JP2006335813A - Liquid crystalline polyester, liquid crystalline polyester solution, method for improving solubility of liquid crystalline polyester and liquid crystalline polyester film and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystalline polyester having sufficiently large solubility in solvents. <P>SOLUTION: This liquid crystalline polyester having monomer units A1 of formula (a1), monomer units A2 of formula (a2), monomer units B of formula (b), and monomer units C1 of formula (c1), wherein the rate of the total amount of the monomer units A1 and the monomer units A2, the rate of the monomer units B, and the rate of the monomer units C1 are 30 to 50 mol.%, 25 to 35 mol.% and 25 to 35 mol.%, respectively, based on the total amount of the monomer units. Therein, Ar<SP>1</SP>is 1,4-phenylene group which may have one or more substituents; Ar<SP>2</SP>is 2,6-naphthalene group which may have one or more substituents; Ar<SP>3</SP>and Ar<SP>4</SP>are each 1,4-phenylene group or the like; X is -O- or -NH-. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid crystal polyester, a liquid crystal polyester solution, a method for improving the solubility of liquid crystal polyester, a liquid crystal polyester film, and a method for producing the same.

  Since liquid crystal polyester exhibits excellent high-frequency characteristics and low hygroscopicity, its application as a film material for electronic substrates and the like has been studied.

  When a liquid crystal polyester is formed into a film by extrusion, generally, molecules are oriented in the extrusion direction, resulting in problems such as an increase in film anisotropy and a decrease in mechanical strength of the film.

Therefore, as a method for obtaining an isotropic liquid crystal polyester film, a so-called solution casting method in which a liquid crystal polyester solution in which a liquid crystal polyester film is dissolved in a solvent is cast on a support substrate and then the solvent is removed is examined. Has been. For example, the present inventors have already prepared (1) a monomer unit derived from an aromatic hydroxycarboxylic acid, (2) a monomer unit derived from an aromatic dicarboxylic acid, and (3) an aromatic diamine. And a liquid crystal polyester solution composition in which a liquid crystal polyester having a monomer unit derived from an aromatic amine selected from aromatic amines having a hydroxyl group is dissolved in an aprotic solvent such as N-methylpyrrolidone is cast on a support substrate. Have proposed a method of removing the solvent after that (for example, Patent Document 1).
JP 2004-315678 A

  However, conventional liquid crystal polyesters are not necessarily sufficiently soluble in an aprotic solvent having low corrosivity. Therefore, the concentration cannot be increased in a liquid crystal polyester solution in which liquid crystal polyester is dissolved in an aprotic solvent. For example, when manufacturing a thick film, the solution is cast on a support substrate and dried. In some cases, it is necessary to repeat the above process twice or more, and there is a problem that the productivity of the film is lowered.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid crystal polyester having sufficiently high solubility in a solvent. Another object of the present invention is to provide a method for producing a liquid crystal polyester film capable of producing a film having sufficiently small anisotropy with high production efficiency, and a liquid crystal polyester solution suitably used for this production method. And Furthermore, an object of the present invention is to provide a method for improving the solubility of liquid crystal polyester, which makes it possible to improve the production efficiency in the production of a liquid crystal polyester film using a liquid crystal polyester film solution.

  As a result of intensive studies on the composition of the liquid crystal polyester in order to solve the above problems, the present inventors have a liquid crystal polyester having a specific monomer unit at a specific ratio, so that the solubility in a solvent is increased. It has been found that it is significantly improved. As a result of further studies based on this knowledge, the present invention has been completed.

  That is, the present invention relates to a monomer unit A1 represented by the following general formula (a1), a monomer unit A2 represented by the following general formula (a2), and a monomer unit B represented by the following general formula (b). The monomer unit C1 represented by the following general formula (c1), and the ratio of the total amount of the monomer unit A1 and the monomer unit A2 is 30 to 50 mol% with respect to the entire monomer unit, The liquid crystal polyester has a ratio of 25 to 35 mol% and a ratio of the monomer unit C of 25 to 35 mol%.

［式（ａ１）及び式（ａ２）中、Ａｒ^１は置換基を有していてもよい１，４−フェニレン基を示し、Ａｒ^２は置換基を有していてもよい２，６−ナフタレン基を示す。］

[In Formula (a1) and Formula (a2), Ar ¹ represents a 1,4-phenylene group which may have a substituent, and Ar ² represents 2,6-naphthalene which may have a substituent. Indicates a group. ]

［式（ｂ）中、Ａｒ^３は置換基を有していてもよい１，４−フェニレン基、置換基を有していてもよい１，３−フェニレン基又は置換基を有していてもよい２，６−ナフタレン基を示す。］

[In the formula (b), Ar ³ may have a 1,4-phenylene group which may have a substituent, a 1,3-phenylene group which may have a substituent or a substituent. A good 2,6-naphthalene group is shown. ]

［式（ｃ１）中、Ａｒ^４は置換基を有していてもよい１，４−フェニレン基、置換基を有していてもよい１，３−フェニレン基又は置換基を有していてもよい２，６−ナフタレン基を示し、Ｘは−Ｏ−又は−ＮＨ−を示す。］

[In the formula (c1), Ar ⁴ may have a 1,4-phenylene group which may have a substituent, a 1,3-phenylene group which may have a substituent or a substituent. A good 2,6-naphthalene group is shown, and X represents —O— or —NH—. ]

  The liquid crystal polyester of the present invention has both the monomer unit A1 and the monomer unit A2 as monomer units derived from the aromatic hydroxycarboxylic acid, and the ratio of the monomer units having the specific structure is within the specific range, so that it can be dissolved in a solvent. Sex became big enough.

In the liquid crystalline polyester of the present invention, it is preferable that n ¹ and n ² satisfy the following formula (1), where n ^{1 is} the number of monomer units A1 and n ² is the number of monomer units A2.
0 <n ² / (n ¹ + n ² ) <0.95 (1)

  Thus, solubility is further improved by setting the ratio of the monomer unit A1 having a phenylene group and the monomer unit A2 having a naphthalene group to a specific range that satisfies the above formula (1).

  The liquid crystal polyester of the present invention further has a monomer unit C2 represented by the following general formula (c2), and the ratio of the total amount of the monomer unit C1 and the monomer unit C2 to the whole monomer unit is 25 to 35 mol%. Preferably there is.

［式（ｃ２）中、Ａｒ^５は置換基を有していてもよいアリーレン基を示す。］

[In the formula (c2), Ar ⁵ represents an arylene group which may have a substituent. ]

  Thereby, since it becomes difficult to melt | dissolve when liquid crystalline polyester is high molecular weight by solid phase polymerization, high molecular weight by solid phase polymerization becomes easy.

  The liquid crystalline polyester solution of the present invention preferably contains 0.01 to 100 parts by weight of the liquid crystalline polyester with respect to 100 parts by weight of the solvent from the viewpoint of improving the production efficiency of the liquid crystalline polyester film.

  The aprotic solvent is preferably one having no halogen atom. In order to improve the solubility of the liquid crystal polyester more significantly, the dipole moment of the aprotic solvent is preferably 3 or more and 5 or less.

  The liquid crystal polyester solution of the present invention is a liquid crystal polyester solution in which the liquid crystal polyester of the present invention is dissolved in a solvent containing an aprotic solvent. When this liquid crystal polyester solution is used for manufacturing a thick liquid crystal polyester film by increasing the concentration of the liquid crystal polyester, it is possible to manufacture the liquid crystal polyester film with high production efficiency. Further, since an aprotic solvent is used as the solvent, the corrosiveness is low and the handling property is excellent.

  In the present invention, the liquid crystal polyester is represented by the monomer unit A1 represented by the general formula (a1), the monomer unit A2 represented by the general formula (a2), and the general formula (b). The monomer unit B and the monomer unit C1 represented by the general formula (c1), and the ratio of the total amount of the monomer unit A1 and the monomer unit A2 is 30 to 50 mol% with respect to the entire monomer unit; This is a method for improving the solubility of the liquid crystal polyester, wherein the monomer unit B has a ratio of 25 to 35 mol% and the monomer unit C has a ratio of 25 to 35 mol%.

Thus, the solubility of liquid crystal polyester improves remarkably by making liquid crystal polyester have a specific monomer unit by a specific ratio. Also in this case, it is preferable that n ¹ and n ² satisfy the above formula (1), where n ^{1 is} the number of monomer units A1 and n ² is the number of monomer units A2. The liquid crystalline polyester further has a monomer unit C2 represented by the general formula (c2), and the ratio of the total amount of the monomer unit C1 and the monomer unit C2 to the whole monomer unit is 25 to 35 mol%. It is more preferable.

  In the method for producing a liquid crystal polyester film of the present invention, a solution layer comprising the liquid crystal polyester solution of the present invention is formed on a support substrate, and the solvent is removed from the solution layer to form a liquid crystal polyester film on the support substrate. To do. Moreover, the liquid crystalline polyester film of the present invention is obtained by this production method.

  According to such a production method, an isotropic liquid crystal polyester film can be produced with high production efficiency by increasing the concentration of the liquid crystal polyester solution. Further, according to this production method, a liquid crystal polyester film having sufficient mechanical strength can be obtained.

  The liquid crystalline polyester of the present invention has a sufficiently large solubility in a solvent. Moreover, according to the manufacturing method of the liquid crystalline polyester film of this invention, it is possible to manufacture a liquid crystalline polyester film with high production efficiency.

  The liquid crystalline polyester solution of the present invention is suitably used in the above production method. According to the method for improving the solubility of the liquid crystalline polyester of the present invention, the concentration of the liquid crystalline polyester in the liquid crystalline polyester solution is sufficiently increased, The production efficiency can be improved in the production of the polyester film.

  Furthermore, the liquid crystalline polyester film of the present invention can have sufficient mechanical strength, and is excellent in performance such as high-frequency characteristics and low water absorption, for electronic parts such as printed wiring boards. It is suitably used for film applications.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  The liquid crystalline polyester of the present invention comprises a monomer unit A1 represented by the general formula (a1), a monomer unit A2 represented by the general formula (a2), and a monomer unit B represented by the general formula (b). And a monomer unit C1 represented by the general formula (c1).

  The ratio of the total amount of the monomer unit A1 and the monomer unit A2 is 30 to 50 mol%, the ratio of the monomer unit B is 25 to 35 mol%, and the ratio of the monomer unit C1 is 25 to the total monomer units of the liquid crystal polyester. 35 mol%. In order to further improve the solubility, the ratio of the total amount of the monomer unit A1 and the monomer unit A2 is 35 to 45 mol%, the ratio of the monomer unit B is 27.5 to 32.5 mol%, the ratio of the monomer unit C Is more preferably 27.5 to 32.5 mol%. If the ratio of the total amount of the monomer unit A1 and the monomer unit A2 is less than 30 mol%, the liquid crystal polyester of the resulting liquid crystal polyester tends to be reduced, and if it exceeds 50 mol%, the solubility is reduced.

  When the ratio of the monomer unit B and the monomer unit C1 is less than 25 mol%, the solubility of the obtained liquid crystal polyester is lowered, and when it exceeds 35 mol%, the liquid crystal property of the obtained liquid crystal polyester tends to be lowered. . Moreover, it is preferable that the monomer unit B and the monomer unit C1 are substantially equimolar. However, for the purpose of controlling the degree of polymerization of the liquid crystal polyester, the amount of the monomer unit B can be adjusted preferably within the range of the amount of the monomer unit C ± 10 mol%.

In order to more significantly improve the solubility of the liquid crystal polyester, when the number of monomer units A1 is n ¹ and the number of monomer units A2 is n ² , n ¹ and n ² satisfy the above formula (1). It is preferable.

  By the way, in general, liquid crystal polyester is produced by melt polymerization of a mixture of monomers. If the liquid crystal polyester is not sufficiently high molecular weight only by melt polymerization, the liquid crystal polyester can be further high molecular weight by so-called solid phase polymerization. The solid-phase polymerization is performed, for example, by pulverizing the solid after melt polymerization into a powder and heating the powdered solid. By increasing the molecular weight of the liquid crystal polyester, a liquid crystal polyester film having a sufficiently large mechanical strength can be obtained.

  However, the conventional liquid crystalline polyester has a plate shape in order to sufficiently increase the molecular weight because the resin is melted again and solidified in a plate shape when solid phase polymerization is performed after the melt polymerization. The resin had to be pulverized into a powder and then subjected to solid phase polymerization again.

On the other hand, in the case of the liquid crystal polyester according to the present invention, n ¹ and n ² satisfy the following formula (2), and more preferably satisfy the following formula (3). In addition, the liquid crystal polyester can be efficiently made to have a high molecular weight. From the viewpoint of easy high molecular weight and improved solubility, n ² / (n ¹ + n ² ) is more preferably 0.1 or more.
0 <n ² / (n ¹ + n ² ) <0.25 (2)
0 <n ² / (n ¹ + n ² ) <0.20 (3)

In the monomer unit A1, Ar ¹ may have a substituent such as a halogen atom, an alkyl group, or an aryl group. The halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom, and the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms represented by a methyl group, an ethyl group, a propyl group, a butyl group or the like, and an aryl group Is preferably an aryl group having 6 to 20 carbon atoms represented by a phenyl group, a naphthyl group, or the like. As the monomer unit A1, a monomer unit represented by the following chemical formula (a1-1) derived from p-hydroxybenzoic acid is particularly preferable.

In the monomer unit A2, Ar ² may have a substituent such as a halogen atom, an alkyl group, or an aryl group. As the halogen atom, alkyl group, and aryl group, those already mentioned in the description of Ar ¹ are preferable. As the monomer unit A2, a monomer unit represented by the following chemical formula (a2-1) derived from 2-hydroxy-6-naphthoic acid is particularly preferable.

The monomer unit B is preferably a monomer unit derived from terephthalic acid, isophthalic acid or 2,6-naphthalenedicarboxylic acid. Among these, from the viewpoint of the solubility of the liquid crystal polyester, those in which Ar ³ derived from isophthalic acid is a 1,3-phenylene group are preferable.

The monomer unit C1 is a monomer unit derived from aromatic diamine, aminophenol, or a derivative thereof. Ar ⁴ in formula (c1) may have a substituent such as a halogen atom, an alkyl group, or an aryl group. As the halogen atom, alkyl group, and aryl group, those already mentioned in the description of Ar ¹ are preferable. Examples of the monomer unit C1 include monomer units derived from 3-aminophenol, 4-aminophenol, 1,4-phenylenediamine, or 1,3-phenylenediamine. Among these, a monomer unit derived from 4-aminophenol and having Ar ⁴ as a 1,4-phenylene group is preferable.

  The liquid crystal polyester of the present invention preferably further has a monomer unit C2 derived from an aromatic diol. In this case, the ratio of the total amount of the monomer unit C1 and the monomer unit C2 is 25 to 35 mol% with respect to the entire monomer unit. That is, the monomer unit C2 is introduced in the form of replacing a part of the monomer unit C1.

Ar ⁵ in formula (c2) may have a 1,4-phenylene group which may have a substituent, a 1,3-phenylene group which may have a substituent, or a substituent. A 4,4′-biphenylene group is preferred. Examples of the substituent for Ar ⁵ include a halogen atom, an alkyl group, and an aryl group. As the halogen atom, alkyl group, and aryl group, those already mentioned in the description of Ar ¹ are preferable. Among these, as the monomer unit C2, a monomer unit derived from hydroquinone and having Ar ⁵ as a 1,4-phenylene group is particularly preferable.

  The liquid crystalline polyester of the present invention is a monomer corresponding to each monomer unit, that is, aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic amine, aminophenol, aromatic diol or ester-forming derivative or amide-forming derivative thereof. Can be produced by polymerization in accordance with an ordinary method (for example, methods described in JP-A Nos. 2002-220444 and 2002-146003).

  More specifically, the liquid crystal polyester of the present invention includes a monomer A1 represented by the following general formula (a11), a monomer A2 represented by the following general formula (a12), and a monomer represented by the following general formula (b10). Heating the monomer mixture containing B and the monomer C1 represented by the following general formula (c11) to obtain a solid, a step of processing the solid into particles, and heating the particles of solid And a step of obtaining a liquid crystal polyester, wherein the ratio of the total amount of monomer A1 and monomer A2 is 30 to 50 mol%, the ratio of monomer B is 25 to 35 mol%, and the ratio of monomer C to the entire monomer mixture Can be suitably obtained by a production method having a content of 25 to 35 mol%.

In the formulas (a11), (a12), (b10), and (c11), Ar ¹ , Ar ² , Ar ³ , Ar ^4, and X represent the above formulas (a1), (a2), (b), and (c1) Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and X are the same as those including preferred embodiments thereof.

In these formulas, R ¹ , R ³ , R ⁷ and R ⁸ each independently represents an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms) which may have a substituent. More specifically, R ¹ , R ³ , R ⁷ and R ⁸ are preferably a methyl group, an ethyl group, a propyl group or an isopropyl group, and among them, a methyl group is particularly preferable. R ² in formula (a11), R ⁴ in formula (a12), and R ⁵ and R ^{6 in} formula (b10) are each independently an alkanoyloxy group which may have a substituent, or a substituent. Represents an alkyloxy group, a halogen atom or a hydroxyl group which may have a hydroxyl group, and particularly preferably a hydroxyl group.

In the above manufacturing method, the number of monomers A1 when ^{n 1,} the number of monomers A2 and ^{n 2,} it is preferable ^{that n 1} and ^{n 2} satisfy the above equation (1) satisfies the above expression (2) It is more preferable that the above formula (3) is satisfied. Here, the ratio of monomer A1, monomer A2, monomer B, and monomer C1 in the monomer mixture is substantially the same as the ratio of monomer unit A1, monomer unit A2, monomer unit B, and monomer unit C1 in the resulting liquid crystal polyester. Needless to say.

  The monomer mixture further contains a monomer C2 represented by the following general formula (c12), and the ratio of the total amount of the monomer C1 and the monomer C2 is preferably 25 to 35 mol% with respect to the entire monomer mixture. .

Wherein (c12), Ar ⁵ is an Ar ⁵ in the formula (c2), which is synonymous, including preferred embodiments thereof. R ⁹ and R ¹⁰ each independently represents an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms) which may have a substituent. More specifically, R ⁹ and R ¹⁰ are preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group, and among them, a methyl group is particularly preferable.

Hereinafter, as a preferred representatives of the above manufacturing ^method, an ^{R 1,} R ^3, R ⁷ and ^{R 8} are optionally substituted alkyl ^{group, R 2, R 4, R} 5 and ^{R 6} Is a hydroxyl group, in other words, the monomer A1 and the monomer A2 are acylated phenolic hydroxyl groups in the aromatic hydroxycarboxylic acid, the monomer B is an aromatic dicarboxylic acid, and the monomer C1 is an aromatic diamine or amino acid. A preferred embodiment in which the amino group or phenolic hydroxyl group in phenol is acylated will be described more specifically.

The monomer A1, the monomer A2, and the monomer C1 are each an aromatic hydroxycarboxylic acid represented by the following general formula (a21), an aromatic hydroxycarboxylic acid represented by the following general formula (a22), and the following general formula (c21). It is obtained by acylating the aromatic diamine or aminophenol represented by the following, for example, by reaction with an acid anhydride. The acylation reaction may be carried out with each compound alone or in a state where these compounds are mixed. In these ^formulas, Ar ^1, Ar ^2, Ar ⁴ and X is the above formula (a1), (a2), and ^{Ar 1, Ar 2, Ar 4} and X in (c1), synonymous, including preferred embodiments thereof belongs to.

  In the acylation reaction, the amount of acid anhydride added is usually 1.0 to 1.2 times equivalent, preferably 1.05 to 1.1 times the total amount of phenolic hydroxyl group and amino group. Is equivalent. When the amount of the acid anhydride is less than 1.0 times equivalent, the acylated product or the raw material monomer tends to sublimate during polycondensation, and the reaction system tends to be clogged. When the amount exceeds 1.2 times equivalent, The resulting liquid crystal polyester tends to be colored.

  The acylation reaction proceeds sufficiently by heating the mixture in which the above compound and acid anhydride are mixed, usually at 130 to 180 ° C. for 5 minutes to 10 hours, preferably at 140 to 160 ° C. for 10 minutes to 3 hours. Can be made.

  As the acid anhydride used in the acylation reaction, a fatty acid anhydride is preferable. Examples of the fatty acid anhydride include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, monobromo anhydride Examples include acetic acid, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, glutaric anhydride, maleic anhydride, succinic anhydride, and β-bromopropionic anhydride. You may use the above together. Among these, acetic anhydride, propionic anhydride, butyric anhydride, and isobutyric anhydride are preferable from the viewpoints of price and handleability, and among these, acetic anhydride is preferable.

  The monomer mixture may be a mixture of monomers prepared separately in advance, or an acylation reaction may be performed in a state where precursors of the respective monomers are mixed, and the mixture after the acylation reaction is used as a monomer. It may be used as a mixture. In the monomer mixture, the amount of carboxyl groups is preferably 0.8 to 1.2 times equivalent to the total amount of acyl groups and amide groups.

  By melt polymerization in which the monomer mixture is heated, a polymerization reaction (polycondensation reaction) such as an ester exchange reaction or an amide exchange reaction proceeds to produce a liquid crystal polyester having a high molecular weight. The produced liquid crystal polyester is taken out from the reaction vessel for melt polymerization and cooled to room temperature, whereby a solid material of liquid crystal polyester is obtained. The melt polymerization is preferably performed at 130 to 400 ° C. while increasing the temperature at a rate of 0.1 to 50 ° C./min, and at 150 to 350 ° C. while increasing the temperature at a rate of 0.3 to 5 ° C./min. It is more preferable. At this time, in order to shift the equilibrium, it is preferable to distill out by-produced fatty acids and unreacted fatty acid anhydrides by evaporating them.

  The acylation reaction and polymerization reaction may be performed in the presence of a catalyst. As the catalyst, those conventionally known as polyester polymerization catalysts, for example, metal salt catalysts such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, N, Organic compound catalysts such as N-dimethylaminopyridine and N-methylimidazole can be used. Among these catalysts, heterocyclic compounds containing two or more nitrogen atoms such as N, N-dimethylaminopyridine and N-methylimidazole are preferably used.

  Subsequently, the solid material after melt polymerization is pulverized and processed into particles such as powder and flakes.

  By heating the particulate solid, the polymerization reaction proceeds to further increase the molecular weight of the liquid crystalline polyester (solid phase polymerization). The increase in the degree of polymerization due to solid phase polymerization can be confirmed, for example, by an increase in the flow start temperature (FT) of the liquid crystal polyester. The solid phase polymerization is preferably performed until the flow start temperature of the liquid crystalline polyester reaches 270 ° C. or higher (preferably 280 to 340 ° C.).

  The solid phase polymerization can be performed by a known method, and specifically, for example, a method of heating in a solid state at 180 to 350 ° C. for 1 to 30 hours under an inert atmosphere such as nitrogen, etc. It is done. The solid phase polymerization may be performed with stirring, or may be performed in a state of standing without stirring. If an appropriate stirring mechanism is employed, melt polymerization and solid phase polymerization can be performed in the same reaction vessel. After the solid-phase polymerization, the obtained liquid crystalline polyester is used in order to obtain a molded product after remaining in the form of particles or pelletized.

  You may use the liquid crystalline polyester of this invention in the state mixed with the filler, the additive, etc. in the range which does not impair the objective of this invention.

  Examples of fillers include organic fillers such as epoxy resin powder, melamine resin powder, urea resin powder, benzoguanamine resin powder, and styrene resin, and inorganic fillers such as silica, alumina, titanium oxide, zirconia, kaolin, calcium carbonate, and calcium phosphate. Etc.

  Examples of the additive include known coupling agents, anti-settling agents, ultraviolet absorbers, and heat stabilizers.

  The liquid crystalline polyester is a thermoplastic resin such as polypropylene, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenyl ether and a modified product thereof, and polyether imide, as long as the object of the present invention is not impaired. Alternatively, it may be used in a state where it is mixed with an elastomer such as a copolymer of glycidyl methacrylate and polyethylene.

  The liquid crystal polyester solution of the present invention is obtained by dissolving the above liquid crystal polyester in a solvent containing an aprotic solvent (preferably a solvent comprising an aprotic solvent), and can be produced by mixing the two.

  The content of the liquid crystalline polyester is preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the solvent. If the amount is less than 0.01 parts by weight, the solution viscosity tends to be too low and uniform coating tends to be difficult. If the amount exceeds 100 parts by weight, the viscosity tends to increase and uniform coating tends to be difficult. . From the viewpoint of workability and economical efficiency, the content of the liquid crystal polyester is more preferably 1 to 50 parts by weight, and further preferably 2 to 40 parts by weight.

  Examples of the aprotic solvent include halogen solvents such as 1-chlorobutane, chlorobenzene, 1,1-dichloroethane, 1,2-dichloroethane, chloroform, 1,1,2,2-tetrachloroethane, diethyl ether, tetrahydrofuran, Ether solvents such as 1,4-dioxane, ketone solvents such as acetone and cyclohexanone, ester solvents such as ethyl acetate, lactone solvents such as γ-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, triethylamine, Amines such as pyridine, nitrile solvents such as acetonitrile and succinonitrile, amides such as N, N′-dimethylformamide, N, N′-dimethylacetamide, tetramethylurea and N-methylpyrrolidone Solvents, nitromethane, nitro-based solvents such as nitrobenzene, dimethyl sulfoxide, sulfide-based solvents, hexamethylphosphoramide, such as sulfolane, phosphoric acid-based solvent such as tri-n- butyl phosphate are preferably used.

  Among these, a solvent containing no halogen atom is preferably used from the viewpoint of influence on the environment, and a solvent having a dipole moment of 3 to 5 is preferably used from the viewpoint of solubility. Specifically, amide solvents such as N, N′-dimethylformamide, N, N′-dimethylacetamide, tetramethylurea and N-methylpyrrolidone, lactone solvents such as γ-butyrolactone, and the like are more preferably used. N, N′-dimethylformamide, N, N′-dimethylacetamide, and N-methylpyrrolidone are more preferably used.

  In the method for producing a liquid crystal polyester film of the present invention, a solution layer comprising the above liquid crystal polyester solution is formed on a support substrate, and the solvent is removed from the solution layer to form a liquid crystal polyester film on the support substrate. According to such a so-called solution casting method, a liquid crystal polyester film having less anisotropy and good mechanical strength can be easily obtained as compared with the case of a method such as extrusion molding.

  The solution layer is formed by casting a liquid crystal polyester solution on a support substrate. Examples of methods that can be uniformly and uniformly cast on the surface include roller coating, dip coating, spray coating, spinner coating, curtain coating, slot coating, and screen printing. It is done. Before casting, it is preferable to remove fine foreign substances contained in the liquid crystal polyester solution by filtering with a filter or the like, if necessary.

  As the support substrate, a sheet-like material appropriately selected according to the use of the obtained liquid crystal polyester film is used. Specifically, for example, a metal foil (preferably a copper foil) such as a copper foil, an aluminum foil, a gold foil, or a silver foil, a glass substrate (for example, a glass plate having a thickness of about 1 mm), or the like is used as a supporting base material. it can.

  The method for removing the solvent from the solution layer is not particularly limited, but it is preferably performed by evaporation of the solvent. Examples of the method for evaporating the solvent include methods such as heating, reduced pressure, and ventilation. Among them, it is preferable to evaporate by heating from the viewpoint of production efficiency and handleability, and it is more preferable to evaporate by heating while ventilating. preferable. The heating conditions at this time preferably include a step of performing preliminary drying at 60 to 200 ° C. for 10 minutes to 2 hours and a step of performing heat treatment at 200 to 400 ° C. for 30 minutes to 5 hours.

  The thickness of the liquid crystal polyester film is not particularly limited, but is preferably 0.5 to 500 μm from the viewpoint of film forming properties and mechanical properties, and more preferably 1 to 200 μm from the viewpoint of handleability. preferable. The method for producing a liquid crystal polyester film of the present invention is particularly useful in the case of producing a relatively thick film such as 5 to 50 μm.

  The liquid crystal polyester film according to the present invention not only has excellent mechanical strength but also exhibits excellent characteristics such as high frequency characteristics and low hygroscopicity. Therefore, semiconductor packages and multilayer printed circuit boards for motherboards, flexible printed wiring boards, tape automated bonding films, other 8 mm video tape base materials, and professional digital video tape bases that have been attracting attention in recent years. Suitable for materials, transparent conductive (ITO) film substrates, polarizing film substrates, various cooked foods, microwave heating packaging films, electromagnetic shielding films, antibacterial films, gas separation films, etc. Can be used.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples.

In the following examples and comparative examples, the flow starting temperature of liquid crystal polyester, the solubility in NMP, and the strength of the liquid crystal polyester film were evaluated by the following methods.
(Flow start temperature)
Using a capillary rheometer with an inner diameter of 1 mm and a length of 10 mm, a temperature at which the melt viscosity shows 48000 poise when the heated melt is extruded from the nozzle at a heating rate of 4 ° C./min under a load of 100 kg / cm ² , It was set as the flow start temperature.
(Solubility in NMP)
Whether or not a predetermined amount of the liquid crystalline polyester was completely dissolved in the solvent was visually confirmed, and the maximum value of the amount (concentration) completely dissolved was used as solubility data in NMP.
(Film strength)
By bending a test piece obtained by forming a liquid crystal polyester film into a strip shape having a width of 1.5 cm and a longitudinal direction of 10 cm at a corner R = 0.38 using a MIT fatigue resistance tester (manufactured by Toyo Seiki Seisakusho), Flexibility was evaluated. The bending resistance was determined according to the following criteria.
A: Even if the number of folding times is 50000 times or more, it does not break B: It is broken when the number of folding times is 10 to 50 C: It is broken by its own weight (not reaching the evaluation of the bending test)

Example 1
In a reactor equipped with a stirrer, a torque meter, a nitrogen gas introduction pipe, a thermometer and a reflux condenser, 94.1 g (0.5 mol) of 2-hydroxy-6-naphthoic acid (hereinafter referred to as “HNA”), p-hydroxybenzoic acid (hereinafter referred to as “PHB”) 69.1 g (0.5 mol), 4-hydroxyacetanilide (hereinafter referred to as “APAP”) 75.6 g (0.5 mol) and isophthalic acid ( Hereinafter, 83.1 g (0.5 mol) and 173.6 g (1.7 mol) of acetic anhydride were added as starting materials. After sufficiently replacing the inside of the reactor with nitrogen gas, the temperature was raised to 150 ° C. over 15 minutes under a nitrogen gas stream, and the temperature was maintained and refluxed for 3 hours.

Thereafter, the temperature was raised to 300 ° C. over 170 minutes while distilling off by-product acetic acid and unreacted acetic anhydride, and the time when an increase in torque was observed was regarded as the end of the reaction (melt polymerization). After completion of the reaction, the solid content taken out was cooled to room temperature and pulverized with a coarse pulverizer to obtain a powdery liquid crystal polyester. The obtained liquid crystal polyester was confirmed to show a schlieren pattern peculiar to the liquid crystal phase at 200 ° C. by observation with a polarizing microscope.
Furthermore, the liquid crystalline polyester in powder form was heated at 240 ° C. for 3 hours in a nitrogen atmosphere to advance the solid phase polymerization to obtain a liquid crystalline polyester having a flow start temperature of 242 ° C.

  When the obtained liquid crystal polyester is added to N-methylpyrrolidone (hereinafter referred to as “NMP”) and heated to 140 ° C., the liquid crystal polyester is completely dissolved when the concentration of the liquid crystal polyester is 10% by mass or less. Thus, a transparent liquid crystal polyester solution was obtained.

(Example 2)
HNA 150.5 g (0.8 mol), PHB 27.6 g (0.2 mol), APAP 75.6 g (0.5 mol), IPA 83.1 g (0.5 mol) and acetic anhydride 173.6 g (1.7 mol) ) Was used as a starting material, and was melt polymerized in the same manner as in Example 1 to obtain a powdery liquid crystal polyester. The obtained liquid crystal polyester was confirmed to show a schlieren pattern peculiar to the liquid crystal phase at 200 ° C. by observation with a polarizing microscope.
Further, the liquid crystalline polyester in a powder state was heated at 240 ° C. for 3 hours under a nitrogen atmosphere to advance the solid phase polymerization to obtain a liquid crystalline polyester having a flow start temperature of 240 ° C.

  When the obtained liquid crystal polyester was added to NMP in a predetermined amount and heated to 140 ° C., the liquid crystal polyester was completely dissolved and a transparent liquid crystal polyester solution was obtained when the liquid crystal polyester concentration was 12% by mass or less. It was.

(Example 3)
HNA 11.3 g (0.06 mol), PHB 102.2 g (0.74 mol), APAP 90.7 g (0.6 mol), IPA 99.7 g (0.6 mol) and acetic anhydride 163.3 g (1.6 mol) ) Was used as a starting material, and was melt polymerized in the same manner as in Example 1 to obtain a powdery liquid crystal polyester. The obtained liquid crystal polyester was confirmed to show a schlieren pattern peculiar to the liquid crystal phase at 200 ° C. by observation with a polarizing microscope.
Further, the liquid crystalline polyester was heated at 240 ° C. for 3 hours in a nitrogen atmosphere to advance the solid phase polymerization to obtain a liquid crystalline polyester having a flow start temperature of 320 ° C.

  When the obtained liquid crystal polyester was added to NMP in a predetermined amount and heated to 140 ° C., the liquid crystal polyester was completely dissolved at a liquid crystal polyester concentration of 16% by mass or less to obtain a transparent liquid crystal polyester solution. It was.

Example 4
37.6 g (0.2 mol) of HNA, 193.4 g (1.4 mol) of PHB, 181.4 g (1.2 mol) of APAP and 199.4 g (1.2 mol) of IPA and 326.7 g (3.2 mol) of acetic anhydride ) Was used as a starting material, and was melt polymerized in the same manner as in Example 1 to obtain a powdery liquid crystal polyester. The obtained liquid crystal polyester was confirmed to show a schlieren pattern peculiar to the liquid crystal phase at 200 ° C. by observation with a polarizing microscope.
Further, the liquid crystalline polyester was heated at 240 ° C. for 3 hours in a nitrogen atmosphere to advance the solid phase polymerization to obtain a liquid crystalline polyester having a flow start temperature of 320 ° C.

  When the obtained liquid crystal polyester was added to NMP in a predetermined amount and heated to 140 ° C., the liquid crystal polyester was completely dissolved at a liquid crystal polyester concentration of 16% by mass or less to obtain a transparent liquid crystal polyester solution. It was.

(Example 5)
HNA 26.3 g (0.14 mol), PHB 91.2 g (0.66 mol), APAP 90.7 g (0.6 mol), IPA 99.7 g (0.6 mol) and acetic anhydride 163.3 g (1.6 mol) ) Was used as a starting material, and was melt polymerized in the same manner as in Example 1 to obtain a powdery liquid crystal polyester. The obtained liquid crystal polyester was confirmed to show a schlieren pattern peculiar to the liquid crystal phase at 200 ° C. by observation with a polarizing microscope.
Further, the liquid crystalline polyester was heated at 240 ° C. for 3 hours in a nitrogen atmosphere to advance the solid phase polymerization to obtain a liquid crystalline polyester having a flow start temperature of 320 ° C.

  When the obtained liquid crystal polyester was added to NMP in a predetermined amount and heated to 140 ° C., the liquid crystal polyester was completely dissolved at a liquid crystal polyester concentration of 16% by mass or less to obtain a transparent liquid crystal polyester solution. It was.

(Example 6)
HNA 131.7 g (0.7 mol), PHB 13.8 g (0.1 mol), APAP 90.7 g (0.6 mol), IPA 99.7 g (0.6 mol) and acetic anhydride 163.3 g (1.6 mol) ) Was used as a starting material, and was melt polymerized in the same manner as in Example 1 to obtain a powdery liquid crystal polyester. The obtained liquid crystal polyester was confirmed to show a schlieren pattern peculiar to the liquid crystal phase at 200 ° C. by observation with a polarizing microscope.
Furthermore, the liquid crystalline polyester in powder form was heated at 240 ° C. for 3 hours in a nitrogen atmosphere to advance the solid phase polymerization to obtain a liquid crystalline polyester having a flow start temperature of 240 to 250 ° C.

  When the obtained liquid crystal polyester was added to NMP in a predetermined amount and heated to 140 ° C., the liquid crystal polyester was completely dissolved at a liquid crystal polyester concentration of 16% by mass or less to obtain a transparent liquid crystal polyester solution. It was.

(Comparative Example 1)
Example 1 except that PHB 138.1 g (1 mol), APAP 75.6 g (0.5 mol), IPA 83.1 g (0.5 mol) and acetic anhydride 173.6 g (1.7 mol) were used as starting materials. In the same manner as above, melt polymerization was performed to obtain a powdery liquid crystal polyester. The obtained liquid crystal polyester was confirmed to show a schlieren pattern peculiar to the liquid crystal phase at 200 ° C. by observation with a polarizing microscope.
Further, the liquid crystalline polyester was heated at 240 ° C. for 3 hours in a nitrogen atmosphere to advance the solid phase polymerization to obtain a liquid crystalline polyester having a flow start temperature of 320 ° C.

  When the obtained liquid crystal polyester is added to NMP in a predetermined amount and heated to 140 ° C., even if the concentration of the liquid crystal polyester is 8% by mass, insoluble matter remains and a transparent solution can be obtained. There wasn't.

(Comparative Example 2)
Example 1 except that 188.2 g (1 mol) of HNA, 75.6 g (0.5 mol) of APAP, 83.1 g (0.5 mol) of IPA and 173.6 g (1.7 mol) of acetic anhydride were used as starting materials. In the same manner as above, melt polymerization was performed to obtain a powdery liquid crystal polyester. The obtained liquid crystal polyester was confirmed to show a schlieren pattern peculiar to the liquid crystal phase at 200 ° C. by observation with a polarizing microscope.
Furthermore, solid phase polymerization was advanced by heating the liquid crystalline polyester in a nitrogen atmosphere at 240 ° C. for 3 hours. However, the flow start temperature of the obtained liquid crystal polyester was 240 ° C.

  When the obtained liquid crystal polyester was added to NMP in a predetermined amount and heated to 140 ° C., the liquid crystal polyester was completely dissolved and a transparent liquid crystal polyester solution was obtained when the liquid crystal polyester concentration was 8% by mass or less. However, when the concentration was higher than this, a clear solution could not be obtained.

(Comparative Example 3)
Implementation was carried out except that 221.0 g (1.6 mol) of PHB, 181.4 g (1.2 mol) of APAP, 199.4 g (1.2 mol) of IPA and 326.7 g (3.2 mol) of acetic anhydride were used as starting materials. Melt polymerization was conducted in the same manner as in Example 1 to obtain a powdery liquid crystal polyester. The obtained liquid crystal polyester was confirmed to show a schlieren pattern peculiar to the liquid crystal phase at 200 ° C. by observation with a polarizing microscope.
Further, the liquid crystalline polyester was heated at 240 ° C. for 3 hours in a nitrogen atmosphere to advance the solid phase polymerization to obtain a liquid crystalline polyester having a flow start temperature of 320 ° C.

  When the obtained liquid crystal polyester is added to NMP in a predetermined amount and heated to 140 ° C., even if the concentration of the liquid crystal polyester is 8% by mass, insoluble matter remains and a transparent solution can be obtained. There wasn't.

As shown in Table 1, according to Examples 1 to 6 in which HNA and PHB were used in combination and the ratio of each monomer was within a specific range, it was confirmed that a liquid crystal polyester having sufficiently large solubility was obtained. It was. In particular, according to Examples 3, 4, and 5 in which the ratio of HNA is within the range in which the above-mentioned n ² / (n ¹ + n ² ) value is less than 0.25, one-time solid-phase polymerization Thus, a liquid crystal polyester having a sufficiently high molecular weight and a high flow start temperature was obtained. On the other hand, Comparative Examples 1 to 3 in which HNA and PHB were not used in combination did not have sufficient solubility.

(Manufacture of liquid crystal polyester film)
The liquid crystal polyesters obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were each stirred and degassed with a transparent liquid crystal polyester solution dissolved in NMP, and then coated on a copper foil with a thickness of 300 μm by bar coating. A solution layer was formed on the copper foil. Then, after removing the solvent in the solution layer by heating on a hot plate at 80 ° C. for 1 hour and further at 120 ° C. for 1 hour, it was further heat-treated at 300 ° C. for 1 hour in a nitrogen atmosphere. Next, the copper foil was removed by etching to obtain a liquid crystal polyester film having a film thickness of 25 μm.

About the obtained liquid crystal polyester film, when film strength was evaluated by said method, the liquid crystal polyester film of Examples 1-6 showed favorable film strength. Among them, the liquid crystal polyester films of Examples 3, 4, and 5 in which the ratio of HNA is within the range in which the value of n ² / (n ¹ + n ² ) is less than 0.25 are particularly excellent films. Intensity was shown.

Claims (12)

Monomer unit A1 represented by the following general formula (a1);
Monomer unit A2 represented by the following general formula (a2);
Monomer unit B represented by the following general formula (b);
A monomer unit C1 represented by the following general formula (c1),
The ratio of the total amount of the monomer unit A1 and the monomer unit A2 is 30 to 50 mol%, the ratio of the monomer unit B is 25 to 35 mol%, and the ratio of the monomer unit C1 is 25 to the entire monomer unit. Liquid crystalline polyester which is 35 mol%.

[In Formula (a1) and Formula (a2), Ar ¹ represents a 1,4-phenylene group which may have a substituent, and Ar ² represents 2,6-naphthalene which may have a substituent. Indicates a group. ]

[In the formula (b), Ar ³ may have a 1,4-phenylene group which may have a substituent, a 1,3-phenylene group which may have a substituent or a substituent. A good 2,6-naphthalene group is shown. ]

[In the formula (c1), Ar ⁴ may have a 1,4-phenylene group which may have a substituent, a 1,3-phenylene group which may have a substituent or a substituent. A good 2,6-naphthalene group is shown, and X represents —O— or —NH—. ] ^{N 1} the number of the monomer units A1, the number of the monomer units A2 is taken as ^{n 2, n 1} and ^{n 2} satisfy the following formula (1), according to claim 1 liquid crystal polyester according.
0 <n ² / (n ¹ + n ² ) <0.95 (1) The monomer unit C2 represented by the following general formula (c2) is further included, and the ratio of the total amount of the monomer unit C1 and the monomer unit C2 to the whole monomer unit is 25 to 35 mol%. Or the liquid crystalline polyester of 2.

[In the formula (c2), Ar ⁵ represents an arylene group which may have a substituent. ]   The liquid crystal polyester solution which melt | dissolved the liquid crystal polyester as described in any one of Claims 1-3 in the solvent containing an aprotic solvent.   The liquid crystal polyester solution according to claim 4, comprising 0.01 to 100 parts by weight of the liquid crystal polyester with respect to 100 parts by weight of the solvent.   The liquid crystalline polyester solution according to claim 4 or 5, wherein the aprotic solvent is an aprotic solvent having no halogen atom.   The liquid crystal polyester solution according to any one of claims 4 to 6, wherein a dipole moment of the aprotic solvent is 3 or more and 5 or less. Liquid crystal polyester,
Monomer unit A1 represented by the following general formula (a1);
Monomer unit A2 represented by the following general formula (a2);
Monomer unit B represented by the following general formula (b);
A monomer unit C1 represented by the following general formula (c1),
The ratio of the total amount of the monomer unit A1 and the monomer unit A2 is 30 to 50 mol%, the ratio of the monomer unit B is 25 to 35 mol%, and the ratio of the monomer unit C1 is 25 to the entire monomer unit. A method for improving the solubility of a liquid crystal polyester, which is 35 mol%.

[In Formula (a1) and Formula (a2), Ar ¹ represents a 1,4-phenylene group which may have a substituent, and Ar ² represents 2,6-naphthalene which may have a substituent. Indicates a group. ]

[In the formula (b), Ar ³ may have a 1,4-phenylene group which may have a substituent, a 1,3-phenylene group which may have a substituent or a substituent. A good 2,6-naphthalene group is shown. ]

[In the formula (c1), Ar ⁴ may have a 1,4-phenylene group which may have a substituent, a 1,3-phenylene group which may have a substituent or a substituent. A good 2,6-naphthalene group is shown, and X represents —O— or —NH—. ] 9. The liquid crystal polyester according to claim 8, wherein n ¹ and n ² satisfy the following formula (1) when the number of the monomer units A ¹ is n ¹ and the number of the monomer units A 2 is n ² . A method for improving the solubility of liquid crystal polyester.
0 <n ² / (n ¹ + n ² ) <0.95 (1) The liquid crystal polyester further has a monomer unit C2 represented by the following general formula (c2), and the ratio of the total amount of the monomer unit C1 and the monomer unit C2 to the whole monomer unit is 25 to 35 mol%. The method for improving the solubility of the liquid crystalline polyester according to claim 8 or 9.

[In the formula (c2), Ar ⁵ represents an arylene group which may have a substituent. ]   A solution layer comprising the liquid crystal polyester solution according to any one of claims 4 to 7 is formed on a support substrate, the solvent is removed from the solution layer, and a liquid crystal polyester film is formed on the support substrate. A method for producing a liquid crystal polyester film.   The liquid-crystal polyester film obtained by the manufacturing method of the liquid-crystal polyester film of Claim 11.