TW202342639A - Liquid crystal polyester composition, method for producing liquid crystal polyester composition, film, and method for producing film - Google Patents

Abstract

The present invention relates to a liquid crystal polyester composition comprising a liquid crystal polyester (A) and a liquid crystal polyester (B), in which the liquid crystal polyester (B) has a repeating unit represented by formula (B1): -O-Arb1-CO- (wherein Arb1 represents a phenylene group, a naphthylene group or a biphenylylene group, in which hydrogen atoms in the group represented by Arb1 may be each independently substituted by a halogen atom, an alkyl group or an aryl group), and the number of the repeating units each represented by formula (B1) relative to the total number (100%) of all of repeating units constituting the liquid crystal polyester (B) is more than 80%.

Description

Liquid crystal polyester composition, liquid crystal polyester composition manufacturing method, film and film manufacturing method

The present invention relates to a liquid crystal polyester composition, a method for manufacturing the liquid crystal polyester composition, a film, and a method for manufacturing the film. This case claims priority based on patent application No. 2022-011708 filed in Japan on January 28, 2022, the content of which is cited here.

Liquid crystal polyester films have attracted attention as substrate materials for electronic products because they have excellent high-frequency characteristics and low water absorption.

Liquid crystal polyester film can provide a laminate that functions as an insulating material (such as copper-clad laminate: Copper Clad Laminate, CCL, flexible copper-clad laminate: Flexible Copper Clad Laminate, FCCL, which has copper foil on both sides. Double-sided CCL, etc.).

Patent Document 1 discloses an aromatic liquid crystal polyester having a specific repeating unit derived from an aromatic hydroxycarboxylic acid. This aromatic liquid crystal polyester can suppress dielectric loss and provide a film with excellent heat resistance and excellent film processability.

On the other hand, Patent Document 2 describes an insulating material for a circuit board made of a liquid crystalline aromatic polyester composed of a specific structural unit, and the insulating material has a small dielectric loss tangent in a high-frequency region. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2005-272819 [Patent Document 2] Patent No. 4363057

[Problem solved by the invention]

However, although the material disclosed in Patent Document 1 is excellent in dielectric loss tangent, there is still room for further improvement in improving processing characteristics in thin film formation. In addition, although the material shown in Patent Document 2 is excellent in dielectric loss tangent, there is still room for further improvement in terms of characteristics required in recent years.

The present invention is made to solve the above-mentioned problems, and aims to provide a liquid crystal polyester composition with an excellent balance between dielectric loss tangent and processing characteristics. Furthermore, the present invention aims to provide a film of the liquid crystal polyester composition and a method for producing the same. [Means to solve the problem]

In order to solve the above-mentioned problems, the present inventors conducted a detailed examination and found that the processing characteristics in thin film production are such that the viscosity of the molding material does not increase even when the temperature of the molding material decreases. Focusing on the improvement of this characteristic, they found that by using a liquid crystal polyester composition When the specific liquid crystal polyester (B) is contained in the liquid crystal polyester composition, the increase in viscosity caused by the temperature drop of the liquid crystal polyester composition can be suppressed, thereby completing the present invention. That is, the present invention has the following aspects.

<1> A liquid crystal polyester composition containing liquid crystal polyester (A) and liquid crystal polyester (B). The liquid crystal polyester (A) has repeating units represented by the following formula (A1), the following formula (A2) ) and the repeating unit represented by the following formula (A3), (A1)-O-Ar ¹ -CO- (A2)-CO-Ar ² -CO- (A3)-X-Ar ³ -Y- (Ar ¹ represents a phenylene group, naphthylene group or biphenylene group. Ar ² and Ar ³ each independently represent a phenylene group, naphthylene group, biphenylene group or a group represented by the following formula (A4). X and Y each independently represents an oxygen atom or an imine group (-NH-). The hydrogen atom in the aforementioned group represented by Ar ¹ , Ar ² or Ar ³ can each independently be substituted by a halogen atom, an alkyl group or an aryl group). (A4)-Ar ⁴ -Z-Ar ⁵ - (Ar ⁴ and Ar ⁵ each 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 alkylene group). With respect to 100% of the total number of repeating units constituting the liquid crystal polyester (A), the number of repeating units represented by the formula (A1) is 30% or more and 80% or less, and the liquid crystal polyester (B) has the following The repeating unit represented by the formula (B1), (B1)-O-Ar ^b1 -CO- (Ar ^b1 represents a phenylene group, naphthylene group or biphenylene group. The hydrogen atoms in the aforementioned groups represented by Ar ^b1 are each independent Can be substituted by halogen atoms, alkyl or aryl groups). The number of repeating units represented by the aforementioned formula (B1) exceeds 80% relative to 100% of the total number of repeating units constituting the liquid crystal polyester (B). <2> The repeating unit represented by the aforementioned formula (B1) contains the repeating unit represented by the following formula (B1-1), (B1-1)-O-Ar ^b1-1 -CO- (Ar ^b1-1 represents a naphthylene group . Each hydrogen atom in the aforementioned group represented by Ar ^b1-1 can be independently substituted by a halogen atom, an alkyl group or an aryl group). The liquid crystal polymer described in <1> above has a number of repeating units represented by the aforementioned formula (B1-1) exceeding 50% and not more than 90% relative to 100% of the total number of repeating units corresponding to the aforementioned formula (B1). Ester composition. <3> When the content ratio of the aforementioned liquid crystal polyester (A) and the aforementioned liquid crystal polyester (B) in the aforementioned liquid crystal polyester composition is expressed as a mass ratio, liquid crystal polyester (A)/liquid crystal polyester (B) = 95/5～25/75 The liquid crystal polyester composition described in the above <1> or <2>. <4> When the content ratio of the aforementioned liquid crystal polyester (A) and the aforementioned liquid crystal polyester (B) in the aforementioned liquid crystal polyester composition is expressed as a mass ratio, liquid crystal polyester (A)/liquid crystal polyester (B) = 95/5 to 50/50 The liquid crystal polyester composition described in the above <1> or <2>. <5> The ratio of the total content of the liquid crystal polyester (A) and the liquid crystal polyester (B) to 100 mass % of the total mass of the liquid crystal polyester composition is 80 mass % or more, as mentioned above <1 The liquid crystal polyester composition described in any one of > to <4>. <6> The liquid crystal polyester (B) is the liquid crystal polyester composition described in any one of the above <1> to <5>, which is composed only of repeating units represented by the above formula (B1). <7> The liquid crystal polyester (A) has the repeating unit represented by the following formula (A1), the repeating unit represented by the following formula (A2), and the repeating unit represented by the following formula (A3). The aforementioned <1> to <6> The liquid crystal polyester composition described in any one of the above. (A1)-O-Ar ¹ -CO- (A2)-CO-Ar ² -CO- (A3)-O-Ar ³ -O- (Ar ¹ represents 2,6-naphthylene, 1,4-ethylene phenyl or 4,4'-biphenylene. Ar ² and Ar ³ each independently represent 2,6-naphthylene, 2,7-naphthylene, 1,4-phenylene, 1,3-phenylene. Phenyl or 4,4'-biphenylene. The hydrogen atoms in the aforementioned groups represented by Ar ¹ , Ar ² or Ar ³ can each independently consist of a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkyl group with 6 to 20 carbon atoms. Aryl substitution). <8> The repeating unit represented by the aforementioned formula (B1) is the aforementioned <1> to <7 consisting only of the repeating unit represented by the following formula (B1-1) and the repeating unit represented by the following formula (B1-2). >The liquid crystal polyester composition described in any one of the above. (B1-1)-O-Ar ^b1-1 -CO- (B1-2)-O-Ar ^b1-2 -CO- (Ar ^b1-1 represents naphthylene group. Ar ^b1-2 represents phenylene group. Ar Each hydrogen atom in the aforementioned group represented by ^b1-1 or Ar ^b1-2 can be independently substituted by a halogen atom, an alkyl group or an aryl group). <9> The aforementioned liquid crystal polyester composition contains components whose retention time ranges from 17.4 to 17.5 minutes when the amine decomposition product obtained under the following amine decomposition conditions was analyzed by liquid chromatography under the following analysis conditions. 4 -(4-Hydroxyphenoxy)benzoic acid was used as a standard substance and the relative content of the aforementioned components relative to the total mass of the aforementioned liquid crystal polyester composition was determined by the absorption peak area of the chromatogram analyzed by the aforementioned liquid chromatography method. In terms of 100% by mass, it is 0.0001% by mass or more and 0.5% by mass or less of the liquid crystal polyester composition described in any one of the above <1> to <8>. (Amine decomposition conditions) The liquid crystal polyester composition and butylamine are mixed and treated at 200° C. for 2 hours or more. Then, a pressure reduction treatment at 60° C. is performed to remove butyl amine, and formic acid is added to neutralize. After treatment, the aforementioned amine decomposition product is obtained. (Analysis conditions) Column: base material (porous spherical silica), modified group (octadecyl), film thickness 3μm, 3mmϕ×15cm Mobile phase: A) 0.1 vol% acetic acid water B) 0.1 vol% Acetic acid acetonitrile gradient: start flowing the liquid with the proportion of the aforementioned mobile phase A of 90 volume % and the proportion of the aforementioned mobile phase B of 10 volume %, and slowly increase the concentration over 30 minutes until the proportion of the aforementioned mobile phase B is 100 volume %. B Measured for 10 minutes at a ratio of 100 volume % Column temperature: 45°C Detector: UV-254nm Flow rate: 0.4mL/min Injection volume: 1μL <10> Among the liquid crystal polyester contained in the aforementioned liquid crystal polyester composition The liquid crystal polyester composition described in any one of the above <1> to <9> has a weight average molecular weight measured using polystyrene as a standard material of 270,000 or more. <11> A method for producing the liquid crystal polyester composition described in any one of the above <1> to <10>, including mixing the liquid crystal polyester (A) and the liquid crystal polyester (B). <12> A film containing liquid crystal polyester (A) and liquid crystal polyester (B), wherein the liquid crystal polyester (A) has a repeating unit represented by the following formula (A1), a repeating unit represented by the following formula (A2) The unit is the same as the repeating unit represented by the following formula (A3), (A1)-O-Ar ¹ -CO- (A2)-CO-Ar ² -CO- (A3)-X-Ar ³ -Y- (Ar ¹ represents Phenylene group, naphthylene group or biphenylene group. Ar ² and Ar ³ each independently represent a phenylene group, naphthylene group, biphenylene group or a group represented by the following formula (A4). X and Y each independently represent Oxygen atom or imine group (-NH-). The hydrogen atoms in the aforementioned groups represented by Ar ¹ , Ar ² or Ar ³ can each be independently substituted by a halogen atom, an alkyl group or an aryl group). (A4)-Ar ⁴ -Z-Ar ⁵ - (Ar ⁴ and Ar ⁵ each 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 alkylene group). With respect to 100% of the total number of repeating units constituting the liquid crystal polyester (A), the number of repeating units represented by the formula (A1) is 30% or more and 80% or less, and the liquid crystal polyester (B) has the following The repeating unit represented by the formula (B1), (B1)-O-Ar ^b1 -CO- (Ar ^b1 represents a phenylene group, naphthylene group or biphenylene group. The hydrogen atoms in the aforementioned groups represented by Ar ^b1 are each independent Can be substituted by halogen atoms, alkyl or aryl groups). A film in which the number of repeating units represented by the aforementioned formula (B1) exceeds 80% relative to 100% of the total number of repeating units constituting the aforementioned liquid crystal polyester (B). <13> A method for producing a film as described in <12> above, which includes melt-forming a film using a liquid crystal polyester composition as described in any one of <1> to <10> as a molding material. <14> The above-mentioned melt forming is the film manufacturing method described in the above <13> which is formed by the inflation method or the T-die method. [Effects of the invention]

According to the present invention, a liquid crystal polyester composition having an excellent balance between dielectric loss tangent and processing characteristics is provided. Furthermore, according to the present invention, there is provided a film of the aforementioned liquid crystal polyester composition and a manufacturing method thereof.

[Types of carrying out the invention]

Embodiments of the liquid crystal polyester composition, the manufacturing method of the liquid crystal polyester composition, the film, and the manufacturing method of the film according to the present invention will be described below.

≪Liquid crystal polyester composition≫ The liquid crystal polyester composition according to the embodiment is a liquid crystal polyester composition containing the following liquid crystal polyester (A) and the following liquid crystal polyester (B). Since the liquid crystal polyester composition of the embodiment contains the aforementioned liquid crystal polyester (A) and liquid crystal polyester (B), it has an excellent balance between dielectric loss tangent and processing characteristics.

In this specification, the term "the liquid crystal polyester composition has excellent processing characteristics" means that the liquid crystal polyester composition is heated to a temperature higher than the endothermic absorption peak detected by a differential scanning calorimeter and is heated to This means that the viscosity of the liquid crystal polyester composition increases slightly when the temperature drops.

The above-mentioned degree of viscosity increase can be confirmed by the difference between the viscosity of the liquid crystal polyester composition at the temperature at the apex of the endothermic absorption peak detected by a differential scanning calorimeter and the self-endothermic absorption peak. The difference in viscosity at the time point when the temperature at the apex position drops by 20°C (eta _{Tm-20 °C} - eta _Tm ). The smaller the value of this difference (eta _{Tm-20 °C} - eta _Tm ), the smaller the degree of increase in viscosity. The above-mentioned degree of viscosity increase can also be confirmed by the following ratio, for example, the viscosity of the liquid crystal polyester composition at the temperature at the apex of the endothermic absorption peak detected by a differential scanning calorimeter, and the viscosity of the self-endothermic absorption peak. The ratio of viscosity at the time when the temperature at the top position drops by 20°C (η _{Tm-20 °C} / eta _Tm ). The smaller the value of this ratio (eta _{Tm-20 ° C./eta Tm} ), the smaller the degree of increase in viscosity.

The lower the value of the dielectric loss tangent of the liquid crystal polyester composition, the better the dielectric loss tangent. As a liquid crystal polyester composition with an excellent balance between dielectric loss tangent and processing characteristics, as an example of a preferable dielectric loss tangent value of the liquid crystal polyester composition, a test piece in the [Dielectric Characteristics Evaluation] described below can be exemplified. The measured dielectric loss tangent value at a frequency of 10 GHz is 0.0010 or less. The so-called "dielectric properties" in this specification refer to the correlation properties between specific conductivity and dielectric loss tangent. Preferred dielectric properties of the liquid crystal polyester composition include a specific conductivity value of 3 or more and 4 or less at a frequency of 10 GHz measured on a test piece in [Dielectric Property Evaluation] described later. The dielectric loss tangent value is between 0.0002 and below 0.0010.

The liquid crystal polyester contained in the liquid crystal polyester composition of this embodiment means a polyester that exhibits liquid crystallinity in a molten state, preferably one that melts at a temperature of 450° C. or lower.

The liquid crystal polyester contained in the liquid crystal polyester composition of this embodiment is preferably a fully aromatic liquid crystal polyester using only aromatic compounds as raw material monomers. The liquid crystal polyester is preferably a fully aromatic liquid crystal polyester having only repeating units derived from aromatic compounds.

Typical examples of liquid crystal polyester include polymerization of aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, and at least one compound selected from the group consisting of aromatic diol, aromatic hydroxylamine, and aromatic diamine. Polymers formed by (polycondensation); polymers formed by polymerizing multiple aromatic hydroxycarboxylic acids; polymers composed of aromatic dicarboxylic acids and free aromatic diols, aromatic hydroxylamines and aromatic diamines A polymer formed by polymerizing at least one compound; a polymer formed by polymerizing polyesters such as polyethylene terephthalate and aromatic hydroxycarboxylic acid. Among them, aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic hydroxylamines and aromatic diamines may also be polymerized derivatives in which a part or all of them are independently substituted.

Examples of polymerizable derivatives of compounds having carboxyl groups such as aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids include esters in which the carboxyl group is converted into an alkoxycarbonyl group or an aryloxycarbonyl group; and esters in which the carboxyl group is converted into Acid halides of halogenated formyl groups; acid anhydrides that convert carboxyl groups into acyloxycarbonyl groups, etc.

Examples of polymerizable derivatives of compounds having hydroxyl groups such as aromatic hydroxycarboxylic acids, aromatic diols, and aromatic hydroxylamines include chelate compounds in which a hydroxyl group is converted into a chelateoxy group through chelation. Examples of polymerizable derivatives of compounds having an amine group such as aromatic hydroxylamine and aromatic diamine include a chelate compound in which an amine group is converted into a amide group through chelation.

The details of the liquid crystal polyester (A) and the liquid crystal polyester (B) contained in the liquid crystal polyester composition of the embodiment will be described below.

<Liquid crystal polyester (A)> The liquid crystal polyester (A) has a repeating unit represented by the following formula (A1), a repeating unit represented by the following formula (A2), and a repeating unit represented by the following formula (A3), ( A1)-O-Ar ¹ -CO- (A2)-CO-Ar ² -CO- (A3)-X-Ar ³ -Y- (Ar ¹ represents phenylene, naphthylene or biphenylene. Ar ² and Ar ³ each independently represent a phenylene group, naphthylene group, biphenylene group or a group represented by the following formula (A4). X and Y each independently represent an oxygen atom or an imine group (-NH-). Ar ¹ The hydrogen atoms in the aforementioned groups represented by Ar ² or Ar ³ can each be independently substituted by a halogen atom, an alkyl group or an aryl group). (A4)-Ar ⁴ -Z-Ar ⁵ - (Ar ⁴ and Ar ⁵ each 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 alkylene group). The number of repeating units represented by the aforementioned formula (A1) is 30% or more and 80% or less relative to the total number of all repeating units constituting the liquid crystal polyester (A) (100%).

The ratio of each repeating unit in the liquid crystal polyester (A) will be described in detail later.

From the viewpoint of making the dielectric loss tangent more excellent, the liquid crystal polyester (A) exemplified above has a repeating unit represented by the following formula (A1) and is represented by the following formula (A2) The repeating unit is preferably the repeating unit represented by the following formula (A3).

Preferable examples of Ar ¹ , Ar ² and Ar ³ in the formulas (A1) to (A3) include the following.

(A1)-O-Ar ¹ -CO- (A2)-CO-Ar ² -CO- (A3)-O-Ar ³ -O- (Ar ¹ , Ar ² and Ar ³ each independently represent phenylene group, phenylene group, Naphthyl or biphenylene group. The hydrogen atoms in the aforementioned groups represented by Ar ¹ , Ar ² or Ar ³ can each be independently substituted by a halogen atom, an alkyl group or an aryl group).

From the viewpoint of making the dielectric loss tangent more excellent, specifically, the liquid crystal polyester (A) exemplified above has a repeating unit represented by the following formula (A1), the following formula ( The repeating unit represented by A2) and the repeating unit represented by the following formula (A3) are preferred.

Examples of preferred Ar ¹ , Ar ² and Ar ³ in the formulas (A1) to (A3) include the following.

(A1)-O-Ar ¹ -CO- (A2)-CO-Ar ² -CO- (A3)-O-Ar ³ -O- (Ar ¹ represents 2,6-naphthylene, 1,4-ethylene phenyl or 4,4'-biphenylene. Ar ² and Ar ³ each independently represent 2,6-naphthylene, 2,7-naphthylene, 1,4-phenylene, 1,3-phenylene. Phenyl or 4,4'-biphenylene. The hydrogen atoms in the aforementioned groups represented by Ar ¹ , Ar ² or Ar ³ can each independently consist of a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an alkyl group with 6 to 20 carbon atoms. Aryl substitution).

Examples of the halogen atom that can be substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkyl group having 1 to 10 carbon atoms that can be substituted for a hydrogen atom include methyl, ethyl, 1-propyl, isopropyl, 1-butyl, isobutyl, sec-butyl, tert-butyl, 1-hexyl, 2-ethylhexyl, 1-octyl and 1-decyl, etc.

Examples of the aryl group having 6 to 20 carbon atoms that can be substituted for a hydrogen atom include monocyclic aromatic groups such as phenyl, o-tolyl, m-tolyl, and p-tolyl, or 1-naphthyl, 2-naphthyl and other condensed ring aromatic groups.

When one or more hydrogen atoms in the aforementioned group represented by Ar ¹ , Ar ² or Ar ³ are substituted by the aforementioned halogen atom, the aforementioned alkyl group having 1 to 10 carbon atoms, or the aforementioned aryl group having 6 to 20 carbon atoms, it is substituted The number of radicals of the aforementioned hydrogen atoms is preferably 1 or 2, more preferably 1, independently of each other represented by Ar ¹ , Ar ² or Ar ³ . The hydrogen atom possessed by Ar ¹ , Ar ² or Ar ³ does not need to be substituted by the above-mentioned group.

The liquid crystal polyester (A) preferably contains a repeating unit having a naphthalene structure. Liquid crystal polyesters containing repeating units with a naphthalene structure tend to have a more excellent dielectric loss tangent than liquid crystal polyesters that do not contain repeating units with a naphthalene structure.

As a liquid crystal polyester having a repeating unit containing a divalent naphthalene structure, a liquid crystal polyester having a repeating unit represented by the above formula (A1), a repeating unit represented by the above formula (A2), and a repeating unit represented by the above formula (A3) , it is preferred that at least one of the plural Ar ¹ , Ar ² and Ar ³ is a naphthylene group, and a 2,6-naphthylene group is preferred.

The content of the liquid crystal polyester (A) based on the number of repeating units containing a naphthalene structure is preferably 40% or more relative to the total number of all repeating units (100%) in the liquid crystal polyester (A). , the one with more than 50% is better, the one with more than 55% is better, the one with more than 60% is better. By setting the content of the repeating unit containing the naphthalene structure above the above lower limit, the dielectric loss tangent of the liquid crystal polyester can be further reduced. The content of the liquid crystal polyester (A) based on the number of repeating units containing a naphthalene structure is preferably 90% or less relative to the total number of all repeating units in the liquid crystal polyester (100%), and is preferably 85% or less. The one with % or less is better, and the one with 80% or less is even better. By setting the content of repeating units containing a naphthalene structure below the above upper limit, reaction stability for producing liquid crystal polyester can be ensured. As an example of the numerical range of the repeating unit containing the naphthalene structure in the liquid crystal polyester (A), it can be 40% or more and 90% or less, it can be 50% or more and 85% or more, or it can be 55% or more and 85%. % or less, it can also be more than 60% and less than 80%.

The liquid crystal polyester having repeating units represented by the above formulas (A1) to (A3) preferably has repeating units in which Ar ¹ and/or Ar ² are 2,6-naphthylene groups. In the liquid crystal polyester (A), the content of the repeating unit Ar ¹ and/or Ar ² represented by the above formulas (A1) to (A3) is a 2,6-naphthylene group, relative to the liquid crystal polyester ( For the total number (100%) of all repeating units in A), based on the number basis, it may contain more than 40%, it may contain more than 40% and less than 90%, it may contain more than 50% and less than 85%, or it may contain more than 50% and less than 85%. It can contain more than 55% and less than 85%, and it can also contain more than 60% and less than 80%.

The repeating unit represented by the above formula (A1) is a repeating unit derived from an aromatic hydroxycarboxylic acid. Examples of the aromatic hydroxycarboxylic acid include p-hydroxybenzoic acid, m-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-3-naphthoic acid, 1-hydroxy-5-naphthoic acid, 4 -Hydroxy-4'-carboxydiphenyl ether, or a part of the hydrogen atoms of the aromatic ring of these aromatic hydroxycarboxylic acids is substituted with a substituent selected from the group consisting of alkyl groups, aryl groups and halogen atoms. Aromatic hydroxycarboxylic acid. The aromatic hydroxycarboxylic acid mentioned above can be used alone or in combination of two or more kinds in the production of liquid crystal polyester. As the repeating unit represented by the above formula (A1), Ar ¹ is a repeating unit of 1,4-phenylene group (for example, a repeating unit derived from 4-hydroxybenzoic acid) and Ar ¹ is a repeating unit of 2,6-naphthylene group. Units (eg, repeating units from 6-hydroxy-2-naphthoic acid) are preferred.

The repeating unit represented by the above formula (A2) is a repeating unit derived from an aromatic dicarboxylic acid. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, biphenyl-4,4'-dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, and diphenyl ether-4 , 4'-dicarboxylic acid, diphenylthioether-4,4'-dicarboxylic acid, or a part of the hydrogen atoms in the aromatic ring of these aromatic dicarboxylic acids is selected from the group consisting of alkyl, aryl and An aromatic dicarboxylic acid substituted with a substituent group consisting of halogen atoms. The above-mentioned aromatic dicarboxylic acid can be used alone or in combination of two or more kinds in the production of liquid crystal polyester. As the repeating unit represented by the above formula (A2), Ar ² is a repeating unit of 1,4-phenylene group (for example, a repeating unit derived from terephthalic acid), and Ar ² is a repeating unit of 1,3-phenylene group. Repeating units (e.g., repeating units derived from isophthalic acid), Ar ² as repeating units of 2,6-naphthylene (e.g., repeating units derived from 2,6-naphthalenedicarboxylic acid), and Ar ² Preferably, they are repeating units of diphenylether-4,4'-diyl (for example, repeating units derived from diphenylether-4,4'-dicarboxylic acid).

The repeating unit represented by the above formula (A3) is a repeating unit derived from aromatic diol, aromatic hydroxylamine or aromatic diamine. Examples of the aromatic diol, aromatic hydroxylamine or aromatic diamine include 4,4'-dihydroxybiphenyl, hydroquinone, methylhydroquinone, resorcinol, and 4,4'-dihydroxybiphenyl. Hydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, bis(4-hydroxyphenyl)methane, 1,2-bis(4-hydroxyphenyl)ethane, 4,4'-dihydroxy Diphenyl sulfide, 4,4'-dihydroxydiphenylthioether, 2,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 4-aminophenol, 1,4-phenylenediamine, 4 -Amino-4'-hydroxybiphenyl, 4,4'-diaminobiphenyl. The aforementioned aromatic diol, aromatic hydroxylamine or aromatic diamine can be used alone or in combination of two or more types in the production of liquid crystal polyester. As the repeating unit represented by the above formula (A3), Ar ³ is the repeating unit of 1,4-phenylene group (for example, the repeating unit derived from hydroquinone, 4-aminophenol or 1,4-phenylenediamine) and Ar ³ is the repeating unit of 4,4'-biphenylene (for example, from 4,4'-dihydroxybiphenyl, 4-amino-4'-hydroxybiphenyl or 4,4'-dihydroxybiphenyl). The repeating unit of aminobiphenyl group) is preferred.

The term "from" in this specification means that the chemical structure of the raw material monomer changes during polymerization, but no other structural changes occur.

The so-called "derived" also includes the concept of originating from polymerizable derivatives of the compound. For example, each repeating unit may also be derived from each chelate compound of aromatic hydroxycarboxylic acid, aromatic diol and aromatic hydroxylamine. Repeating units.

Moreover, when the liquid crystal polyester composition of the embodiment is particularly required to have good heat resistance, the smaller the number of these substituents, the better, especially those having substituents such as alkyl groups.

The content of the repeating unit represented by the aforementioned formula (A1) (hereinafter also referred to as repeating unit (A1)) in the liquid crystal polyester (A) on a number basis, relative to the total number of all repeating units (100%) It is preferably between 30% and below 80%, preferably between 40% and below 70%, and preferably above 45% and below 65%.

The content of the repeating unit represented by the aforementioned formula (A2) (hereinafter also referred to as repeating unit (A2)) in the liquid crystal polyester (A) on a number basis, relative to the total number of all repeating units (100%) In other words, 35% or less is better, 10% or more and 35% or less is better, 15% or more and 30% or less is better, 17.5% or more and 27.5% or less is particularly good.

The content of the repeating unit represented by the aforementioned formula (A3) (hereinafter referred to as repeating unit (A3)) in the liquid crystal polyester (A) on a number basis, relative to the total number of all repeating units (100%) In terms of ratio, 35% or less is better, 10% or more and 35% or less is better, 15% or more and 30% or less is better, 17.5% or more and 27.5% or less is particularly good.

In liquid crystal polyester (A), the greater the content of the repeating unit (A1), the easier it is to improve melt fluidity, heat resistance, strength and rigidity. However, when too much, the melt temperature or melt viscosity is likely to be high, which is problematic for molding. The necessary temperature tends to become high.

In the liquid crystal polyester (A), the ratio of the content of the repeating unit (A2) to the content of the repeating unit (A3) is [content of the repeating unit (A2)]/[content of the repeating unit (A3)] ( (number/number), 0.9/1 to 1/0.9 is preferred, 0.95/1 to 1/0.95 is preferred, and 0.98/1 to 1/0.98 is preferred.

In addition, the liquid crystal polyester (A) may have two or more independent repeating units (A1) to (A3). In addition, the liquid crystal polyester may have repeating units other than the repeating units (A1) to (A3). However, the content is 10% relative to the total number of all repeating units constituting the liquid crystal polyester (A) (100%). The following is preferred, below 5% is preferred, and 0% is preferred.

The sum of the content rate of the repeating unit (A1) of the liquid crystal polyester (A), the content rate of the repeating unit (A2) of the liquid crystal polyester (A), and the content rate of the repeating unit (A3) of the liquid crystal polyester (A) It will not exceed 100% based on the number of units.

In this specification, the number of each repeating unit (the degree of polymerization of each repeating unit) represents a value that can be obtained by the analysis method described in Japanese Patent Application Laid-Open No. 2000-19168. Specifically, the liquid crystal polyester resin is reacted with a lower alcohol (alcohol having 1 to 3 carbon atoms) in a supercritical state, and the liquid crystal polyester resin is depolymerized until the monomer of the repeating unit is derived, as a depolymerization product. When the obtained monomers derived from each repeating unit are quantified by liquid chromatography, the number of each repeating unit can be calculated. For example, when the liquid crystal polyester resin is composed of repeating units (A1) to (A3), the number of repeating units (A1) can be determined by the number of monomers from which the repeating units (A1) to (A3) are derived. The molar concentration is calculated by liquid chromatography by calculating the molar concentration of the monomers derived from the repeating units (A1) to (A3) when the sum of the molar concentrations of the monomers derived from the repeating units (A1) to (A3) is taken as 100%. The ratio of molar concentration can be obtained.

<Liquid crystal polyester (B)> The aforementioned liquid crystal polyester (B) has a repeating unit represented by the following formula (B1), (B1)-O-Ar ^b1 -CO- (Ar ^b1 represents a phenylene group, naphthylene group or Biphenylene group. Each of the hydrogen atoms in the aforementioned group represented by Ar ^b1 can be independently substituted by a halogen atom, an alkyl group or an aryl group). The number of repeating units represented by the aforementioned formula (B1) exceeds 80% relative to the total number (100%) of all repeating units constituting the aforementioned liquid crystal polyester (B).

Examples of the phenylene group, naphthylene group and biphenylene group in Ar ^b1 include the same groups exemplified in the liquid crystal polyester (A).

Examples of the halogen atom, alkyl group or aryl group in Ar ^b1 include the same groups exemplified in the above-mentioned liquid crystal polyester (A).

In the liquid crystal polyester (B), the higher the content ratio of the repeating unit represented by the aforementioned formula (B1) is contained in the liquid crystal polyester composition, the more excellent the effect of suppressing an increase in viscosity due to a temperature drop will be. From this point of view, the number of repeating units represented by the aforementioned formula (B1) exceeds 80% with respect to the total number (100%) of all repeating units constituting the aforementioned liquid crystal polyester (B), and is 85% or more and 100% or less. Preferably, it is more than 90% and not more than 100%, more preferably not less than 95% and not more than 100%, more preferably not less than 98% and not more than 100%, the aforementioned liquid crystal polyester (B) is essentially only composed of Those composed of repeating units represented by the aforementioned formula (B1) (the number of repeating units represented by the aforementioned formula (B1) is 100%) are particularly preferred.

From the viewpoint of being contained in a liquid crystal polyester composition and having an even better inhibitory effect on a rise in viscosity due to a drop in temperature, as the liquid crystal polyester (B) exemplified above, the liquid crystal polyester (B) represented by the above formula (B1) The repeating unit preferably contains the repeating unit represented by the following formula (B1-1). (B1-1)-O-Ar ^b1-1 -CO- (Ar ^b1-1 represents a naphthylene group. The hydrogen atoms in the aforementioned groups represented by Ar ^b1-1 can each be independently substituted by a halogen atom, an alkyl group or an aryl group. ).

Regarding the total number of repeating units (100%) corresponding to the aforementioned formula (B1), the number of repeating units represented by the aforementioned formula (B1-1) is preferably more than 50% and less than 90%, preferably 65% or more and 80% The following are better. In the liquid crystal polyester (B), when the content ratio of the repeating unit represented by the aforementioned formula (B1-1) is set within the above numerical range, the liquid crystal polyester composition has the effect of suppressing an increase in viscosity caused by a temperature drop. It can achieve a higher level of excellence and can exhibit excellent dielectric loss tangent.

More specifically, as the liquid crystal polyester (B) exemplified above, the repeating unit represented by the aforementioned formula (B1) contains the repeating unit represented by the following formula (B1-1) and the following formula (B1-2 The repeating unit represented by ) is preferred, and the repeating unit represented by the following formula (B1-1) and the repeating unit represented by the following formula (B1-2) are preferred. (B1-1)-O-Ar ^b1-1 -CO- (B1-2)-O-Ar ^b1-2 -CO- (Ar ^b1-1 represents naphthylene group. Ar ^b1-2 represents phenylene group. Ar Each hydrogen atom in the aforementioned group represented by ^b1-1 or Ar ^b1-2 can be independently substituted by a halogen atom, an alkyl group or an aryl group).

Examples of the naphthylene group in Ar ^b1-1 include the same groups exemplified in the liquid crystal polyester (A). Examples of the phenylene group in Ar ^b1-2 include the same groups exemplified in the liquid crystal polyester (A).

Examples of the halogen atom, alkyl group or aryl group in Ar ^b1-1 and Ar ^b1-2 include the same atoms or groups exemplified in the liquid crystal polyester (A).

More specifically, the liquid crystal polyester (B) exemplified above is composed only of repeating units represented by the aforementioned formula (B1). The repeating units represented by the aforementioned formula (B1) include the following formula (B1-1 ) and the repeating unit represented by the following formula (B1-2) are preferred, and only the repeating unit represented by the following formula (B1-1) and the repeating unit represented by the following formula (B1-2) What is achieved is better. (B1-1)-O-Ar ^b1-1 -CO- (B1-2)-O-Ar ^b1-2 -CO- (Ar ^b1-1 represents 2,6-naphthylene. Ar ^b1-2 represents 1 , 4-phenylene group. Each of the hydrogen atoms in the aforementioned group represented by Ar ^b1-1 or Ar ^b1-2 can be independently substituted by a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 20 carbon atoms) .

The repeating unit represented by the above formula (B1) is a repeating unit derived from an aromatic hydroxycarboxylic acid. Examples of the repeating unit derived from the aromatic hydroxycarboxylic acid include the same repeating units exemplified as the repeating units represented by the above formula (A1).

The liquid crystal polyester according to the embodiment may have the following side effects. <15> When the repeating unit represented by the aforementioned formula (B1) contains a repeating unit represented by the following formula (B1-1) and a repeating unit represented by the following formula (B1-2), relative to the composition of the aforementioned liquid crystal polyester ( For the total number of all repeating units (100%) of B), as an example, it can be The number of repeating units represented by the aforementioned formula (B1-1) exceeds 50% and is less than 90%, The number of repeating units represented by the aforementioned formula (B1-2) may be more than 10% and less than 50%, The number of repeating units represented by the aforementioned formula (B1-1) is not less than 65% and not more than 80%, The number of repeating units represented by the aforementioned formula (B1-2) may be 20% or more and 35% or less of the liquid crystal polyester composition described in any one of the aforementioned <1> to <10>.

Furthermore, the liquid crystal polyester (B) may have two or more independent repeating units represented by the aforementioned formula (B1). In addition, although the liquid crystal polyester may have repeating units other than the repeating units represented by the aforementioned formula (B1), the content is relative to the total number (100%) of all repeating units constituting the liquid crystal polyester (B). It is preferably less than 10%, more preferably less than 5%, and even more preferably 0%.

In the above illustration, as a particularly optimal combination of types of liquid crystal polyester (A) and liquid crystal polyester (B), the liquid crystal polyester of the embodiment can have the following side effects.

<16> The liquid crystal polyester (A) is preferably a liquid crystal polyester having a repeating unit represented by the following formula (A1), a repeating unit represented by the following formula (A2), and a repeating unit represented by the following formula (A3). The liquid crystal polyester (A) is a liquid crystal polyester composed only of repeating units represented by the following formula (A1), repeating units represented by the following formula (A2), and repeating units represented by the following formula (A3), ( A1)-O-Ar ¹ -CO- (A2)-CO-Ar ² -CO- (A3)-O-Ar ³ -O- (Ar ¹ represents 2,6-naphthylene group. Each of Ar ² and Ar ³ Independently represents 2,6-naphthylene or 1,4-phenylene. The hydrogen atoms in the aforementioned groups represented by Ar ¹ , Ar ² or Ar ³ each independently can also be composed of a halogen atom, an alkyl group with 1 to 10 carbon atoms or substituted with an aryl group having 6 to 20 carbon atoms). The liquid crystal polyester (B) consists only of any of the aforementioned <1> to <10> and <15> consisting of repeating units represented by the following formula (B1-1) and repeating units represented by the following formula (B1-2). A described liquid crystal polyester composition. (B1-1)-O-Ar ^b1-1 -CO- (B1-2)-O-Ar ^b1-2 -CO- (Ar ^b1-1 represents 2,6-naphthylene. Ar ^b1-2 represents 1 , 4-phenylene group. Each of the hydrogen atoms in the aforementioned group represented by Ar ^b1-1 or Ar ^b1-2 can be independently substituted by a halogen atom, an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 20 carbon atoms) . Furthermore, when the content ratio of the liquid crystal polyester (A) and the liquid crystal polyester (B) in the liquid crystal polyester composition described in <16> is expressed as a mass ratio, the liquid crystal polyester (A)/liquid crystal polyester Ester (B)=95/5～25/75 is better, 95/5～30/70 is better, 95/5～40/60 is better, 95/5～50/50 is better As for the best, 95/5 to 50/50 (excluding 50/50) is better, 90/10 to 60/40 is even better, and on the other hand, 80/20 to 30/70 is better As for the best, 80/20～60/40 is better, and 70/30～60/40 is even better.

The flow start temperature of the liquid crystal polyester composition of the embodiment containing the liquid crystal polyester (A) and the liquid crystal polyester (B) is preferably 260°C or higher, more preferably 260°C or higher and 400°C or lower, and 260°C or higher Below 380℃ is better. The higher the flow start temperature of the liquid crystal polyester composition, the higher the heat resistance and strength of the liquid crystal polyester composition tend to be. On the other hand, when the flow start temperature of the liquid crystal polyester composition exceeds 400°C, the melting temperature or melt viscosity of the liquid crystal polyester composition tends to become high. Therefore, the temperature necessary for molding the liquid crystal polyester composition tends to become higher.

Preferable values of the flow start temperature of the liquid crystal polyester (A) include the same values as those illustrated as the flow start temperature of the liquid crystal polyester composition according to the embodiment.

Preferable values of the flow start temperature of the liquid crystal polyester (B) include the same values as those exemplified as the flow start temperature of the liquid crystal polyester composition according to the embodiment.

In this specification, the flow start temperature of the liquid crystal polyester composition is also called the liquid flow temperature or the flow temperature, and becomes the target temperature of the molecular weight of the liquid crystal polyester (refer to Nao Koide, "Liquid Crystal Polymer - Synthesis, Molding, Application - ”, CMC Co., Ltd., June 5, 1987, p.95). The flow start temperature is to use a flow tester to melt the liquid crystal polyester composition under a load of 9.8MPa (100kg/cm ² ) at a speed of 4°C/min, through a nozzle with an inner diameter of 1mm and a length of 10mm. When extruded, the liquid crystal polyester composition shows a viscosity of 4800 Pa･s (48000 poise).

The weight average molecular weight (Mw) of the liquid crystal polyester contained in the liquid crystal polyester composition is preferably 50,000 or more, more preferably 100,000 or more, and more preferably 270,000 or more. The weight average molecular weight (Mw) of the liquid crystal polyester contained in the liquid crystal polyester composition is preferably 1,000,000 or less, more preferably 700,000 or less, and more preferably 500,000 or less. As an example of the above numerical range, the weight average molecular weight (Mw) of the liquid crystal polyester contained in the liquid crystal polyester composition is preferably from 50,000 to 1,000,000, preferably from 100,000 to 700,000, and from 270,000 to 500,000. The following are better. When the weight average molecular weight of the liquid crystal polyester is equal to or less than the above-mentioned upper limit, it can be further easily processed into a thin film with excellent isotropy. If the weight average molecular weight of the liquid crystal polyester is not less than the above-mentioned lower limit, it is preferable because the mechanical strength can be further improved.

The number average molecular weight (Mn) of the liquid crystal polyester contained in the liquid crystal polyester composition is preferably 1,000 or more, more preferably 5,000 or more, and more preferably 7,000 or more. The number average molecular weight (Mn) of the liquid crystal polyester contained in the liquid crystal polyester composition is preferably 500,000 or less, more preferably 300,000 or less, and more preferably 100,000 or less. As an example of the above-mentioned numerical range, the number average molecular weight (Mn) of the liquid crystal polyester contained in the liquid crystal polyester composition is preferably 1,000 to 500,000, preferably 5,000 to 300,000, and 7,000 or more. Those below 100,000 are better. When the number average molecular weight of the liquid crystal polyester is equal to or less than the above-mentioned upper limit, it can be easily processed into a thin film with excellent isotropy. When the number average molecular weight of the liquid crystal polyester is not less than the above-mentioned lower limit, it is preferable because it can exhibit better mechanical strength.

In this specification, the term "film with excellent isotropy" refers to the difference in the orientation of the molecules of the liquid crystal polyester contained in the film between the film's film-making direction (MD: Machine Direction) and the MD-perpendicular direction (TD: Transverse Direction). The meaning of smaller film.

The polydispersity (Mw/Mn) of the liquid crystal polyester contained in the liquid crystal polyester composition is not particularly limited, but can be exemplified by 1.0 or more and 4.0 or less.

In the embodiment, the liquid crystal polyester contained in the liquid crystal polyester composition may contain the above-mentioned liquid crystal polyester (A) and the above-mentioned liquid crystal polyester (B).

In addition, the values of the weight average molecular weight (Mw), number average molecular weight (Mn) and polydispersity (Mw/Mn) of the liquid crystal polyester (A) contained in the liquid crystal polyester composition include: The numerical values are the same as those illustrated in each item (weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (Mw/Mn)) of the liquid crystal polyester contained in the liquid crystal polyester composition.

In addition, the values of the weight average molecular weight (Mw), number average molecular weight (Mn) and polydispersity (Mw/Mn) of the liquid crystal polyester (B) contained in the liquid crystal polyester composition include: The numerical values exemplified for each item (weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (Mw/Mn)) of the liquid crystal polyester contained in the liquid crystal polyester composition are the same as those illustrated.

In this specification, the so-called "weight average molecular weight" and "number average molecular weight" mean that they can be obtained by gel permeation chromatography (GPC) analysis based on the standard curve obtained by measuring the molecular weight of standard polystyrene. The meaning of the value obtained by converting polystyrene.

The liquid crystal polyester composition according to the embodiment contains an amine decomposition product obtained by subjecting the liquid crystal polyester composition to the following amine decomposition conditions, and the amine decomposition product is analyzed by liquid chromatography under the following analysis conditions, and the retention time is in the range of 17.4 to 17.5 minutes. The tested ingredients are the best. (Amine decomposition conditions) The liquid crystal polyester composition and butylamine are mixed and treated at 200°C for 2 hours or more, and then the butylamine is removed by a reduced pressure treatment at 60°C, and formic acid is added for neutralization to obtain the amine decomposition product. . (Analysis conditions) Column: base material (porous spherical silica), modified group (octadecyl), film thickness 3μm, 3mmϕ×15cm Mobile phase: A) 0.1 volume% acetic acid water B) 0.1 volume% acetic acid acetonitrile Slope: Start flowing the liquid with the proportion of the aforementioned mobile phase A of 90 volume % and the proportion of the aforementioned mobile phase B of 10 volume %. After 30 minutes, gradually increase the concentration to the proportion of the aforementioned mobile phase B of 100 volume %. 10 minutes measurement at 100 volume % ratio Column temperature: 45℃ Detector: UV-254nm Flow rate: 0.4mL/minute Injection volume: 1μL

The amount of butylamine used in the above amine decomposition conditions is an amount that can fully decompose the liquid crystal polyester in the liquid crystal polyester composition.

The relative values of the components detected in the aforementioned retention time range of 17.4 to 17.5 minutes were determined from the absorption peak area of the chromatogram analyzed by the aforementioned liquid chromatography using 4-(4-hydroxyphenoxy)benzoic acid as a standard substance. The content is preferably 0.5 mass% or less, more preferably 0.1 mass% or less, and more preferably 0.05 mass% or less relative to the total mass (100 mass%) of the liquid crystal polyester composition.

The relative values of the components detected in the aforementioned retention time range of 17.4 to 17.5 minutes were determined from the absorption peak area of the chromatogram analyzed by the aforementioned liquid chromatography using 4-(4-hydroxyphenoxy)benzoic acid as a standard substance. The content is preferably 0.0001 mass% or more, more preferably 0.005 mass% or more, and more preferably 0.01 mass% or more relative to the total mass (100 mass%) of the liquid crystal polyester composition.

As an example of the above-mentioned numerical range of the above-mentioned relative content of the above-mentioned components, relative to the total mass of the above-mentioned polyester composition (100 mass%), it is preferably 0.0001 mass% or more and 0.5 mass% or less, and 0.005 mass% or more The content is preferably 0.1 mass% or less, and the content is more than 0.01 mass% and 0.05 mass% or less is even more preferred. Among the components detected in the aforementioned retention time range of 17.4 to 17.5 minutes, 4-(4-hydroxyphenoxy)benzoic acid was used as a standard material and the relative ratio was determined from the absorption peak area of the chromatogram analyzed by the aforementioned liquid chromatography method. When the content is within the above numerical range, thin film processing with excellent isotropy can be more easily performed, and further good mechanical strength can be exerted.

The ratio of the content of the liquid crystal polyester (A) to the liquid crystal polyester (B) in the liquid crystal polyester composition is, from the viewpoint of excellent balance between dielectric loss tangent and processing characteristics, a mass ratio of Liquid crystal polyester (A)/liquid crystal polyester (B) =95/5~25/75 is better, 95/5~30/70 is better, 95/5~40/60 is better, 95/5 to 50/50 is preferred, 95/5 to 50/50 (except 50/50) is preferred, and 90/10 to 60/40 is preferred. From the viewpoint of further optimizing the mechanical strength, the ratio of the content of the liquid crystal polyester (A) to the liquid crystal polyester (B) is, in terms of mass ratio, liquid crystal polyester (A)/liquid crystal polyester (B). )=80/20～30/70 is better, 80/20～60/40 is better, and 70/30～60/40 is better.

The content ratio of the liquid crystal polyester may be 50 mass% or more, 80 mass% or more, or 100 mass% relative to the total mass (100 mass%) of the liquid crystal polyester composition.

The ratio of the total content of the liquid crystal polyester (A) and the liquid crystal polyester (B) may be 50 mass % or more relative to 100 mass % of the total mass of the liquid crystal polyester contained in the liquid crystal polyester composition, It may be 80 mass % or more, or 100 mass %.

Moreover, the ratio of the total content of the liquid crystal polyester (A) and the liquid crystal polyester (B) relative to the total mass (100 mass %) of the liquid crystal polyester composition may be 50 mass % or more, or may be 80 mass %. % or more, and may also be 100 mass%.

(Production method of liquid crystal polyester) The liquid crystal polyester is preferably produced by melt-polymerizing raw material monomers corresponding to the repeating units constituting it, and optionally solid-phase polymerizing the resulting polymer. This makes it possible to produce high molecular weight liquid crystal polyester with high heat resistance and high strength and rigidity with good operability. Melt polymerization can also be carried out in the presence of a catalyst. Examples of the catalyst include metal compounds such as magnesium acetate, first tin acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, or 4-(dimethylamino) ) Nitrogen-containing heterocyclic compounds such as pyridine and 1-methylimidazole, it is better to use nitrogen-containing heterocyclic compounds.

＜Optional ingredients＞ The liquid crystal polyester composition of this embodiment may further contain any components other than the above-mentioned liquid crystal polyester. The liquid crystal polyester composition of the embodiment may contain the aforementioned liquid crystal polyester in such a manner that the total content (mass %) of the liquid crystal polyester composition does not exceed the total mass of the liquid crystal polyester composition (100 mass %). Ester (A) and the aforementioned liquid crystal polyester (B), and other optional components used as necessary.

Examples of optional components include fillers, resins other than the above-mentioned liquid crystal polyester, flame retardants, conductive materials, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, and insect repellents. , deodorant, coloring inhibitor, heat stabilizer, release agent, antistatic agent, plasticizer, lubricant, dye, foaming agent, foaming agent, viscosity adjuster, surfactant, etc.

Since the liquid crystal polyester composition described above contains the above-mentioned liquid crystal polyester (A) and the above-mentioned liquid crystal polyester (B), compared with the case where only the above-mentioned liquid crystal polyester (A) is contained, it can suppress the temperature drop caused by The viscosity increases and processing characteristics are improved. In the liquid crystal polyester composition, suppression of viscosity increase due to temperature drop can be confirmed by the following difference (eta _{Tm - 20 ° C.} - eta _Tm ) in the [Curing Speed Evaluation] below. The smaller the numerical value calculated from this evaluation is, the slower the curing speed of the sample is and the lower the degree of viscosity increase caused by the temperature drop, and the processing characteristics are judged to be better.

[Evaluation of curing speed] Using a rheometer (for example, Discovery HR-20 manufactured by TA Instruments Co., Ltd.), compare the endothermic absorption detected by a differential scanning calorimetry device with a sample of the liquid crystal polyester composition to be measured. After melting at the temperature of the peak height, the viscosity is measured when cooling at a cooling rate of 10°C/min. The measurement conditions are described below. Calculate the ratio of the viscosity of each sample at the temperature at the apex position of the endothermic absorption peak detected by a differential scanning calorimeter to the viscosity at the time point when the temperature at the apex position of the endothermic absorption peak drops by 20°C (eta _{Tm-20 °C} /n _Tm ). Further calculate the difference between the viscosity of each sample at the temperature at the apex position of the endothermic absorption peak detected by the differential scanning calorimetry device and the viscosity at the time point when the temperature at the apex position of the endothermic absorption peak dropped by 20°C (eta _{Tm-20 ℃} - η _Tm ). Measurement starting temperature: The temperature higher than the endothermic absorption peak detected by the differential scanning calorimetry device Cooling rate: 10°C/min Frequency: 1Hz Deformation: 0.05

As a liquid crystal polyester composition excellent in balance between dielectric loss tangent and processing characteristics, an example of the value of the above-mentioned difference in viscosity of the liquid crystal polyester composition (η _{Tm - 20 ℃} - η _Tm ) is 700 Pa･s below, it can be below 600Pa･s, it can be above 50Pa･s and below 680Pa･s, it can be above 50Pa･s and below 650Pa･s, it can be above 50Pa･s and below 500Pa･s, it can be above 100Pa･s and below 400Pa･ s or less.

As an example of a liquid crystal polyester composition having an excellent balance between dielectric loss tangent and processing characteristics, the viscosity of the liquid crystal polyester composition can be 1.52 or less as an example of the above-mentioned ratio (eta _{Tm-20 °C} /eta _Tm ). It can be above 1 and below 1.51, and it can be above 1.3 and below 1.50.

Furthermore, the temperature of the endothermic absorption peak detected by differential scanning calorimetry of the liquid crystal polyester contained in the liquid crystal polyester composition is preferably 250°C or higher, more preferably 250°C or higher and 350°C or lower, and 280°C or higher. The temperature between 300°C and 340°C is more preferred, and the temperature between 300°C and 330°C is particularly preferred. If the temperature of the endothermic absorption peak of the liquid crystal polyester is not less than the above-mentioned lower limit, it is preferable because it has good heat resistance.

The temperature of the endothermic absorption peak of liquid crystal polyester is measured using a differential scanning calorimetry device (such as Shimadzu Corporation's "DSC-60A Plus") by increasing the temperature from room temperature (23°C) at a rate of 10°C/min. The temperature (°C) at the top position of the endothermic absorption peak of the liquid crystal polyester sample.

Since the liquid crystal polyester composition contains the above-mentioned liquid crystal polyester (A) and the above-mentioned liquid crystal polyester (B), compared with the case where only the above-mentioned liquid crystal polyester (B) is contained, the dielectric properties measured by the following evaluation are The value of dielectric loss tangent is small.

The dielectric properties of the liquid crystal polyester composition can be obtained by the following [dielectric property evaluation].

[Dielectric Characteristics Evaluation] Using an injection molding machine (such as PNX40-5A manufactured by Nissei Plastics Industry Co., Ltd.), the sample to be measured is used as a molding material to produce a molded body with a width of 64 mm, a length of 64 mm, and a thickness of 1 mm. Then, a test piece with a thickness of 0.2 mm is cut out from both sides. piece. For the obtained test piece, a vector network analyzer (such as N5290A manufactured by Keysight Technology Co., Ltd.) and a split cylindrical resonator (such as CR710 manufactured by Electromagnetic (EM) Laboratory Co., Ltd.) are used to measure the specific conductance in 10 GHz. rate and dielectric loss tangent. ･Measurement environment: 23℃, 50%RH

The liquid crystal polyester composition according to the embodiment preferably has a specific conductivity value of 4 or less at a frequency of 10 GHz measured on the test piece in the above [Dielectric Characteristics Evaluation], preferably 3.8 or less, and 3.6 or less. The following are better. In addition, the liquid crystal polyester composition of the embodiment may have a specific conductivity value of 3 or more, 3.2 or more, or 3.4 at a frequency of 10 GHz measured on the test piece in the above [Dielectric Characteristics Evaluation]. above. The upper limit and lower limit of the specific conductivity value of the liquid crystal polyester composition can be freely combined. As an example of the numerical range of the specific conductivity value of the liquid crystal polyester composition, it may be 3 or more and 4 or less, it may be 3.2 or more and 3.8 or less, and it may be 3.4 or more and 3.6 or less.

In the liquid crystal polyester composition of the embodiment, the dielectric loss tangent value at a frequency of 10 GHz measured on the test piece in the above [Dielectric Characteristics Evaluation] is preferably 0.0010 or less, and more preferably 0.0009 or less. The one below 0.0008 is better. In addition, in the liquid crystal polyester composition according to the embodiment, the lower limit of the dielectric loss tangent value at a frequency of 10 GHz measured on the test piece in the above [Dielectric Characteristics Evaluation] is not particularly limited, but may be 0.0002 or more. , can be more than 0.0003, can be more than 0.0004. The upper limit and lower limit of the dielectric loss tangent value of the liquid crystal polyester composition can be freely combined. As an example of the numerical range of the dielectric loss tangent value of the liquid crystal polyester composition, it may be 0.0002 or more and 0.0010 or less, it may be 0.0003 or more and 0.0009 or less, and it may be 0.0004 or more and 0.0008 or less.

Since the liquid crystal polyester composition contains the above-mentioned liquid crystal polyester (A) and the above-mentioned liquid crystal polyester (B), compared with the case where it only contains the above-mentioned liquid crystal polyester (A), and the case where it only contains the above-mentioned liquid crystal polyester (B) , which can improve the mechanical strength value. The mechanical strength of the liquid crystal polyester composition was evaluated using the bending strength and bending elastic modulus measured on the following test pieces in the following [Bending Characteristics Evaluation] as indicators.

[Evaluation of bending characteristics] Using an injection molding machine (for example, PNX40-5A manufactured by Nissei Plastics Industry Co., Ltd.), the sample to be measured was used as a molding material to produce rod-shaped test pieces of each example with a width of 12.7 mm, a length of 127 mm, and a thickness of 6.4 mm. The obtained rod-shaped test piece was subjected to a bending test in accordance with ASTM D790, and the bending strength and bending elastic modulus at 23°C were measured.

In the liquid crystal polyester composition according to the embodiment, the bending strength measured on the test piece in the above [Flexibility Evaluation] may be, for example, 124 MPa or more, 130 MPa or more, 140 MPa or more, 300 MPa or less, or 150 MPa. Above 200MPa and below.

In the liquid crystal polyester composition according to the embodiment, the bending elastic modulus measured on the test piece in the above [flexural characteristics evaluation] may be, for example, 5 GPa or more, 5.5 MPa or more and 20 GPa or less, or 7 MPa or more and 10 GPa or less. .

The liquid crystal polyester composition according to the embodiment described above contains the above-mentioned liquid crystal polyester (A) and liquid crystal polyester (B), and therefore has an excellent balance between dielectric loss tangent and processing characteristics.

The liquid crystal polyester composition has excellent processing characteristics, that is, the heated liquid crystal polyester composition can suppress the increase in viscosity caused by the subsequent temperature drop, easily maintain a processable state for a long time, and can be easily processed into a desired shape.

[Production method of liquid crystal polyester composition] The manufacturing method of the liquid crystal polyester composition of this embodiment includes the method of mixing the said liquid crystal polyester (A) and the said liquid crystal polyester (B).

The liquid crystal polyester composition of this embodiment can be obtained by mixing the liquid crystal polyester (A) and the liquid crystal polyester (B) that have been individually polymerized in advance.

The liquid crystal polyester composition of the embodiment can be obtained by mixing the above-mentioned liquid crystal polyester (A), the above-mentioned liquid crystal polyester (B), and optional components at once or in an appropriate order.

As the aforementioned mixing, a mixture can be obtained by mixing the powdered liquid crystal polyester (A) and the powdered liquid crystal polyester (B) using a mixer or the like. However, the powdered liquid crystal polyester (A) It is preferable that the powdery liquid crystal polyester (B) is mixed with a mixer and then melt-kneaded. The liquid crystal polyester composition of this embodiment can be obtained by melting and kneading the above-mentioned liquid crystal polyester (A), the above-mentioned liquid crystal polyester (B) and optional components using an extruder, and then pelletizing them. And provide.

Regarding the manufacturing method of the liquid crystal polyester composition according to the embodiment, the liquid crystal polyester (A), the liquid crystal polyester (B) and any optional components can be exemplified by the components described in the above «Liquid crystal polyester composition» of the same ingredients.

In the method for producing the liquid crystal polyester composition, the ratio of the blending amounts of the liquid crystal polyester (A) and the liquid crystal polyester (B) is determined from the viewpoint of achieving an excellent balance between the dielectric loss tangent and the processing characteristics. In terms of mass ratio, liquid crystal polyester (A)/liquid crystal polyester (B) = 95/5~25/75 is better, 95/5~30/70 is better, and 95/5~40/60 is better. The better is 95/5 to 50/50, the better is 95/5 to 50/50 (but not 50/50), and the better is 90/10 to 60/40. From the viewpoint of obtaining more excellent mechanical strength, the ratio of the blending amounts of the liquid crystal polyester (A) and the liquid crystal polyester (B) is calculated as the mass ratio of liquid crystal polyester (A)/liquid crystal polyester ( B)=80/20～30/70 is better, 80/20～60/40 is better, 70/30～60/40 is better.

The liquid crystal polyester composition thus obtained, particularly the particles of the liquid crystal polyester composition, can be suitably used as a composition for film forming materials used in the production of films described below.

≪Film≫ The film of the embodiment is a film produced using the liquid crystal polyester composition of the above embodiment. The film of the embodiment can be obtained by molding the liquid crystal polyester composition of the embodiment into a film shape. An example of the film of this embodiment is a film containing the liquid crystal polyester composition of the embodiment. An example of the film of this embodiment is a film made of the liquid crystal polyester composition of the embodiment.

The film of the embodiment contains liquid crystal polyester (A) and liquid crystal polyester (B), and the following films can be exemplified.

A film containing liquid crystal polyester (A) and liquid crystal polyester (B), wherein the liquid crystal polyester (A) has a repeating unit represented by the following formula (A1), a repeating unit represented by the following formula (A2) and the following The repeating unit represented by the formula (A3), (A1)-O-Ar ¹ -CO- (A2)-CO-Ar ² -CO- (A3)-X-Ar ³ -Y- (Ar ¹ represents phenylene group , naphthylene group or biphenylene group. Ar ² and Ar ³ each independently represent a phenylene group, naphthylene group, biphenylene group or a group represented by the following formula (A4). X and Y each independently represent an oxygen atom or Imine group (-NH-). The hydrogen atoms in the aforementioned groups represented by Ar ¹ , Ar ² or Ar ³ can each be independently substituted by a halogen atom, an alkyl group or an aryl group). (A4)-Ar ⁴ -Z-Ar ⁵ - (Ar ⁴ and Ar ⁵ each 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 alkylene group). The number of repeating units represented by the aforementioned formula (A1) is not less than 30% and not more than 80% relative to the total number (100%) of all repeating units constituting the aforementioned liquid crystal polyester (A), and the aforementioned liquid crystal polyester (B) has the following The repeating unit represented by the formula (B1), (B1)-O-Ar ^b1 -CO- (Ar ^b1 represents a phenylene group, naphthylene group or biphenylene group. The hydrogen atoms in the aforementioned groups represented by Ar ^b1 are each independent Can be substituted by halogen atoms, alkyl or aryl groups). The number of repeating units represented by the aforementioned formula (B1) exceeds 80% relative to the total number (100%) of all repeating units constituting the aforementioned liquid crystal polyester (B).

The film of the embodiment may further contain optional components other than the aforementioned liquid crystal polyester (A) and the aforementioned liquid crystal polyester (B).

The types and contents of the liquid crystal polyester (A), the liquid crystal polyester (B) and optional components in the film of the embodiment can be exemplified by the same content as those described in the above "Liquid crystal polyester composition" By.

The film according to the embodiment can be used as a film for electronic components such as printed wiring boards. The film of the embodiment can be provided as a substrate (for example, a flexible substrate) or a laminate (for example, a flexible copper-clad laminate), a printed substrate, a printed wiring board, a printed circuit board, etc. having this as an insulating material.

Although the thickness of the film in the embodiment is not particularly limited, the preferred thickness of the film for electronic parts is 5 μm or more and 50 μm or less, more preferably 7 μm or more and 40 μm or less, and more preferably 10 μm or more and 33 μm or less. The best, the one with 15μm or more and 20μm or less is particularly good. In this specification, "thickness" is the average value of 10 selected thicknesses measured in accordance with JIS standards (K7130-1992).

The content ratio of the liquid crystal polyester relative to 100 mass% of the total mass of the film of the embodiment is 50 mass% or more and 100 mass% or less, and may be 80 mass% or more and 95 mass% or less.

In the past, when liquid crystal polyester was used as a molding material for film formation, it was difficult to provide a film with excellent isotropy because molecular alignment in the direction of film formation was easy to occur, and the viscosity increased rapidly as the temperature dropped.

Since the film of the embodiment is produced using the liquid crystal polyester composition of the above embodiment as a raw material, it can be formed with good processing characteristics and exhibits excellent isotropy and excellent dielectric loss tangent.

≪Production method of thin film≫ The method for producing a film according to an embodiment includes a method of melt-molding a film using the liquid crystal polyester composition of the above-mentioned embodiment as a molding material.

In the melt molding method, the liquid crystal polyester composition can be heated and softened, and can be molded into a desired shape.

Examples of melt molding methods include extrusion molding such as injection molding, T-die method, and inflation, compression molding, blow molding, vacuum molding, and press molding. Among them, inflation or The T-shaped die method is better.

In the past, when liquid crystal polyester was used as a molding material for film formation, it was difficult to provide a film with excellent isotropy because molecular alignment in the direction of film formation was easy to occur, and the viscosity increased rapidly as the temperature dropped.

In the film manufacturing method according to the embodiment, since the liquid crystal polyester composition of the above embodiment is used as a raw material, the film can be formed with good processing characteristics and can exhibit excellent dielectric loss tangent. The liquid crystal polyester composition has excellent processing characteristics in the film manufacturing method. That is, the heated liquid crystal polyester composition can suppress the increase in viscosity caused by the subsequent temperature drop, so it can be easily maintained for a long time and can be processed condition. Therefore, according to the film manufacturing method of the embodiment, the alignment relaxation of the liquid crystal polyester can be easily promoted during film production, and for example, a thin film processing with excellent isotropy can be easily achieved. [Example]

Next, the present invention will be described in further detail using examples, but the present invention is not limited to the following examples.

≪Measurement･Evaluation≫ [Measurement of the flow start temperature of the liquid crystal polyester sample] Using a flow tester (Model CFT-500 manufactured by Shimadzu Corporation), approximately 2 g of the liquid crystal polyester sample was filled into a container with an inner diameter of 1 mm. In the cylinder of the mold with a nozzle length of 10mm, under a load of 9.8MPa (100kg/cm ² ), while heating up at a rate of 4°C/min, the liquid crystal polyester sample is melted and extruded from the nozzle. The measurement shows 4800Pa The viscosity temperature (FT) of ･s(48000P).

[Measurement of endothermic absorption peaks of liquid crystal polyester samples] Use a differential scanning calorimeter (DSC-60A Plus manufactured by Shimadzu Corporation) to measure the endothermic absorption peak of the liquid crystal polyester sample while raising the temperature from room temperature (23°C) at a rate of 10°C/min. Get the temperature (℃) of the vertex position.

[Evaluation of dielectric properties of liquid crystal polyester samples] Using an injection molding machine (PNX40-5A manufactured by Nissei Plastics Industry Co., Ltd.), the liquid crystal polyester particles or liquid crystal polyester composition particles obtained in each example or comparative example were used as molding materials, and the conditions shown in Table 1 were Next, a molded body with a width of 64mm, a length of 64mm, and a thickness of 1mm was produced, and then a test piece with a thickness of 0.2mm was cut out from both sides. The obtained test piece was measured for specific conductivity and Dielectric loss tangent. ･Measurement environment: 23℃, 50%RH

[Evaluation of curing speed of liquid crystal polyester samples] Using a rheometer (Discovery HR-20 manufactured by TA Instruments Co., Ltd.), the liquid crystal polyester particles or liquid crystal polyester compositions obtained in each example or comparative example were measured. The pellets were used as samples, and the viscosity was measured when the particles were melted at 340°C and then cooled at a cooling rate of 10°C/min. The measurement conditions are described below. Calculate the ratio of the viscosity of each sample at the temperature at the apex of the endothermic absorption peak detected by the differential scanning calorimeter to the viscosity at the time point when the temperature at the apex of the endothermic absorption peak drops by 20°C (eta _{Tm-20 °C} / eta _Tm ), and the difference between the viscosity at the temperature at the apex position of the endothermic absorption peak detected by the differential scanning calorimetry device and the viscosity at the time point when the temperature at the apex position of the endothermic absorption peak drops by 20°C (eta _{Tm- 20 ℃} - τ _Tm ). Measurement starting temperature: 340℃ Cooling rate: 10℃/min Frequency: 1Hz Deformation: 0.05

[Evaluation of bending characteristics of liquid crystal polyester samples] Using an injection molding machine (PNX40-5A manufactured by Nissei Plastics Industry Co., Ltd.), the liquid crystal polyester particles or liquid crystal polyester composition particles obtained in each example or comparative example were used as molding materials, and the conditions shown in Table 1 were Below, each rod-shaped test piece with a width of 12.7mm, a length of 127mm, and a thickness of 6.4mm was manufactured. Secondly, the obtained rod-shaped test piece can be subjected to a bending test according to ASTM D790 to measure the bending strength and bending elastic modulus at 23°C.

[Measurement of molecular weight of liquid crystal polyester samples] A high-speed GPC device (HLC-8220 manufactured by Tosoh Corporation), a column (TSKgel SuperHM-H manufactured by Tosoh Corporation (2 pieces), φ6.0mm×15cm), and a solvent (pentafluorophenol/chloroform (weight ratio 35/65) were used )), the particles of the liquid crystal polyester or the particles of the liquid crystal polyester composition obtained in each example or comparative example were freeze-pulverized into powder form as a sample, and the number average molecular weight of the liquid crystal polyester contained in the sample was measured ( Mn) and weight average molecular weight (Mw). The sample solution for measurement was prepared by adding 2 mg of the sample to 1.4 g of pentafluorophenol, dissolving it at 80°C for 2 hours, cooling to room temperature, adding 2.6 g of chloroform, and further adding the solvent (pentafluorophenol/chloroform (weight ratio 35/65) )) After diluting 2 times, filter using a filter with a pore size of 0.45μm to prepare. The molecular weight was calculated using polystyrene as a standard substance.

[LC analysis of amine decomposition products of liquid crystal polyester] The particles of each liquid crystal polyester composition of Examples 1 to 8 and the particles of each liquid crystal polyester of Comparative Examples 1 to 2 were freeze-pulverized into powder form, and an ultrahigh-speed liquid chromatograph (Nexera manufactured by Shimadzu Corporation) was used. ), decompose the amine under the following conditions, and perform LC analysis. 4-(4-Hydroxyphenoxy)benzoic acid was used as a standard substance, and the content of the component detected at a retention time of 17.4 to 5 minutes was determined from the absorption peak area of the liquid chromatograph.

(Amine decomposition procedure) 1) Take out about 0.05g of the powdered sample into a flat-bottomed flask 2) Add 30 mL of NMP (special grade) and 10 mL of butylamine (special grade) into the above flat-bottomed flask with a straw. 3) Place the flat-bottomed flask in the reflux device, and heat it in a sand bath set to 200°C until the sample is completely dissolved. 4) After the sample is dissolved, heat for another 2 hours 5) Take out the reflux device from the sand bath and cool it for 1 hour with water flowing in to obtain the amine decomposition liquid 6) Take out the flat-bottomed flask from the reflux device and move the amine decomposition liquid into a 100mL eggplant-shaped flask. 7) Wash the flat-bottomed flask twice with methanol (20 mL in total) and recover the remaining amine decomposition liquid. 8) Use an evaporator to remove methanol and butylamine under the following conditions to obtain an amine decomposition product 1. Methanol removal Water bath temperature: 60℃ Evaporator pressure: start at 100mmHg (about 133hPa) for 5 minutes 2. Remove butylamine Water bath temperature: 60℃ Evaporator pressure: 15 minutes at 50mmHg (about 67hPa) 9) Add 1 mL of formic acid (special grade) to the amine decomposition product through a pipette and neutralize the liquid to obtain the amine decomposition product (neutralized product) 10) Gently shake the container to mix, and transfer the amine decomposition product (neutralized product) to a 50 mL eggplant-shaped flask 11) While co-washing with NMP, cool to room temperature, and then add NMP to reach 50 mL to obtain a sample for LC analysis. Perform LC analysis under the following measurement conditions.

(LC measurement conditions) Column: L-Column ODS, base material (porous spherical silica, high-purity silica: silica 99.99 mass% or more), modified group (octadecyl), film thickness 3 μm, 3mmϕ×15cm Mobile phase: A) 0.1 volume% acetic acid water B) 0.1 volume% acetic acid acetonitrile Slope: Start flowing the liquid with the proportion of the aforementioned mobile phase A at 90 volume % and the proportion of the aforementioned mobile phase B at 10 volume %. After 30 minutes, gradually increase the concentration until the proportion of the aforementioned mobile phase B is 100 volume %. 10 minutes measurement at 100 volume % ratio Column temperature: 45℃ Detector: UV-254nm Flow rate: 0.4mL/minute Sample injection volume for LC analysis: 1 μL

Furthermore, the structure of the LC device is as follows. Degassing unit: DGU-20A5 Liquid delivery unit: LC-30AD ×2 Autosampler: SIL-30AC Tube column oven: CTO-20AC Absorbance detector: SPD-20A System controller: CBM-20A System software: LabSolution

≪Manufacturing≫ The following describes the production of each liquid crystal polyester and liquid crystal polyester composition. Furthermore, the liquid crystal polyester (a2) is included in the concept of the liquid crystal polyester (A) in the composition of the present invention. The liquid crystal polyester (b1) is included in the concept of the liquid crystal polyester (B) in the composition of the present invention.

[Comparative Example 1: Production of liquid crystal polyester (a2)] In a reactor equipped with a stirring device, a torque meter, a nitrogen inlet pipe, a thermometer and a reflux cooler, put 1034.99g (5.5 mol) of 2-hydroxy-6-naphthoic acid and 378.33g of 2,6-naphthalenedicarboxylic acid. (1.75 mol), 83.07g terephthalic acid (0.5 mol), 272.52g hydroquinone (2.475 mol, relative to the total molar amount of 2,6-naphthalene dicarboxylic acid and terephthalic acid, 0.225 molar excess), 1226.87g of acetic anhydride (12 moles) and 0.17g of 1-methylimidazole as a catalyst. After the gas in the reactor was replaced by nitrogen, the temperature was raised from room temperature to 145°C over 15 minutes while stirring under a nitrogen flow, and then refluxed at 145°C for 1 hour.

Next, while distilling off the by-produced acetic acid and unreacted acetic anhydride, the mixture was cooled from 145°C to 310°C over 3 hours and 30 minutes. After maintaining at 310°C for 3 hours, the contents were taken out and cooled to room temperature. The obtained solid material was pulverized with a pulverizer to obtain powdery liquid crystal polyester (a1). The flow start temperature of the liquid crystal polyester (a1) is 265°C.

The liquid crystal polyester (a1) was heated from room temperature to 215°C over 50 minutes in a nitrogen environment, then from 215°C to 230°C over 1 hour, from 230°C to 300°C over 11 hours and 40 minutes, and at 300°C After keeping for 10 hours, powdery liquid crystal polyester (a2) was obtained after solid-state polymerization. The flow start temperature of the liquid crystal polyester (a2) is 328.7°C. Next, using a 2-axis extruder (PCM-30 manufactured by Ikegai Iron Works Co., Ltd.), the liquid crystal polyester (a2) was granulated at a cylinder temperature of 345°C to obtain pellets of the liquid crystal polyester (a2). The flow start temperature of the granulated liquid crystal polyester (a2) is 307.2°C. Furthermore, the temperature at the apex of the endothermic absorption peak of the granulated liquid crystal polyester (a2) was 322°C.

[Comparative Example 2: Production of liquid crystal polyester (b1)] According to the method described in Example 1 described in Japanese Patent Application Laid-Open No. 2004-250620, 1511.1 g (8.03 mol) of 2-hydroxy-6-naphthoic acid and 410.2 g (2.97 mol) of p-hydroxybenzoic acid were used as Raw material, synthetic liquid crystal polyester (b1). The flow start temperature of the liquid crystal polyester (b1) is 303.5°C. Next, using a 2-axis extruder (PCM-30 manufactured by Ikegai Iron Works Co., Ltd.), the liquid crystal polyester (b1) was granulated at a cylinder temperature of 320° C. to obtain pellets of the liquid crystal polyester (b1). The flow start temperature of the granulated liquid crystal polyester (b1) is 291.8°C. Furthermore, the temperature at the top of the endothermic absorption peak of the granulated liquid crystal polyester (b1) was 312°C.

[Example 1: Production of liquid crystal polyester composition (c)] The powdered liquid crystal polyester (a2) and the powdered liquid crystal polyester (b1) obtained above were mixed at a mass ratio of a2/b1=90/10 to obtain a liquid crystal polyester composition (c). The flow start temperature of the liquid crystal polyester composition (c) is 323.0°C. Next, the liquid crystal polyester composition (c) was granulated using a 2-axis extruder (PCM-30 manufactured by Ikegai Iron Works Co., Ltd.) at a cylinder temperature of 340° C. to obtain the liquid crystal polyester composition (c). Particles. The flow start temperature of the granulated liquid crystal polyester composition (c) was 304.6°C. Furthermore, the temperature at the apex of the endothermic absorption peak of the granulated liquid crystal polyester composition (c) was 322°C.

[Example 2: Production of liquid crystal polyester composition (d)] The powdered liquid crystal polyester (a2) and powdered liquid crystal polyester (b1) obtained above were mixed at a mass ratio of a2/b1=80/20 to obtain a liquid crystal polyester composition (d). The flow start temperature of the liquid crystal polyester composition (d) is 315.1°C. Next, the liquid crystal polyester composition (d) was granulated using a 2-axis extruder (PCM-30 manufactured by Ikegai Iron Works Co., Ltd.) at a cylinder temperature of 330°C to obtain the liquid crystal polyester composition (d). particles. The flow start temperature of the granulated liquid crystal polyester composition (d) is 302.5°C. Furthermore, the temperature at the apex of the endothermic absorption peak of the granulated liquid crystal polyester composition (d) was 321°C.

[Example 3: Production of liquid crystal polyester composition (e)] The powdered liquid crystal polyester (a2) and powdered liquid crystal polyester (b1) obtained above were mixed at a mass ratio of a2/b1=70/30 to obtain a liquid crystal polyester composition (e). The flow start temperature of the liquid crystal polyester composition (e) is 312.5°C. Next, the liquid crystal polyester composition (e) was granulated using a 2-axis extruder (PCM-30 manufactured by Ikegai Iron Works Co., Ltd.) at a cylinder temperature of 330°C to obtain the liquid crystal polyester composition (e). particles. The flow start temperature of the granulated liquid crystal polyester composition (e) is 302.2°C. Furthermore, the temperature at the apex of the endothermic absorption peak of the granulated liquid crystal polyester composition (e) was 319°C.

[Example 4: Production of liquid crystal polyester composition (f)] The powdered liquid crystal polyester (a2) and the powdered liquid crystal polyester (b1) obtained above were mixed at a mass ratio of a2/b1=60/40 to obtain a liquid crystal polyester composition (f). The flow start temperature of the liquid crystal polyester composition (f) is 311.0°C. Next, the liquid crystal polyester composition (f) was granulated using a 2-axis extruder (PCM-30 manufactured by Ikegai Iron Works Co., Ltd.) at a cylinder temperature of 325°C to obtain the liquid crystal polyester composition (f). particles. The flow start temperature of the granulated liquid crystal polyester composition (f) is 300.5°C. Furthermore, the temperature at the apex of the endothermic absorption peak of the granulated liquid crystal polyester composition (f) was 320°C.

[Example 5: Production of liquid crystal polyester composition (g)] The powdered liquid crystal polyester (a2) and the powdered liquid crystal polyester (b1) obtained above were mixed at a mass ratio of a2/b1=50/50 to obtain a liquid crystal polyester composition (g). The flow start temperature of the liquid crystal polyester composition (g) was 309.4°C. Next, the liquid crystal polyester composition (g) was granulated using a 2-axis extruder (PCM-30 manufactured by Ikegai Iron Works Co., Ltd.) at a cylinder temperature of 325°C to obtain the liquid crystal polyester composition (g). particles. The flow start temperature of the granulated liquid crystal polyester composition (g) was 299.9°C. Moreover, the temperature at the top position of the endothermic absorption peak of the liquid crystal polyester composition (g) after granulation was 315°C.

[Example 6: Production of liquid crystal polyester composition (h)] The powdered liquid crystal polyester (a2) and the powdered liquid crystal polyester (b1) obtained above were mixed at a mass ratio of a2/b1=40/60 to obtain a liquid crystal polyester composition (h). The flow start temperature of the liquid crystal polyester composition (h) is 311.6°C. Next, the liquid crystal polyester composition (h) was granulated using a 2-axis extruder (PCM-30 manufactured by Ikegai Iron Works Co., Ltd.) at a cylinder temperature of 325°C to obtain the liquid crystal polyester composition (h). particles. The flow start temperature of the granulated liquid crystal polyester composition (h) was 299.1°C. Furthermore, the temperature at the top of the endothermic absorption peak of the granulated liquid crystal polyester composition (h) was 310°C.

[Example 7: Production of liquid crystal polyester composition (i)] The powdered liquid crystal polyester (a2) and the powdered liquid crystal polyester (b1) obtained above were mixed at a mass ratio of a2/b1=30/70 to obtain a liquid crystal polyester composition (i). The flow start temperature of the liquid crystal polyester composition (i) is 310.2°C. Next, the liquid crystal polyester composition (i) was granulated using a 2-axis extruder (PCM-30 manufactured by Ikegai Iron Works Co., Ltd.) at a cylinder temperature of 330°C to obtain the liquid crystal polyester composition (i). particles. The flow start temperature of the granulated liquid crystal polyester composition (i) was 298.2°C. Furthermore, the temperature at the apex of the endothermic absorption peak of the granulated liquid crystal polyester composition (i) was 312°C.

[Example 8: Production of liquid crystal polyester composition (j)] The powdered liquid crystal polyester (a2) and the powdered liquid crystal polyester (b1) obtained above were mixed at a mass ratio of a2/b1=95/5 to obtain a liquid crystal polyester composition (j). The flow start temperature of the liquid crystal polyester composition (j) is 327.3°C. Next, the liquid crystal polyester composition (j) was granulated using a 2-axis extruder (PCM-30 manufactured by Ikegai Iron Works Co., Ltd.) at a cylinder temperature of 340° C. to obtain the liquid crystal polyester composition (j). particles. The flow start temperature of the granulated liquid crystal polyester composition (j) was 305.2°C. Furthermore, the temperature at the top of the endothermic absorption peak of the granulated liquid crystal polyester composition (j) was 320°C.

For the liquid crystal polyester composition, the results of the evaluation of each item are shown in Table 2.

Comparing the liquid crystal polyester compositions of Examples 1 to 8 with the liquid crystal polyester of Comparative Example 1, the viscosity increase evaluated by the difference in viscosity at the endothermic absorption peak position (η _{Tm - 20 °C} - η _Tm ) is difficult to increase. It has excellent processing characteristics and has a smaller dielectric loss tangent value than the liquid crystal polyester of Comparative Example 2. From this, it can be seen that the liquid crystal polyester compositions of Examples 1 to 8 containing the liquid crystal polyester (a2) and the liquid crystal polyester (b1) exhibit excellent balance between dielectric loss tangent and processing characteristics.

In addition, when referring to the bending characteristics, especially the molded articles of the liquid crystal polyester compositions of Examples 2 to 7 have higher bending strength and bending elastic modulus than the molded articles of the liquid crystal polyester of Comparative Examples 1 and 2. . From this, it can be seen that by containing both the liquid crystal polyester (a2) and the liquid crystal polyester (b1), a synergistic improvement effect exceeding the predetermined bending characteristics is confirmed.

Each structure and these combinations in each embodiment are examples, and the addition, omission, substitution, etc. of the structure can be changed without departing from the scope of the invention. In addition, the present invention is not limited to each embodiment but only to the scope of the patent application.

Claims (14)

A liquid crystal polyester composition, which contains liquid crystal polyester (A) and liquid crystal polyester (B). The liquid crystal polyester (A) has a repeating unit represented by the following formula (A1) and a repeating unit represented by the following formula (A2). The repeating unit is the same as the repeating unit represented by the following formula (A3), (A1)-O-Ar ¹ -CO- (A2)-CO-Ar ² -CO- (A3)-X-Ar ³ -Y- (Ar ¹ represents a phenylene group, naphthylene group or biphenylene group; Ar ² and Ar ³ each independently represent a phenylene group, naphthylene group, biphenylene group or a group represented by the following formula (A4); X and Y each independently represent Represents an oxygen atom or an imine group (-NH-); the hydrogen atoms in the aforementioned groups represented by Ar ¹ , Ar ² or Ar ³ can each be independently substituted by a halogen atom, an alkyl group or an aryl group) (A4)-Ar ⁴ - Z-Ar ⁵ - (Ar ⁴ and Ar ⁵ each 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 alkylene group) With respect to the liquid crystal polyester (A) constituting the aforementioned liquid crystal polyester (A) For 100% of the total number of repeating units, the number of repeating units represented by the aforementioned formula (A1) is not less than 30% and not more than 80%. The aforementioned liquid crystal polyester (B) has repeating units represented by the following formula (B1), (B1)-O-Ar ^b1 -CO- (Ar ^b1 represents a phenylene group, naphthylene group or biphenylene group; the hydrogen atoms in the aforementioned groups represented by Ar ^b1 can each be independently composed of a halogen atom, an alkyl group or an aryl group. Substitution) The number of repeating units represented by the aforementioned formula (B1) exceeds 80% relative to 100% of the total number of repeating units constituting the aforementioned liquid crystal polyester (B). The liquid crystal polyester composition of claim 1, wherein the repeating unit represented by the aforementioned formula (B1) contains the repeating unit represented by the following formula (B1-1), (B1-1)-O-Ar ^b1-1 -CO- (Ar ^b1-1 represents a naphthylene group, and each hydrogen atom in the aforementioned group represented by Ar ^b1-1 may be independently substituted by a halogen atom, an alkyl group or an aryl group) relative to the total number of repeating units corresponding to the aforementioned formula (B1) In terms of 100%, the number of repeating units represented by the aforementioned formula (B1-1) exceeds 50% and is not more than 90%. The liquid crystal polyester composition of claim 1 or 2, wherein the content ratio of the aforementioned liquid crystal polyester (A) and the aforementioned liquid crystal polyester (B) in the aforementioned liquid crystal polyester composition is expressed as a mass ratio, the liquid crystal polyester (A)/LCD polyester (B)=95/5～25/75. The liquid crystal polyester composition of claim 1 or 2, wherein the content ratio of the aforementioned liquid crystal polyester (A) and the aforementioned liquid crystal polyester (B) in the aforementioned liquid crystal polyester composition is expressed as a mass ratio, the liquid crystal polyester (A)/LCD polyester (B)=95/5～50/50. The liquid crystal polyester composition of claim 1 or 2, wherein the total content of the liquid crystal polyester (A) and the liquid crystal polyester (B) is 100% by mass of the total mass of the liquid crystal polyester composition. The proportion is more than 80% by mass. Such as the liquid crystal polyester composition of claim 1 or 2, wherein the liquid crystal polyester (B) is composed only of repeating units represented by the aforementioned formula (B1). The liquid crystal polyester composition of claim 1 or 2, wherein the liquid crystal polyester (A) has a repeating unit represented by the following formula (A1), a repeating unit represented by the following formula (A2) and the following formula (A3) The repeating unit shown is, (A1)-O-Ar ¹ -CO- (A2)-CO-Ar ² -CO- (A3)-O-Ar ³ -O- (Ar ¹ represents 2,6-naphthylene, 1,4-phenylene or 4,4'-biphenylene; Ar ² and Ar ³ each independently represent 2,6-naphthylene, 2,7-naphthylene, 1,4-phenylene, 1,3-phenylene group or 4,4'-biphenylene group; each hydrogen atom in the aforementioned group represented by Ar ¹ , Ar ² or Ar ³ can be independently composed of a halogen atom, an alkyl group with 1 to 10 carbon atoms or a carbon Aryl groups with numbers 6 to 20 are substituted). The liquid crystal polyester composition of claim 1 or 2, wherein the repeating unit represented by the aforementioned formula (B1) is only repeated by the repeating unit represented by the following formula (B1-1) and the following formula (B1-2) Units formed by; (B1-1)-O-Ar ^b1-1 -CO- (B1-2)-O-Ar ^b1-2 -CO- (Ar ^b1-1 represents naphthylene; Ar ^b1-2 represents Phenylene group; each hydrogen atom in the aforementioned group represented by Ar ^b1-1 or Ar ^b1-2 can be independently substituted by a halogen atom, an alkyl group or an aryl group). The liquid crystal polyester composition of Claim 1 or 2, wherein the amine decomposition product obtained by subjecting the liquid crystal polyester composition to the following amine decomposition conditions contains an amine decomposition product, and the retention time is detected by liquid chromatography analysis under the following analysis conditions: 17.4 Components within the range of ~17.5 minutes, Using 4-(4-hydroxyphenoxy)benzoic acid as a standard substance, the relative content of the aforementioned components was calculated from the absorption peak area of the chromatogram analyzed by the aforementioned liquid chromatography method, relative to the aforementioned liquid crystal polyester composition. The total mass is 0.0001 mass% or more and 0.5 mass% or less based on 100 mass% of the total mass; (Amine decomposition conditions) The liquid crystal polyester composition and butylamine are mixed and treated at 200°C for more than 2 hours. The butylamine is removed by a reduced pressure treatment at 60°C, and formic acid is added for neutralization to obtain the aforementioned amine decomposition. thing; (Analysis conditions) Column: base material (porous spherical silica), modified group (octadecyl), film thickness 3μm, 3mmϕ×15cm Mobile phase: A) 0.1 volume% acetic acid water B) 0.1 volume% acetic acid acetonitrile Slope: Start flowing the liquid with the ratio of mobile phase A to 90% by volume and the ratio of mobile phase B to 10% by volume, and gradually increase the concentration over 30 minutes until the ratio of mobile phase B is 100% by volume. The proportion of phase B is 100% by volume and measured for 10 minutes; Column temperature: 45℃ Detector: UV-254nm Flow rate: 0.4mL/minute Injection volume: 1μL. The liquid crystal polyester composition of claim 1 or 2, wherein the weight average molecular weight of the liquid crystal polyester contained in the liquid crystal polyester composition measured using polystyrene as a standard material is 270,000 or more. A method for manufacturing a liquid crystal polyester composition according to claim 1 or 2, which includes mixing the aforementioned liquid crystal polyester (A) and the aforementioned liquid crystal polyester (B). A film containing liquid crystal polyester (A) and liquid crystal polyester (B). The liquid crystal polyester (A) has a repeating unit represented by the following formula (A1), a repeating unit represented by the following formula (A2) and the following The repeating unit represented by the formula (A3), (A1)-O-Ar ¹ -CO- (A2)-CO-Ar ² -CO- (A3)-X-Ar ³ -Y- (Ar ¹ represents phenylene group , naphthylene group or biphenylene group; Ar ² and Ar ³ each independently represent a phenylene group, naphthylene group, biphenylene group or a group represented by the following formula (A4); X and Y each independently represent an oxygen atom or Imine group (-NH-); The hydrogen atoms in the aforementioned groups represented by Ar ¹ , Ar ² or Ar ³ can each be independently substituted by a halogen atom, an alkyl group or an aryl group) (A4)-Ar ⁴ -Z-Ar ⁵ - (Ar ⁴ and Ar ⁵ each 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 alkylene group) With respect to all repeating units constituting the aforementioned liquid crystal polyester (A) For 100% of the total, the number of repeating units represented by the aforementioned formula (A1) is not less than 30% and not more than 80%, and the aforementioned liquid crystal polyester (B) has repeating units represented by the following formula (B1), (B1)- O-Ar ^b1 -CO- (Ar ^b1 represents a phenylene group, naphthylene group or biphenylene group; the hydrogen atoms in the aforementioned groups represented by Ar ^b1 can each be independently substituted by a halogen atom, an alkyl group or an aryl group) relative to The number of repeating units represented by the aforementioned formula (B1) exceeds 80% based on 100% of the total number of repeating units constituting the liquid crystal polyester (B). The method for producing a film according to claim 12, which includes melting the liquid crystal polyester composition according to claim 1 or 2 as a forming material to form a film. The method for manufacturing a film according to claim 13, wherein the melt forming is formed by an inflation method or a T-die method.