for 5 hours. The flow initiation temperature of the resulting heat-treated liquid crystal polyester (H) was measured to be 297°C. Next, using a twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.), the liquid crystal polyester was melt-kneaded and granulated at a die head temperature of 300°C and a screw rotation speed of 150 rpm to obtain liquid crystal polyester pellets. These pellets were then injection-molded using an injection molding machine (PNX40, manufactured by Nissei Plastic Industrial Co., Ltd.) at a cylinder temperature of 310°C and a mold temperature of 130°C to form a 64mm x 64mm x 3mm plate, which was used as the measurement sample.

[0220] <Manufacturing of liquid crystal polyester fine particle powder> [Manufacturing Example 1] • Manufacturing of liquid crystal polyester (A) In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser, 1034.99 g (5.5 mol) of 2-hydroxy-6-naphthoic acid, 378.33 g (1.75 mol) of 2,6-naphthalenedicarboxylic acid, 83.07 g (0.5 mol) of terephthalic acid, 272.52 g (2.475 mol, 0.225 mol excess of the total molar amount of 2,6-naphthalenedicarboxylic acid and terephthalic acid), 1226.87 g (12 mol) of acetic anhydride, and 0.17 g of 1-methylimidazole as a catalyst were added. After replacing the gas in the reactor with nitrogen gas, the temperature was raised from room temperature to 145°C over 15 minutes while stirring under a nitrogen gas stream, and then refluxed at 145°C for 1 hour. Next, while distilling off the by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 145°C to 310°C over 3 hours and 30 minutes, and held at 310°C for 3 hours. After that, the contents of the reactor were removed in a molten state and cooled to obtain liquid crystal polyester (A). The flow initiation temperature of this liquid crystal polyester (A) was 268°C. This liquid crystal polyester (A) was pulverized using a cutter mill VM-16 manufactured by Orient Grinding Machinery Co., Ltd. to obtain liquid crystal polyester (A) powder with an average particle size of 394 μm.

[0221] • Manufacturing of liquid crystal polyester fine particle powder Next, using a jet mill (KJ-200 manufactured by Kurimoto Iron Works, with a grinding nozzle diameter of 4.5 mm), the liquid crystal polyester (A) powder was ground with a classification rotor rotation speed of 10,000 rpm, a grinding nozzle pressure of 0.64 MPa, and a processing speed of 2.1 kg / hour to obtain the liquid crystal polyester fine particle powder of Production Example 1. The average particle size (D) of this liquid crystal polyester fine particle powder was determined. 50 The particle size was 10 μm. Furthermore, the melting point of the liquid crystal polyester fine particle powder of Production Example 1 was measured using a differential scanning calorimetry analyzer and was found to be 290°C. The liquid crystal polyester fine particle powder of Production Example 1 corresponds to the liquid crystal polyester powder according to the embodiment of the present invention.

[0222] [Manufacturing Example 2] The above liquid crystal polyester (A) powder was not pulverized with a jet mill, but instead classified by sieving, with particles that did not pass through a sieve with a mesh size of 75 μm being separated to obtain the average particle size (D). 50 ) yielded a liquid crystal polyester fine particle powder with a size of 64 μm.

[0223] [Manufacturing Example 3] Manufacturing of liquid crystal polyester (B) A reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer and reflux condenser, 994.5g (7.2 mol) of parahydroxybenzoic acid, 4,4'-dihydroxybiphenate 446.9g (2.4 mol), terephthalic acid 299.0g (1.8 mol), isophthalic acid 99.7 g (0.6 mol) of acid and 1347.6 g (13.2 mol) of acetic anhydride were charged, and 0.20 g of 1-methylimidazole was added as a catalyst. After replacing the gas in the reactor with nitrogen gas, the temperature was raised from room temperature to 150°C over 30 minutes while stirring under a nitrogen gas stream, and then refluxed at 150°C for 1 hour. Next, while distilling off the by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 150°C to 320°C over 2 hours and 50 minutes. The reaction was considered complete when an increase in torque was observed, and liquid crystal polyester (B) was obtained. The flow initiation temperature of this liquid crystal polyester (B) was 250°C. This liquid crystal polyester (B) was pulverized using a cutter mill VM-16 manufactured by Orient Grinding Machinery Co., Ltd. to obtain liquid crystal polyester (B) powder with an average particle size of 492 μm.

[0224] • Manufacturing of liquid crystal polyester fine particle powder Next, using a jet mill (KJ-200 manufactured by Kurimoto Iron Works, with a grinding nozzle diameter of 4.5 mm), the liquid crystal polyester (B) powder was ground with a classification rotor rotation speed of 10,000 rpm, a grinding nozzle pressure of 0.64 MPa, and a processing speed of 2.1 kg / hour to obtain the liquid crystal polyester fine particle powder of Production Example 3. The average particle size (D) of this liquid crystal polyester fine particle powder was determined. 50) was 10 μm. Also, as a result of measuring the melting point of the liquid crystal polyester fine particle powder of Production Example 3 using a differential scanning calorimeter, it was 290°C. The liquid crystal polyester fine particle powder of Production Example 3 corresponds to the liquid crystal polyester powder according to the embodiment of the present invention.

[0225] [Production Example 4] ·Production of Liquid Crystal Polyester (C) Into a reactor equipped with a stirrer, a torque meter, a nitrogen gas introduction tube, a thermometer, and a reflux condenser, 182.3 g (1.3 mol) of p-hydroxybenzoic acid, 1759.5 g (9.4 mol) of 2-hydroxy-6-naphthoic acid, 54.8 g (0.3 mol) of isophthalic acid, and 1165.6 g (11.4 mol) of acetic anhydride were charged, and 0.06 g of 1-methylimidazole was added as a catalyst. After replacing the gas in the reactor with nitrogen gas, while stirring under a nitrogen gas stream, the temperature was raised from room temperature to 150°C over 30 minutes and refluxed at 150°C for 1 hour. Next, while distilling off the by-produced acetic acid and unreacted acetic anhydride, the temperature was raised from 150°C to 300°C over 3 hours and 30 minutes, and the point when an increase in torque was observed was regarded as the end of the reaction, and liquid crystal polyester (C) was obtained. The flow start temperature of this liquid crystal polyester (C) was 280°C. This liquid crystal polyester (C) was pulverized with a cutter mill VM-16 manufactured by Orient Milling Co., Ltd. to obtain a powder of liquid crystal polyester (C) having an average particle size of 450 μm.

[0226] ·Production of Liquid Crystal Polyester Fine Particle Powder Next, using a jet mill (``KJ-200'' manufactured by Kurimoto Iron Works, pulverization nozzle diameter: 4.5 mm), with the classification rotor rotation speed set at 10,000 rpm, the pulverization nozzle pressure at 0.64 MPa, and the processing speed at 2.1 kg / hour, the powder of liquid crystal polyester (C) was pulverized to obtain the liquid crystal polyester fine particle powder of Production Example 4. The average particle size (D 50The particle size was 9 μm. Furthermore, the melting point of the liquid crystal polyester fine particle powder of Production Example 4 was measured using a differential scanning calorimetry analyzer and was found to be 322°C. The liquid crystal polyester fine particle powder of Production Example 4 corresponds to the liquid crystal polyester powder according to the embodiment of the present invention.

[0227] [Manufacturing Example 5] • Manufacturing of liquid crystal polyester (D) In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser, 354.0 g (2.6 mol) of parahydroxybenzoic acid, 1573.2 g (8.4 mol) of 2-hydroxy-6-naphthoic acid, 12.8 g (0.1 mol) of isophthalic acid, and 1193.2 g (11.7 mol) of acetic anhydride were charged, along with 0.06 g of 1-methylimidazole as a catalyst. After replacing the gas in the reactor with nitrogen gas, the temperature was raised from room temperature to 150°C over 30 minutes while stirring under a nitrogen gas stream, and then refluxed at 150°C for 1 hour. Next, while distilling off the by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 150°C to 300°C over 3 hours and 30 minutes. The reaction was considered complete when an increase in torque was observed, and liquid crystal polyester (D) was obtained. The flow initiation temperature of this liquid crystal polyester (D) was 269.7°C. This liquid crystal polyester (D) was pulverized using a cutter mill VM-16 manufactured by Orient Grinding Machinery Co., Ltd. to obtain liquid crystal polyester (D) powder with an average particle size of 423 μm.

[0228] • Manufacturing of liquid crystal polyester fine particle powder Next, using a jet mill (KJ-200 manufactured by Kurimoto Iron Works, with a grinding nozzle diameter of 4.5 mm), the liquid crystal polyester (D) powder was ground at a classification rotor speed of 10,000 rpm, a grinding nozzle pressure of 0.64 MPa, and a processing speed of 2.1 kg / hour to obtain the liquid crystal polyester fine particle powder of Production Example 5. The average particle size (D) of this liquid crystal polyester fine particle powder was determined. 50The particle size was 10 μm. Furthermore, the melting point of the liquid crystal polyester fine particle powder of Production Example 5 was measured using a differential scanning calorimetry analyzer and was found to be 305°C. The liquid crystal polyester fine particle powder of Production Example 5 corresponds to the liquid crystal polyester powder according to the embodiment of the present invention.

[0229] [Manufacturing Example 6] • Manufacturing of liquid crystal polyester (E) In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser, 273.5 g (2.0 mol) of parahydroxybenzoic acid, 1676.7 g (8.9 mol) of 2-hydroxy-6-naphthoic acid, 20.5 g (0.1 mol) of 4,4'-dihydroxybiphenyl, and 1213.6 g (11.9 mol) of acetic anhydride were charged, along with 0.06 g of 1-methylimidazole as a catalyst. After replacing the gas in the reactor with nitrogen gas, the temperature was raised from room temperature to 150°C over 30 minutes while stirring under a nitrogen gas stream, and then refluxed at 150°C for 1 hour. Next, while distilling off the by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 150°C to 300°C over 3 hours and 30 minutes. The reaction was considered complete when an increase in torque was observed, yielding liquid crystal polyester (E). The flow initiation temperature of this liquid crystal polyester (E) was 266.4°C. This liquid crystal polyester (E) was pulverized using a cutter mill VM-16 manufactured by Orient Grinding Machinery Co., Ltd. to obtain liquid crystal polyester (E) powder with an average particle size of 526 μm.

[0230] • Manufacturing of liquid crystal polyester fine particle powder Next, using a jet mill (KJ-200 manufactured by Kurimoto Iron Works, with a grinding nozzle diameter of 4.5 mm), the liquid crystal polyester (E) powder was ground with a classification rotor rotation speed of 10,000 rpm, a grinding nozzle pressure of 0.64 MPa, and a processing speed of 2.1 kg / hour to obtain the liquid crystal polyester fine particle powder of Production Example 6. The average particle size (D) of this liquid crystal polyester fine particle powder was determined. 50The particle size was 10 μm. Furthermore, the melting point of the liquid crystal polyester fine particle powder of Production Example 6 was measured using a differential scanning calorimetry analyzer and was found to be 311°C. The liquid crystal polyester fine particle powder of Production Example 6 corresponds to the liquid crystal polyester powder according to the embodiment of the present invention.

[0231] [Manufacturing Example 7] Manufacturing of liquid crystal polyester (F) In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser, 45.6 g (0.3 mol) of parahydroxybenzoic acid, 1407.6 g (7.5 mol) of 2-hydroxy-6-naphthoic acid, 297.0 g (1.6 mol) of 4,4'-dihydroxybiphenyl, 265.0 g (1.6 mol) of isophthalic acid, and 1201.6 g (11.8 mol) of acetic anhydride were charged, along with 0.06 g of 1-methylimidazole as a catalyst. After replacing the gas in the reactor with nitrogen gas, the temperature was raised from room temperature to 150°C over 30 minutes while stirring under a nitrogen gas stream, and then refluxed at 150°C for 1 hour. Next, while distilling off the by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 150°C to 300°C over 3 hours and 30 minutes. The reaction was considered complete when an increase in torque was observed, yielding liquid crystal polyester (F). The flow initiation temperature of this liquid crystal polyester (F) was 262.4°C. This liquid crystal polyester (F) was pulverized using a cutter mill VM-16 manufactured by Orient Grinding Machinery Co., Ltd. to obtain liquid crystal polyester (F) powder with an average particle size of 438 μm.

[0232] • Manufacturing of liquid crystal polyester fine particle powder Next, using a jet mill (KJ-200 manufactured by Kurimoto Iron Works, with a grinding nozzle diameter of 4.5 mm), the liquid crystal polyester (F) powder was ground with a classification rotor rotation speed of 10,000 rpm, a grinding nozzle pressure of 0.64 MPa, and a processing speed of 2.1 kg / hour to obtain the liquid crystal polyester fine particle powder of Production Example 7. The average particle size (D) of this liquid crystal polyester fine particle powder was determined. 50The particle size was 10 μm. Furthermore, the melting point of the liquid crystal polyester fine particle powder of Production Example 7 was measured using a differential scanning calorimetry analyzer and found to be 302°C. The liquid crystal polyester fine particle powder of Production Example 7 corresponds to the liquid crystal polyester powder according to the embodiment of the present invention.

[0233] [Manufacturing Example 8] • Manufacturing of liquid crystal polyester (G) In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser, 76.0 g (0.6 mol) of parahydroxybenzoic acid, 1345.5 g (7.2 mol) of 2-hydroxy-6-naphthoic acid, 307.2 g (1.7 mol) of 4,4'-dihydroxybiphenyl, 255.8 g (1.5 mol) of terephthalic acid, and 1201.6 g (11.8 mol) of acetic anhydride were charged, along with 0.06 g of 1-methylimidazole as a catalyst. After replacing the gas in the reactor with nitrogen gas, the temperature was raised from room temperature to 150°C over 30 minutes while stirring under a nitrogen gas stream, and then refluxed at 150°C for 1 hour. Next, while distilling off the by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 150°C to 300°C over 3 hours and 30 minutes. The reaction was considered complete when an increase in torque was observed, yielding liquid crystal polyester (G). The flow initiation temperature of this liquid crystal polyester (G) was 244.8°C. This liquid crystal polyester (G) was pulverized using a cutter mill VM-16 manufactured by Orient Grinding Machinery Co., Ltd. to obtain liquid crystal polyester (G) powder with an average particle size of 442 μm.

[0234] • Manufacturing of liquid crystal polyester fine particle powder Next, using a jet mill (KJ-200 manufactured by Kurimoto Iron Works, with a grinding nozzle diameter of 4.5 mm), the liquid crystal polyester (G) powder was ground with a classification rotor rotation speed of 10,000 rpm, a grinding nozzle pressure of 0.64 MPa, and a processing speed of 2.1 kg / hour to obtain the liquid crystal polyester fine particle powder of Production Example 8. The average particle size (D) of this liquid crystal polyester fine particle powder was determined. 50The particle size was 11 μm. Furthermore, the melting point of the liquid crystal polyester fine particle powder of Production Example 8 was measured using a differential scanning calorimetry analyzer and was found to be 285°C. The liquid crystal polyester fine particle powder of Production Example 8 corresponds to the liquid crystal polyester powder according to the embodiment of the present invention.

[0235] [Manufacturing Example 9] • Manufacturing of liquid crystal polyester (H) In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser, 76.0 g (0.6 mol) of parahydroxybenzoic acid, 993.6 g (7.2 mol) of 2-hydroxy-6-naphthoic acid, 481.4 g (2.6 mol) of 4,4'-dihydroxybiphenyl, 429.4 g (2.6 mol) of terephthalic acid, and 1201.6 g (11.8 mol) of acetic anhydride were charged, along with 0.06 g of 1-methylimidazole as a catalyst. After replacing the gas in the reactor with nitrogen gas, the temperature was raised from room temperature to 150°C over 30 minutes while stirring under a nitrogen gas stream, and then refluxed at 150°C for 1 hour. Next, while distilling off the by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 150°C to 300°C over 3 hours and 30 minutes. The reaction was considered complete when an increase in torque was observed, and liquid crystal polyester (H) was obtained. The flow initiation temperature of this liquid crystal polyester (H) was 239.8°C. This liquid crystal polyester (H) was pulverized using a cutter mill VM-16 manufactured by Orient Grinding Machinery Co., Ltd. to obtain liquid crystal polyester (H) powder with an average particle size of 301 μm.

[0236] • Manufacturing of liquid crystal polyester fine particle powder Next, using a jet mill (KJ-200 manufactured by Kurimoto Iron Works, with a grinding nozzle diameter of 4.5 mm), the liquid crystal polyester (H) powder was ground at a classification rotor speed of 10,000 rpm, a grinding nozzle pressure of 0.64 MPa, and a processing speed of 2.1 kg / hour to obtain the liquid crystal polyester fine particle powder of Production Example 9. The average particle size (D) of this liquid crystal polyester fine particle powder was then determined. 50The particle size was 10 μm. Furthermore, the melting point of the liquid crystal polyester fine particle powder of Production Example 9 was measured using a differential scanning calorimetry analyzer and was found to be 272°C. The liquid crystal polyester fine particle powder of Production Example 9 corresponds to the liquid crystal polyester powder according to the embodiment of the present invention.

[0237] Table 1 shows the measurement results for particle size and specific gravity of the liquid crystal polyester fine particle powders from manufacturing examples 1 to 9.

[0238] [Table 1]

[0239] <Liquid Composition> <Measurement method> [Measurement of the specific gravity of the dispersion medium] Water was used as the reference substance, and the specific gravity was measured at a temperature of 23°C and 1 atmosphere in accordance with the method specified in JIS Z 8804:2012 (hydrometer).

[0240] [Measurement of viscosity of dispersion medium] The viscosity of the dispersion medium at 20-25°C was measured in accordance with the method specified in JIS Z 8803.

[0241] <Manufacturing of liquid compositions> [Comparative Examples 1-6, Examples 1-10] Fourteen parts by mass of the liquid crystal polyester fine particle powder of the liquid crystal polyester (A) produced in the above production example 1 were added to 86 parts by mass of each dispersion medium listed in Table 2, and stirred using a stirring and defoaming machine AR-500 manufactured by Thinky Co., Ltd. to obtain a liquid composition which is a dispersion liquid with each medium as the dispersion medium.

[0242] [Comparative Example 7] Fourteen parts by mass of the liquid crystal polyester fine particle powder of the liquid crystal polyester (A) produced in the above production example 2 were added to 86 parts by mass of the dispersion medium (ethylene glycol) listed in Table 2, and stirred using a stirring and defoaming machine AR-500 manufactured by Thinky Co., Ltd. to obtain a liquid composition which is a dispersion liquid with the medium as the dispersion medium.

[0243] [Comparative Example 8, Examples 11-16] 25 parts by mass of the liquid crystal polyester fine particle powder of liquid crystal polyester (B) produced in the above production example 3 was added to 75 parts by mass of each dispersion medium listed in Table 3, and stirred using a stirring and defoaming machine AR-500 manufactured by Thinky Co., Ltd. to obtain a liquid composition which is a dispersion liquid with each medium as the dispersion medium.

[0244] [Comparative Example 9, Examples 17-21] 25 parts by mass of liquid crystal polyester fine particle powder of liquid crystal polyester (C) produced in the above production example 4 was added to 75 parts by mass of each dispersion medium listed in Table 4, and stirred using a stirring and defoaming machine AR-500 manufactured by Thinky Co., Ltd. to obtain a liquid composition which is a dispersion liquid with each medium as the dispersion medium.

[0245] [Comparative Example 10, Examples 22-26] Eight parts by mass of the liquid crystal polyester (D) fine particle powder produced in the above production example 5 were added to 92 parts by mass of each dispersion medium listed in Table 5, and stirred using a stirring and defoaming machine AR-500 manufactured by Thinky Co., Ltd. to obtain a liquid composition which is a dispersion liquid with each medium as the dispersion medium.

[0246] [Comparative Example 11, Examples 27-31] 25 parts by mass of the liquid crystal polyester (E) fine particle powder produced in the above production example 6 was added to 75 parts by mass of each dispersion medium listed in Table 6, and stirred using a stirring and defoaming machine AR-500 manufactured by Thinky Co., Ltd. to obtain a liquid composition which is a dispersion liquid with each medium as the dispersion medium.

[0247] [Comparative Example 12, Examples 32-36] 25 parts by mass of liquid crystal polyester (F) fine particle powder produced in the above production example 7 was added to 75 parts by mass of each dispersion medium listed in Table 7, and stirred using a stirring and defoaming machine AR-500 manufactured by Thinky Co., Ltd. to obtain a liquid composition which is a dispersion liquid with each medium as the dispersion medium.

[0248] [Comparative Example 13, Examples 37-41] Fourteen parts by mass of the liquid crystal polyester (G) fine particle powder produced in the above production example 8 were added to 86 parts by mass of each dispersion medium listed in Table 8, and stirred using a stirring and defoaming machine AR-500 manufactured by Thinky Co., Ltd. to obtain a liquid composition which is a dispersion liquid with each medium as the dispersion medium.

[0249] [Comparative Example 14, Examples 42-46] 25 parts by mass of the liquid crystal polyester (H) fine particle powder produced in the above production example 9 was added to 75 parts by mass of each dispersion medium listed in Table 9, and stirred using a stirring and defoaming machine AR-500 manufactured by Thinky Co., Ltd. to obtain a liquid composition which is a dispersion liquid with each medium as the dispersion medium.

[0250] [Evaluation of dispersion of liquid crystal polyester fine particle powder] For the liquid compositions prepared in each of the above examples and comparative examples, the liquid compositions were observed immediately after preparation, and the dispersion was evaluated according to the following criteria. E (Excellent): No layer separation of the dispersion medium and the liquid crystal polyester fine particle powder was observed, and no accumulation of liquid crystal polyester fine particle powder was observed at the bottom of the container holding the liquid composition. G (Good): No layer separation between the dispersion medium and the liquid crystal polyester fine particle powder was observed, but a slight accumulation of liquid crystal polyester fine particle powder was observed at the bottom of the container holding the liquid composition. F (Failure): The dispersion medium and the liquid crystal polyester fine particle powder separate into layers.

[0251] [Evaluation of sedimentation suppression of liquid crystal polyester fine particle powder] For the liquid compositions prepared in each of the above examples and comparative examples, the liquid compositions were observed from immediately after preparation to after a predetermined number of days had elapsed, and the sedimentation state was evaluated according to the following criteria. E (Excellent): No layer separation of the dispersion medium and the liquid crystal polyester fine particle powder is observed. G (Good): Slight sedimentation of the liquid crystal polyester fine particles is observed, and slight layer separation between the dispersion medium and the liquid crystal polyester fine particles is observed. F (Failure): The liquid crystal polyester fine particles completely settle at the bottom of the container, and the dispersion medium and the liquid crystal polyester fine particles separate into layers.

[0252] Tables 2-9 show each of the above items and their results.

[0253] [Table 2]

[0254] [Table 3]

[0255] [Table 4]

[0256] [Table 5]

[0257] [Table 6]

[0258] [Table 7]

[0259] [Table 8]

[0260] [Table 9]

[0261] Figure 4 is an image showing the liquid composition (dispersion medium: cyclohexanone) of Example 5, in which sedimentation suppression was evaluated. Figure 5 is an image showing the liquid composition (dispersion medium: ethylene glycol) of Example 10, in which sedimentation suppression was evaluated. Figures 6-11 are images showing the liquid compositions of Examples 17-46, in which sedimentation suppression was evaluated.

[0262] According to the results shown in Table 2, the average particle size (D 50 The liquid compositions of Examples 1 to 16, which contain liquid crystal polyester fine particle powder having a particle size of 30 μm or less and a medium with a specific gravity of 0.90 or higher, exhibited excellent dispersion of the liquid crystal polyester fine particle powder and were suitable for use in the production of liquid crystal polyester films.

[0263] Furthermore, as shown in Table 3, both the liquid crystal polyester fine particle powder of liquid crystal polyester (A) produced in Production Example 1 and the liquid crystal polyester fine particle powder of liquid crystal polyester (B) produced in Production Example 3 yielded liquid compositions with excellent dispersion of liquid crystal polyester fine particle powder. This indicates that the present invention can be applied even when the composition of the structural units of the liquid crystal polyester differs, by using the dispersion medium used in each example.

[0264] On the other hand, the average particle size (D) of the above liquid crystal polyester fine particle powder 50 ) or the liquid compositions of Comparative Examples 1 to 8, which did not meet the specific gravity value of the medium, had inferior dispersion of liquid crystal polyester fine particle powder.

[0265] From the results of each example, it can be seen that both the high viscosity of the dispersion medium and the small difference in specific gravity between the dispersion medium and the liquid crystal polyester fine particle powder are influencing the suppression of sedimentation of the liquid crystal polyester fine particle powder. It can be said that the higher the viscosity of the dispersion medium, the more favorable it is in terms of suppressing the sedimentation of the liquid crystal polyester fine particle powder (Examples 1, 2, 9, 10, 11, 12, 16). Even when the viscosity of the dispersion medium was not very high, sedimentation suppression was good when the difference in specific gravity between the dispersion medium and the liquid crystal polyester fine particle powder was particularly small (Examples 8, 15).

[0266] Furthermore, referring to the results shown in Tables 4-9, the results for liquid compositions containing the liquid crystal polyester fine particle powders of each liquid crystal polyester (C)-(H) produced in Production Examples 4-9 (Comparative Examples 9-14, Examples 17-46) also showed similar dispersion and sedimentation tendencies to those obtained in the same dispersion medium as described above.

[0267] Each configuration and combination thereof in each embodiment is merely an example, and additions, omissions, substitutions, and other modifications are possible without departing from the spirit of the present invention. Furthermore, the present invention is not limited by each embodiment, but is limited only by the scope of the claims. [Explanation of Symbols]

[0268] 1...Liquid crystal polyester powder, 3...Medium, 30...Liquid composition, 10...Liquid crystal polyester film, 11...Liquid crystal polyester film, 12...Support, 13...Metal layer, 20,21...Laminate, 22...Laminate precursor, 40...Liquid crystal polyester film precursor

Claims

1. A liquid crystal polyester powder containing liquid crystal polyester with an average particle size of 0.5 μm or more and 30 μm or less, Including the medium, The specific gravity of the aforementioned medium, measured in accordance with JIS Z 8804 with water as the reference substance, is 0.90 or higher. The viscosity of the medium measured at 20-25°C is 10 mPa·s or more and 80 mPa·s or less. A liquid composition wherein the medium is at least one selected from the group consisting of propylene glycol, ethylene glycol, and sulfolane.

2. The liquid crystal polyester powder is insoluble in the medium, The liquid composition according to claim 1, wherein the liquid crystal polyester powder is dispersed in the liquid medium.

3. The liquid composition according to claim 1 or 2, wherein the difference in specific gravity between the specific gravity of the liquid crystal polyester powder measured by JIS K 7112 (Method A) and the specific gravity measured in accordance with JIS Z 8804 using water as the reference substance in the medium is 0.48 or less.

4. The liquid composition according to any one of claims 1 to 3, wherein the specific gravity measured in accordance with JIS Z 8804 with water as the reference substance in the medium is 0.95 or higher.

5. The liquid composition according to any one of claims 1 to 4, wherein the specific gravity measured in accordance with JIS Z 8804 using water as the reference substance in the medium is 1.03 or higher.

6. A liquid composition according to any one of claims 1 to 5, wherein the content of liquid crystal polyester soluble in the medium is less than 5% by mass, based on 100% by mass of the total amount of liquid crystal polyester.

7. A liquid composition according to any one of claims 1 to 6, wherein the specific gravity of the liquid crystal polyester powder, as measured by JIS K 7112 (Method A), is 1.35 or more and 1.40 or less.

8. The liquid composition according to any one of claims 1 to 7, wherein the liquid crystal polyester contains a structural unit represented by the following formula (1). (1) -O-Ar1-CO- (Ar1 represents a divalent aromatic hydrocarbon group, One or more hydrogen atoms in the group represented by Ar1 may be independently substituted with halogen atoms, C1-C10 alkyl groups, or C6-C20 aryl groups.

9. The liquid composition according to any one of claims 1 to 8, wherein the liquid crystal polyester contains structural units including a naphthalene structure.

10. The liquid composition according to claim 9, wherein the liquid crystal polyester contains 40 mol% or more of the structural unit represented by the following formula (1) relative to the total amount of all structural units in the liquid crystal polyester. (1)-O-Ar1-CO- (Ar1 represents a 2,6-naphthylene group, One or more hydrogen atoms in the group represented by Ar1 may be independently substituted with halogen atoms, C1-C10 alkyl groups, or C6-C20 aryl groups.

11. A liquid crystal polyester powder containing liquid crystal polyester with an average particle size of 30 μm or less, The process includes mixing the medium and The specific gravity of the aforementioned medium, measured in accordance with JIS Z 8804 with water as the reference substance, is 0.90 or higher. The viscosity of the medium, measured at 20-25°C, is 10 mPa·s or more and 80 mPa·s or less. A method for producing a liquid composition according to any one of claims 1 to 10.

12. A method for producing a liquid crystal polyester film, comprising applying a liquid composition according to any one of claims 1 to 10 onto a support and heat-treating it to obtain a liquid crystal polyester film containing liquid crystal polyester.

13. A method for producing a laminate, comprising applying a liquid composition according to any one of claims 1 to 10 onto a support, heat-treating it to form a liquid crystal polyester film containing a liquid crystal polyester, thereby obtaining a laminate comprising the support and the liquid crystal polyester film.

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