WO2011033986A1 - Process for production of liquid crystal polyester film, and liquid crystal polyester film - Google Patents
Process for production of liquid crystal polyester film, and liquid crystal polyester film Download PDFInfo
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- WO2011033986A1 WO2011033986A1 PCT/JP2010/065529 JP2010065529W WO2011033986A1 WO 2011033986 A1 WO2011033986 A1 WO 2011033986A1 JP 2010065529 W JP2010065529 W JP 2010065529W WO 2011033986 A1 WO2011033986 A1 WO 2011033986A1
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- liquid crystal
- crystal polyester
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- polyester film
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
Definitions
- the present invention is a liquid crystal polyester film (film made of liquid crystal polyester) that has a barrier property against the permeation of gases such as oxygen and water vapor, that is, a gas barrier property, and is used as a packaging material for packaging foods, pharmaceuticals, electronic parts and other products. And a liquid crystal polyester film.
- the liquid crystal polyester is a crystalline polymer and crystallizes due to molecular orientation during extrusion. Therefore, the obtained liquid crystal polyester film is milky white and light transmittance is lowered. Therefore, this liquid crystal polyester film cannot be applied to applications that require light transmission due to the necessity of visually recognizing the contents from the outside.
- the present invention provides a liquid crystal polyester precursor film preparation step in which a liquid composition containing a liquid crystal polyester and a solvent is cast on a substrate and dried to prepare a liquid crystal polyester precursor film containing the solvent.
- a liquid crystal polyester film preparation step of preparing a liquid crystal polyester film by heat-treating the liquid crystal polyester precursor film by raising the temperature, in the liquid crystal polyester film preparation step Provided is a method for producing a liquid crystal polyester film, wherein a temperature increase rate during heat treatment of the liquid crystal polyester precursor film is 5 ° C./min or less, and a maximum temperature during heat treatment of the liquid crystal polyester precursor film is 300 ° C. or less.
- X and Y each independently represents O or NH.
- the hydrogen atom bonded to the aromatic ring of Ar 1, Ar 2 and Ar 3 are substituted with a halogen atom, an alkyl group or an aryl group May be.
- (4) -Ar 11 -Z-Ar 12 - In the formula, Ar 11 and Ar 12 each independently represent phenylene or naphthylene, and Z represents O, CO, or SO 2. )
- the solvent is N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N-methyl. It preferably contains at least one selected from propionamide, dimethyl sulfoxide, ⁇ -butyrolactone, dimethylimidazolidinone, tetramethylphosphoric amide and ethyl cellosolve acetate.
- the liquid composition is dried at 160 ° C. or less, and in the liquid crystal polyester film preparation step, the maximum temperature during heat treatment of the liquid crystal polyester precursor film is set to 200 ° C. or higher. It is preferable.
- the liquid crystal polyester precursor film when the liquid crystal polyester precursor film is heat-treated by increasing the temperature during the production of the liquid crystal polyester film, the temperature increase rate of the liquid crystal polyester precursor film is suppressed, and the liquid crystal polyester precursor film Since the maximum temperature during heat treatment is suppressed, a liquid crystal polyester film having gas barrier properties and excellent light transmittance can be obtained.
- Embodiment 1 of the Invention is a film made of a specific liquid crystal polyester, and has a light transmittance of 50% or more at a wavelength of 600 nm and a moisture permeability of 0.5 g / m 2 ⁇ 24 h or less. is there.
- the film preferably has a thickness of 0.001 to 0.1 mm.
- the liquid crystal polyester is preferably a polyester that exhibits optical anisotropy when melted and has the property of forming an anisotropic melt at a temperature of 450 ° C. or lower.
- the liquid crystal polyester includes a structural unit represented by the following formula (1) (hereinafter referred to as “formula (1) structural unit”) and a structural unit represented by the following formula (2) (hereinafter referred to as “formula (2)”. And a structural unit represented by the following formula (3) (hereinafter referred to as “formula (3) structural unit”), and represented by the formula (1) with respect to the total of all structural units.
- a liquid crystal polyester having 30 to 80 mol% of structural units, 35 to 10 mol% of structural units represented by formula (2), and 35 to 10 mol% of structural units represented by formula (3) is preferable.
- Ar 1 represents phenylene or naphthylene
- Ar 2 represents phenylene, naphthylene, or a group represented by the following formula (4)
- Ar 3 represents phenylene or a group represented by the following formula (4).
- the structural unit of the formula (1) is a structural unit derived from an aromatic hydroxycarboxylic acid.
- aromatic hydroxycarboxylic acid examples include parahydroxybenzoic acid, metahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, Examples thereof include 2-hydroxy-3-naphthoic acid and 1-hydroxy-4-naphthoic acid.
- the structural unit of the formula (2) is a structural unit derived from an aromatic dicarboxylic acid, and examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid.
- aromatic amine having a phenolic hydroxyl group examples include 4-aminophenol (p-aminophenol) and 3-aminophenol.
- aromatic diamine examples include 1,4-phenylenediamine, 1 , 3-phenylenediamine and the like.
- this formula (3 ′) structural unit is advantageous in that the liquid crystal polyester has a lower water absorption in addition to sufficient solvent solubility of the liquid crystal polyester.
- the formula (3) structural unit is more preferably contained in the range of 33 to 25 mol% with respect to the total of all the structural units, and by doing so, the solvent solubility is further improved.
- the molar fraction of the formula (2) structural unit and the formula (3) structural unit is expressed by [formula (2) structural unit] / [formula ( 3) Structural unit], a range of 0.9 / 1.0 to 1.0 / 0.9 is preferable.
- Such a method for producing a liquid crystal polyester is described in, for example, JP-A No. 2002-220444 or JP-A No. 2002-146003.
- the addition amount of the fatty acid anhydride is preferably 1.0 to 1.2 times equivalent, more preferably 1.05 to 1.1 times equivalent to the total of the phenolic hydroxyl group and amino group. Is more preferable. If the added amount of the fatty acid anhydride is less than 1.0 times equivalent, the acylated product or raw material monomer tends to sublimate during polymerization and the reaction system tends to be blocked, and if it exceeds 1.2 times equivalent, There is a tendency that coloring of the liquid crystal polyester obtained becomes remarkable.
- the acylation 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 acyl group of the acylated product is preferably 0.8 to 1.2 times equivalent to the carboxyl group.
- the solvent is not particularly limited as long as it dissolves the liquid crystalline polyester.
- These solvents may be used alone or in combination of two or more.
- the rate of temperature increase during the heat treatment of the liquid crystal polyester precursor film is 5 ° C./min or less, preferably 1 ° C./min or less.
- the lower limit of the rate of temperature increase during the heat treatment of the liquid crystal polyester precursor film is not particularly defined, but is usually preferably 0.05 ° C./min or more and more preferably 0.1 ° C./min or more from the viewpoint of productivity. preferable.
- the maximum temperature during the heat treatment of the liquid crystal polyester precursor film is set to 300 ° C. or lower. By carrying out like this, the light transmittance of a liquid crystal polyester film can be hold
- the minimum of the maximum temperature at the time of heat processing of a liquid crystalline polyester precursor film is not specifically defined, if the maximum temperature is 200 degreeC or more, it is preferable at the point which the gas barrier property of a liquid crystalline polyester film improves remarkably. Conversely, if this maximum temperature is less than 200 ° C., the gas barrier properties may be insufficient.
- the holding time at this maximum temperature is not particularly limited, but is usually 0 to 5 hours.
- this liquid crystalline polyester precursor film is charged into an inert oven, and the temperature is increased from room temperature (30 ° C.) to the maximum temperature of 200 ° C. during the heat treatment over 10 hours in a nitrogen atmosphere (that is, 0.28 ° C./min heating rate) Temperature). After the internal temperature of the inert oven reached the maximum temperature during the heat treatment, it was held at the same temperature (200 ° C.) for 3 hours, and then cooled to produce a liquid crystal polyester film. In addition, when the thickness of this liquid crystal polyester film was measured using the micrometer made from Mitutoyo Corporation, the thickness was 15 micrometers.
- ⁇ Comparative Example 1> The maximum temperature during the heat treatment of the liquid crystal polyester precursor film was set to 320 ° C., and the temperature increase rate during the heat treatment of the liquid crystal polyester precursor film was set to 0.48 ° C./minute (specifically, from 30 ° C. A liquid crystal polyester film was produced by the same procedure as in Example 1 except that the temperature was raised to 320 ° C. over 10 hours. In addition, when the thickness of this liquid crystal polyester film was measured using the micrometer made from Mitutoyo Corporation, the thickness was 13 micrometers.
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyesters Or Polycarbonates (AREA)
- Moulding By Coating Moulds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A liquid crystal polyester film having improved light permeability can be produced. A liquid composition comprising a liquid crystal polyester and a solvent is casted on a base material, and the resulting product is dried, thereby preparing a liquid crystal polyester precursor film that still contains the solvent. The liquid crystal polyester precursor film is heat-treated by raising the temperature to prepare a liquid crystal polyester film. In the heat treatment of the liquid crystal polyester precursor film, the temperature-raising rate is set at 5˚C/min or less, and the highest temperature of the heat-treatment of the liquid crystal polyester precursor film is set at 300°C or lower. In this manner, a liquid crystal polyester film having gas barrier properties and excellent light permeability can be produced.
Description
本発明は、酸素や水蒸気などのガスの透過に対するバリア性、つまりガスバリア性を有し、食品、医薬品、電子部品その他の製品を包装する包装材料として用いられる液晶ポリエステルフィルム（液晶ポリエステルからなるフィルム）の製造方法および液晶ポリエステルフィルムに関するものである。
The present invention is a liquid crystal polyester film (film made of liquid crystal polyester) that has a barrier property against the permeation of gases such as oxygen and water vapor, that is, a gas barrier property, and is used as a packaging material for packaging foods, pharmaceuticals, electronic parts and other products. And a liquid crystal polyester film.
従来、この種の包装材料としては、液晶ポリエステルを押出成形した液晶ポリエステルフィルムが提案されていた（例えば、特許文献１参照）。
Conventionally, as this type of packaging material, a liquid crystal polyester film obtained by extruding liquid crystal polyester has been proposed (for example, see Patent Document 1).
一方、溶媒可溶性の液晶ポリエステルを溶媒キャスト法で成形することにより、成形時の分子配向に起因する引裂強度などの機械物性の異方性を改良する液晶ポリエステルフィルムが提案されていた（例えば、特許文献２参照）。
On the other hand, a liquid crystal polyester film has been proposed which improves the anisotropy of mechanical properties such as tear strength due to molecular orientation during molding by molding a solvent-soluble liquid crystal polyester by a solvent casting method (for example, patents) Reference 2).
しかしながら、特許文献１で提案された技術においては、液晶ポリエステルは結晶性ポリマーであり、押出成形時の分子配向によって結晶化する。そのため、得られる液晶ポリエステルフィルムは、乳白色を呈し、光透過性が低下する。したがって、内容物を外部から視認する必要性などから光透過性が要求される用途には、この液晶ポリエステルフィルムを適用することができない。
However, in the technique proposed in Patent Document 1, the liquid crystal polyester is a crystalline polymer and crystallizes due to molecular orientation during extrusion. Therefore, the obtained liquid crystal polyester film is milky white and light transmittance is lowered. Therefore, this liquid crystal polyester film cannot be applied to applications that require light transmission due to the necessity of visually recognizing the contents from the outside.
また、特許文献２で提案された技術によれば、得られる液晶ポリエステルフィルムは、機械物性の異方性は改良されるものの、特許文献１で提案された技術と同様、乳白色を呈し、光透過性が低下する。したがって、内容物を外部から視認する必要性などから光透過性が要求される用途には、この液晶ポリエステルフィルムを適用することができない。
Further, according to the technique proposed in Patent Document 2, the obtained liquid crystal polyester film is improved in the anisotropy of mechanical properties, but exhibits a milky white color similar to the technique proposed in Patent Document 1 and transmits light. Sex is reduced. Therefore, this liquid crystal polyester film cannot be applied to applications that require light transmission due to the necessity of visually recognizing the contents from the outside.
そこで、本発明は、このような事情に鑑み、ガスバリア性を有し、かつ、光透過性に優れた液晶ポリエステルフィルムを得ることが可能な液晶ポリエステルフィルムの製造方法および液晶ポリエステルフィルムを提供することを目的とする。
Therefore, in view of such circumstances, the present invention provides a method for producing a liquid crystal polyester film and a liquid crystal polyester film capable of obtaining a liquid crystal polyester film having gas barrier properties and excellent light transmittance. With the goal.
かかる目的を達成するために、本発明者が鋭意検討したところ、液晶ポリエステルフィルムの光透過性を高めるべく、液晶ポリエステルフィルムの製造に際して、液晶ポリエステル前駆体フィルムを昇温により熱処理するときに、この液晶ポリエステル前駆体フィルムの昇温速度に上限を設けることに着目し、本発明を完成するに至った。
In order to achieve such an object, the present inventors diligently studied, and in order to increase the light transmittance of the liquid crystal polyester film, when the liquid crystal polyester precursor film is heat-treated at an elevated temperature, Focusing on setting an upper limit for the rate of temperature rise of the liquid crystal polyester precursor film, the present invention has been completed.
すなわち、本発明は、液晶ポリエステルおよび溶媒を含む液状組成物を基材上に流延して乾燥させて、前記溶媒を含んだ状態の液晶ポリエステル前駆体フィルムを調製する液晶ポリエステル前駆体フィルム調製工程と、前記液晶ポリエステル前駆体フィルムを昇温することにより熱処理して、液晶ポリエステルフィルムを調製する液晶ポリエステルフィルム調製工程とを含む液晶ポリエステルフィルムの製造方法であって、前記液晶ポリエステルフィルム調製工程において、前記液晶ポリエステル前駆体フィルムの熱処理時の昇温速度を５℃／分以下とし、かつ前記液晶ポリエステル前駆体フィルムの熱処理時の最高温度を３００℃以下とする液晶ポリエステルフィルムの製造方法を提供する。
That is, the present invention provides a liquid crystal polyester precursor film preparation step in which a liquid composition containing a liquid crystal polyester and a solvent is cast on a substrate and dried to prepare a liquid crystal polyester precursor film containing the solvent. And a liquid crystal polyester film preparation step of preparing a liquid crystal polyester film by heat-treating the liquid crystal polyester precursor film by raising the temperature, in the liquid crystal polyester film preparation step, Provided is a method for producing a liquid crystal polyester film, wherein a temperature increase rate during heat treatment of the liquid crystal polyester precursor film is 5 ° C./min or less, and a maximum temperature during heat treatment of the liquid crystal polyester precursor film is 300 ° C. or less.
また、前記液晶ポリエステルは、以下の式（１）、（２）および（３）で示される構造単位を有し、全構造単位の合計に対して、式（１）で示される構造単位が３０～８０モル％、式（２）で示される構造単位が３５～１０モル％、式（３）で示される構造単位が３５～１０モル％の液晶ポリエステルであることが好ましい。
（１）－Ｏ－Ａｒ１－ＣＯ－
（２）－ＣＯ－Ａｒ２－ＣＯ－
（３）－Ｘ－Ａｒ３－Ｙ－
（式中、Ａｒ１は、フェニレンまたはナフチレンを表し、Ａｒ２は、フェニレン、ナフチレンまたは下記式（４）で示される基を表し、Ａｒ３はフェニレンまたは下記式（４）で示される基を表し、ＸおよびＹは、それぞれ独立に、ＯまたはＮＨを表す。なお、Ａｒ１、Ａｒ２およびＡｒ３の芳香環に結合している水素原子は、ハロゲン原子、アルキル基またはアリール基で置換されていてもよい。）
（４）－Ａｒ１１－Ｚ－Ａｒ１２－
（式中、Ａｒ１１、Ａｒ１２は、それぞれ独立に、フェニレンまたはナフチレンを表し、Ｚは、Ｏ、ＣＯまたはＳＯ２を表す。） Further, the liquid crystalline polyester has structural units represented by the following formulas (1), (2) and (3), and 30 structural units represented by the formula (1) with respect to the total of all structural units. It is preferably a liquid crystal polyester having ˜80 mol%, 35 to 10 mol% of the structural unit represented by the formula (2), and 35 to 10 mol% of the structural unit represented by the formula (3).
(1) —O—Ar 1 —CO—
(2) —CO—Ar 2 —CO—
(3) —X—Ar 3 —Y—
(In the formula, Ar 1 represents phenylene or naphthylene, Ar 2 represents phenylene, naphthylene, or a group represented by the following formula (4), and Ar 3 represents phenylene or a group represented by the following formula (4). , X and Y each independently represents O or NH. the hydrogen atom bonded to the aromatic ring of Ar 1, Ar 2 and Ar 3 are substituted with a halogen atom, an alkyl group or an aryl group May be.)
(4) -Ar 11 -Z-Ar 12 -
(In the formula, Ar 11 and Ar 12 each independently represent phenylene or naphthylene, and Z represents O, CO, or SO 2. )
（１）－Ｏ－Ａｒ１－ＣＯ－
（２）－ＣＯ－Ａｒ２－ＣＯ－
（３）－Ｘ－Ａｒ３－Ｙ－
（式中、Ａｒ１は、フェニレンまたはナフチレンを表し、Ａｒ２は、フェニレン、ナフチレンまたは下記式（４）で示される基を表し、Ａｒ３はフェニレンまたは下記式（４）で示される基を表し、ＸおよびＹは、それぞれ独立に、ＯまたはＮＨを表す。なお、Ａｒ１、Ａｒ２およびＡｒ３の芳香環に結合している水素原子は、ハロゲン原子、アルキル基またはアリール基で置換されていてもよい。）
（４）－Ａｒ１１－Ｚ－Ａｒ１２－
（式中、Ａｒ１１、Ａｒ１２は、それぞれ独立に、フェニレンまたはナフチレンを表し、Ｚは、Ｏ、ＣＯまたはＳＯ２を表す。） Further, the liquid crystalline polyester has structural units represented by the following formulas (1), (2) and (3), and 30 structural units represented by the formula (1) with respect to the total of all structural units. It is preferably a liquid crystal polyester having ˜80 mol%, 35 to 10 mol% of the structural unit represented by the formula (2), and 35 to 10 mol% of the structural unit represented by the formula (3).
(1) —O—Ar 1 —CO—
(2) —CO—Ar 2 —CO—
(3) —X—Ar 3 —Y—
(In the formula, Ar 1 represents phenylene or naphthylene, Ar 2 represents phenylene, naphthylene, or a group represented by the following formula (4), and Ar 3 represents phenylene or a group represented by the following formula (4). , X and Y each independently represents O or NH. the hydrogen atom bonded to the aromatic ring of Ar 1, Ar 2 and Ar 3 are substituted with a halogen atom, an alkyl group or an aryl group May be.)
(4) -Ar 11 -Z-Ar 12 -
(In the formula, Ar 11 and Ar 12 each independently represent phenylene or naphthylene, and Z represents O, CO, or SO 2. )
また、前記溶媒が、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、Ｎ－メチルカプロラクタム、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジエチルホルムアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ－メチルプロピオンアミド、ジメチルスルホキシド、γ－ブチロラクトン、ジメチルイミダゾリジノン、テトラメチルホスホリックアミドおよびエチルセロソルブアセテートから選択される１種以上を含有していることが好ましい。
The solvent is N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N-methyl. It preferably contains at least one selected from propionamide, dimethyl sulfoxide, γ-butyrolactone, dimethylimidazolidinone, tetramethylphosphoric amide and ethyl cellosolve acetate.
また、前記液晶ポリエステル前駆体フィルム調製工程において、前記液状組成物を１６０℃以下で乾燥させ、前記液晶ポリエステルフィルム調製工程において、前記液晶ポリエステル前駆体フィルムの熱処理時の最高温度を２００℃以上とすることが好ましい。
In the liquid crystal polyester precursor film preparation step, the liquid composition is dried at 160 ° C. or less, and in the liquid crystal polyester film preparation step, the maximum temperature during heat treatment of the liquid crystal polyester precursor film is set to 200 ° C. or higher. It is preferable.
また、本発明は、以下の式（１）、（２）および（３）で示される構造単位を有し、全構造単位の合計に対して、式（１）で示される構造単位が３０～８０モル％、式（２）で示される構造単位が３５～１０モル％、式（３）で示される構造単位が３５～１０モル％の液晶ポリエステルからなる液晶ポリエステルフィルムであって、波長６００ｎｍにおける光線透過率が５０％以上で、かつ透湿度が０．５ｇ／ｍ２・２４ｈ以下である液晶ポリエステルフィルムを提供する。
（１）－Ｏ－Ａｒ１－ＣＯ－
（２）－ＣＯ－Ａｒ２－ＣＯ－
（３）－Ｘ－Ａｒ３－Ｙ－
（式中、Ａｒ１は、フェニレンまたはナフチレンを表し、Ａｒ２は、フェニレン、ナフチレンまたは下記式（４）で示される基を表し、Ａｒ３はフェニレンまたは下記式（４）で示される基を表し、ＸおよびＹは、それぞれ独立に、ＯまたはＮＨを表す。なお、Ａｒ１、Ａｒ２およびＡｒ３の芳香環に結合している水素原子は、ハロゲン原子、アルキル基またはアリール基で置換されていてもよい。）
（４）－Ａｒ１１－Ｚ－Ａｒ１２－
（式中、Ａｒ１１、Ａｒ１２は、それぞれ独立に、フェニレンまたはナフチレンを表し、Ｚは、Ｏ、ＣＯまたはＳＯ２を表す。） In addition, the present invention has structural units represented by the following formulas (1), (2) and (3), and 30 to 30 structural units represented by the formula (1) with respect to the total of all structural units. A liquid crystal polyester film comprising 80 mol%, 35 to 10 mol% of a structural unit represented by formula (2), and 35 to 10 mol% of a structural unit represented by formula (3), and having a wavelength of 600 nm A liquid crystal polyester film having a light transmittance of 50% or more and a moisture permeability of 0.5 g / m 2 · 24 h or less is provided.
(1) —O—Ar 1 —CO—
(2) —CO—Ar 2 —CO—
(3) —X—Ar 3 —Y—
(In the formula, Ar 1 represents phenylene or naphthylene, Ar 2 represents phenylene, naphthylene, or a group represented by the following formula (4), and Ar 3 represents phenylene or a group represented by the following formula (4). , X and Y each independently represents O or NH. the hydrogen atom bonded to the aromatic ring of Ar 1, Ar 2 and Ar 3 are substituted with a halogen atom, an alkyl group or an aryl group May be.)
(4) -Ar 11 -Z-Ar 12 -
(In the formula, Ar 11 and Ar 12 each independently represent phenylene or naphthylene, and Z represents O, CO, or SO 2. )
（１）－Ｏ－Ａｒ１－ＣＯ－
（２）－ＣＯ－Ａｒ２－ＣＯ－
（３）－Ｘ－Ａｒ３－Ｙ－
（式中、Ａｒ１は、フェニレンまたはナフチレンを表し、Ａｒ２は、フェニレン、ナフチレンまたは下記式（４）で示される基を表し、Ａｒ３はフェニレンまたは下記式（４）で示される基を表し、ＸおよびＹは、それぞれ独立に、ＯまたはＮＨを表す。なお、Ａｒ１、Ａｒ２およびＡｒ３の芳香環に結合している水素原子は、ハロゲン原子、アルキル基またはアリール基で置換されていてもよい。）
（４）－Ａｒ１１－Ｚ－Ａｒ１２－
（式中、Ａｒ１１、Ａｒ１２は、それぞれ独立に、フェニレンまたはナフチレンを表し、Ｚは、Ｏ、ＣＯまたはＳＯ２を表す。） In addition, the present invention has structural units represented by the following formulas (1), (2) and (3), and 30 to 30 structural units represented by the formula (1) with respect to the total of all structural units. A liquid crystal polyester film comprising 80 mol%, 35 to 10 mol% of a structural unit represented by formula (2), and 35 to 10 mol% of a structural unit represented by formula (3), and having a wavelength of 600 nm A liquid crystal polyester film having a light transmittance of 50% or more and a moisture permeability of 0.5 g / m 2 · 24 h or less is provided.
(1) —O—Ar 1 —CO—
(2) —CO—Ar 2 —CO—
(3) —X—Ar 3 —Y—
(In the formula, Ar 1 represents phenylene or naphthylene, Ar 2 represents phenylene, naphthylene, or a group represented by the following formula (4), and Ar 3 represents phenylene or a group represented by the following formula (4). , X and Y each independently represents O or NH. the hydrogen atom bonded to the aromatic ring of Ar 1, Ar 2 and Ar 3 are substituted with a halogen atom, an alkyl group or an aryl group May be.)
(4) -Ar 11 -Z-Ar 12 -
(In the formula, Ar 11 and Ar 12 each independently represent phenylene or naphthylene, and Z represents O, CO, or SO 2. )
本発明によれば、液晶ポリエステルフィルムの製造に際して、液晶ポリエステル前駆体フィルムを昇温により熱処理するときに、この液晶ポリエステル前駆体フィルムの昇温速度が抑制されるとともに、この液晶ポリエステル前駆体フィルムの熱処理時の最高温度が抑制されることから、ガスバリア性を有し、かつ、光透過性に優れた液晶ポリエステルフィルムを得ることが可能となる。
According to the present invention, when the liquid crystal polyester precursor film is heat-treated by increasing the temperature during the production of the liquid crystal polyester film, the temperature increase rate of the liquid crystal polyester precursor film is suppressed, and the liquid crystal polyester precursor film Since the maximum temperature during heat treatment is suppressed, a liquid crystal polyester film having gas barrier properties and excellent light transmittance can be obtained.
以下、本発明の実施の形態について説明する。
Hereinafter, embodiments of the present invention will be described.
［発明の実施の形態１］
本発明の実施の形態１に係る液晶ポリエステルフィルムは、特定の液晶ポリエステルからなるフィルムであり、波長６００ｎｍにおける光線透過率が５０％以上で、かつ透湿度が０．５ｇ／ｍ２・２４ｈ以下である。前記フィルムは厚さが０．００１～０．１ｍｍであることが好ましい。 Embodiment 1 of the Invention
The liquid crystal polyester film according to Embodiment 1 of the present invention is a film made of a specific liquid crystal polyester, and has a light transmittance of 50% or more at a wavelength of 600 nm and a moisture permeability of 0.5 g / m 2 · 24 h or less. is there. The film preferably has a thickness of 0.001 to 0.1 mm.
本発明の実施の形態１に係る液晶ポリエステルフィルムは、特定の液晶ポリエステルからなるフィルムであり、波長６００ｎｍにおける光線透過率が５０％以上で、かつ透湿度が０．５ｇ／ｍ２・２４ｈ以下である。前記フィルムは厚さが０．００１～０．１ｍｍであることが好ましい。 Embodiment 1 of the Invention
The liquid crystal polyester film according to Embodiment 1 of the present invention is a film made of a specific liquid crystal polyester, and has a light transmittance of 50% or more at a wavelength of 600 nm and a moisture permeability of 0.5 g / m 2 · 24 h or less. is there. The film preferably has a thickness of 0.001 to 0.1 mm.
この液晶ポリエステルは、溶融時に光学異方性を示し、４５０℃以下の温度で異方性溶融体を形成するという特性を有するポリエステルであることが好ましい。この液晶ポリエステルとしては、以下の式（１）で示される構造単位（以下、「式（１）構造単位」という）、以下の式（２）で示される構造単位（以下、「式（２）構造単位」という）および以下の式（３）で示される構造単位（以下、「式（３）構造単位」という）を有し、全構造単位の合計に対して、式（１）で示される構造単位が３０～８０モル％、式（２）で示される構造単位が３５～１０モル％、式（３）で示される構造単位が３５～１０モル％の液晶ポリエステルであることが好ましい。
（１）－Ｏ－Ａｒ１－ＣＯ－
（２）－ＣＯ－Ａｒ２－ＣＯ－
（３）－Ｘ－Ａｒ３－Ｙ－
（式中、Ａｒ１は、フェニレンまたはナフチレンを表し、Ａｒ２は、フェニレン、ナフチレンまたは下記式（４）で示される基を表し、Ａｒ３はフェニレンまたは下記式（４）で示される基を表し、ＸおよびＹは、それぞれ独立に、ＯまたはＮＨを表す。なお、Ａｒ１、Ａｒ２およびＡｒ３の芳香環に結合している水素原子は、ハロゲン原子、アルキル基またはアリール基で置換されていてもよい。）
（４）－Ａｒ１１－Ｚ－Ａｒ１２－
（式中、Ａｒ１１、Ａｒ１２は、それぞれ独立に、フェニレンまたはナフチレンを表し、Ｚは、Ｏ、ＣＯまたはＳＯ２を表す。） The liquid crystal polyester is preferably a polyester that exhibits optical anisotropy when melted and has the property of forming an anisotropic melt at a temperature of 450 ° C. or lower. The liquid crystal polyester includes a structural unit represented by the following formula (1) (hereinafter referred to as “formula (1) structural unit”) and a structural unit represented by the following formula (2) (hereinafter referred to as “formula (2)”. And a structural unit represented by the following formula (3) (hereinafter referred to as “formula (3) structural unit”), and represented by the formula (1) with respect to the total of all structural units. A liquid crystal polyester having 30 to 80 mol% of structural units, 35 to 10 mol% of structural units represented by formula (2), and 35 to 10 mol% of structural units represented by formula (3) is preferable.
(1) —O—Ar 1 —CO—
(2) —CO—Ar 2 —CO—
(3) —X—Ar 3 —Y—
(In the formula, Ar 1 represents phenylene or naphthylene, Ar 2 represents phenylene, naphthylene, or a group represented by the following formula (4), and Ar 3 represents phenylene or a group represented by the following formula (4). , X and Y each independently represent O or NH, wherein the hydrogen atom bonded to the aromatic ring of Ar 1 , Ar 2 and Ar 3 is substituted with a halogen atom, an alkyl group or an aryl group. May be.)
(4) -Ar 11 -Z-Ar 12 -
(In the formula, Ar 11 and Ar 12 each independently represent phenylene or naphthylene, and Z represents O, CO, or SO 2. )
（１）－Ｏ－Ａｒ１－ＣＯ－
（２）－ＣＯ－Ａｒ２－ＣＯ－
（３）－Ｘ－Ａｒ３－Ｙ－
（式中、Ａｒ１は、フェニレンまたはナフチレンを表し、Ａｒ２は、フェニレン、ナフチレンまたは下記式（４）で示される基を表し、Ａｒ３はフェニレンまたは下記式（４）で示される基を表し、ＸおよびＹは、それぞれ独立に、ＯまたはＮＨを表す。なお、Ａｒ１、Ａｒ２およびＡｒ３の芳香環に結合している水素原子は、ハロゲン原子、アルキル基またはアリール基で置換されていてもよい。）
（４）－Ａｒ１１－Ｚ－Ａｒ１２－
（式中、Ａｒ１１、Ａｒ１２は、それぞれ独立に、フェニレンまたはナフチレンを表し、Ｚは、Ｏ、ＣＯまたはＳＯ２を表す。） The liquid crystal polyester is preferably a polyester that exhibits optical anisotropy when melted and has the property of forming an anisotropic melt at a temperature of 450 ° C. or lower. The liquid crystal polyester includes a structural unit represented by the following formula (1) (hereinafter referred to as “formula (1) structural unit”) and a structural unit represented by the following formula (2) (hereinafter referred to as “formula (2)”. And a structural unit represented by the following formula (3) (hereinafter referred to as “formula (3) structural unit”), and represented by the formula (1) with respect to the total of all structural units. A liquid crystal polyester having 30 to 80 mol% of structural units, 35 to 10 mol% of structural units represented by formula (2), and 35 to 10 mol% of structural units represented by formula (3) is preferable.
(1) —O—Ar 1 —CO—
(2) —CO—Ar 2 —CO—
(3) —X—Ar 3 —Y—
(In the formula, Ar 1 represents phenylene or naphthylene, Ar 2 represents phenylene, naphthylene, or a group represented by the following formula (4), and Ar 3 represents phenylene or a group represented by the following formula (4). , X and Y each independently represent O or NH, wherein the hydrogen atom bonded to the aromatic ring of Ar 1 , Ar 2 and Ar 3 is substituted with a halogen atom, an alkyl group or an aryl group. May be.)
(4) -Ar 11 -Z-Ar 12 -
(In the formula, Ar 11 and Ar 12 each independently represent phenylene or naphthylene, and Z represents O, CO, or SO 2. )
式（１）構造単位は、芳香族ヒドロキシカルボン酸由来の構造単位であり、この芳香族ヒドロキシカルボン酸としては、例えば、パラヒドロキシ安息香酸、メタヒドロキシ安息香酸、２－ヒドロキシ－６－ナフトエ酸、２－ヒドロキシ－３－ナフトエ酸、１－ヒドロキシ－４－ナフトエ酸などが挙げられる。
The structural unit of the formula (1) is a structural unit derived from an aromatic hydroxycarboxylic acid. Examples of the aromatic hydroxycarboxylic acid include parahydroxybenzoic acid, metahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, Examples thereof include 2-hydroxy-3-naphthoic acid and 1-hydroxy-4-naphthoic acid.
式（２）構造単位は、芳香族ジカルボン酸由来の構造単位であり、この芳香族ジカルボン酸としては、例えば、テレフタル酸、イソフタル酸、２，６－ナフタレンジカルボン酸、１，５－ナフタレンジカルボン酸、ジフェニルエ－テル－４，４’－ジカルボン酸、ジフェニルスルホン－４，４’－ジカルボン酸、ジフェニルケトン－４，４’－ジカルボン酸などが挙げられる。
The structural unit of the formula (2) is a structural unit derived from an aromatic dicarboxylic acid, and examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid. Diphenyl ether-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, diphenyl ketone-4,4′-dicarboxylic acid, and the like.
式（３）構造単位は、芳香族ジオール、フェノール性ヒドロキシル基（フェノール性水酸基）を有する芳香族アミンまたは芳香族ジアミンに由来する構造単位である。この芳香族ジオールとしては、例えば、ハイドロキノン、レゾルシン、２，２－ビス（４－ヒドロキシ－３，５－ジメチルフェニル）プロパン、ビス（４－ヒドロキシフェニル）エーテル、ビス－（４－ヒドロキシフェニル）ケトン、ビス－（４－ヒドロキシフェニル）スルホン等が挙げられる。
The structural unit (3) is a structural unit derived from an aromatic diol, an aromatic amine having a phenolic hydroxyl group (phenolic hydroxyl group) or an aromatic diamine. Examples of the aromatic diol include hydroquinone, resorcin, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) ether, and bis- (4-hydroxyphenyl) ketone. Bis- (4-hydroxyphenyl) sulfone and the like.
また、このフェノール性ヒドロキシル基を有する芳香族アミンとしては、４－アミノフェノール（ｐ－アミノフェノール）、３－アミノフェノール等が挙げられ、この芳香族ジアミンとしては、１，４－フェニレンジアミン、１，３－フェニレンジアミン等が挙げられる。
Examples of the aromatic amine having a phenolic hydroxyl group include 4-aminophenol (p-aminophenol) and 3-aminophenol. Examples of the aromatic diamine include 1,4-phenylenediamine, 1 , 3-phenylenediamine and the like.
本発明に用いる液晶ポリエステルは溶媒可溶性であり、かかる溶媒可溶性とは、温度５０℃において、１質量％以上の濃度で溶媒（溶剤）に溶解することを意味する。この場合の溶媒とは、後述する液状組成物の調製に用いる好適な溶媒のいずれか１種であり、詳細は後述する。
The liquid crystalline polyester used in the present invention is solvent-soluble, and such solvent-soluble means that it is dissolved in a solvent (solvent) at a concentration of 1% by mass or more at a temperature of 50 ° C. The solvent in this case is any one of suitable solvents used for preparing the liquid composition described later, and details will be described later.
このような溶媒可溶性を有する液晶ポリエステルとしては、前記式（３）構造単位として、フェノール性ヒドロキシル基を有する芳香族アミンに由来する構造単位および／または芳香族ジアミンに由来する構造単位を含むものが好ましい。すなわち、式（３）構造単位として、ＸおよびＹの少なくとも一方がＮＨである構造単位（式（３’）で示される構造単位、以下、「式（３’）構造単位」という）を含むと、後述する好適な溶媒（非プロトン性極性溶媒）に対する溶媒可溶性が優れる傾向がある点で好ましい。特に、実質的に全ての式（３）構造単位が式（３’）構造単位であることが好ましい。また、この式（３’）構造単位は液晶ポリエステルの溶媒可溶性を十分にすることに加え、液晶ポリエステルがより低吸水性となる点でも有利である。
（３’）－Ｘ－Ａｒ３－ＮＨ－
（式中、Ａｒ３およびＸは前記式（３）と同義である。） Examples of the solvent-soluble liquid crystal polyester include those having a structural unit derived from an aromatic amine having a phenolic hydroxyl group and / or a structural unit derived from an aromatic diamine as the structural unit of the formula (3). preferable. That is, when the structural unit of formula (3) includes a structural unit in which at least one of X and Y is NH (a structural unit represented by formula (3 ′), hereinafter referred to as “formula (3 ′) structural unit”). The solvent solubility in a suitable solvent (aprotic polar solvent) described later tends to be excellent. In particular, it is preferable that substantially all the structural units of the formula (3) are the structural units of the formula (3 ′). Further, this formula (3 ′) structural unit is advantageous in that the liquid crystal polyester has a lower water absorption in addition to sufficient solvent solubility of the liquid crystal polyester.
(3 ′) — X—Ar 3 —NH—
(In the formula, Ar 3 and X have the same meanings as the formula (3)).
（３’）－Ｘ－Ａｒ３－ＮＨ－
（式中、Ａｒ３およびＸは前記式（３）と同義である。） Examples of the solvent-soluble liquid crystal polyester include those having a structural unit derived from an aromatic amine having a phenolic hydroxyl group and / or a structural unit derived from an aromatic diamine as the structural unit of the formula (3). preferable. That is, when the structural unit of formula (3) includes a structural unit in which at least one of X and Y is NH (a structural unit represented by formula (3 ′), hereinafter referred to as “formula (3 ′) structural unit”). The solvent solubility in a suitable solvent (aprotic polar solvent) described later tends to be excellent. In particular, it is preferable that substantially all the structural units of the formula (3) are the structural units of the formula (3 ′). Further, this formula (3 ′) structural unit is advantageous in that the liquid crystal polyester has a lower water absorption in addition to sufficient solvent solubility of the liquid crystal polyester.
(3 ′) — X—Ar 3 —NH—
(In the formula, Ar 3 and X have the same meanings as the formula (3)).
式（１）構造単位は全構造単位の合計に対して、３０～８０モル％の範囲で含むと好ましく、３５～５０モル％の範囲で含むとより好ましい。このようなモル分率で式（１）構造単位を含む液晶ポリエステルは、液晶性を十分維持しながらも、耐熱性がより優れる傾向にある。さらに、式（１）構造単位を誘導する芳香族ヒドロキシカルボン酸の入手性も併せて考慮すると、この芳香族ヒドロキシカルボン酸としては、パラヒドロキシ安息香酸および／または２－ヒドロキシ－６－ナフトエ酸が好適である。
Formula (1) The structural unit is preferably contained in the range of 30 to 80 mol%, more preferably in the range of 35 to 50 mol%, based on the total of all the structural units. The liquid crystal polyester containing the structural unit of the formula (1) at such a mole fraction tends to be more excellent in heat resistance while sufficiently maintaining liquid crystallinity. Further, considering the availability of the aromatic hydroxycarboxylic acid from which the structural unit of formula (1) is derived, the aromatic hydroxycarboxylic acid may be parahydroxybenzoic acid and / or 2-hydroxy-6-naphthoic acid. Is preferred.
式（２）構造単位は全構造単位の合計に対して、３５～１０モル％の範囲で含むと好ましく、３３～２５モル％の範囲で含むとより好ましい。このようなモル分率で式（２）構造単位を含む液晶ポリエステルは、液晶性を十分維持しながらも、耐熱性がより優れる傾向にある。さらに、式（２）構造単位を誘導する芳香族ジカルボン酸の入手性も併せて考慮すると、この芳香族ジカルボン酸としては、テレフタル酸、イソフタル酸および２，６－ナフタレンジカルボン酸からなる群より選ばれる少なくとも１種であると好ましい。
Formula (2) The structural unit is preferably contained in the range of 35 to 10 mol%, more preferably in the range of 33 to 25 mol%, based on the total of all the structural units. The liquid crystal polyester containing the structural unit of the formula (2) at such a mole fraction tends to have more excellent heat resistance while sufficiently maintaining liquid crystallinity. Further, considering the availability of the aromatic dicarboxylic acid derived from the structural unit of formula (2), the aromatic dicarboxylic acid is selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid. It is preferable that it is at least one kind.
式（３）構造単位は全構造単位の合計に対して、３３～２５モル％の範囲で含むとより好ましく、こうすることにより、溶媒可溶性は一層良好になる。
The formula (3) structural unit is more preferably contained in the range of 33 to 25 mol% with respect to the total of all the structural units, and by doing so, the solvent solubility is further improved.
また、得られる液晶ポリエステルがより高度の液晶性を発現する点では、式（２）構造単位と式（３）構造単位とのモル分率は、［式（２）構造単位］／［式（３）構造単位］で表して、０．９／１．０～１．０／０．９の範囲が好適である。
In addition, in the point that the obtained liquid crystal polyester exhibits higher liquid crystallinity, the molar fraction of the formula (2) structural unit and the formula (3) structural unit is expressed by [formula (2) structural unit] / [formula ( 3) Structural unit], a range of 0.9 / 1.0 to 1.0 / 0.9 is preferable.
次に、液晶ポリエステルの製造方法について簡単に説明する。
Next, a method for producing liquid crystal polyester will be briefly described.
この液晶ポリエステルは、種々公知の方法により製造可能である。好適な液晶ポリエステル、すなわち、式（１）構造単位、式（２）構造単位および式（３）構造単位からなる液晶ポリエステルを製造する場合、これら構造単位を誘導するモノマーを、エステル形成性・アミド形成性誘導体に転換した後、重合させて液晶ポリエステルを製造する方法が、操作が簡便である点で好ましい。
This liquid crystal polyester can be produced by various known methods. In the case of producing a suitable liquid crystal polyester, that is, a liquid crystal polyester comprising the structural unit of formula (1), the structural unit of formula (2) and the structural unit of formula (3), the monomer for deriving these structural units is selected from ester-forming amide The method of producing a liquid crystal polyester by polymerization after conversion to a formable derivative is preferred in that the operation is simple.
前記エステル形成性・アミド形成性誘導体について、例を挙げて説明する。
Examples of the ester-forming / amide-forming derivatives will be described below.
芳香族ヒドロキシカルボン酸や芳香族ジカルボン酸のように、カルボキシル基を有するモノマーのエステル形成性・アミド形成性誘導体としては、当該カルボキシル基が、ポリエステルやポリアミドを生成する反応を促進するように、酸塩化物、酸無水物等の反応活性の高い基になっているものや、当該カルボキシル基が、エステル交換・アミド交換反応によりポリエステルやポリアミドを生成するようにアルコール類やエチレングリコールなどとエステルを形成しているもの等が挙げられる。
As an ester-forming / amide-forming derivative of a monomer having a carboxyl group, such as an aromatic hydroxycarboxylic acid or an aromatic dicarboxylic acid, an acid is used so that the carboxyl group promotes a reaction to form a polyester or polyamide. Form esters with alcohols, ethylene glycol, etc., such as those with highly reactive groups such as chlorides, acid anhydrides, and the like, such that the carboxyl group generates polyester or polyamide by transesterification / amide exchange reaction And the like.
芳香族ヒドロキシカルボン酸や芳香族ジオール等のように、フェノール性ヒドロキシル基を有するモノマーのエステル形成性・アミド形成性誘導体としては、エステル交換反応によりポリエステルやポリアミドを生成するように、フェノール性ヒドロキシル基がカルボン酸類とエステルを形成しているもの等が挙げられる。
As an ester-forming / amide-forming derivative of a monomer having a phenolic hydroxyl group, such as an aromatic hydroxycarboxylic acid or aromatic diol, a phenolic hydroxyl group is formed so as to form a polyester or a polyamide by a transesterification reaction. Are those that form esters with carboxylic acids.
また、芳香族ジアミンのように、アミノ基を有するモノマーのアミド形成性誘導体としては、例えば、アミド交換反応によりポリアミドを生成するように、アミノ基がカルボン酸類とアミドを形成しているもの等が挙げられる。
Examples of the amide-forming derivative of a monomer having an amino group, such as an aromatic diamine, 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. Can be mentioned.
これらの中でも液晶ポリエステルをより簡便に製造するうえでは、芳香族ヒドロキシカルボン酸と、芳香族ジオール、フェノール性ヒドロキシル基を有する芳香族アミン、芳香族ジアミンといったフェノール性ヒドロキシル基および／またはアミノ基を有するモノマーとを、脂肪酸無水物でアシル化してエステル形成性・アミド形成性誘導体（アシル化物）とした後、このアシル化物のアシル基と、カルボキシル基を有するモノマーのカルボキシル基とがエステル交換・アミド交換を生じるようにして重合させ、液晶ポリエステルを製造する方法が特に好ましい。
Among these, in order to more easily produce the liquid crystalline polyester, it has an aromatic hydroxycarboxylic acid, an aromatic diol, an aromatic amine having a phenolic hydroxyl group, an phenolic hydroxyl group such as an aromatic diamine and / or an amino group. The monomer is acylated with a fatty acid anhydride to form an ester-forming / amide-forming derivative (acylated product), and then the acyl group of this acylated product and the carboxyl group of the monomer having a carboxyl group are transesterified / amide-exchanged. Particularly preferred is a method for producing a liquid crystal polyester by polymerizing in such a manner as to produce the above.
このような液晶ポリエステルの製造方法は、例えば、特開２００２－２２０４４４号公報または特開２００２－１４６００３号公報に記載されている。
Such a method for producing a liquid crystal polyester is described in, for example, JP-A No. 2002-220444 or JP-A No. 2002-146003.
アシル化においては、フェノール性ヒドロキシル基とアミノ基との合計に対して、脂肪酸無水物の添加量が１．０～１．２倍当量であることが好ましく、１．０５～１．１倍当量であるとより好ましい。脂肪酸無水物の添加量が１．０倍当量未満では、重合時にアシル化物や原料モノマーが昇華して反応系が閉塞しやすい傾向があり、また、１．２倍当量を超える場合には、得られる液晶ポリエステルの着色が著しくなる傾向がある。
In the acylation, the addition amount of the fatty acid anhydride is preferably 1.0 to 1.2 times equivalent, more preferably 1.05 to 1.1 times equivalent to the total of the phenolic hydroxyl group and amino group. Is more preferable. If the added amount of the fatty acid anhydride is less than 1.0 times equivalent, the acylated product or raw material monomer tends to sublimate during polymerization and the reaction system tends to be blocked, and if it exceeds 1.2 times equivalent, There is a tendency that coloring of the liquid crystal polyester obtained becomes remarkable.
アシル化は、１３０～１８０℃で５分～１０時間反応させることが好ましく、１４０～１６０℃で１０分～３時間反応させることがより好ましい。
The acylation 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.
アシル化に使用される脂肪酸無水物は、価格と取扱性の観点から、無水酢酸、無水プロピオン酸、無水酪酸、無水イソ酪酸またはこれらから選ばれる２種以上の混合物が好ましく、特に好ましくは、無水酢酸である。
The fatty acid anhydride used for the acylation is preferably acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride or a mixture of two or more selected from these, particularly preferably anhydrous, from the viewpoint of price and handleability. Acetic acid.
アシル化に続く重合は、１３０～４００℃で０．１～５０℃／分の割合で昇温しながら行うことが好ましく、１５０～３５０℃で０．３～５℃／分の割合で昇温しながら行うことがより好ましい。
The polymerization following acylation is preferably carried out at 130 to 400 ° C. while raising the temperature at a rate of 0.1 to 50 ° C./min, and at 150 to 350 ° C. with a rate of 0.3 to 5 ° C./min. More preferably.
また、重合においては、アシル化物のアシル基がカルボキシル基の０．８～１．２倍当量であることが好ましい。
In the polymerization, the acyl group of the acylated product is preferably 0.8 to 1.2 times equivalent to the carboxyl group.
アシル化および／または重合の際には、ル・シャトリエ‐ブラウンの法則（平衡移動の原理）により、平衡を移動させるため、副生する脂肪酸や未反応の脂肪酸無水物は蒸発させる等して系外へ留去することが好ましい。
During acylation and / or polymerization, the equilibrium is shifted according to Le Chatelier-Brown's law (equilibrium transfer principle), and by-product fatty acids and unreacted fatty acid anhydrides are evaporated, etc. It is preferable to distill out.
なお、アシル化や重合は触媒の存在下に行ってもよい。この触媒としては、従来からポリエステルの重合用触媒として公知のものを使用することができ、例えば、酢酸マグネシウム、酢酸第一錫、テトラブチルチタネート、酢酸鉛、酢酸ナトリウム、酢酸カリウム、三酸化アンチモン等の金属塩触媒、Ｎ，Ｎ－ジメチルアミノピリジン、Ｎ－メチルイミダゾール等の有機化合物触媒を挙げることができる。
In addition, you may perform acylation and superposition | polymerization in presence of a catalyst. As this 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.
これらの触媒の中でも、Ｎ，Ｎ－ジメチルアミノピリジン、Ｎ－メチルイミダゾール等の窒素原子を２個以上含む複素環状化合物が好ましく使用される（特開２００２－１４６００３号公報参照）。
Among these catalysts, heterocyclic compounds containing 2 or more nitrogen atoms such as N, N-dimethylaminopyridine and N-methylimidazole are preferably used (see JP 2002-146003 A).
この触媒は、通常モノマーの投入時に一緒に投入され、アシル化後も除去することは必ずしも必要ではなく、この触媒を除去しない場合には、アシル化からそのまま重合に移行することができる。
This catalyst is usually added together with the monomer, and it is not always necessary to remove it even after acylation. If this catalyst is not removed, it is possible to shift from acylation to polymerization as it is.
このような重合で得られた液晶ポリエステルはそのまま、本発明に用いることができるが、耐熱性や液晶性という特性の更なる向上のためには、より高分子量化させることが好ましく、かかる高分子量化には固相重合を行うことが好ましい。この固相重合に係る一連の操作を説明する。前記の重合で得られた、比較的低分子量の液晶ポリエステルを取り出し、粉砕してパウダー状またはフレーク状にする。続いて、この粉砕後の液晶ポリエステルを、例えば、窒素等の不活性ガスの雰囲気下、２０～３５０℃で、１～３０時間固相状態で加熱処理するという操作により固相重合は実施できる。この固相重合は、攪拌しながら行ってもよく、攪拌することなく静置した状態で行ってもよい。なお、後述する好適な流動開始温度の液晶ポリエステルを得るという観点から、この固相重合の好適条件を詳述すると、反応温度として２１０℃を越えることが好ましく、より一層好ましくは２２０℃～３５０℃の範囲である。反応時間は１～１０時間から選択されることが好ましい。
The liquid crystal polyester obtained by such polymerization can be used in the present invention as it is, but it is preferable to increase the molecular weight in order to further improve the properties such as heat resistance and liquid crystallinity. For the conversion, it is preferable to perform solid phase polymerization. A series of operations relating to this solid phase polymerization will be described. The relatively low molecular weight liquid crystal polyester obtained by the above polymerization is taken out and pulverized into powder or flakes. Subsequently, solid phase polymerization can be carried out by subjecting the pulverized liquid crystal polyester to a heat treatment in a solid state at 20 to 350 ° C. for 1 to 30 hours in an atmosphere of an inert gas such as nitrogen, for example. This solid phase polymerization may be performed with stirring, or may be performed in a state of standing without stirring. From the viewpoint of obtaining a liquid crystalline polyester having a suitable flow start temperature described later, the preferred conditions for this solid phase polymerization will be described in detail. The reaction temperature is preferably higher than 210 ° C, and more preferably 220 ° C to 350 ° C. Range. The reaction time is preferably selected from 1 to 10 hours.
本発明に用いる液晶ポリエステルとしては、その流動開始温度が２５０℃以上であると好ましい。この液晶ポリエステルの流動開始温度がこの範囲であると、この液晶ポリエステルを含む層上に導電層（電極）を形成させたとき、この液晶ポリエステルを含む層とこの導電層との間に、より高度の密着性が得られる傾向がある。なお、ここでいう流動開始温度とは、フローテスターによる溶融粘度の評価において、９．８ＭＰａの圧力下で液晶ポリエステルの溶融粘度が４８００Ｐａ・ｓ以下になる温度をいう。なお、この流動開始温度とは、液晶ポリエステルの分子量の目安として当業者には周知のものである（例えば、小出直之編「液晶ポリマー－合成・成形・応用－」第９５～１０５頁、シーエムシー、１９８７年６月５日発行を参照）。
The liquid crystal polyester used in the present invention preferably has a flow start temperature of 250 ° C. or higher. When the flow start temperature of the liquid crystal polyester is within this range, when a conductive layer (electrode) is formed on the layer containing the liquid crystal polyester, the liquid crystal polyester has a higher level between the layer containing the liquid crystal polyester and the conductive layer. There is a tendency that the adhesion of is obtained. In addition, the flow start temperature here means the temperature at which the melt viscosity of the liquid crystal polyester is 4800 Pa · s or less under a pressure of 9.8 MPa in the evaluation of the melt viscosity by a flow tester. The flow initiation temperature is well known to those skilled in the art as a measure of the molecular weight of liquid crystal polyester (for example, Naoyuki Koide, “Liquid Crystal Polymer—Synthesis / Molding / Application”, pages 95 to 105, see (See MC, published 5 June 1987).
液晶ポリエステルの流動開始温度の上限は、この液晶ポリエステルが溶媒に可溶である範囲で決定されるが、３５０℃以下であることが好ましい。流動開始温度の上限がこの範囲であれば、液晶ポリエステルの溶媒に対する溶解性がより良好になることに加え、後述する液状組成物を得たとき、その粘度が著増しないので、この液状組成物の取扱性が良好となる傾向がある。なお、液晶ポリエステルの流動開始温度をこのような好適な範囲に制御するには、前記固相重合の重合条件を適宜最適化すればよい。
The upper limit of the flow start temperature of the liquid crystal polyester is determined within a range in which the liquid crystal polyester is soluble in the solvent, but is preferably 350 ° C. or lower. If the upper limit of the flow starting temperature is within this range, the liquid crystal polyester has better solubility in the solvent, and when the liquid composition described later is obtained, its viscosity does not increase significantly. It tends to be easy to handle. In order to control the flow start temperature of the liquid crystal polyester within such a suitable range, the polymerization conditions for the solid phase polymerization may be optimized as appropriate.
次に、液状組成物について説明する。
Next, the liquid composition will be described.
この液状組成物は、上述した液晶ポリエステルおよび溶媒の２成分からなるものである。
This liquid composition is composed of the two components of the liquid crystal polyester and the solvent described above.
この溶媒としては、液晶ポリエステルを溶解するものであれば特に限定されないが、例えば、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、Ｎ－メチルカプロラクタム、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジエチルホルムアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ－メチルプロピオンアミド、ジメチルスルホキシド、γ－ブチロラクトン、ジメチルイミダゾリジノン、テトラメチルホスホリックアミドおよびエチルセロソルブアセテート、並びにパラフルオロフェノール、パラクロロフェノール、ペルフルオロフェノールなどのハロゲン化フェノール類などが挙げられる。これらの溶媒は、単独で用いてもよく、２種以上を組み合わせて用いても構わない。
The solvent is not particularly limited as long as it dissolves the liquid crystalline polyester. For example, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N-methylpropionamide, dimethyl sulfoxide, γ-butyrolactone, dimethylimidazolidinone, tetramethylphosphoric amide and ethyl cellosolve acetate, and parafluorophenol, parachlorophenol, perfluoro And halogenated phenols such as phenol. These solvents may be used alone or in combination of two or more.
かかる溶媒の中でも、取り扱いの観点から、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、Ｎ－メチルカプロラクタム、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジエチルホルムアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ－メチルプロピオンアミド、ジメチルスルホキシド、γ－ブチロラクトン、ジメチルイミダゾリジノン、テトラメチルホスホリックアミドおよびエチルセロソルブアセテートからなる群から選択される非プロトン性有機溶媒が好適である。
Among such solvents, from the viewpoint of handling, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide Preferred is an aprotic organic solvent selected from the group consisting of N-methylpropionamide, dimethyl sulfoxide, γ-butyrolactone, dimethylimidazolidinone, tetramethylphosphoric amide and ethyl cellosolve acetate.
この溶媒の使用量は、液晶ポリエステルを０．１質量％以上含有する液状組成物を調製するような量であれば、適用する溶媒の種類に応じて適宜選択することができるが、溶媒１００質量部に対して液晶ポリエステル０．５～５０質量部であることが好ましく、７～３０質量部であることがより好ましい。液晶ポリエステルが０．５質量部未満であると、液状組成物の粘度が低すぎて均一に塗工できない傾向があり、５０質量部を超えると、高粘度化する傾向がある。このようにして得られた液状組成物を前記有機溶媒で希釈してこの液晶ポリエステルの０．５ｇ／ｄｌ溶液としたときの２５℃における固有粘度は、０．１～１０である。
The amount of the solvent used can be appropriately selected depending on the type of the solvent to be applied, as long as it is an amount capable of preparing a liquid composition containing 0.1% by mass or more of liquid crystal polyester. The amount of liquid crystal polyester is preferably 0.5 to 50 parts by mass, more preferably 7 to 30 parts by mass with respect to parts. If the liquid crystalline polyester is less than 0.5 parts by mass, the liquid composition tends to be too low in viscosity to be applied uniformly, and if it exceeds 50 parts by mass, the viscosity tends to increase. The intrinsic viscosity at 25 ° C. when the liquid composition thus obtained is diluted with the organic solvent to give a 0.5 g / dl solution of this liquid crystalline polyester is 0.1 to 10.
そして、本発明の液晶ポリエステルフィルムを製造する際には次の手順による。
And when manufacturing the liquid crystalline polyester film of the present invention, the following procedure is followed.
まず、液晶ポリエステル前駆体フィルム調製工程で、上述した液状組成物を基材上に流延し、所定の温度で所定の時間だけ乾燥する。すると、溶媒を含んだ状態の液晶ポリエステル前駆体フィルムが得られる。
First, in the liquid crystal polyester precursor film preparation step, the above-described liquid composition is cast on a substrate and dried at a predetermined temperature for a predetermined time. As a result, a liquid crystal polyester precursor film containing a solvent is obtained.
ここで、液晶ポリエステル前駆体フィルムとは、液晶ポリエステルフィルムの製造過程において、最終目的物である液晶ポリエステルフィルムよりも前の段階にあって、熱処理によって液晶ポリエステルフィルムに変わりうるフィルムを意味する。
Here, the liquid crystal polyester precursor film means a film that can be converted into a liquid crystal polyester film by heat treatment in a stage before the liquid crystal polyester film that is the final target in the process of manufacturing the liquid crystal polyester film.
また、基材としては、液晶ポリエステル前駆体フィルムを剥離可能な基材であれば、特に制限されないが、ガラス板、ステンレス箔、ポリエチレンテレフタレートフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、ポリメチルペンテンフィルム、ポリテトラフルオロエチレンシート等が好ましい。
In addition, the substrate is not particularly limited as long as the liquid crystal polyester precursor film can be peeled off. However, the glass plate, stainless steel foil, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, polytetra A fluoroethylene sheet or the like is preferable.
また、液状組成物を基材上に流延する手段としては、例えば、ローラーコート法、グラビアコート法、ナイフコート法、ブレードコート法、ロッドコート法、ディップコート法、スプレイコート法、カーテンコート法、スロットコート法、スクリーン印刷法などを挙げることができる。これらの中でも、制御が容易であるとともに、膜厚を精度よく均一にできる観点から、ナイフコート法またはスロットコート法が好ましい。
Examples of means for casting the liquid composition on the substrate include, for example, a roller coating method, a gravure coating method, a knife coating method, a blade coating method, a rod coating method, a dip coating method, a spray coating method, and a curtain coating method. , Slot coating method, screen printing method and the like. Among these, the knife coating method or the slot coating method is preferable from the viewpoint of easy control and uniform film thickness.
また、液状組成物を乾燥するときの温度および時間は特に制限されない。例えば、この温度は１６０℃以下とすることが好ましく、１５０℃以下とすることがより好ましく、１４０℃以下とすることがさらに好ましい。この温度が高すぎると、塗膜面に欠陥が生じる可能性がある。一方、この温度が低すぎると、溶媒除去にかかる時間が長くなり、生産性が低下する恐れがある。そのため、この液状組成物の乾燥は、少なくとも６０℃以上で行うことが好ましい。
Also, the temperature and time for drying the liquid composition are not particularly limited. For example, this temperature is preferably 160 ° C. or lower, more preferably 150 ° C. or lower, and further preferably 140 ° C. or lower. If this temperature is too high, defects may occur on the coating surface. On the other hand, if this temperature is too low, the time required for removing the solvent becomes longer, which may reduce productivity. Therefore, the liquid composition is preferably dried at 60 ° C. or higher.
さらに、液晶ポリエステル前駆体フィルム中の残存溶媒量は１８質量％～２質量％であることが好ましい。さらに好ましくは１５質量％～５質量％である。残存溶媒量が１８質量％以下であれば、液晶ポリエステル前駆体フィルムの表面の粘着性が抑制でき、フィルム同士の互着を防止することができる。また、残存溶媒量が２質量％以上であれば、液晶ポリエステル前駆体フィルムのフィルム強度を維持することが可能となり、基材から液晶ポリエステル前駆体フィルムを剥離する際や、次に述べる液晶ポリエステルフィルム調製工程における熱処理の際に、液晶ポリエステルフィルムの破れを防止することができる。
Furthermore, the amount of residual solvent in the liquid crystal polyester precursor film is preferably 18% by mass to 2% by mass. More preferably, it is 15% by mass to 5% by mass. If the amount of residual solvent is 18 mass% or less, the adhesiveness of the surface of a liquid crystal polyester precursor film can be suppressed, and the mutual adhesion of films can be prevented. Further, if the residual solvent amount is 2% by mass or more, the film strength of the liquid crystal polyester precursor film can be maintained, and when the liquid crystal polyester precursor film is peeled from the substrate, the liquid crystal polyester film described below is used. During the heat treatment in the preparation process, the liquid crystal polyester film can be prevented from being broken.
こうして液晶ポリエステル前駆体フィルムが調製されたところで、この液晶ポリエステルの分子量を増大させ、フィルムにガスバリア性および耐熱性を発現させるべく、液晶ポリエステルフィルム調製工程に移行し、液晶ポリエステル前駆体フィルムを昇温しながら熱処理する。すると、この熱処理により、液晶ポリエステル前駆体フィルムが液晶ポリエステルフィルムに変わる。
When the liquid crystal polyester precursor film is prepared in this way, the liquid crystal polyester precursor film is transferred to the liquid crystal polyester film preparation step in order to increase the molecular weight of the liquid crystal polyester and to make the film exhibit gas barrier properties and heat resistance. Heat treatment. Then, by this heat treatment, the liquid crystal polyester precursor film is changed to a liquid crystal polyester film.
このとき、液晶ポリエステル前駆体フィルムの熱処理時の昇温速度を５℃／分以下、好ましくは１℃／分以下とする。こうすることにより、液晶ポリエステルフィルムの光透過性を保持することができるとともに、残存溶媒の揮発速度と液晶ポリエステルの分子量増大のバランスが取れるため、液晶ポリエステルフィルムの破れを防止することができる。なお、液晶ポリエステル前駆体フィルムの熱処理時の昇温速度の下限は特に定められないが、通常は生産性の観点から、０．０５℃／分以上が好ましく、０．１℃／分以上がさらに好ましい。
At this time, the rate of temperature increase during the heat treatment of the liquid crystal polyester precursor film is 5 ° C./min or less, preferably 1 ° C./min or less. By doing so, the light transmittance of the liquid crystal polyester film can be maintained, and the balance between the volatilization rate of the residual solvent and the increase in the molecular weight of the liquid crystal polyester can be achieved, so that the liquid crystal polyester film can be prevented from being broken. The lower limit of the rate of temperature increase during the heat treatment of the liquid crystal polyester precursor film is not particularly defined, but is usually preferably 0.05 ° C./min or more and more preferably 0.1 ° C./min or more from the viewpoint of productivity. preferable.
また、液晶ポリエステル前駆体フィルムの熱処理時の最高温度を３００℃以下とする。こうすることにより、液晶ポリエステルフィルムの光透過性を保持することができる。なお、液晶ポリエステル前駆体フィルムの熱処理時の最高温度の下限は特に定められないが最高温度が２００℃以上であれば、液晶ポリエステルフィルムのガスバリア性が著しく向上する点で好ましい。逆に、この最高温度が２００℃未満だと、ガスバリア性が不十分となる恐れがある。
Also, the maximum temperature during the heat treatment of the liquid crystal polyester precursor film is set to 300 ° C. or lower. By carrying out like this, the light transmittance of a liquid crystal polyester film can be hold | maintained. In addition, although the minimum of the maximum temperature at the time of heat processing of a liquid crystalline polyester precursor film is not specifically defined, if the maximum temperature is 200 degreeC or more, it is preferable at the point which the gas barrier property of a liquid crystalline polyester film improves remarkably. Conversely, if this maximum temperature is less than 200 ° C., the gas barrier properties may be insufficient.
さらに、この最高温度での保持時間には特に制限はないが、通常、０～５時間である。
Furthermore, the holding time at this maximum temperature is not particularly limited, but is usually 0 to 5 hours.
また、液晶ポリエステル前駆体フィルムを熱処理する形態については、特に制限されない。例えば、液晶ポリエステル前駆体フィルムと基材とからなる積層体をそのまま熱処理してもよく、液晶ポリエステル前駆体フィルムを基材から一旦剥離した後、金属枠などに固定した状態で熱処理しても構わない。
Further, the form of heat-treating the liquid crystal polyester precursor film is not particularly limited. For example, a laminate comprising a liquid crystal polyester precursor film and a substrate may be heat treated as it is, or after the liquid crystal polyester precursor film is once peeled from the substrate, it may be heat treated in a state of being fixed to a metal frame or the like. Absent.
ここで、液晶ポリエステルフィルムの製造工程が終了する。
Here, the manufacturing process of the liquid crystal polyester film is completed.
［発明のその他の実施の形態］
なお、上述した実施の形態１では、液晶ポリエステルおよび溶媒の２成分からなる液状組成物について説明した。しかし、液晶ポリエステルフィルムの用途に応じて、他の成分、例えば各種の充填剤（ガラス繊維、ガラス粉末、マイカ、タルク、炭素繊維など）を添加しても構わない。 [Other Embodiments of the Invention]
In the first embodiment described above, the liquid composition composed of two components of the liquid crystal polyester and the solvent has been described. However, other components such as various fillers (glass fiber, glass powder, mica, talc, carbon fiber, etc.) may be added depending on the use of the liquid crystal polyester film.
なお、上述した実施の形態１では、液晶ポリエステルおよび溶媒の２成分からなる液状組成物について説明した。しかし、液晶ポリエステルフィルムの用途に応じて、他の成分、例えば各種の充填剤（ガラス繊維、ガラス粉末、マイカ、タルク、炭素繊維など）を添加しても構わない。 [Other Embodiments of the Invention]
In the first embodiment described above, the liquid composition composed of two components of the liquid crystal polyester and the solvent has been described. However, other components such as various fillers (glass fiber, glass powder, mica, talc, carbon fiber, etc.) may be added depending on the use of the liquid crystal polyester film.
また、上述した実施の形態１では、液晶ポリエステル前駆体フィルム調製工程と液晶ポリエステルフィルム調製工程の２工程のみからなる液晶ポリエステルフィルムの製造方法について説明したが、各種の前処理工程や後処理工程を付加することも勿論できる。
Moreover, in Embodiment 1 mentioned above, although the manufacturing method of the liquid crystalline polyester film which consists only of 2 processes of a liquid crystalline polyester precursor film preparation process and a liquid crystalline polyester film preparation process was demonstrated, various pre-processing processes and post-processing processes are performed. Of course, it can be added.
以下、本発明の実施例について説明する。なお、本発明は実施例に限定されるものではない。
Hereinafter, examples of the present invention will be described. In addition, this invention is not limited to an Example.
＜実施例１＞
攪拌装置、トルクメータ、窒素ガス導入管、温度計および還流冷却器を備えた反応器に、２－ヒドロキシ－６－ナフトエ酸９４１ｇ（５．０モル）、４－アミノフェノール２７３ｇ（２．５モル）、イソフタル酸４１５．３ｇ（２．５モル）および無水酢酸１１２３ｇ（１１モル）を仕込んだ。反応器内を十分に窒素ガスで置換した後、窒素ガス気流下で１５分かけて１５０℃まで昇温し、温度を保持して３時間還流させた。 <Example 1>
A reactor equipped with a stirrer, a torque meter, a nitrogen gas inlet tube, a thermometer and a reflux condenser was charged with 941 g (5.0 mol) of 2-hydroxy-6-naphthoic acid and 273 g (2.5 mol) of 4-aminophenol. ), 415.3 g (2.5 mol) of isophthalic acid and 1123 g (11 mol) of acetic anhydride. 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.
攪拌装置、トルクメータ、窒素ガス導入管、温度計および還流冷却器を備えた反応器に、２－ヒドロキシ－６－ナフトエ酸９４１ｇ（５．０モル）、４－アミノフェノール２７３ｇ（２．５モル）、イソフタル酸４１５．３ｇ（２．５モル）および無水酢酸１１２３ｇ（１１モル）を仕込んだ。反応器内を十分に窒素ガスで置換した後、窒素ガス気流下で１５分かけて１５０℃まで昇温し、温度を保持して３時間還流させた。 <Example 1>
A reactor equipped with a stirrer, a torque meter, a nitrogen gas inlet tube, a thermometer and a reflux condenser was charged with 941 g (5.0 mol) of 2-hydroxy-6-naphthoic acid and 273 g (2.5 mol) of 4-aminophenol. ), 415.3 g (2.5 mol) of isophthalic acid and 1123 g (11 mol) of acetic anhydride. 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.
その後、留出する副生酢酸および未反応の無水酢酸を留去しながら１７０分かけて３２０℃まで昇温し、トルクの上昇が認められる時点を反応終了とみなし、内容物を取り出した。こうして得られた固形分は、室温まで冷却し、粗粉砕機で粉砕した後、窒素雰囲気下２５０℃で３時間保持し、固相で重合反応を進めた。こうして得られた粉末は、３５０℃で偏光顕微鏡により液晶相に特有のシュリーレン模様が観察された。また、この粉末８ｇをＮ－メチル－２－ピロリドン９２ｇに加え、１２０℃に加熱すると、完全に溶解して透明な溶液が得られた。
Thereafter, the temperature was raised to 320 ° C. over 170 minutes while distilling off the distilling by-product acetic acid and unreacted acetic anhydride, and the time when an increase in torque was observed was regarded as the completion of the reaction, and the contents were taken out. The solid content thus obtained was cooled to room temperature, pulverized with a coarse pulverizer, then held at 250 ° C. for 3 hours in a nitrogen atmosphere, and the polymerization reaction proceeded in a solid phase. In the powder thus obtained, a schlieren pattern peculiar to the liquid crystal phase was observed at 350 ° C. with a polarizing microscope. When 8 g of this powder was added to 92 g of N-methyl-2-pyrrolidone and heated to 120 ° C., it completely dissolved and a transparent solution was obtained.
次に、フィルムアプリケーターを用いて、この溶液をガラス板（基材）上に塗工厚さ３００μｍで塗工した。この溶液をガラス板とともに８０℃で１時間乾燥した後、ガラス板から剥離することにより、液晶ポリエステル前駆体フィルムを得た。なお、（株）ミツトヨ製のマイクロメーターを用いて、この液晶ポリエステル前駆体フィルムの厚さを測定したところ、その厚さは１８μｍであった。また、この液晶ポリエステル前駆体フィルムについて、（株）島津製作所製の熱重量測定装置「ＴＧＡ５０」を用いて、昇温速度１０℃／分で６６℃から２５０℃まで昇温し、重量減少から残存溶媒量を算出したところ、その残存溶媒量は１１％であった。
Next, this solution was applied on a glass plate (base material) with a coating thickness of 300 μm using a film applicator. This solution was dried with a glass plate at 80 ° C. for 1 hour, and then peeled from the glass plate to obtain a liquid crystal polyester precursor film. In addition, when the thickness of this liquid crystal polyester precursor film was measured using the micrometer made from Mitutoyo Corporation, the thickness was 18 micrometers. The liquid crystal polyester precursor film was heated from 66 ° C. to 250 ° C. at a temperature rising rate of 10 ° C./min using a thermogravimetric measuring device “TGA50” manufactured by Shimadzu Corporation, and remained from weight reduction. When the amount of solvent was calculated, the amount of residual solvent was 11%.
そして、この液晶ポリエステル前駆体フィルムをイナートオーブンに仕込み、窒素雰囲気下、常温（３０℃）から熱処理時の最高温度の２００℃まで１０時間かけて（つまり、０．２８℃／分の昇温速度で）昇温した。イナートオーブンの内温が熱処理時の最高温度に到達した後、同温度（２００℃）で３時間保持し、その後冷却することにより、液晶ポリエステルフィルムを製造した。なお、（株）ミツトヨ製のマイクロメーターを用いて、この液晶ポリエステルフィルムの厚さを測定したところ、その厚さは１５μｍであった。
Then, this liquid crystalline polyester precursor film is charged into an inert oven, and the temperature is increased from room temperature (30 ° C.) to the maximum temperature of 200 ° C. during the heat treatment over 10 hours in a nitrogen atmosphere (that is, 0.28 ° C./min heating rate) Temperature). After the internal temperature of the inert oven reached the maximum temperature during the heat treatment, it was held at the same temperature (200 ° C.) for 3 hours, and then cooled to produce a liquid crystal polyester film. In addition, when the thickness of this liquid crystal polyester film was measured using the micrometer made from Mitutoyo Corporation, the thickness was 15 micrometers.
＜実施例２＞
液晶ポリエステル前駆体フィルムの熱処理時の最高温度を２３５℃としたことと、液晶ポリエステル前駆体フィルムの熱処理時の昇温速度を０．３４℃／分としたこと（具体的には、３０℃から２３５℃まで１０時間かけて昇温したこと）を除き、上述した実施例１と同様の手順により、液晶ポリエステルフィルムを製造した。なお、（株）ミツトヨ製のマイクロメーターを用いて、この液晶ポリエステルフィルムの厚さを測定したところ、その厚さは１５μｍであった。 <Example 2>
The maximum temperature during the heat treatment of the liquid crystal polyester precursor film was set to 235 ° C., and the temperature increase rate during the heat treatment of the liquid crystal polyester precursor film was set to 0.34 ° C./minute (specifically, from 30 ° C. A liquid crystal polyester film was produced by the same procedure as in Example 1 except that the temperature was raised to 235 ° C. over 10 hours. In addition, when the thickness of this liquid crystal polyester film was measured using the micrometer made from Mitutoyo Corporation, the thickness was 15 micrometers.
液晶ポリエステル前駆体フィルムの熱処理時の最高温度を２３５℃としたことと、液晶ポリエステル前駆体フィルムの熱処理時の昇温速度を０．３４℃／分としたこと（具体的には、３０℃から２３５℃まで１０時間かけて昇温したこと）を除き、上述した実施例１と同様の手順により、液晶ポリエステルフィルムを製造した。なお、（株）ミツトヨ製のマイクロメーターを用いて、この液晶ポリエステルフィルムの厚さを測定したところ、その厚さは１５μｍであった。 <Example 2>
The maximum temperature during the heat treatment of the liquid crystal polyester precursor film was set to 235 ° C., and the temperature increase rate during the heat treatment of the liquid crystal polyester precursor film was set to 0.34 ° C./minute (specifically, from 30 ° C. A liquid crystal polyester film was produced by the same procedure as in Example 1 except that the temperature was raised to 235 ° C. over 10 hours. In addition, when the thickness of this liquid crystal polyester film was measured using the micrometer made from Mitutoyo Corporation, the thickness was 15 micrometers.
＜実施例３＞
液晶ポリエステル前駆体フィルムの熱処理時の最高温度を２６０℃としたことと、液晶ポリエステル前駆体フィルムの熱処理時の昇温速度を０．３８℃／分としたこと（具体的には、３０℃から２６０℃まで１０時間かけて昇温したこと）を除き、上述した実施例１と同様の手順により、液晶ポリエステルフィルムを製造した。なお、（株）ミツトヨ製のマイクロメーターを用いて、この液晶ポリエステルフィルムの厚さを測定したところ、その厚さは１４μｍであった。 <Example 3>
The maximum temperature during heat treatment of the liquid crystal polyester precursor film was set to 260 ° C., and the temperature increase rate during heat treatment of the liquid crystal polyester precursor film was set to 0.38 ° C./minute (specifically, from 30 ° C. A liquid crystal polyester film was produced by the same procedure as in Example 1 except that the temperature was raised to 260 ° C. over 10 hours. In addition, when the thickness of this liquid crystal polyester film was measured using the micrometer made from Mitutoyo Corporation, the thickness was 14 micrometers.
液晶ポリエステル前駆体フィルムの熱処理時の最高温度を２６０℃としたことと、液晶ポリエステル前駆体フィルムの熱処理時の昇温速度を０．３８℃／分としたこと（具体的には、３０℃から２６０℃まで１０時間かけて昇温したこと）を除き、上述した実施例１と同様の手順により、液晶ポリエステルフィルムを製造した。なお、（株）ミツトヨ製のマイクロメーターを用いて、この液晶ポリエステルフィルムの厚さを測定したところ、その厚さは１４μｍであった。 <Example 3>
The maximum temperature during heat treatment of the liquid crystal polyester precursor film was set to 260 ° C., and the temperature increase rate during heat treatment of the liquid crystal polyester precursor film was set to 0.38 ° C./minute (specifically, from 30 ° C. A liquid crystal polyester film was produced by the same procedure as in Example 1 except that the temperature was raised to 260 ° C. over 10 hours. In addition, when the thickness of this liquid crystal polyester film was measured using the micrometer made from Mitutoyo Corporation, the thickness was 14 micrometers.
＜比較例１＞
液晶ポリエステル前駆体フィルムの熱処理時の最高温度を３２０℃としたことと、液晶ポリエステル前駆体フィルムの熱処理時の昇温速度を０．４８℃／分としたこと（具体的には、３０℃から３２０℃まで１０時間かけて昇温したこと）を除き、上述した実施例１と同様の手順により、液晶ポリエステルフィルムを製造した。なお、（株）ミツトヨ製のマイクロメーターを用いて、この液晶ポリエステルフィルムの厚さを測定したところ、その厚さは１３μｍであった。 <Comparative Example 1>
The maximum temperature during the heat treatment of the liquid crystal polyester precursor film was set to 320 ° C., and the temperature increase rate during the heat treatment of the liquid crystal polyester precursor film was set to 0.48 ° C./minute (specifically, from 30 ° C. A liquid crystal polyester film was produced by the same procedure as in Example 1 except that the temperature was raised to 320 ° C. over 10 hours. In addition, when the thickness of this liquid crystal polyester film was measured using the micrometer made from Mitutoyo Corporation, the thickness was 13 micrometers.
液晶ポリエステル前駆体フィルムの熱処理時の最高温度を３２０℃としたことと、液晶ポリエステル前駆体フィルムの熱処理時の昇温速度を０．４８℃／分としたこと（具体的には、３０℃から３２０℃まで１０時間かけて昇温したこと）を除き、上述した実施例１と同様の手順により、液晶ポリエステルフィルムを製造した。なお、（株）ミツトヨ製のマイクロメーターを用いて、この液晶ポリエステルフィルムの厚さを測定したところ、その厚さは１３μｍであった。 <Comparative Example 1>
The maximum temperature during the heat treatment of the liquid crystal polyester precursor film was set to 320 ° C., and the temperature increase rate during the heat treatment of the liquid crystal polyester precursor film was set to 0.48 ° C./minute (specifically, from 30 ° C. A liquid crystal polyester film was produced by the same procedure as in Example 1 except that the temperature was raised to 320 ° C. over 10 hours. In addition, when the thickness of this liquid crystal polyester film was measured using the micrometer made from Mitutoyo Corporation, the thickness was 13 micrometers.
＜比較例２＞
液晶ポリエステル前駆体フィルムの熱処理時の最高温度を３２０℃としたことと、液晶ポリエステル前駆体フィルムの熱処理時の昇温速度を０．１６℃／分としたこと（具体的には、３０℃から３２０℃まで３０時間かけて昇温したこと）を除き、上述した実施例１と同様の手順により、液晶ポリエステルフィルムを製造した。なお、（株）ミツトヨ製のマイクロメーターを用いて、この液晶ポリエステルフィルムの厚さを測定したところ、その厚さは１３μｍであった。 <Comparative Example 2>
The maximum temperature during the heat treatment of the liquid crystal polyester precursor film was set to 320 ° C., and the temperature increase rate during the heat treatment of the liquid crystal polyester precursor film was set to 0.16 ° C./minute (specifically, from 30 ° C. A liquid crystal polyester film was produced by the same procedure as in Example 1 except that the temperature was raised to 320 ° C. over 30 hours. In addition, when the thickness of this liquid crystal polyester film was measured using the micrometer made from Mitutoyo Corporation, the thickness was 13 micrometers.
液晶ポリエステル前駆体フィルムの熱処理時の最高温度を３２０℃としたことと、液晶ポリエステル前駆体フィルムの熱処理時の昇温速度を０．１６℃／分としたこと（具体的には、３０℃から３２０℃まで３０時間かけて昇温したこと）を除き、上述した実施例１と同様の手順により、液晶ポリエステルフィルムを製造した。なお、（株）ミツトヨ製のマイクロメーターを用いて、この液晶ポリエステルフィルムの厚さを測定したところ、その厚さは１３μｍであった。 <Comparative Example 2>
The maximum temperature during the heat treatment of the liquid crystal polyester precursor film was set to 320 ° C., and the temperature increase rate during the heat treatment of the liquid crystal polyester precursor film was set to 0.16 ° C./minute (specifically, from 30 ° C. A liquid crystal polyester film was produced by the same procedure as in Example 1 except that the temperature was raised to 320 ° C. over 30 hours. In addition, when the thickness of this liquid crystal polyester film was measured using the micrometer made from Mitutoyo Corporation, the thickness was 13 micrometers.
＜比較例３＞
液晶ポリエステル前駆体フィルムの熱処理時の最高温度を３２０℃としたことと、液晶ポリエステル前駆体フィルムの熱処理時の昇温速度を９．７℃／分としたこと（具体的には、３０℃から３２０℃まで３０分かけて昇温したこと）を除き、上述した実施例１と同様の手順により、液晶ポリエステルフィルムを製造した。なお、（株）ミツトヨ製のマイクロメーターを用いて、この液晶ポリエステルフィルムの厚さを測定したところ、その厚さは１４μｍであった。 <Comparative Example 3>
The maximum temperature during the heat treatment of the liquid crystal polyester precursor film was set to 320 ° C., and the temperature increase rate during the heat treatment of the liquid crystal polyester precursor film was set to 9.7 ° C./minute (specifically, from 30 ° C. A liquid crystal polyester film was produced by the same procedure as in Example 1 except that the temperature was raised to 320 ° C. over 30 minutes. In addition, when the thickness of this liquid crystal polyester film was measured using the micrometer made from Mitutoyo Corporation, the thickness was 14 micrometers.
液晶ポリエステル前駆体フィルムの熱処理時の最高温度を３２０℃としたことと、液晶ポリエステル前駆体フィルムの熱処理時の昇温速度を９．７℃／分としたこと（具体的には、３０℃から３２０℃まで３０分かけて昇温したこと）を除き、上述した実施例１と同様の手順により、液晶ポリエステルフィルムを製造した。なお、（株）ミツトヨ製のマイクロメーターを用いて、この液晶ポリエステルフィルムの厚さを測定したところ、その厚さは１４μｍであった。 <Comparative Example 3>
The maximum temperature during the heat treatment of the liquid crystal polyester precursor film was set to 320 ° C., and the temperature increase rate during the heat treatment of the liquid crystal polyester precursor film was set to 9.7 ° C./minute (specifically, from 30 ° C. A liquid crystal polyester film was produced by the same procedure as in Example 1 except that the temperature was raised to 320 ° C. over 30 minutes. In addition, when the thickness of this liquid crystal polyester film was measured using the micrometer made from Mitutoyo Corporation, the thickness was 14 micrometers.
＜比較例４＞
液晶ポリエステル前駆体フィルムを熱処理せず、そのまま液晶ポリエステルフィルムとした。
＜液晶ポリエステルフィルムの光透過性の評価＞ <Comparative Example 4>
The liquid crystal polyester precursor film was used as it was without being heat-treated.
<Evaluation of light transmittance of liquid crystal polyester film>
液晶ポリエステル前駆体フィルムを熱処理せず、そのまま液晶ポリエステルフィルムとした。
＜液晶ポリエステルフィルムの光透過性の評価＞ <Comparative Example 4>
The liquid crystal polyester precursor film was used as it was without being heat-treated.
<Evaluation of light transmittance of liquid crystal polyester film>
そして、（株）日立製作所製のＵ３５００型分光光度計に積分球を備え付け、実施例１～３、比較例１～４についてそれぞれ、波長６００ｎｍにおいて、液晶ポリエステルフィルムの光線透過率を測定した。その結果をまとめて表１に示す。
The U3500 spectrophotometer manufactured by Hitachi, Ltd. was equipped with an integrating sphere, and the light transmittance of the liquid crystal polyester film was measured for each of Examples 1 to 3 and Comparative Examples 1 to 4 at a wavelength of 600 nm. The results are summarized in Table 1.
表１から明らかなように、比較例１～３では、液晶ポリエステルフィルムの光線透過率が０～２５％と低く、光透過性に優れなかった。これに対して、実施例１～３では、液晶ポリエステルフィルムの光線透過率が５９～７７％と高く、光透過性に優れる結果が得られた。
As is clear from Table 1, in Comparative Examples 1 to 3, the light transmittance of the liquid crystal polyester film was as low as 0 to 25%, and the light transmittance was not excellent. On the other hand, in Examples 1 to 3, the light transmittance of the liquid crystal polyester film was as high as 59 to 77%, and the result of excellent light transmittance was obtained.
＜液晶ポリエステルフィルムのガスバリア性の評価＞
また、ＧＴＲテック（株）製の透湿度測定装置「ＧＴＲ－３０ＸＡＳＣ」を用いて、実施例１～３、比較例１～４についてそれぞれ、温度４０℃、相対湿度９０％の条件で液晶ポリエステルフィルムの透湿度（単位：ｇ／ｍ２・２４ｈ）を測定した。その結果をまとめて表１に示す。 <Evaluation of gas barrier properties of liquid crystal polyester film>
In addition, using a moisture permeability measuring device “GTR-30XASC” manufactured by GTR Tech Co., Ltd., Examples 1 to 3 and Comparative Examples 1 to 4 were each a liquid crystal polyester film at a temperature of 40 ° C. and a relative humidity of 90%. The water vapor permeability (unit: g / m 2 · 24 h) was measured. The results are summarized in Table 1.
また、ＧＴＲテック（株）製の透湿度測定装置「ＧＴＲ－３０ＸＡＳＣ」を用いて、実施例１～３、比較例１～４についてそれぞれ、温度４０℃、相対湿度９０％の条件で液晶ポリエステルフィルムの透湿度（単位：ｇ／ｍ２・２４ｈ）を測定した。その結果をまとめて表１に示す。 <Evaluation of gas barrier properties of liquid crystal polyester film>
In addition, using a moisture permeability measuring device “GTR-30XASC” manufactured by GTR Tech Co., Ltd., Examples 1 to 3 and Comparative Examples 1 to 4 were each a liquid crystal polyester film at a temperature of 40 ° C. and a relative humidity of 90%. The water vapor permeability (unit: g / m 2 · 24 h) was measured. The results are summarized in Table 1.
表１から明らかなように、実施例１～３および比較例１～３では、液晶ポリエステルフィルムの透湿度が０．３～０．５ｇ／ｍ２・２４ｈと低く、ガスバリア性が高い結果となった。これに対して、比較例４では、液晶ポリエステル前駆体フィルムを熱処理していないため、液晶ポリエステルフィルムの透湿度が１．９ｇ／ｍ２・２４ｈとなり、ガスバリア性が大幅に低下した。
As is clear from Table 1, in Examples 1 to 3 and Comparative Examples 1 to 3, the liquid crystal polyester film has a low water vapor transmission rate of 0.3 to 0.5 g / m 2 · 24 h, and has a high gas barrier property. It was. In contrast, in Comparative Example 4, since no heat treatment of the liquid crystal polyester precursor film, moisture permeability 1.9g / m 2 · 24h next liquid crystal polyester film, the gas barrier properties were significantly reduced.
本発明は、食品、医薬品、電子部品などの製品を包装する包装材料や、レンズ、フィルターなど各種の光学素子の材料その他、光透過性が要求される用途に広く適用することができる。
The present invention can be widely applied to packaging materials for packaging products such as foods, pharmaceuticals, and electronic parts, materials for various optical elements such as lenses and filters, and other uses that require light transmission.
Claims (5)
- 液晶ポリエステルおよび溶媒を含む液状組成物を基材上に流延して乾燥させて、前記溶媒を含んだ状態の液晶ポリエステル前駆体フィルムを調製する液晶ポリエステル前駆体フィルム調製工程と、
前記液晶ポリエステル前駆体フィルムを昇温することにより熱処理して、液晶ポリエステルフィルムを調製する液晶ポリエステルフィルム調製工程と
を含む液晶ポリエステルフィルムの製造方法であって、
前記液晶ポリエステルフィルム調製工程において、前記液晶ポリエステル前駆体フィルムの熱処理時の昇温速度を５℃／分以下とし、かつ前記液晶ポリエステル前駆体フィルムの熱処理時の最高温度を３００℃以下とする液晶ポリエステルフィルムの製造方法。 A liquid composition containing a liquid crystal polyester and a solvent is cast on a substrate and dried to prepare a liquid crystal polyester precursor film preparation step for preparing a liquid crystal polyester precursor film containing the solvent;
A liquid crystal polyester film manufacturing method comprising: a liquid crystal polyester film preparation step of preparing a liquid crystal polyester film by heat-treating the liquid crystal polyester precursor film by heating the liquid crystal polyester film,
In the liquid crystal polyester film preparation step, a liquid crystal polyester having a temperature rising rate during heat treatment of the liquid crystal polyester precursor film of 5 ° C./min or less and a maximum temperature during heat treatment of the liquid crystal polyester precursor film of 300 ° C. or less. A method for producing a film. - 前記液晶ポリエステルは、以下の式（１）、（２）および（３）で示される構造単位を有し、全構造単位の合計に対して、式（１）で示される構造単位が３０～８０モル％、式（２）で示される構造単位が３５～１０モル％、式（３）で示される構造単位が３５～１０モル％の液晶ポリエステルである請求項１に記載の液晶ポリエステルフィルムの製造方法。
（１）－Ｏ－Ａｒ１－ＣＯ－
（２）－ＣＯ－Ａｒ２－ＣＯ－
（３）－Ｘ－Ａｒ３－Ｙ－
（式中、Ａｒ１は、フェニレンまたはナフチレンを表し、Ａｒ２は、フェニレン、ナフチレンまたは下記式（４）で示される基を表し、Ａｒ３はフェニレンまたは下記式（４）で示される基を表し、ＸおよびＹは、それぞれ独立に、ＯまたはＮＨを表す。なお、Ａｒ１、Ａｒ２およびＡｒ３の芳香環に結合している水素原子は、ハロゲン原子、アルキル基またはアリール基で置換されていてもよい。）
（４）－Ａｒ１１－Ｚ－Ａｒ１２－
（式中、Ａｒ１１、Ａｒ１２は、それぞれ独立に、フェニレンまたはナフチレンを表し、Ｚは、Ｏ、ＣＯまたはＳＯ２を表す。） The liquid crystalline polyester has structural units represented by the following formulas (1), (2), and (3), and the structural unit represented by the formula (1) is 30 to 80 with respect to the total of all the structural units. 2. The production of the liquid crystalline polyester film according to claim 1, wherein the liquid crystalline polyester comprises a mol%, a structural unit represented by the formula (2) of 35 to 10 mol%, and a structural unit represented by the formula (3) of 35 to 10 mol%. Method.
(1) —O—Ar 1 —CO—
(2) —CO—Ar 2 —CO—
(3) —X—Ar 3 —Y—
(In the formula, Ar 1 represents phenylene or naphthylene, Ar 2 represents phenylene, naphthylene, or a group represented by the following formula (4), and Ar 3 represents phenylene or a group represented by the following formula (4). , X and Y each independently represent O or NH, wherein the hydrogen atom bonded to the aromatic ring of Ar 1 , Ar 2 and Ar 3 is substituted with a halogen atom, an alkyl group or an aryl group. May be.)
(4) -Ar 11 -Z-Ar 12 -
(In the formula, Ar 11 and Ar 12 each independently represent phenylene or naphthylene, and Z represents O, CO, or SO 2. ) - 前記溶媒が、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、Ｎ－メチルカプロラクタム、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジエチルホルムアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ－メチルプロピオンアミド、ジメチルスルホキシド、γ－ブチロラクトン、ジメチルイミダゾリジノン、テトラメチルホスホリックアミドおよびエチルセロソルブアセテートから選択される１種以上を含有している請求項１または２に記載の液晶ポリエステルフィルムの製造方法。 The solvent is N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N-methylpropionamide The method for producing a liquid crystal polyester film according to claim 1 or 2, comprising at least one selected from the group consisting of dimethyl sulfoxide, γ-butyrolactone, dimethylimidazolidinone, tetramethylphosphoric amide and ethyl cellosolve acetate.
- 前記液晶ポリエステル前駆体フィルム調製工程において、前記液状組成物を１６０℃以下で乾燥させ、
前記液晶ポリエステルフィルム調製工程において、前記液晶ポリエステル前駆体フィルムの熱処理時の最高温度を２００℃以上とする、請求項１～３のいずれか一項に記載の液晶ポリエステルフィルムの製造方法。 In the liquid crystal polyester precursor film preparation step, the liquid composition is dried at 160 ° C. or lower,
The method for producing a liquid crystal polyester film according to any one of claims 1 to 3, wherein in the liquid crystal polyester film preparation step, a maximum temperature during heat treatment of the liquid crystal polyester precursor film is set to 200 ° C or higher. - 以下の式（１）、（２）および（３）で示される構造単位を有し、全構造単位の合計に対して、式（１）で示される構造単位が３０～８０モル％、式（２）で示される構造単位が３５～１０モル％、式（３）で示される構造単位が３５～１０モル％の液晶ポリエステルからなる液晶ポリエステルフィルムであって、
波長６００ｎｍにおける光線透過率が５０％以上で、かつ透湿度が０．５ｇ／ｍ２・２４ｈ以下である液晶ポリエステルフィルム。
（１）－Ｏ－Ａｒ１－ＣＯ－
（２）－ＣＯ－Ａｒ２－ＣＯ－
（３）－Ｘ－Ａｒ３－Ｙ－
（式中、Ａｒ１は、フェニレンまたはナフチレンを表し、Ａｒ２は、フェニレン、ナフチレンまたは下記式（４）で示される基を表し、Ａｒ３はフェニレンまたは下記式（４）で示される基を表し、ＸおよびＹは、それぞれ独立に、ＯまたはＮＨを表す。なお、Ａｒ１、Ａｒ２およびＡｒ３の芳香環に結合している水素原子は、ハロゲン原子、アルキル基またはアリール基で置換されていてもよい。）
（４）－Ａｒ１１－Ｚ－Ａｒ１２－
（式中、Ａｒ１１、Ａｒ１２は、それぞれ独立に、フェニレンまたはナフチレンを表し、Ｚは、Ｏ、ＣＯまたはＳＯ２を表す。） The structural unit represented by the following formulas (1), (2) and (3) has a structural unit represented by the formula (1) of 30 to 80 mol%, A liquid crystal polyester film comprising a liquid crystal polyester having a structural unit represented by 2) of 35 to 10 mol% and a structural unit represented by formula (3) of 35 to 10 mol%,
A liquid crystal polyester film having a light transmittance at a wavelength of 600 nm of 50% or more and a moisture permeability of 0.5 g / m 2 · 24 h or less.
(1) —O—Ar 1 —CO—
(2) —CO—Ar 2 —CO—
(3) —X—Ar 3 —Y—
(In the formula, Ar 1 represents phenylene or naphthylene, Ar 2 represents phenylene, naphthylene, or a group represented by the following formula (4), and Ar 3 represents phenylene or a group represented by the following formula (4). , X and Y each independently represent O or NH, wherein the hydrogen atom bonded to the aromatic ring of Ar 1 , Ar 2 and Ar 3 is substituted with a halogen atom, an alkyl group or an aryl group. May be.)
(4) -Ar 11 -Z-Ar 12 -
(In the formula, Ar 11 and Ar 12 each independently represent phenylene or naphthylene, and Z represents O, CO, or SO 2. )
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| JP2008195786A (en) * | 2007-02-09 | 2008-08-28 | Sumitomo Chemical Co Ltd | Solution composition |
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| JPH08281817A (en) * | 1995-04-11 | 1996-10-29 | Sumitomo Chem Co Ltd | Wholly aromatic liquid crystal polyester film and manufacture thereof |
| JPH1160757A (en) * | 1997-08-18 | 1999-03-05 | Sumitomo Chem Co Ltd | Bag for liquid |
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| CN112625226B (en) * | 2020-06-02 | 2024-03-15 | 长兴材料工业股份有限公司 | Aromatic liquid crystal polyester, liquid crystal polyester composition and method for preparing liquid crystal polyester film |
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