Liquid crystal polyester compositions, molded articles, and films
A liquid crystal polyester composition with a defined polymer and naphthalene structure addresses anisotropy issues, enhancing the mechanical strength and stability of molded articles and films.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- SUMITOMO CHEM CO LTD
- Filing Date
- 2024-11-21
- Publication Date
- 2026-06-02
Smart Images
Figure 2026089953000008 
Figure 2026089953000001 
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Abstract
Description
[Technical Field]
[0001] This disclosure relates to liquid crystal polyester compositions, molded articles, and films. [Background technology]
[0002] Liquid crystal polyester is known for its high chemical stability, heat resistance, and dimensional accuracy, and is used in a variety of fields, including electrical, electronic, mechanical, optical, automotive, aerospace, and medical industries. Among these fields, liquid crystal polyester is attracting particular attention as a material for electronic components due to its high-frequency properties and water absorption capabilities. For example, Patent Document 1 discloses a microbranched liquid crystal polyester having five specific repeating units in a predetermined ratio. The microbranched liquid crystal polyester disclosed in Patent Document 1 is said to be useful for materials to be attached to the surface of electronic components and for manufacturing thin film products. [Prior art documents] [Patent Documents]
[0003] [Patent Document 1] Chinese Patent Application Publication No. 116178686 Specification [Overview of the project] [Problems that the invention aims to solve]
[0004] However, when using liquid crystal polyester as a molding material, anisotropy becomes a problem. When conventional molding materials containing liquid crystal polyester are used, the liquid crystal polyester tends to orient in the flow direction (MD). Therefore, in molded articles, weakness to forces in the TD direction (perpendicular to the MD direction) becomes a problem, as they are prone to tearing. This disclosure has been made in view of the above circumstances and aims to provide a liquid crystal polyester composition containing liquid crystal polyester that can reduce anisotropy, as well as molded articles and films containing the same. [Means for solving the problem]
[0005] To solve the above problems, the present disclosure includes the following aspects.
[0006] [1] A liquid crystal polyester composition containing a polymer (P1) represented by the following formula (p1) and a liquid crystal polyester (P0) (excluding those corresponding to the polymer (P1)), wherein the content of the polymer (P1) is 0.1 part by mass or more and 15 parts by mass or less with respect to a total of 100 parts by mass of the polymer (P1) and the liquid crystal polyester (P0), and the liquid crystal polyester (P0) has a repeating unit (N0) containing a naphthalene structure, and the number of the repeating units (N0) is 35% or more with respect to 100% of the total number of all repeating units constituting the liquid crystal polyester (P0).
[0007] [Chemical formula] [In formula (p1), Ar 20 represents an (n + m)-valent aromatic group. R 10 represents -CO-O-H or -O-H. R 20 represents -CO-R 201 or -O-R 202 represents. R 201 represents a liquid crystal polyester chain or a polymer chain in which the chemical structure of a functional group contributing to the bond with -CO in the polymer (P1) has changed. R 202 represents a liquid crystal polyester chain or a polymer chain in which the chemical structure of a functional group contributing to the bond with -O in the polymer (P1) has changed. n represents an integer of 1 or more, m represents an integer of 0 or more, and n + m is 3 or more and 6 or less.]
[0008] [2] The liquid crystal polyester composition according to [1], wherein the R 201 or the R 202 includes a liquid crystal polyester chain having a repeating unit (N1) containing a naphthalene structure, and the number of the repeating units (N1) is 50% or more with respect to 100% of the total number of all repeating units constituting the liquid crystal polyester chain in the polymer (P1).
[0009] [3] A molded article comprising the liquid crystal polyester composition described in [1] or [2]. [4] A film comprising the liquid crystal polyester composition described in [1] or [2]. [Effects of the Invention]
[0010] According to this disclosure, it is possible to provide a liquid crystal polyester composition containing liquid crystal polyester that can reduce anisotropy, as well as molded articles and films containing the same. [Brief explanation of the drawing]
[0011] [Figure 1] This is a cross-sectional view showing one embodiment of the film. [Modes for carrying out the invention]
[0012] (Liquid crystal polyester composition) One embodiment of the liquid crystal polyester composition contains a polymer (P1) represented by the following formula (p1) and a liquid crystal polyester (P0) (excluding those corresponding to the polymer (P1)).
[0013] [ka] [In formula (p1), Ar 20 R represents an aromatic group with (n+m) valency. 10 R represents -CO-OH or -OH. 20 -CO-R 201 OR 202 Represents R 201 This represents a liquid crystal polyester chain, or a polymer chain in which the chemical structure of the functional group contributing to the bond with -CO- in the polymer (P1) has been altered. 202 This represents a liquid crystal polyester chain, or a polymer chain in which the chemical structure of the functional group contributing to the bond with -O- in the polymer (P1) has been altered. n represents an integer greater than or equal to 1, m represents an integer greater than or equal to 0, and n+m is between 3 and 6.
[0014] In the liquid crystal polyester composition of this embodiment, the content of the polymer (P1) is 0.1 parts by mass or more and 15 parts by mass or less, based on 100 parts by mass of the total of the polymer (P1) and the liquid crystal polyester (P0). The liquid crystal polyester (P0) has repeating units (N0) containing a naphthalene structure, and the number of repeating units (N0) is 35% or more of the total number of repeating units constituting the liquid crystal polyester (P0) (100%).
[0015] As used herein, "liquid crystal polyester composition" refers to a mixture obtained by mixing liquid crystal polyester (P0), polymer (P1) represented by formula (p1), and other components, and includes those in powder or pellet form.
[0016] <Liquid crystal polyester (P0)> The liquid crystal polyester (P0) has repeating units (N0) containing a naphthalene structure. The number of repeating units (N0) is 35% or more of the total number of repeating units constituting the liquid crystal polyester (P0) (100%). Liquid crystal polyester (P0) shall exclude those that fall under the category of polymer (P1).
[0017] The liquid crystal polyester (P0) is not particularly limited as long as it is a polyester resin that exhibits liquid crystal properties in a molten state. Preferably, the liquid crystal polyester melts at a temperature of 450°C or lower.
[0018] The flow initiation temperature for liquid crystal polyester (P0) is preferably 250°C or higher, more preferably 270°C or higher, and even more preferably 280°C or higher. Furthermore, the flow initiation temperature of the liquid crystal polyester (P0) is preferably 400°C or lower, more preferably 385°C or lower, and even more preferably 370°C or lower. For example, the flow initiation temperature of liquid crystal polyester (P0) is preferably 250°C to 400°C, more preferably 275°C to 385°C, and even more preferably 300°C to 370°C.
[0019] In this specification, the flow initiation temperature of liquid crystal polyester is determined using a flow tester, where the liquid crystal polyester is subjected to 9.8 MPa (100 kg / cm³). 2 The liquid crystal polyester is melted while being heated at a rate of 4°C / min under a load of ), and when extruded from a nozzle with an inner diameter of 1 mm and a length of 10 mm, it exhibits a viscosity of 4800 Pa·s (48000 poise).
[0020] Liquid crystal polyester (P0) has repeating units (N0) that include a naphthalene structure. Furthermore, the liquid crystal polyester (P0) may have two or more repeating units (N0) with different chemical structures. In the liquid crystal polyester (P0), the number of repeating units (N0) is 35% or more of the total number of repeating units constituting the liquid crystal polyester (P0) (100%), preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more. Liquid crystal polyester in which the number of repeating units (N0) is equal to or greater than the lower limit value has low relative permittivity and dielectric loss tangent, and excellent dielectric properties. When there are two or more repeating units (N0) with different chemical structures, the number of repeating units (N0) here refers to the total number of repeating units (N0).
[0021] In the liquid crystal polyester (P0), the number of repeating units (N0) is preferably 90% or less, more preferably 85% or less, and even more preferably 80% or less, relative to 100% of the total number of repeating units constituting the liquid crystal polyester (P0). By keeping the number of repeating units (N0) below the preferred upper limit, reaction stability during liquid crystal polyester production can be ensured.
[0022] As an example of the numerical range for the number of repeating units (N0), it may be 35% to 90%, 50% to 90%, 60% to 85%, or 70% to 80% of the total number of repeating units constituting the liquid crystal polyester (P0) as 100%.
[0023] In this specification, the number of repeating units constituting the liquid crystal polyester can be calculated based on the sum of the amounts of substance (moles) of each repeating unit, obtained by dividing the mass of each repeating unit constituting the liquid crystal polyester by the formula weight of that repeating unit. The number of each repeating unit constituting the liquid crystal polyester can be determined by the analytical method described in Japanese Patent Publication No. 2000-19168. Specifically, the liquid crystal polyester is depolymerized by reacting it with a lower alcohol in a supercritical state, and the number of each repeating unit relative to the total number of repeating units can be calculated by quantifying the depolymerization product (monomer that induces each repeating unit) by liquid chromatography.
[0024] The liquid crystal polyester (P0) is preferably a fully aromatic liquid crystal polyester having only repeating units derived from aromatic compounds.
[0025] In this specification, "derived from" means that in the polymerization of the raw material monomer, the chemical structure of the functional group contributing to polymerization changes, while the other chemical structures remain unchanged. Here, "derived from" also includes cases where the derivative is a polymerizable derivative of the raw material monomer.
[0026] Examples of polymerizable derivatives of compounds having a carboxyl group, such as aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids, include esters obtained by converting the carboxyl group to an alkoxycarbonyl group or an aryloxycarbonyl group; acid halides obtained by converting the carboxyl group to a haloformyl group; and acid anhydrides obtained by converting the carboxyl group to an acyloxycarbonyl group.
[0027] Examples of polymerizable derivatives of compounds having a hydroxyl group, such as aromatic hydroxycarboxylic acids, aromatic diols, and aromatic hydroxyamines, include acylated compounds obtained by acyling the hydroxyl group to convert it to an acyloxyl group. Examples of polymerizable derivatives of compounds having an amino group, such as aromatic hydroxyamines and aromatic diamines, include acylated compounds obtained by acyling the amino group to convert it into an acylamino group.
[0028] The liquid crystal polyester (P0) has repeating units (N0) containing a naphthalene structure, and preferably has repeating units represented by the following formula (1) (hereinafter also referred to as "repeating unit (1)").
[0029] (1)-O-Ar 1 -CO- In formula (1), Ar 1 This represents a phenylene group, a naphthylene group, or a biphenylylene group. Ar 1 One or more hydrogen atoms in the group represented by the above may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
[0030] The liquid crystal polyester (P0) has the repeating unit (N0), and more preferably has the repeating unit (1), a repeating unit represented by the following formula (2) (hereinafter also referred to as "repeating unit (2)"), and a repeating unit represented by the following formula (3) (hereinafter also referred to as "repeating unit (3)").
[0031] (1)-O-Ar 1 -CO- (2) New CO-Ar 2 -CO- (3)-X-Ar 3 -Y- In formulas (1) to (3), Ar 1 represents a phenylene group, a naphthylene group, or a biphenylylene group, and Ar 2 and Ar 3The terms and represent, independently of each other, a phenylene group, a naphthylene group, a biphenylylene group, or a group represented by the following formula (4), and X and Y represent, independently of each other, an oxygen atom or an imino group (-NH-). 1 Ar 2 Or Ar 3 One or more hydrogen atoms in the group represented by the above may be independently substituted with a halogen atom, a C1-C10 alkyl group, or a C6-C20 aryl group.
[0032] (4)-Ar 4 -Z-Ar 5 - In formula (4), Ar 4 and Ar 5 The 'A's represent a phenylene group or a naphthylene group independently of each other, and 'Z' represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylidene group having 1 to 10 carbon atoms. 4 Or Ar 5 One or more hydrogen atoms in the group represented by the above may be independently substituted with a halogen atom, a C1-C10 alkyl group, or a C6-C20 aryl group. The alkylidene group in Z in formula (4) is an alkylidene group having 1 to 10 carbon atoms, such as a methylene group, ethylidene group, isopropylidene group, n-butylidene group, or 2-ethylhexylidene group.
[0033] Ar 1 Ar 2 Ar 3 Ar 4 Or Ar 5 Examples of halogen atoms that can substitute for the hydrogen atom in the molecule include fluorine, chlorine, bromine, and iodine.
[0034] Ar 1 Ar 2 Ar 3 Ar 4 Or Ar 5Examples of alkyl groups that can be substituted for hydrogen atoms include alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, and n-decyl group. The alkyl group may be linear or branched.
[0035] Ar 1 Ar 2 Ar 3 Ar 4 Or Ar 5 Examples of aryl groups that can be substituted for hydrogen atoms include aryl groups having 6 to 20 carbon atoms, such as phenyl, o-tolyl, m-tolyl, p-tolyl, 1-naphthyl, and 2-naphthyl groups. The aryl group may be a monocyclic or fused ring. Furthermore, the aryl group may be a group in which the hydrogen atoms of the aromatic ring are substituted with alkyl groups, such as the tolyl group.
[0036] Ar 1 Ar 2 Ar 3 Ar 4 Or Ar 5 When the hydrogen atoms in are substituted with the above-mentioned group, the number of substitutions is preferably one or two, and more preferably one. Ar 1 Ar 2 Ar 3 Ar 4 Or Ar 5 The hydrogen atoms in this compound do not necessarily have to be substituted with the aforementioned group.
[0037] The repeating unit (1) is Ar 1 A repeating unit in which is a 1,4-phenylene group or a repeating unit in which is a 2,6-naphthylene group is preferred.
[0038] The repeating unit (2) is Ar 2The repeating unit is preferably a 1,4-phenylene group, a 1,3-phenylene group, a 2,6-naphthylene group, a 2,7-naphthylene group, a 4,4'-biphenylylene group, or a diphenyl ether-4,4'-diyl group, and Ar 2 Repeating units having a 1,4-phenylene group, repeating units having a 1,3-phenylene group, or repeating units having a 2,6-naphthylene group are more preferred.
[0039] The repeating unit (3) is Ar 3 A repeating unit in which is a 1,4-phenylene group or a repeating unit in which is a 4,4'-biphenylene group is preferred.
[0040] The repeating unit (3) is preferable if it has repeating units where X and Y are each oxygen atoms, as this tends to lower the melt viscosity of the liquid crystal polyester, and it is even more preferable if the repeating unit (3) consists only of repeating units where X and Y are each oxygen atoms.
[0041] The liquid crystal polyester (P0) having repeating units (1) to (3) here is such that the number of repeating units (N0) containing a naphthalene structure is 35% or more of the total number of repeating units constituting the liquid crystal polyester (P0) (100%), and may be 35% to 90%, 50% to 90%, 60% to 85%, or 70% to 80%.
[0042] The number of repeating units (1) is preferably 30% to 80%, more preferably 40% to 70%, and even more preferably 45% to 70%, of 100% of the total number of repeating units constituting the liquid crystal polyester (P0).
[0043] The number of repeating units (2) is preferably 10% to 35%, more preferably 15% to 30%, and even more preferably 15% to 27.5%, relative to 100% of the total number of repeating units constituting the liquid crystal polyester (P0).
[0044] The number of repeating units (3) is more preferably 10% to 35%, more preferably 15% to 30%, and even more preferably 15% to 27.5%, relative to 100% of the total number of repeating units constituting the liquid crystal polyester (P0).
[0045] The liquid crystal polyester (P0) having repeating units (1) to (3) is preferably such that, for example, the number of repeating units (1) is 30% to 80% of the total number of repeating units constituting the liquid crystal polyester (P0), and the number of repeating units (2) and repeating units (3) are both 10% to 35% of the total number of repeating units constituting the liquid crystal polyester (P0).
[0046] Furthermore, it is more preferable that the number of repeating units (1) in the liquid crystal polyester (P0) is 40% to 70% of the total number of repeating units constituting the liquid crystal polyester (P0), and that the number of repeating units (2) and the number of repeating units (3) are both 15% to 30% of the total number of repeating units constituting the liquid crystal polyester (P0).
[0047] Furthermore, it is particularly preferable that the liquid crystal polyester (P0) has a repeating unit (1) number that is 45% or more and 70% or less of the total number of repeating units constituting the liquid crystal polyester (P0) (100%), and that the number of repeating units (2) and the number of repeating units (3) are both 15% or more and 27.5% or less of the total number of repeating units constituting the liquid crystal polyester (P0) (100%).
[0048] The ratio of the content of repeating units (2) to the content of repeating units (3) is expressed as [number of repeating units (2)] / [number of repeating units (3)], and is preferably 0.9 / 1 to 1 / 0.9, more preferably 0.95 / 1 to 1 / 0.95, and even more preferably 0.98 / 1 to 1 / 0.98.
[0049] Furthermore, the liquid crystal polyester (P0) may have two or more types of repeating units (1), repeating units (2), and repeating units (3). Furthermore, the liquid crystal polyester (P0) may have other repeating units besides repeating unit (N0), repeating unit (1), repeating unit (2), and repeating unit (3), but the number of such units is preferably 10% or less, and more preferably 5% or less, of the total number of repeating units constituting the liquid crystal polyester (P0) (100%). In a liquid crystal polyester (P0) having repeating units (N0), repeating units (1), repeating units (2), and repeating units (3), the sum of the content of repeating units (N0), repeating units (1), repeating units (2), repeating units (3), and other repeating units is 100%.
[0050] More specifically, as the liquid crystal polyester (P0) having the repeating units (1) to (3) described above, it is more preferable that it has the repeating unit (N0) and a repeating unit represented by the following formula (11) (hereinafter also referred to as "repeating unit (11)"), a repeating unit represented by the following formula (12) (hereinafter also referred to as "repeating unit (12)"), and a repeating unit represented by the following formula (13) (hereinafter also referred to as "repeating unit (13)").
[0051] (11)-O-Ar 11 -CO- (12)-CO-Ar 12 -CO- (13)-O-Ar 13 -O- In formulas (11) to (13), Ar 11 represents a 2,6-naphthylene group or a 1,4-phenylene group. 12 Ar represents a 2,6-naphthylene group, a 2,7-naphthylene group, a 1,4-phenylene group, a 1,3-phenylene group, a 4,4'-biphenylylene group, or a diphenyl ether-4,4'-diyl group. 13 Ar represents a 1,4-phenylene group or a 4,4'-biphenylene group. 11 Ar 12 Or Ar 13One or more hydrogen atoms in the group represented by the above may be independently substituted with a halogen atom, a C1-C10 alkyl group, or a C6-C20 aryl group.
[0052] In the liquid crystal polyester (P0) having the repeating unit (N0), and the repeating unit (11), the repeating unit (12), and the repeating unit (13), the number of repeating units having a 2,6-naphthylene group or a 2,7-naphthylene group is 35% or more of the total number of repeating units constituting the liquid crystal polyester (P0) (100%), and may be 35% to 90%, 50% to 90%, 60% to 85%, or 70% to 80%.
[0053] The liquid crystal polyester (P0) has the above repeating units (11) to (13), and the Ar in the repeating unit (11) 1 However, it represents a 2,6-naphthylene group, and the Ar in the repeating unit (12) 2 However, it represents a 2,6-naphthylene group or a 1,4-phenylene group, and the Ar in the repeating unit (13) 3 However, it is preferable that the liquid crystal polyester represents a 1,4-phenylene group.
[0054] The liquid crystal polyester (P0) has the following repeating units (11-1), repeating unit (12-1), repeating unit (12-2), and repeating unit (13-1), and the number of repeating units (N0) containing a naphthalene structure may be 35% or more of the total number of repeating units constituting the liquid crystal polyester (P0) (100%). (11-1)-O-Ar 11-1 -CO- (12-1)-CO-Ar 12-1 -CO- (12-2)-CO-Ar 12-2 -CO- (13-1)-O-Ar 13-1 -O- Ar 11-1 This represents a 2,6-naphthylene group. Ar 12-1 This represents a 2,6-naphthylene group. Ar 12-2 This represents a 1,4-phenylene group. Ar 13-1 This represents a 1,4-phenylene group. Ar 11-1 Ar 12-1 Ar 12-2 Or Ar 13-1 Each hydrogen atom in the group represented by the above 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.
[0055] The liquid crystal polyester composition of this embodiment may contain one type of liquid crystal polyester (P0), or it may contain two or more types of liquid crystal polyester (P0). The content of liquid crystal polyester (P0) in the liquid crystal polyester composition of this embodiment, relative to the total mass (100% by mass), may be 85% by mass or more and 99.9% by mass or less, 90% by mass or more and 99.8% by mass or less, or 93% by mass or more and 99.7% by mass or less.
[0056] [Method for manufacturing liquid crystal polyester (P0)] Liquid crystal polyester (P0) can be produced by melt polymerization of raw material monomers corresponding to the repeating units constituting the liquid crystal polyester (P0), and then solid-phase polymerization of the resulting polymer. For example, it can be produced by a manufacturing method including the following acylation step and polymerization step, as described in Japanese Patent No. 6439027.
[0057] Acylation process: A process to obtain an acylated product by acyling the phenolic hydroxyl group of the raw material monomer with a fatty acid anhydride (e.g., acetic anhydride). Polymerization step: A step to obtain a liquid crystal polyester by polymerizing the acyl group of the acylated product with the carboxyl group of the acylated product of aromatic dicarboxylic acid and aromatic hydroxycarboxylic acid in a manner that undergoes transesterification.
[0058] <Polymer (P1)> Polymer (P1) is a compound represented by the following formula (p1). Polymer (P1) may be an all-aromatic polyester or a semi-aromatic polyester, and from the perspective of heat resistance, it may also be an all-aromatic polyester.
[0059] [Chemical formula] [In formula (p1), Ar 20 represents an (n + m)-valent aromatic group. R 10 represents -CO-O-H or -O-H. R 20 represents -CO-R 201 or -O-R 202 represents. R 201 represents a liquid crystal polyester chain or a polymer chain in which the chemical structure of the functional group contributing to the bond with -CO in the polymer (P1) has changed. R 202 represents a liquid crystal polyester chain or a polymer chain in which the chemical structure of the functional group contributing to the bond with -O in the polymer (P1) has changed. n represents an integer of 1 or more, m represents an integer of 0 or more, and n + m is 3 or more and 6 or less.]
[0060] In the above formula (p1), the (n + m)-valent aromatic group in Ar 20 is a residue obtained by removing (n + m) hydrogen atoms bonded to its ring structure from an aromatic compound. The ring structure here may be an aromatic hydrocarbon ring, an aromatic heterocyclic ring in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted by heteroatoms, a condensed ring of an aromatic hydrocarbon ring and an aliphatic ring, or a condensed ring of an aromatic heterocyclic ring and an aliphatic ring. Among these, the ring structure is preferably an aromatic hydrocarbon ring. Ar 20Examples of the aromatic compounds in this context include aromatic hydrocarbons such as benzene, triphenylbenzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, fluorene, tetraphenylbenzene, pentaphenylbenzene, and hexaphenylbenzene; heteroaromatic compounds such as pyridine, bipyridine, terpyridine, and terthiophene; and aromatic hydrocarbons containing aromatic heterocycles such as phenylpyridine, diphenylpyridine, triphenylpyridine, phenylterpyridine, benzoquinoline, and phenylquinoline. Among these, Ar 20 The aromatic compound in this case is preferably an aromatic hydrocarbon, more preferably benzene, more preferably triphenylbenzene, and even more preferably triphenylbenzene, for example, 1,3,5-triphenylbenzene.
[0061] In the above equation (p1), R 10 This represents -CO-OH or -OH. In the above equation (p1), R 20 -CO-R 201 OR 202 It represents. R 201 This represents a liquid crystal polyester chain, or a polymer chain in which the chemical structure of the functional group contributing to the bond with -CO- in the polymer (P1) has been altered. R 202 This represents a liquid crystal polyester chain, or a polymer chain in which the chemical structure of the functional group contributing to the bond with -O- in the polymer (P1) has been altered.
[0062] In the above equation (p1), R 201 and R 202 Examples include aromatic polyester chains, or aromatic polyesters with Ar 20 Examples include polymer chains containing Ar, and from the viewpoint of heat resistance, all aromatic polyester chains, or all aromatic polyesters with Ar 20 Polymer chains containing the above are preferred.
[0063] R in the above equation (p1) 201 and R 202Preferably, each of these contains a liquid crystal polyester chain having a repeating unit (N1) that includes a naphthalene structure. R 201 and R 202 The liquid crystal polyester constituting the liquid crystal polyester chain in the present invention has the repeating unit (N1), preferably has the repeating unit (1), and more preferably has the repeating unit (N1), the repeating unit (1), the repeating unit (2), and the repeating unit (3). That is, R 201 and R 202 It is more preferable that the liquid crystal polyester constituting the liquid crystal polyester chain in this product has the same structure as the liquid crystal polyester (P0) described above.
[0064] In the above equation (p1), n+m is between 3 and 6, and m is a non-negative integer. n is an integer greater than or equal to 1, preferably an integer between 2 and 6, more preferably 3 or 4, and even more preferably 3.
[0065] The number of repeating units (N1) is preferably 50% or more of the total number of repeating units constituting the liquid crystal polyester chain in the polymer (P1) relative to 100%, and may be 50% to 90%, 60% to 85%, or 70% to 80%. Liquid crystal polyester chains in which the number of repeating units (N1) is equal to or greater than the lower limit value have low relative permittivity and dielectric loss tangent values, and excellent dielectric properties. In addition, they are more easily miscible with liquid crystal polyester (P0).
[0066] The number of repeating units (1) described above is preferably 30% to 80%, more preferably 40% to 70%, and even more preferably 45% to 70%, based on 100% of the total number of repeating units constituting the liquid crystal polyester chain in the polymer (P1). The number of repeating units (2) described above is preferably 10% to 35%, more preferably 15% to 30%, and even more preferably 15% to 27.5%, based on 100% of the total number of repeating units constituting the liquid crystal polyester chain in the polymer (P1). The number of repeating units (3) described above is more preferably 10% to 35%, more preferably 15% to 30%, and even more preferably 15% to 27.5%, relative to 100% of the total number of repeating units constituting the liquid crystal polyester chain in the polymer (P1).
[0067] In the polymer (P1) having repeating units (1) to (3), the preferred combinations of repeating units (1), (2), and (3), as well as the content ratio of repeating units (1) to (3), are the same as in the case of the liquid crystal polyester (P0) having repeating units (1) to (3) described above.
[0068] The liquid crystal polyester composition of this embodiment may contain one polymer (P1) or two or more polymers (P1). The polymer (P1) content relative to the total mass (100% by mass) of the liquid crystal polyester composition of this embodiment may be 0.1% by mass or more and 15% by mass or less, 0.2% by mass or more and 10% by mass or less, 0.25% by mass or more and 7% by mass or less, or 0.3% by mass or more and 7% by mass or less.
[0069] [Method for producing polymer (P1)] Polymer (P1) is, for example, R in formula (p1) above. 201 and R 202 It can be produced by condensing a liquid crystal polyester that constitutes a liquid crystal polyester chain with an aromatic compound represented by the following formula (p1-0).
[0070] (p1-0) Ar 20 -(R 10 ) n+m [In the formula, Ar 20 R represents an aromatic group with (n+m) valency.10 The symbol represents -CO-OH or -OH. n represents an integer greater than or equal to 1, m represents an integer greater than or equal to 0, and n+m is between 3 and 6 (inclusive).
[0071] The aromatic compound represented by the above formula (p1-0) is an aromatic carboxylic acid (R 10 (-CO-OH), phenols (R 10 (-OH) is one example. The aromatic carboxylic acid represented by formula (p1-0) may be an ester obtained by converting the carboxyl group (-CO-OH) to an alkoxycarbonyl group or an aryloxycarbonyl group; an acid halide obtained by converting the carboxyl group to a haloformyl group; or an acid anhydride obtained by converting the carboxyl group to an acyloxycarbonyl group, etc.
[0072] As the aromatic carboxylic acid represented by formula (p1-0), for example, trimesic acid and 1,3,5-tris(4-carboxyphenyl)benzene can be used, and from the viewpoint of reactivity with liquid crystal polyester, it is preferable to use 1,3,5-tris(4-carboxyphenyl)benzene. Examples of phenols represented by the formula (p1-0) include phloroglucinol and 1,3,5-tris(4-hydroxyphenyl)benzene.
[0073] After the condensation reaction is complete, the polymer (P1) in the reaction product may be isolated and purified. Conventional known methods can be used for isolation and purification. Alternatively, after the condensation reaction is complete, the reaction product containing the polymer (P1) may be used as is and mixed with the liquid crystal polyester (P0).
[0074] Polymer (P1) is, as another example, R in formula (p1) above. 201 and R 202 It can be produced by adding and reacting the aromatic compound represented by formula (p1-0) when polymerizing the raw material monomers of the liquid crystal polyester that constitute the liquid crystal polyester chain in the above. However, compared to a manufacturing method in which an aromatic compound represented by formula (p1-0) is added and reacted during the polymerization of the raw material monomers, a manufacturing method in which the liquid crystal polyester obtained after polymerization of the raw material monomers is reacted with the aromatic compound represented by formula (p1-0) is preferred because it is easier to synthesize the desired n-branched polymer (P1) and an effect of reducing the anisotropy of the liquid crystal polyester can be obtained.
[0075] [Measurement of the content of each component in the reaction product containing polymer (P1)] In the method for producing polymer (P1), Ar 20 A (n+m) valence aromatic group is given -R 20 In addition to the target compound (n-functional polymer (P1)) in which n units are bonded, -R 20 A reaction product is prepared in which the aromatic compound represented by formula (p1-0) is not bonded and remains as is (n=0), and is mixed with the compound. Note -R 20 Aromatic compounds represented by formula (p1-0) that are not bonded are included in the other components described later. The content of each component in this reaction product can be measured as follows.
[0076] First, the reaction product containing polymer (P1) is used as the sample, and the sample is subjected to freeze-grinding. Next, the freeze-dried sample is mixed with N-methyl-2-pyrrolidone and n-butylamine, and refluxed to obtain a reaction mixture (amine decomposition, decomposition to each monomer). The resulting reaction mixture is concentrated, and formic acid is added to the residue, followed by N-methyl-2-pyrrolidone to prepare the measurement solution. Liquid chromatography-mass spectrometry (LC-MS) is performed on the measurement solution to determine the area percentage of the peaks for each component. The content (mass %) of each component in the reaction product is calculated by dividing the area percentage of the peak of each component by the sum of the area percentage of the peak of each component and the area percentage of the peak of the aromatic compound represented by the formula (p1-0) above.
[0077] ≪Content ratio of liquid crystal polyester (P0) and polymer (P1)≫ In the liquid crystal polyester composition of this embodiment, the content of the polymer (P1) is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.2 parts by mass or more and 10 parts by mass or less, more preferably 0.2 parts by mass or more and 7 parts by mass or less, and even more preferably 0.3 parts by mass or more and 7 parts by mass or less, based on 100 parts by mass of the total of the polymer (P1) and the liquid crystal polyester (P0). If the polymer (P1) content is within the above range, the anisotropy of the film can be reduced. In addition, if the polymer (P1) content is below the upper limit of the above range, the smoothness of the film surface can be improved. Furthermore, if the polymer (P1) content is below the upper limit of the above preferred range, the heat resistance can be improved.
[0078] The total content of liquid crystal polyester (P0) and polymer (P1) relative to the total mass (100% by mass) of the liquid crystal polyester composition of this embodiment may be 80% by mass or more, 90% by mass or more, or 99% by mass or more. Furthermore, the total content of liquid crystal polyester (P0) and polymer (P1) relative to the total mass (100% by mass) of the liquid crystal polyester composition of this embodiment may be 100% by mass or less, or 99.99% by mass or less. The lower and upper limits of the total content can be combined arbitrarily. The total content of liquid crystal polyester (P0) and polymer (P1) relative to the total mass (100% by mass) of the liquid crystal polyester composition of this embodiment may be 80% by mass or more and 100% by mass or less, 90% by mass or more and 100% by mass or less, or 99% by mass or more and 99.99% by mass or less.
[0079] <Other ingredients> The liquid crystal polyester composition of this embodiment may optionally contain other components in addition to the liquid crystal polyester (P0) and polymer (P1) described above.
[0080] The liquid crystal polyester composition of this embodiment may further contain a fibrous filler. Including a fibrous filler improves the mechanical properties of the molded article. The fibrous filler may be an inorganic filler or an organic filler. Examples of fibrous inorganic fillers include glass fibers, irregularly shaped cross-section glass fibers, carbon fibers, silica fibers, alumina fibers, ceramic fibers, metal fibers, silicon carbide fibers, or whiskers. Examples of fibrous organic fillers include polyester fibers; para-aramid fibers; and poly-para-phenylenebenzobisoxazole (PBO) fibers.
[0081] The liquid crystal polyester composition of this embodiment may further contain external additives such as higher fatty acid metal salts. Furthermore, the liquid crystal polyester composition of this embodiment may further contain other resins other than liquid crystal polyester, fillers other than fibrous fillers, flame retardants, conductivity imparters, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insecticides, deodorants, color inhibitors, heat stabilizers, antistatic agents, plasticizers, lubricants, dyes, foaming agents, antifoaming agents, viscosity modifiers, surfactants, and the like as other components.
[0082] Other resins besides liquid crystal polyester include fluororesins, polyolefin resins, vinyl resins, polystyrene resins, polyamide resins, polyester resins, polysulfone resins, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene ether, and polyimide resins.
[0083] Fillers other than fibrous fillers include plate-shaped fillers, spherical fillers, and powder-shaped fillers. Examples of plate-shaped fillers include talc, mica, glass flakes, and graphite. Plate-shaped fillers may be surface-treated or untreated. Examples of mica include natural mica such as muscovite, phlogopite, fluorinated phlogopite, and tetrasilicate mica, as well as artificially produced synthetic mica. Examples of spherical fillers include glass beads and glass balloons. Examples of powder-shaped fillers include calcium carbonate, dolomite, clay barium sulfate, titanium dioxide, carbon black, conductive carbon, and fine silica.
[0084] [Method for producing liquid crystal polyester composition] The liquid crystal polyester composition of this embodiment can be produced by mixing the above-mentioned liquid crystal polyester (P0), polymer (P1), and other components used as needed, either all at once or in an appropriate order. In other words, the liquid crystal polyester composition of this embodiment is a composition comprising the above-mentioned liquid crystal polyester (P0), polymer (P1), and other components used as needed. For the aforementioned mixing, melt kneading is preferred. The liquid crystal polyester composition of this embodiment can be prepared, for example, by melt kneading liquid crystal polyester (P0), polymer (P1), and other components using a kneader.
[0085] As described above, the liquid crystal polyester composition of this embodiment uses a combination of liquid crystal polyester (P0) and a branched-chain polymer (P1) represented by formula (p1). This weakens the tendency of the liquid crystal polyester to orient in the flow direction (MD). For example, by using the liquid crystal polyester composition of this embodiment, the strength against force in the TD direction perpendicular to the MD direction is increased, making it possible to manufacture molded articles that are less prone to tearing. Thus, the liquid crystal polyester composition of this embodiment can reduce the anisotropy of the liquid crystal polyester.
[0086] In addition, the liquid crystal polyester (P0) used in the liquid crystal polyester composition of this embodiment has 35% or more repeating units (N0) containing a naphthalene structure relative to 100% of the total number of repeating units constituting the liquid crystal polyester (P0). The monomer that provides these repeating units containing a naphthalene structure is a monomer that is effective in reducing the dielectric loss tangent. Therefore, a liquid crystal polyester composition containing such a specific liquid crystal polyester (P0) can provide a molding material with further reduction in dielectric loss tangent. Thus, the liquid crystal polyester composition of this embodiment reduces the anisotropy of the liquid crystal polyester and exhibits excellent electrical properties (low dielectric loss tangent, low relative permittivity).
[0087] (Molded body) One embodiment of the molded article includes the liquid crystal polyester composition of the embodiment described above. The molded article of this embodiment can be obtained by a known molding method using the liquid crystal polyester composition of the above-described embodiment. A preferred method for forming a molded article from a liquid crystal polyester composition is melt molding, and examples of such methods include injection molding, extrusion molding, compression molding, blow molding, vacuum molding, and press molding.
[0088] For example, when using a liquid crystal polyester composition as a molding material and molding by injection molding, the liquid crystal polyester composition is melted using a known injection molding machine, and the molten liquid crystal polyester composition is injected into a mold to perform the molding. The cylinder temperature of the injection molding machine is appropriately determined according to the type of liquid crystal polyester, for example, and is preferably set to a temperature 10 to 50°C higher than its flow start temperature, for example, 300 to 400°C.
[0089] The molded body of this embodiment can be applied, for example, to automotive parts and electronic components such as connectors, sockets, bobbins, and relay components.
[0090] (film) Figure 1 is a cross-sectional view showing one embodiment of the film. The film 10 shown in Figure 1 contains the liquid crystal polyester composition of the embodiment described above. The film 10 can be manufactured by melt-molding the liquid crystal polyester composition of the above-described embodiment. Examples of melt-molding methods include extrusion molding methods such as the T-die method and the inflation method. Even when the film 10 is manufactured using, for example, a T-die method, it contains the liquid crystal polyester composition of the embodiment described above, thus reducing anisotropy.
[0091] In addition, since the film 10 is made of a resin composition containing liquid crystal polyester (P0) having repeating units (N0) containing a naphthalene structure, it is also effective in imparting electrical properties (low dielectric loss tangent, low relative permittivity). Therefore, film 10 can be applied to films for diaphragms, resonators, filters, antennas, circuit boards, or multilayer circuit element substrates, for example. Furthermore, film 10 is also suitable as a substrate material for 5G devices that require high speed, large capacity, high reliability, low latency, and numerous simultaneous connections.
[0092] To address the aforementioned issues, this disclosure also encompasses the following other aspects.
[0093] [5] A polymer (P1) represented by the following formula (p1), Liquid crystal polyester (P0) (excluding those corresponding to the polymer (P1) mentioned above) and A liquid crystal polyester composition containing,
[0094] [ka] [In formula (p1), Ar 20 R represents an aromatic group with (n+m) valency. 10 R represents -CO-OH or -OH. 20 -CO-R 201 OR 202 Represents R 201This represents a liquid crystal polyester chain, or a polymer chain in which the chemical structure of the functional group contributing to the bond with -CO- in the polymer (P1) has been altered. 202 This represents a liquid crystal polyester chain, or a polymer chain in which the chemical structure of the functional group contributing to the bond with -O- in the polymer (P1) has been altered. n represents an integer greater than or equal to 1, m represents an integer greater than or equal to 0, and n+m is between 3 and 6.
[0095] The content of the polymer (P1) is 0.1 parts by mass or more and 15 parts by mass or less, based on 100 parts by mass of the total of the polymer (P1) and the liquid crystal polyester (P0). The liquid crystal polyester (P0) has repeating units (N0) containing a naphthalene structure, The number of repeating units (N0) is 35% or more of the total number of repeating units constituting the liquid crystal polyester (P0), The aforementioned Ar 20 A liquid crystal polyester composition comprising a residue obtained by removing (n+m) hydrogen atoms bonded to the ring structure of at least one aromatic hydrocarbon selected from the group consisting of benzene and triphenylbenzene.
[0096] [6] The liquid crystal polyester (P0) has the repeating unit (N0), A liquid crystal polyester composition according to [1], [2], or [5], comprising a repeating unit (1) represented by the following formula (1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) represented by the following formula (3). (1)-O-Ar 1 -CO- (2) New CO-Ar 2 -CO- (3)-X-Ar 3 -Y- [In formulas (1) to (3), Ar 1 represents a phenylene group, a naphthylene group, or a biphenylylene group, and Ar 2 and Ar 3The terms and represent, independently of each other, a phenylene group, a naphthylene group, a biphenylylene group, or a group represented by the following formula (4), and X and Y represent, independently of each other, an oxygen atom or an imino group (-NH-). 1 Ar 2 Or Ar 3 One or more hydrogen atoms in the group represented by the above may be independently substituted with a halogen atom, a C1-C10 alkyl group, or a C6-C20 aryl group. (4)-Ar 4 -Z-Ar 5 - In formula (4), Ar 4 and Ar 5 The 'A's represent a phenylene group or a naphthylene group independently of each other, and 'Z' represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylidene group having 1 to 10 carbon atoms. 4 Or Ar 5 One or more hydrogen atoms in the group represented by the above may be independently substituted with halogen atoms, C1-C10 alkyl groups, or C6-C20 aryl groups.
[0097] [7] The liquid crystal polyester composition according to [6], wherein the number of repeating units (1) in the liquid crystal polyester (P0) is 30% or more and 80% or less of the total number of repeating units constituting the liquid crystal polyester (P0), and the number of repeating units (2) and the number of repeating units (3) are both 10% or more and 35% or less of the total number of repeating units constituting the liquid crystal polyester (P0).
[0098] [8] R in equation (p1) 201 and R 202 The liquid crystal polyester composition according to any one of [1], [2], or [5] to [7], wherein the liquid crystal polyester constituting the liquid crystal polyester chain in the liquid crystal polyester composition has the same structure as the liquid crystal polyester (P0).
[0099] A molded article comprising a liquid crystal polyester composition as described in any one of the following items: [9] [1], [2], or [5] to [8]. A film comprising the liquid crystal polyester composition described in any one of the following items:
[10] [1], [2], or [5] to [8]. [Examples]
[0100] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to the following examples.
[0101] [Measurement of the flow initiation temperature of liquid crystal polyester] Using a flow tester (Shimadzu Corporation's "CFT-500EX" model), approximately 2 g of liquid crystal polyester was placed in a cylinder fitted 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, the sample was melted while the temperature was increased at a rate of 4°C / min, and extruded from the nozzle. The temperature at which the liquid crystal polyester exhibited a viscosity of 4800 Pa·s was measured and defined as the flow initiation temperature.
[0102] [Measurement of the content of each component in reaction product L3 (LC-MS analysis)] The reaction product L3 was freeze-milled using the following apparatus and coolant, under conditions of a freezing time of 5 minutes and a grinding time of 15 minutes. Equipment: JFC-300 cryogenic grinder manufactured by Nippon Analytical Industry Co., Ltd. Coolant: Liquid nitrogen Next, 25 mg of freeze-dried reaction product L3, 10 mL of N-methyl-2-pyrrolidone, and 2.5 mL of n-butylamine were mixed, and the resulting mixture was refluxed at 125°C for 2 hours to obtain the reaction mixture. The resulting reaction mixture was then concentrated under reduced pressure after adding 2 mL of methanol. 0.5 mL of formic acid was added to the residue, followed by N-methyl-2-pyrrolidone to prepare a 20 mL measurement solution. LC-MS analysis was performed on the obtained measurement solutions, and the area percentage of each peak of the compound in which 1,3,5-tris(4-carboxyphenyl)benzene was each n-butylamidated was determined. The content (mass %) of each component in reaction product L3, which contains compounds L31, L32, and L33 represented by the following formula (p1), was calculated by dividing the area percentage of the peak of each compound by the sum of the area percentage of the peak of each compound and the area percentage of the peak of 1,3,5-tris(4-carboxyphenyl)benzene.
[0103] (p1) (HO-OC) m -Ar 20 -(CO-OR 201 ) n In formula (p1), Ar 20 This represents the structure derived from the trivalent aromatic group 1,3,5-triphenylbenzene, and R 201 The ∫ represents the liquid crystal polyester chain in the reaction product L3 described later, where n is 1 to 3, m is 0 to 2, and n+m is 3.
[0104] Liquid crystal polyester L2 and reaction product L3 were produced using the manufacturing examples shown below.
[0105] <Example of Liquid Crystal Polyester L2 Manufacturing> In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser, 1034.99 g (5.5 mol) of 6-hydroxy-2-naphthoic acid, 272.52 g (2.475 mol, with an excess of 0.225 mol) of hydroquinone, 378.33 g (1.75 mol) of 2,6-naphthalenedicarboxylic acid, 83.07 g (0.5 mol) of terephthalic acid, and 1226.87 g (11.9 mol) of acetic anhydride were added, and the mixture was held at 145°C for 1 hour. Subsequently, 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 the mixture was held at the same temperature for 3 hours to obtain liquid crystal polyester L1. The obtained L1 was cooled to room temperature and pulverized to obtain powdered L1. The flow initiation temperature of the powdered L1 was 261°C.
[0106] Powdered L1 was heated from 25°C to 250°C over 1 hour. Then, it was further heated to 315°C over 5 hours and held at that temperature for 3 hours to obtain powdered liquid crystal polyester L2. Liquid crystal polyester L2 had repeating units (N0) containing a naphthalene structure, and the number of repeating units (N0) was 72.5% of the total number of repeating units constituting liquid crystal polyester L2 (100%).
[0107] <Example of preparation of reaction product L3> In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser, 1 kg of powdered L1 and 17.6 g of 1,3,5-tris(4-carboxyphenyl)benzene were added and stirred at approximately 350°C for 4 hours to obtain reaction product L3 containing L31, L32, and L33. In reaction product L3, the liquid crystal polyester chain had repeating units (N1) containing naphthalene structures, and the number of repeating units (N1) was 72.5% of the total number of repeating units constituting the liquid crystal polyester chain (100%).
[0108] The reaction product L3, containing L31, L32, and L33, was subjected to the above-described LC-MS analysis, and the content of each component in reaction product L3 was measured. The measurement results are shown below. Content of compound L33 (trifunctional compound; n=3, m=0) in reaction product L3: 64% by mass Content of compound L32 (bifunctional; n=2, m=1) in reaction product L3: 23% by mass Content of compound L31 (monofunctional; n=1, m=2) in reaction product L3: 11% by mass Content of 1,3,5-tris(4-carboxyphenyl)benzene (unreacted; n=0, m=3) in reaction product L3: 2% by mass In other words, the reaction product L3 was confirmed by the above LC-MS analysis to be a polymer mixture consisting of 64% by mass of trifunctional polymer, 23% by mass of difunctional polymer, 11% by mass of monofunctional polymer, and 2% by mass of unreacted polymer.
[0109] Compounds L31, L32, and L33 correspond to polymer (P1) in this disclosure. Liquid crystal polyester L2 corresponds to liquid crystal polyester (P0) in this disclosure.
[0110] <Examples of liquid crystal polyester composition production> (Comparative Example 1) L2 was used as is to obtain the liquid crystal polyester composition of Comparative Example 1.
[0111] (Example 2) The 3.35 g of L3 obtained above and 46.65 g of L2 were mixed, and the resulting mixture was placed in a tabletop compact kneader Xplore and melt-kneaded at a set temperature of 330°C to obtain a liquid crystal polyester composition.
[0112] (Example 1, Example 3, Comparative Example 2) The liquid crystal polyester compositions shown in Table 1 were obtained in the same manner as in Example 2, except that the mixing ratio of L3 and L2 obtained above was changed.
[0113] <Examples of film manufacturing> The obtained liquid crystal polyester composition was extruded from a T-die equipped with a heater set to 320°C to obtain a film with a width of 60 mm, a thickness of 0.07 mm, and a length of 300 mm in the extrusion direction.
[0114] <Rating> The anisotropy of the obtained films was evaluated using the MD / TD ratio as an indicator, and the heat resistance was evaluated using the 1% weight loss temperature as an indicator.
[0115] [Method for measuring MD / TD of film] From the obtained film, two test pieces for measuring the MD storage modulus (MD length 40 mm, TD length 4 mm, thickness 0.07 mm) and two test pieces for measuring the TD storage modulus (TD length 40 mm, MD length 4 mm, thickness 0.07 mm) were cut out. The storage modulus of each test piece was measured using a dynamic viscoelasticity measuring device DVA-225 manufactured by IT Measurement Control Co., Ltd. at 170°C, a frequency of 10 Hz, and a strain of 1%. The average of the storage moduli of two test specimens used for measuring the MD storage modulus was defined as the MD storage modulus value (MD value) of the film, and the average of the storage moduli of two test specimens used for measuring the TD storage modulus was defined as the TD storage modulus value (TD value) of the film. The ratio of the MD value to the TD value (hereinafter referred to as "MD / TD") was then calculated. The relative MD / TD of each film was calculated by setting the MD / TD of the film containing the liquid crystal polyester composition of Comparative Example 1, i.e., the film containing only L2, to 100. The results of this calculation are shown in Table 1. A smaller MD / TD value indicates less anisotropy in the film. In Table 1, for Comparative Example 2 (*), although a film was obtained, the film had numerous holes, and many irregularities were observed on the film surface.
[0116] [Method for measuring dielectric loss tangent] From the films obtained using each of the liquid crystal polyester compositions from Example 2, Example 3, and Comparative Example 1 as molding materials, test pieces for dielectric loss tangent measurement with a TD length of 60 mm and an MD length of 130 mm were cut out. The thickness of the test pieces was measured at 20 locations, and the arithmetic mean was taken as the sample thickness. The dielectric loss tangent of this test specimen was measured at a frequency of 10 GHz using the cylindrical cavity resonator method with an Agilent Technologies cylindrical resonator consisting of a vector network analyzer HP8510C, a synthesized sweeper HP83651A, and a test set HP8517B (inner diameter φ42 mm, height 30 mm). The results are shown in Table 1.
[0117] [Table 1]
[0118] The results shown in Table 1 confirm that the films containing the liquid crystal polyester compositions of Examples 1 to 3 exhibit reduced anisotropy compared to the film containing the liquid crystal polyester composition of Comparative Example 1.
[0119] [Method for measuring the 1% weight loss temperature of film] 5 mg of film was cut from each film containing the liquid crystal polyester composition of Example 1, Example 3, and Comparative Example 1 to obtain measurement samples. Using a Shimadzu Corporation DTG-60H differential thermal and thermogravimetric analyzer, the sample was heated to 600°C at a heating rate of 10°C / min, and the change in mass of the sample was measured. The 1% weight loss temperature was defined as the temperature at which the mass of the sample decreased by 1% compared to the mass at 150°C. The results are shown below. 1% weight loss temperature Film containing the liquid crystal polyester composition of Comparative Example 1 at 447°C Film containing the liquid crystal polyester composition of Example 1 at 463°C Film containing the liquid crystal polyester composition of Example 3 at 445°C
[0120] The film containing the liquid crystal polyester composition of Example 1 was found to have a higher 1% weight loss temperature and higher heat resistance compared to the films containing the liquid crystal polyester compositions of Example 3 and Comparative Example 1.
[0121] Each configuration and combination thereof in each embodiment is merely an example, and modifications such as additions, omissions, and substitutions of configurations are possible without departing from the spirit of this disclosure. Furthermore, this disclosure is not limited to each embodiment, but is limited only to the claims. [Explanation of symbols]
[0122] 10 films
Claims
1. A polymer (P1) represented by the following formula (p1), Liquid crystal polyester (P0) (excluding those corresponding to the polymer (P1) above) and A liquid crystal polyester composition containing, The content of the polymer (P1) is 0.1 parts by mass or more and 15 parts by mass or less, based on 100 parts by mass of the total of the polymer (P1) and the liquid crystal polyester (P0). The liquid crystal polyester (P0) has repeating units (N0) containing a naphthalene structure, A liquid crystal polyester composition in which the number of repeating units (N0) is 35% or more of the total number of repeating units constituting the liquid crystal polyester (P0) as 100%. 【Chemistry 1】 [In formula (p1), Ar ２０ R represents an aromatic group with (n+m) valency. １０ R represents -CO-O-H or -O-H. ２０ is, -CO-R ２０１ OR OR ２０２ Represents R ２０１ R represents a liquid crystal polyester chain, or a polymer chain in which the chemical structure of the functional group contributing to the bond with -CO- in the polymer (P1) has been altered. ２０２ This represents a liquid crystal polyester chain, or a polymer chain in which the chemical structure of the functional group contributing to the bond with -O- in the polymer (P1) has been altered. n represents an integer of 1 or more, m represents an integer of 0 or more, and n+m is between 3 and 6.
2. Said R ２０１ or said R ２０２ contains a liquid crystal polyester chain having a repeating unit (N1) containing a naphthalene structure, The liquid crystal polyester composition according to claim 1, wherein the number of repeating units (N1) is 50% or more of the total number of repeating units constituting the liquid crystal polyester chain in the polymer (P1) relative to 100% of the total number of repeating units.
3. A molded article comprising the liquid crystal polyester composition according to claim 1 or 2.
4. A film comprising the liquid crystal polyester composition according to claim 1 or 2.