JP4946065B2 - Liquid crystalline polyester and film using the same - Google Patents

Description

  The present invention relates to a liquid crystal polyester and a film using the same.

  Liquid crystal polyesters are widely used in electronic parts such as printed wiring boards because they have a low dielectric constant, high mechanical strength, and excellent heat resistance and thin moldability. Along with the demand for further thinner electronic components, a material having a lower dielectric constant is also demanded. Therefore, the present inventors have already proposed a liquid crystal polyester composed of a structural unit derived from 2-hydroxy-6-naphthoic acid, aromatic diol and aromatic dicarboxylic acid (see Patent Document 1). As an embodiment, a liquid crystal polyester in which the aromatic diol is 4,4′-dihydroxybiphenyl is described.

JP 2004-196930 A

  However, the liquid crystal polyester described in Patent Document 1 has a low dielectric loss tangent and gives a molded article excellent in high-frequency characteristics, but a further low dielectric constant has been demanded. Further, the liquid crystal polyester resin may generally be deteriorated by hydrolysis, and a liquid crystal polyester having durability by hydrolysis (hereinafter referred to as hydrolysis resistance) has been desired. An object of the present invention is to provide a liquid crystal polyester that gives a molded article having a low dielectric constant and excellent resistance to hydrolysis. Further, a film made of the liquid crystalline polyester, an electronic component having the film, and a molded article obtained from the film Is to provide.

  In order to solve the above-mentioned problems, the present inventors have conducted extensive research on the constituent components of liquid crystal polyester, and as a result, obtained by using 4,4′-dihydroxydiphenyl ether instead of 4,4′-dihydroxybiphenyl. Not only does the dielectric constant of the liquid crystal polyester to be obtained further lower, but also surprisingly, it has been found that the liquid crystal polyester is also excellent in hydrolysis resistance, and various studies have been made to complete the present invention.

＜３＞（ロ）が下記式（B1）で示される繰り返し構造単位及び／又は下記式（B3）で示される繰り返し構造単位を含有する前記＜１＞又は＜２＞に記載の液晶ポリエステル。

＜４＞（ハ）が下記式（C1）で示される繰り返し構造単位を含有する前記＜１＞又は＜２＞に記載の液晶ポリエステル。

＜５＞（イ）として前記式（A3）で示される繰り返し構造単位、（ロ）として前記の式（B1）、式（B3）で示される繰り返し構造単位のうち少なくとも１つの繰り返し構造単位、（ハ）として前記（C1）で示される繰り返し構造単位を、それぞれ含有する前記＜１＞〜＜４＞の何れかに記載の液晶ポリエステル。
＜６＞（イ）、（ロ）および（ハ）の総モル数に対して、（イ）が３０〜８０モル％、（ロ）が３５〜１０モル％、（ハ）が３５〜１０モル％である前記＜１＞〜＜５＞何れかに記載の液晶ポリエステル。
＜７＞前記の式（A3）、式（B1）、式（B3）及び式（C1）で表される繰り返し構造単位の総モル数に対して、前記式（A3）で示される繰り返し構造単位が３０〜８０モル％、前記の式（B1）、式（B3）で示される繰り返し構造単位のうち少なくとも１つの繰り返し構造単位が３５〜１０モル％、前記（C1）で示される繰り返し構造単位が３５〜１０モル％である前記＜５＞に記載の液晶ポリエステル。
＜８＞さらに、（ニ）以下の式（２）で示される繰り返し構造単位を含有する前記何れかに記載の液晶ポリエステル。
−Ｘ−Ａｒ２−Ｙ− （２）
（式中、Ａｒ２は、２，６−ナフチレン、１，４−フェニレン、１，３−フェニレンまたは４，４’−ビフェニレン（これらはハロゲン原子、炭素数１〜１０のアルキル基または炭素数６〜２０のアリール基で置換されていてもよい。）であり、Ｘ、Ｙは独立にＯまたはＮＨを表す。） That is, the present invention provides the following liquid crystal polyester.
<1> containing a repeating structural unit derived from (a) an aromatic hydroxycarboxylic acid, (b) a repeating structural unit derived from an aromatic dicarboxylic acid, and (c) a structural unit represented by the following formula (1): Liquid crystalline polyester characterized by
-X-Ar1-O-Ar1-Y- (1)
(In the formula, Ar1 is 1,4-phenylene which may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X and Y are independently O or NH represents.)
<2> The liquid crystalline polyester according to <1>, wherein (a) contains a repeating structural unit represented by the following formula (A3).

<3> The liquid crystalline polyester according to <1> or <2>, wherein (b) contains a repeating structural unit represented by the following formula (B1) and / or a repeating structural unit represented by the following formula (B3).

<4> The liquid crystalline polyester according to <1> or <2>, in which (c) contains a repeating structural unit represented by the following formula (C1).

<5> (a) as the repeating structural unit represented by the formula (A3), (b) as the repeating formula unit represented by the formula (B1) and the formula (B3) as at least one repeating structural unit, ( C) The liquid crystalline polyester according to any one of <1> to <4>, which contains the repeating structural unit represented by (C1) as (c).
<6> With respect to the total number of moles of (A), (B) and (C), (A) is 30 to 80 mol%, (B) is 35 to 10 mol%, and (C) is 35 to 10 mol. % The liquid crystal polyester according to any one of <1> to <5>.
<7> The repeating structural unit represented by the formula (A3) with respect to the total number of moles of the repeating structural unit represented by the formula (A3), the formula (B1), the formula (B3), and the formula (C1). 30 to 80 mol%, 35 to 10 mol% of at least one repeating structural unit among the repeating structural units represented by the above formulas (B1) and (B3), and the repeating structural unit represented by (C1) The liquid crystalline polyester according to <5>, which is 35 to 10 mol%.
<8> The liquid crystalline polyester according to any one of the above, further comprising (d) a repeating structural unit represented by the following formula (2).
-X-Ar2-Y- (2)
(In the formula, Ar2 represents 2,6-naphthylene, 1,4-phenylene, 1,3-phenylene or 4,4′-biphenylene (these are a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms). And optionally substituted with 20 aryl groups), and X and Y independently represent O or NH.)

（式中、Ａはハロゲン原子またはトリハロゲン化メチル基を示し、ｉは１以上５以下の整数値を示す。）
＜１５＞前記いずれかに記載の液状組成物を支持体上に流延したのちに、溶媒を除去し、次いで加熱処理し、支持体を剥離して得られるフィルム。
＜１６＞前記＜９＞又は＜１５＞の何れかに記載のフィルムからなる層を有することを特徴とする積層体。
＜１７＞前記＜９＞又は＜１５＞の何れかにフィルムからなる層と導体からなる層とを有することを特徴とする積層体。
＜１８＞前記＜９＞又は＜１５＞に記載のフィルムを成形してなる液晶ポリエステル成形品。 Furthermore, the present invention relates to the liquid crystal polyester described above, and provides the following composition and use.
<9> A film comprising the liquid crystal polyester according to any one of the above.
<10> A liquid composition comprising the liquid crystal polyester according to any one of the above and a solvent.
<11> The liquid composition according to <11>, wherein the solvent contains an aprotic solvent.
<12> The liquid composition according to <11>, wherein the solvent contains an amide solvent.
<13> The liquid composition according to <11>, wherein the solvent contains a protic solvent.
<14> The liquid composition according to <11>, wherein the solvent contains a halogen-substituted phenol compound represented by the following formula (L ₁ ).

(In the formula, A represents a halogen atom or a trihalogenated methyl group, and i represents an integer value of 1 or more and 5 or less.)
<15> A film obtained by casting the liquid composition according to any one of the above on a support, removing the solvent, then heat-treating, and peeling the support.
<16> A laminate having a layer made of the film according to any one of <9> and <15>.
<17> A laminate having a layer made of a film and a layer made of a conductor in any one of <9> and <15>.
<18> A liquid crystal polyester molded product obtained by molding the film according to <9> or <15>.

  Since the liquid crystal polyester of the present invention has a low dielectric constant and is excellent in hydrolysis resistance, the film made of the liquid crystal polyester also has a low dielectric constant and excellent hydrolysis resistance. The laminate having a layer made of the film of the present invention can be used for printed wiring boards such as embedded, film carriers, high-density magnetic tape materials, wire coating agents, film capacitors, etc. in the electrical and electronic fields, and industrially. Very useful.

  Hereinafter, the best embodiment of the present invention will be described.

The liquid crystalline polyester of the present invention comprises (a) a repeating structural unit derived from an aromatic hydroxycarboxylic acid, (b) a repeating structural unit derived from an aromatic dicarboxylic acid, and (c) a repeating represented by the following formula (1). Contains structural units.
-X-Ar1-O-Ar1-Y- (1)
In the formula (1), Ar1 is 1,4-phenylene which may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X and Y are independently O or NH is represented. That is, the repeating structural unit represented by the formula (1) specifically represents any one of the repeating structural units represented by the following formulas C _{1 to} C ₃ .

上記（C1）〜（C3）は、ハロゲン原子、炭素数１〜１０のアルキル基または炭素数６〜２０のアリール基で置換されていてもよい。

The above (C1) to (C3) may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

  The above (C1) is a repeating structural unit derived from an aromatic diol, (C2) is a repeating structural unit derived from an aromatic amine having a phenolic hydroxyl group, and (C3) is derived from an aromatic diamine. Repeating structural unit. Among these, since the hydrolysis resistance is good, the repeating structural unit represented by (C1) is preferable.

  Specific examples of the repeating structural unit derived from (i) an aromatic hydroxycarboxylic acid include those represented by the following formulas (A1) to (A5). It can also be used.

上記の（A1）〜（A5）は、ハロゲン原子、炭素数１〜１０のアルキル基または炭素数６〜２０のアリール基で置換されていてもよい。

Said (A1)-(A5) may be substituted by the halogen atom, the C1-C10 alkyl group, or the C6-C20 aryl group.

Among the above, (a) preferably includes one or more repeating structural units selected from the group consisting of (A1), (A3), and (A5). From the viewpoint of dielectric properties, (A3 ) Is particularly preferred.

  Specific examples of (b) a repeating structural unit derived from an aromatic dicarboxylic acid include those represented by the following formulas (B1) to (B8), and two or more of these are used. You can also.

上記の（B1）〜（B8）は、ハロゲン原子、炭素数１〜１０のアルキル基または炭素数６〜２０のアリール基で置換されていてもよい。

Said (B1)-(B8) may be substituted by the halogen atom, the C1-C10 alkyl group, or the C6-C20 aryl group.

  Among these, one or more selected from the group consisting of (B1), (B2), (B3), (B5) and (B6) is preferable. From the viewpoint of dielectric properties and hydrolysis resistance, (B1 It is more preferable that at least one of the repeating structural units represented by (B3) or (B3) is contained.

  Here, (a) is 30 to 80 mol%, (b) is 35 to 10 mol%, and (c) is 35 to 35 mol%, based on the total number of moles of (A), (B), and (C). A liquid crystalline polyester of 10 mol% is preferred. Further, a liquid crystal polyester in which (A) is 40 to 70 mol%, (B) is 30 to 15 mol%, and (C) is 30 to 15 mol% is more preferable. Particularly preferred are liquid crystal polyesters in which (A) is 45 to 65 mol%, (B) is 27.5 to 17.5 mol%, and (C) is 27.5 to 17.5 mol%.

  Furthermore, liquid crystal polyesters composed of the repeating structural units represented by the formula (A3), the formula (B1), the formula (B3) and the formula (C1), which are the preferred repeating structural units shown above, are suitable. 30 to 80 mol% of the repeating structural unit represented by the formula (A3) with respect to the total number of moles, and at least one repeating structural unit among the repeating structural units represented by the formula (B1) and the formula (B3). Is particularly preferably a liquid crystal polyester in which 35 to 10 mol% and the repeating structural unit represented by (C1) is from 35 to 10 mol%.

  The liquid crystal obtained when (b) exceeds 80 mol% or (b) or (c) is less than 10 mol% with respect to the total number of moles of (a), (b) and (c). There exists a tendency for the solubility with respect to the solvent of polyester to fall. Moreover, when (I) is less than 30 mol%, or (B) or (C) exceeds 35 mol%, the liquid crystal polyester of the resulting liquid crystal polyester tends to deteriorate.

  Here, (b) and (c) are preferably used in substantially equal amounts, but the degree of polymerization of the liquid crystalline polyester can be increased or decreased by increasing or decreasing the other repeating structural unit relative to one repeating structural unit. It can also be controlled.

Moreover, the liquid crystalline polyester of the present invention may further contain (d) a repeating structural unit represented by the following formula (2) in addition to the repeating structural unit described above.
-X-Ar2-Y- (2)
In the formula (2), Ar2 is 2,6-naphthylene, 1,4-phenylene, 1,3-phenylene or 4,4′-biphenylene (these are a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon number) And optionally substituted with 6 to 20 aryl groups), and X and Y independently represent O or NH. That is, the repeating structural unit represented by the formula (2) specifically represents any one of the repeating structural units represented by the following formulas (C4) to (C6).

上記の（C4）〜（C6）は、ハロゲン原子、炭素数１〜１０のアルキル基または炭素数６〜２０のアリール基で置換されていてもよい。

Said (C4)-(C6) may be substituted by the halogen atom, the C1-C10 alkyl group, or the C6-C20 aryl group.

  The above (C4) is a repeating structural unit derived from an aromatic diol, (C5) is a repeating structural unit derived from an aromatic amine having a phenolic hydroxyl group, and (C6) is derived from an aromatic diamine. Repeating structural unit.

  When the liquid crystalline polyester of the present invention contains (d), it preferably contains repeating structural units represented by the following formulas (C7) to (C12), more preferably (C8). Repeating structural unit.

上記の（C7）〜（C12）は、ハロゲン原子、炭素数１〜１０のアルキル基または炭素数６〜２０のアリール基で置換されていてもよい。

The above (C7) to (C12) may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

  In addition, as a halogen atom which may be substituted by the repeating structural unit represented by the above (A1) to (A5), (B1) to (B8) or (C1) to (C12), a fluorine atom, a chlorine atom, Bromine atoms and iodine atoms are usually used, and among them, fluorine atoms and chlorine atoms are preferable. Typical examples of the alkyl group having 1 to 10 carbon atoms which may be substituted on the repeating structural unit include a methyl group, an ethyl group, a propyl group and a butyl group. A representative example of the aryl group having 6 to 20 carbon atoms that may be substituted on the repeating structural unit is a phenyl group.

  In addition, the repeating structural unit represented by the formula (2) is usually used by replacing part of the repeating structural unit represented by the formula (1). For example, assuming that the total amount of (c) is 100 mol, about 0.1 to 50 mol is used by replacing (d) with (d).

  By containing (d), there is a tendency that the solubility of the liquid crystalline polyester of the present invention in a solvent can be controlled.

  In addition, although the liquid crystalline polyester of this invention contains the above repeating structural units, in the range which does not impair the objective of this invention, you may contain another repeating structural unit.

  Next, a method for producing the liquid crystalline polyester of the present invention will be described. The method is not limited to the following.

  As the raw material, aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diamine, aromatic amine having a phenolic hydroxyl group, aromatic diol, etc., which can constitute the above repeating structural unit, can be used. Instead of these, these ester-forming derivatives or amide-forming derivatives can also be used.

  Here, as the ester-forming derivative of carboxylic acid, for example, the carboxyl group is a derivative having high reactivity during the transesterification reaction, such as an acid chloride or an acid anhydride that accelerates the polyester formation reaction. And those in which the carboxyl group forms an ester with an alcohol or ethylene glycol that forms a polyester by a transesterification reaction.

  Examples of the ester-forming derivative of a phenolic hydroxyl group include those in which a phenolic hydroxyl group forms an ester with a carboxylic acid so that a polyester is produced by a transesterification reaction.

  Examples of the amide-forming derivative of an amino group include those in which an amino group forms an amide with a carboxylic acid so that a polyamide is formed by an amide exchange reaction.

  The liquid crystal polyester of the present invention is obtained by, for example, acylating the above raw material with an excess amount of fatty acid anhydride to obtain an acylated product, and esterifying the obtained acylated product with an aromatic hydroxycarboxylic acid and / or an aromatic dicarboxylic acid. It can obtain by the method of superposing | polymerizing by exchanging. Moreover, as the acylated product, a fatty acid ester obtained by acylation in advance may be used (see JP 2002-220444 A and JP 2002-146003 A).

  In the acylation reaction, the amount of fatty acid anhydride added is preferably 1.0 to 1.2 times equivalent, more preferably 1.05 to 1.1 times equivalent to the total of phenolic hydroxyl groups and amino groups. is there. If the amount of fatty acid anhydride added is small, acylated products, aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, etc., sublimate during polymerization by transesterification, and the reactor piping tends to be clogged. When there is too much addition amount of a thing, coloring of the liquid crystal polyester obtained may become remarkable.

  The acylation reaction is preferably performed at 130 to 180 ° C. for 5 minutes to 10 hours, more preferably at 140 to 160 ° C. for 10 minutes to 3 hours.

  The fatty acid anhydride used in the acylation reaction is not particularly limited. For example, acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoic anhydride, monochloroacetic anhydride , Dichloroacetic anhydride, trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, glutaric anhydride, maleic anhydride, succinic anhydride, β- Examples thereof include bromopropionic acid, and two or more of these may be used in combination. From the viewpoint of price and operability, acetic anhydride, propionic anhydride, butyric anhydride, or isobutyric anhydride is preferable, and acetic anhydride is more preferable.

  In the polymerization by transesterification, the acyl group of the acylated product is preferably 0.8 to 1.2 equivalents of the carboxyl group. The polymerization temperature is preferably 400 ° C. or lower, more preferably 350 ° C. or lower. Moreover, it is preferable that the temperature increase rate at the time of heating up to superposition | polymerization temperature is 0.1-50 degreeC / min, More preferably, it is 0.3-5 degreeC / min. At this time, in order to promote polymerization, it is preferable to distill out the by-product fatty acid and the unreacted fatty acid anhydride to the outside of the system by evaporating or the like.

  In addition, you may perform the polymerization by acylation reaction and transesterification in presence of a catalyst. As the catalyst, those conventionally known as polyester polymerization catalysts can be used, such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide and the like. And organic compound catalysts such as N, N-dimethylaminopyridine and N-methylimidazole. Among these catalysts, heterocyclic compounds containing two or more nitrogen atoms such as N, N-dimethylaminopyridine and N-methylimidazole may be preferably used (see JP 2002-146003 A). The catalyst is usually present during the acylation reaction, and it is not always necessary to remove it after the acylation reaction. If the catalyst is not removed, the next treatment can be carried out as it is. Further, when the next treatment is performed, the above-described catalyst may be further added.

  The polymerization by transesterification is usually performed by melt polymerization, but melt polymerization and solid phase polymerization may be used in combination. The solid phase polymerization can be performed by a known solid phase polymerization method after the polymer is extracted from the melt polymerization step, solidified, pulverized into powder or flakes. Specifically, for example, a method of heat treatment in a solid state at 20 to 350 ° C. for 1 to 30 hours under an inert atmosphere such as nitrogen can be used. Solid phase polymerization may be carried out while stirring or in a state of standing without stirring. In addition, by providing an appropriate stirring mechanism, the melt polymerization tank and the solid phase polymerization tank can be made the same reaction tank. After the solid phase polymerization, the obtained liquid crystal polyester may be used after being pelletized by a known method.

  The liquid crystalline polyester of the present invention can be produced using, for example, a batch device, a continuous device, or the like.

  In addition, the liquid crystal polyester may contain a known filler, additive, thermoplastic resin and the like as long as the object of the present invention is not impaired. In this case, as the filler, for example, epoxy resin powder, melamine resin powder, urea resin powder, benzoguanamine resin powder, organic filler such as styrene resin, silica, alumina, titanium oxide, zirconia, kaolin, calcium carbonate, calcium phosphate And inorganic fillers such as aluminum borate, potassium titanate, magnesium sulfate, zinc oxide, silicon carbide, silicon nitride, glass fiber, and alumina fiber. Examples of the additive include known coupling agents, anti-settling agents, ultraviolet absorbers, and heat stabilizers. The thermoplastic resin includes polypropylene, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenyl ether and modified products thereof, polyether imide, and a copolymer of glycidyl methacrylate and polyethylene. Etc.

  Next, a method for producing the liquid composition of the present invention using the liquid crystal polyester and the solvent will be described. Examples of the solvent used for the production of the liquid composition of the present invention include an aprotic solvent and / or a solvent containing a protic solvent.

  Examples of the aprotic solvent include halogen solvents such as methylene chloride, 1-chlorobutane, chlorobenzene, 1,1-dichloroethane, 1,2-dichloroethane, chloroform, 1,1,2,2-tetrachloroethane, diethyl ether, and the like. , Ether solvents such as tetrahydrofuran and 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 , Amine solvents such as triethylamine and pyridine, nitrile solvents such as acetonitrile and succinonitrile, N, N′-dimethylformamide, N, N′-dimethylacetamide, tetramethylurea, N-methylpyrrolide Amide solvents such as nitromethane, nitro-based solvents such as nitrobenzene, dimethyl sulfoxide, sulfide-based solvent such as sulfolane, hexamethylphosphoramide, and phosphoric acid-based solvent such as tri-n- butyl phosphate and the like.

  Among the above aprotic solvents, amide solvents such as N, N′-dimethylformamide, N, N′-dimethylacetamide, tetramethylurea, and N-methylpyrrolidone easily dissolve liquid crystalline polyester, preferable. More preferred are N, N′-dimethylacetamide and N-methylpyrrolidone. . The aprotic solvent is usually contained in an amount of 30% by weight or more based on the total solvent, and is preferably 60% by weight or more, and more preferably 99% by weight or more because the liquid crystalline polyester is easily dissolved.

  The amount of the aprotic solvent used for the liquid crystal polyester can be appropriately selected according to the use, but is usually 0.01 to 100 parts by weight of the liquid crystal polyester with respect to 100 parts by weight of the aprotic solvent. Is used. If the liquid crystal polyester is less than 0.01 parts by weight, the viscosity of the liquid composition is too low, and when the film is produced, the resulting film tends not to have a uniform thickness. Moreover, when liquid crystalline polyester exceeds 100 weight part, it may become difficult to melt | dissolve. From the viewpoint of operability and economy, the liquid crystalline polyester is preferably 1 to 50 parts by weight, and more preferably 2 to 40 parts by weight with respect to 100 parts by weight of the aprotic liquid.

（式中、Ａはハロゲン原子またはトリハロゲン化メチル基を示し、ｉは１以上５以下の整数値を示す。）
ここで、ｉが２以上の場合、複数存在するＡは同一でも異なっていてもよい。 Examples of the protic solvent include a solvent having a phenolic hydroxyl group, and those containing a halogen-substituted phenol compound represented by the following formula (L ₁ ) are preferable because they easily dissolve the liquid crystal polyester.

(In the formula, A represents a halogen atom or a trihalogenated methyl group, and i represents an integer value of 1 or more and 5 or less.)
Here, when i is 2 or more, a plurality of A may be the same or different.

  Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom and a chlorine atom are preferable because the liquid crystal polyester is easily dissolved. Examples thereof include pentafluorophenol, tetrafluorophenol, o-chlorophenol, p-chlorophenol and the like. Furthermore, o-chlorophenol and p-chlorophenol are preferable, and p-chlorophenol is particularly preferable. In addition, the protic solvent is usually contained in an amount of 30% by weight or more based on the total amount of the solvent, and the liquid crystalline polyester is easily dissolved.

  Although the usage-amount with respect to liquid crystalline polyester of said protic solvent can be suitably selected according to a use, 0.01-100 weight part of liquid crystalline polyester is normally used with respect to 100 weight part of protic solvents. When the liquid crystal polyester is less than 0.01 parts by weight, the viscosity of the liquid composition is lowered, and when the film is produced, the thickness of the resulting film tends not to be uniform. Moreover, when liquid crystalline polyester exceeds 100 weight part, it may become difficult to melt | dissolve. From the viewpoint of operability and economy, the liquid crystalline polyester is preferably 0.5 to 50 parts by weight and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the protic liquid.

  Further, as the solvent, a protic solvent and an aprotic solvent can be used as a mixture, and one or more selected from the protic solvents described above and the aprotic solvent described above One or two or more selected from the above can be mixed and used.

  In the liquid composition of the present invention, it is preferable that the liquid crystal polyester does not precipitate during storage, casting described later, and the like.

  The film of the present invention can be obtained, for example, by casting the above liquid composition on a support, removing the solvent, then heat-treating, and peeling the support. When the heat treatment is performed, the temperature is preferably set to 200 to 450 ° C. in a nitrogen atmosphere. As the support, glass or the like is usually used, but a conductor can also be used. Examples of such conductors include metal plates or metal foils such as gold, silver, copper, aluminum, and nickel. Preferably, it is a copper foil.

  As a method of casting the liquid composition on the support, the liquid composition is filtered with a filter or the like as necessary to remove foreign matters contained in the liquid composition, and then roller coated on the support. Examples thereof include a method in which the surface is smooth and uniformly cast by a method such as a dip coating method, a spray coating method, a spinner coating method, a curtain coating method, a slot coating method, a screen printing method, or a bar coating method.

  Moreover, as a method of removing a solvent, it carries out by the method of evaporating a solvent normally. 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 in terms of production efficiency and operability. preferable. The temperature and time at this time preferably include a step of performing preliminary drying at 50 to 100 ° C. for 10 minutes to 2 hours and a step of performing heat treatment at 200 to 450 ° C. for 30 minutes to 6 hours.

  The thickness of the film thus obtained is usually 0.5 to 500 μm from the viewpoint of film forming properties and mechanical properties, and preferably 1 to 100 μm from the viewpoint of handleability.

  Moreover, the laminated body of this invention which has the layer which consists of a conductor, and the layer which consists of a film using the film of this invention can be manufactured as follows. Apply a solution containing an adhesive on a conductor such as copper foil using a reverse roll coater, comma coater, die coater, etc., and dry at 80 ° C. to 120 ° C. for 3 to 10 minutes. A conductor coated with an adhesive of about 10 to 40 μm is obtained, and this and the film of the present invention are bonded together, heat-pressed with a roll laminator, and aftercured as necessary to completely cure the adhesive. Thereby, the laminated body of this invention can be manufactured. Moreover, you may manufacture a laminated body like the above except apply | coating an adhesive agent on the film of this invention, and bonding this and a conductor. Examples of the adhesive described in any of the above include resins made of epoxy, phenol, polyester, NBR, acrylic, polyimide, and the like.

  The laminate of the present invention can also be obtained by casting the liquid composition of the present invention on a conductor such as a copper foil and subjecting it to heat treatment, and then removing the conductor.

  Moreover, the laminated body of this invention can be manufactured also by forming the layer which consists of a conductor in the layer which consists of a film, using the method of vapor-depositing a conductor on the film of this invention. In this case, examples of the deposition method include an ion beam sputtering method, a high frequency sputtering method, a direct current sputtering method, and a glow discharge method.

  In addition, a desired circuit is drawn on the copper foil of the laminate of the present invention using a resist, etching is performed to dissolve and remove copper under acidic conditions, and further, the copper circuit is formed by removing the resist. A printed wiring board can be obtained by laminating a cover film on the copper circuit. Moreover, the film of this invention can also be used for the said cover film.

  The term “film” used in the present invention includes a sheet-like ultrathin film to a thick film. In addition, the film made of the liquid crystalline polyester of the present invention can be used to obtain various molded products (including bottle-shaped container forms, etc.) by inflation molding, blow molding, sheet molding, rolling molding, and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated using an Example, it cannot be overemphasized that this invention is not what is limited by an Example.

The hydrolysis resistance was evaluated by the following pressure cooker test.
A test piece molded to a thickness of 0.3 mm using liquid crystal polyester powder was prepared, the tensile strength was measured using a pressure cooker test apparatus, and the tensile strength retention was calculated according to the following formula. It shows that the hydrolysis resistance of liquid crystalline polyester is so favorable that the value of this tensile strength retention is large.
(Tensile strength retention) = (Tensile strength of the test piece after treatment) × 100 / (Tensile strength of the test piece before treatment)
In the formula, the treated specimen is a sample that is left to stand for 100 hours in an environment at a temperature of 120 ° C. and a relative humidity of 100%, and is then left to stand for 24 hours in an environment at a temperature of 23 ° C. and a relative humidity of 100%. The test piece before the treatment is a test piece left to stand for 72 hours in an environment of a temperature of 23 ° C. and a relative humidity of 100%.

Production Example 1
To a reactor equipped with a stirrer, a torque meter, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 282.3 g (1.5 mol) of 2-hydroxy-6-naphthoic acid, 4,4′-dihydroxydiphenyl ether 166 was added. .8 g (0.825 mol), 2,6-naphthalenedicarboxylic acid 162.1 g (0.75 mol) and acetic anhydride 369.8 g (3.62 mol) were charged. 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, while distilling off distilling by-product acetic acid and unreacted acetic anhydride, the temperature was raised to 320 ° C. over 170 minutes. The time point at which an increase in torque was observed was regarded as completion of the reaction, and the contents were taken out. The obtained solid content was cooled to room temperature, pulverized with a coarse pulverizer, held at 250 ° C. for 3 hours in a nitrogen atmosphere, and the polymerization reaction proceeded in a solid phase to obtain a powder.

Production Example 2
In a reactor equipped with a stirrer, a torque meter, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 128 g (0.68 mol) of 2-hydroxy-6-naphthoic acid and 63.3 g of 4,4′-dihydroxybiphenyl were added. (0.34 mol), isophthalic acid 56.5 g (0.34 mol) and acetic anhydride 152.7 g (1.50 mol) were charged. 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, while distilling off distilling by-product acetic acid and unreacted acetic anhydride, the temperature was raised to 320 ° C. over 170 minutes. The time point at which an increase in torque was observed was regarded as completion of the reaction, and the contents were taken out. The obtained solid content was cooled to room temperature, pulverized with a coarse pulverizer, held at 250 ° C. for 3 hours in a nitrogen atmosphere, and the polymerization reaction proceeded in a solid phase to obtain a powder.

Production Example 3
In a reactor equipped with a stirrer, a torque meter, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 846.8 g (4.5 mol) of 2-hydroxy-6-naphthoic acid, 4,4′-dihydroxydiphenyl ether 455 0.0 g (2.25 mol), 2,9.1-naphthalenedicarboxylic acid 389.1 g (1.8 mol), terephthalic acid 74.8 g (0.45 mol) and acetic anhydride 1056.63 (10.35 mol) Prepared. 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, while distilling off distilling by-product acetic acid and unreacted acetic anhydride, the temperature was raised to 320 ° C. over 170 minutes. The time point at which an increase in torque was observed was regarded as completion of the reaction, and the contents were taken out. The obtained solid content was cooled to room temperature, pulverized with a coarse pulverizer, held at 270 ° C. for 3 hours in a nitrogen atmosphere, and the polymerization reaction proceeded in a solid phase to obtain a powder.

Example 1
The powder obtained in Production Example 1 was pressed at 325 ° C. for 10 minutes under a load of 100 kgf to obtain a test piece having a thickness of 2 mm. When the dielectric constant of the obtained test piece was measured by an impedance material analyzer manufactured by Hewlett-Packard Co., Ltd., the relative dielectric constant was 2.8 (frequency: 1 GHz). Moreover, when the test piece shape | molded by thickness 0.3mm using the powder obtained in manufacture example 1 was produced and the pressure cooker test was done, tensile strength retention was 96%.

Example 2
As a result of mixing 1 g of the powder obtained in Production Example 1 and 9 g of p-chlorophenol and heating to 170 ° C., a completely dissolved liquid composition was obtained. The liquid composition was stirred and degassed, cast on a 18 μm copper foil by a bar coating method, and then heat-treated at 100 ° C. for 1 hour and at 250 ° C. for 1 hour to obtain a layer comprising the film of the present invention. A flexible laminate having a conductor layer was obtained.

Example 3
The powder obtained in Production Example 3 was pressed at 320 ° C. for 10 minutes under a load of 100 kgf to obtain a test piece having a thickness of 2 mm. When the dielectric constant of the obtained test piece was measured with an impedance material analyzer manufactured by Hewlett-Packard Co., Ltd., the relative dielectric constant was 2.9 (frequency: 1 GHz). Moreover, when the test piece shape | molded by thickness 0.3mm using the powder obtained by manufacture example 3 was produced and the pressure cooker test was done, the tensile strength retention was 100%.

Example 4
As a result of mixing 1 g of the powder obtained in Production Example 3 and 9 g of p-chlorophenol and heating to 150 ° C., a completely dissolved liquid composition was obtained. The liquid composition was stirred and degassed, cast on a 18 μm copper foil by a bar coating method, and then heat-treated at 100 ° C. for 1 hour and at 250 ° C. for 1 hour to obtain a layer comprising the film of the present invention. A flexible laminate having a conductor layer was obtained.

Comparative Example 1
The powder obtained in Production Example 2 was pressed at 310 ° C. for 10 minutes under a load of 100 kgf to obtain a test piece having a thickness of 2 mm. When the dielectric constant of the obtained test piece was measured with an impedance material analyzer manufactured by Hewlett-Packard Co., Ltd., the relative dielectric constant was 3.1 (frequency: 1 GHz). Moreover, when the test piece shape | molded by thickness 0.3mm using the powder obtained by manufacture example 2 was made, and the pressure cooker test was done, the tensile strength retention was 59%.

Claims (16)

(B) a liquid crystalline polyester containing a repeating structural unit derived from an aromatic hydroxycarboxylic acid, (b) a repeating structural unit derived from an aromatic dicarboxylic acid, and (c) a repeating structural unit represented by the following formula (1): A liquid crystal polyester characterized in that (B) contains a repeating structural unit represented by the following formula (B3) .
-X-Ar1-O-Ar1-Y- (1)
(In the formula, Ar1 is 1,4-phenylene which may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X and Y are independently O or NH represents.)

The liquid crystalline polyester according to claim 1, wherein (a) contains a repeating structural unit represented by the following formula (A3).

(B) further liquid crystalline polyester according to claim 1 or 2 containing a repeating structural unit of represented by the following formula (B1).

The liquid crystalline polyester according to any one of claims 1 to 3, wherein (c) contains a repeating structural unit represented by the following formula (C1).

(Ii) is 30 to 80 mol%, (ii) is 35 to 10 mol%, and (iii) is 35 to 10 mol% with respect to the total number of moles of (ii), (ii) and (iii). Liquid crystal polyester in any one of Claims 1-4 . Furthermore, (d) Liquid crystalline polyester in any one of Claims 1-5 containing the repeating structural unit shown by the following formula | equation (2).
-X-Ar2-Y- (2)
(In the formula, Ar2 represents 2,6-naphthylene, 1,4-phenylene, 1,3-phenylene or 4,4′-biphenylene (these are a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms). And optionally substituted with 20 aryl groups), and X and Y independently represent O or NH.) Film characterized by containing a liquid crystal polyester according to any one of claims 1-6. Liquid composition characterized by containing the liquid crystal polyester and a solvent according to any one of claims 1-6. The liquid composition according to claim 8, wherein the solvent contains an aprotic solvent. The liquid composition according to claim 8, wherein the solvent contains an amide solvent. The liquid composition according to claim 8, wherein the solvent contains a protic solvent. The liquid composition according to claim 8, wherein the solvent contains a halogen-substituted phenol compound represented by the following formula (L ₁ ).

(In the formula, A represents a halogen atom or a trihalogenated methyl group, and i represents an integer value of 1 or more and 5 or less.) A film obtained by casting the liquid composition according to any one of claims 8 to 12 on a support, removing the solvent, then heat-treating, and peeling the support. A laminate comprising a layer made of the film according to claim 7 or 13 . A laminate comprising a layer made of the film according to claim 7 or 13 and a layer made of a conductor. A liquid crystal polyester molded product obtained by molding the film according to claim 7 or 13 .