JP2008100528A - Aromatic liquid crystal polyester and film thereof - Google Patents

Abstract

A laminate comprising an aromatic liquid crystal polyester film having a small dielectric loss in a wide frequency range and a metal layer is provided.
[Solution]
Repeating structural units. 30 to 60 mol% derived from 2-hydroxy-6-naphthoic acid, the repeating structural units. 35 to 20 mol% derived from a specific aromatic diol, and repeating structural units derived from a specific aromatic dicarboxylic acid Provided is a laminate comprising a film made of an aromatic liquid crystal polyester substantially composed of 35 to 20 mol% and having an intrinsic viscosity in the range of 0.3 to 5, and a metal layer .
[Selection figure] None

Description

The present invention relates to a laminate of an aromatic liquid crystal polyester film and a metal layer .

Aromatic liquid crystal polyesters are widely used in electronic parts such as connectors because of their low water absorption and excellent heat resistance and thin moldability. Aromatic liquid-crystalline polyesters are also used for high-frequency multilayer printed boards because of their low dielectric loss in the high-frequency range.
As conventional aromatic liquid crystal polyesters, those mainly composed of a repeating structural unit derived from parahydroxybenzoic acid are well known (see Patent Document 1). However, a repeating structural unit derived from parahydroxybenzoic acid is known. The aromatic liquid crystal polyester as the main component has a small dielectric loss in the gigahertz band, but there is still room for improvement in the dielectric loss at the frequency in the megahertz band.

JP2002-179776

An object of the present invention is to provide a laminate comprising an aromatic liquid crystal polyester film having a small dielectric loss in a wide frequency range and a metal layer .

As a result of intensive studies to find an aromatic liquid crystal polyester that can solve the above-described problems, the present inventors have found that 30 to 60 mol% of repeating structural units derived from 2-hydroxy-6-naphthoic acid, aromatic repeating structural units. 35 to 20 mol% derived from family diols, and aromatic liquid crystal polyester consisting essentially of repeating structural units. 35 to 20 mol% derived from aromatic dicarboxylic acids, it small dielectric loss in a wide frequency range As a result, the present invention has been completed.

That is, the present invention is at least selected from the group consisting of 30 to 60 mol% of repeating structural units derived from 2-hydroxy-6-naphthoic acid, hydroquinone, resorcinol, 4,4′-dihydroxybiphenyl, bisphenol A and bisphenol S. At least one compound ( aromatic dicarboxylic acid ) selected from the group consisting of 35 to 20 mol% of repeating structural units derived from one kind of compound ( aromatic diol ) and terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid ) substantially becomes a repeating structural unit. 35 to 20 mol% derived from the intrinsic viscosity of the aromatic liquid-crystalline polyester is in the range of 0.3 to 5 film (the aromatic liquid-crystalline polyester film), the metal layer A laminated body is provided.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the laminated body provided with the aromatic liquid crystal polyester film with a small dielectric loss in a wide frequency range.

The present invention will be described in detail below.
The aromatic liquid crystal polyester used in the present invention is a polyester called a thermotropic liquid crystal polymer that exhibits optical anisotropy when melted, and includes a repeating structural unit derived from 2-hydroxy-6-naphthoic acid and an aromatic diol. It consists essentially of a repeating structural unit derived from and a repeating structural unit derived from an aromatic dicarboxylic acid.
In order to obtain the aromatic liquid crystal polyester of the present invention, ester-forming derivatives of 2-hydroxy-6-naphthoic acid, aromatic diol, and aromatic dicarboxylic acid may be used.

Examples of ester-forming derivatives of carboxylic acids include those in which the carboxyl group is a highly reactive derivative such as an acid chloride or acid anhydride that promotes the polyester formation reaction, and the carboxyl group is transesterified. Examples include those that form esters with alcohols, ethylene glycol, or the like that generate polyester by 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.

  In addition, aromatic dicarboxylic acids and aromatic diols are halogen atoms such as chlorine atoms and fluorine atoms, alkyl groups such as methyl groups and ethyl groups, aryl groups such as phenyl groups, etc., as long as they do not inhibit ester formation. May be substituted.

The repeating structural unit derived from 2-hydroxy-6-naphthoic acid needs to be contained in an amount of 30 to 60 mol%, preferably 35 to 60 mol%, and preferably 40 to 60 mol% of the whole aromatic liquid crystal polyester. It is more preferable that it is contained.
When the repeating structural unit derived from 2-hydroxy-6-naphthoic acid is less than 30 mol%, the obtained aromatic liquid crystal polyester does not exhibit liquid crystallinity, and when it exceeds 80 mol%, it melts or dissolves in an organic solvent. It becomes difficult to process.

Repeating units derived from aromatic dicarboxylic acids are repeating structural units derived from at least one compound selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalene dicarboxylic acid.
From the viewpoint of heat resistance, it is preferably a repeating structural unit derived from terephthalic acid or a repeating structural unit derived from two types of compounds of terephthalic acid and 2,6-naphthalenedicarboxylic acid, from the viewpoint of low thermal expansion. Is preferably a repeating structural unit derived from 2,6-naphthalenedicarboxylic acid, and is preferably a repeating structural unit derived from isophthalic acid from the viewpoint of solubility in a solvent.

Repeating units derived from aromatic diols are hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, is a repeating structural unit derived from at least one compound selected from the group consisting of bisphenol A and bisphenol S, heat resistance, From the viewpoint of low thermal expansion, it is preferably a repeating structural unit derived from 4,4′-dihydroxybiphenyl.

The repeating structural unit derived from the aromatic dicarboxylic acid needs to be contained in an amount of 35 to 20 mol% of the entire aromatic liquid crystal polyester, preferably 32.5 to 20 mol%, and preferably 30 to 20 mol%. Is more preferable.
The repeating structural unit derived from the aromatic diol needs to be contained in an amount of 35 to 20 mol%, preferably 32.5 to 20 mol%, and preferably 30 to 20 mol% of the entire aromatic liquid crystal polyester. More preferred.
The molar ratio of the repeating structural unit derived from the aromatic dicarboxylic acid and the repeating structural unit derived from the aromatic diol is preferably 95/100 to 100/95. Outside this range, the degree of polymerization does not increase and the mechanical strength tends to decrease.

The aromatic liquid crystal polyester used in the present invention has a tendency that when the degree of polymerization is low, the mechanical properties tend to be lowered. Therefore , its intrinsic viscosity is 0.3 or more , and more preferably 0.5 or more.
On the other hand, when the degree of polymerization is high, the melt viscosity or solution viscosity tends to increase, and the processability tends to decrease. Therefore , the intrinsic viscosity is 5 or less, and more preferably 3.3 or less.
From the balance of mechanical properties and workability, the intrinsic viscosity is particularly preferably 0.5 to 3.

The method for producing the aromatic liquid crystal polyester used in the present invention is not particularly limited. For example, at least one selected from the group consisting of 2-hydroxy-6-naphthoic acid and aromatic diol is added with an excess amount of fatty acid anhydride. Acylation product is obtained by acylation, and melt polymerization is performed by transesterification (polycondensation) of the obtained acylation product and at least one selected from the group consisting of 2-hydroxy-6-naphthoic acid and aromatic dicarboxylic acid. The method of doing is mentioned. As the acylated product, a fatty acid ester obtained by acylation in advance may be used (see JP 2002-220444, JP 2002-146003).

  In the acylation reaction, 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 phenolic hydroxyl group. When the amount of fatty acid anhydride added is less than 1.0 equivalent, acylated products, 2-hydroxy-6-naphthoic acid, aromatic dicarboxylic acid and the like tend to sublimate during transesterification (polycondensation), and the reaction system tends to block. When the amount exceeds 1.2 times equivalent, the resulting aromatic liquid crystal polyester tends to be remarkably colored.

  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, and examples thereof include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, anhydrous 2-ethylhexanoic acid, and 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 handleability, acetic anhydride, propionic anhydride, butyric anhydride, and isobutyric anhydride are preferable, and acetic anhydride is more preferable.

  In the transesterification, the acyl group of the acylated product is preferably 0.8 to 1.2 times the carboxyl group.

  The transesterification is preferably performed while increasing the temperature at 130 to 400 ° C. at a rate of 0.1 to 50 ° C./min, and at 150 to 350 ° C. while increasing the temperature at a rate of 0.3 to 5 ° C./min. It is more preferable.

  When transesterifying a fatty acid ester obtained by acylation with a carboxylic acid, it is preferable to distill out the by-product fatty acid and the unreacted fatty acid anhydride by evaporating or the like in order to move the equilibrium. .

The acylation reaction and transesterification may be performed in the 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 an organic compound catalyst 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 are preferably used (Japanese Patent Laid-Open No. 2002-146003).
The catalyst is usually added when the monomers are added, and it is not always necessary to remove the catalyst after acylation. If the catalyst is not removed, transesterification can be carried out as it is.

Polycondensation by transesterification is usually performed by melt polymerization, but melt polymerization and solid phase polymerization may be used in combination. The solid phase polymerization is preferably carried out by a known solid phase polymerization method after the polymer is extracted from the melt polymerization step and then 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 crystalline polyester may be pelletized and molded by a known method.
The aromatic liquid crystal polyester can be produced using, for example, a batch apparatus, a continuous apparatus or the like.

In the aromatic liquid crystal polyester used in the present invention, known fillers, additives and the like may be added as long as the object of the present invention is not impaired.
Examples of the filler include epoxy resin powder, melamine resin powder, urea resin powder, benzoguanamine resin powder, polyester resin powder, organic filler such as styrene resin, silica, alumina, titanium oxide, zirconia, kaolin, calcium carbonate, calcium phosphate. And inorganic fillers.
Examples of the additive include known coupling agents, anti-settling agents, ultraviolet absorbers, and heat stabilizers.

In addition, the aromatic liquid crystal polyester used in the present invention includes polypropylene, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenyl ether, and modified products thereof within a range not impairing the object of the present invention. In addition, one or two or more thermoplastic resins such as polyetherimide and elastomers such as a copolymer of glycidyl methacrylate and polyethylene may be added.

Aromatic liquid crystal polyester film is a method in which aromatic liquid crystal polyester is melted to form a film (hereinafter referred to as melting method) . Aromatic liquid crystal polyester is dissolved in an organic solvent to obtain a solution, and the organic solvent is removed from the solution. (Hereinafter referred to as a melt casting method).
As a film obtained by the melting method, an aromatic liquid crystalline polyester is melt-kneaded with an extruder, and a uniaxially oriented film obtained by winding the molten resin extruded through a T-die while stretching it in the direction of the winder (longitudinal direction). Or a biaxially stretched film.

  Although the setting conditions of the extruder at the time of manufacture of a uniaxially oriented film can be appropriately set according to the monomer composition of the aromatic liquid crystal polyester, the set temperature of the cylinder is preferably 200 to 400 ° C, more preferably 230 to 380 ° C. When the set temperature of the cylinder is outside this range, the aromatic liquid crystal polyester tends to be thermally decomposed or film formation tends to be difficult.

  The slit interval of the T die is preferably 0.1 to 2 mm. The draft ratio of the uniaxially oriented film in the present invention is preferably in the range of 1.1 to 45. The draft ratio here refers to a value obtained by dividing the cross-sectional area of the T-die slit by the film cross-sectional area in the longitudinal direction. When the draft ratio is less than 1.1, the film strength tends to be insufficient, and when the draft ratio exceeds 45, the surface smoothness of the film tends to be insufficient. The draft ratio can be adjusted by the setting conditions of the extruder, the winding speed, and the like.

  The biaxially stretched film has the same extruder setting conditions as the uniaxially oriented film, that is, the cylinder set temperature is preferably 200 to 400 ° C., more preferably 230 to 380 ° C., and the T-die slit interval is preferably 0.1 to A method in which melt extrusion is performed in the range of 2 mm and the melt sheet extruded from the T die is stretched simultaneously in the longitudinal direction and the longitudinal direction (transverse direction), or the melt sheet extruded from the T die is first in the longitudinal direction. Then, the stretched sheet can be obtained by a sequential stretching method in which the stretched sheet is stretched in the transverse direction from the tenter at a high temperature of 100 to 400 ° C. in the same process.

  The stretching ratio of the biaxially stretched film is preferably in the range of 1.1 to 20 times in the longitudinal direction and 1.1 to 20 times in the transverse direction. If the stretch ratio is out of the above range, the strength of the obtained film tends to be insufficient, or it becomes difficult to obtain a film having a uniform thickness.

  An inflation film can also be obtained by forming a melt sheet extruded from a cylindrical die by an inflation method.

The inflation film can be produced by the following method.
Aromatic liquid crystal polyester is supplied to a melt kneading extruder equipped with a die having an annular slit, and melt kneading is preferably performed at a cylinder set temperature of 200 to 400 ° C, more preferably 230 to 380 ° C. A cylindrical aromatic liquid crystal polyester film is extruded upward or downward from the slit. The interval between the annular slits is usually 0.1 to 5 mm, preferably 0.2 to 2 mm, and the diameter of the annular slit is usually 20 to 100 mm, preferably 25 to 600 mm.

  A draft is applied in the longitudinal direction (MD) to the melt-extruded tubular molten resin film, and air or an inert gas such as nitrogen gas is blown from the inside of the tubular melt-resin film so that the longitudinal direction The film is stretched and stretched in the transverse direction (TD) at right angles.

The blow-up ratio (the ratio between the final tube diameter and the initial diameter) is preferably 1.5 to 10, and the preferred MD stretch ratio is 1.5 to 40. If it is out of the above range, it tends to be difficult to obtain a high-strength aromatic liquid crystal polyester film having a uniform thickness and no wrinkles.
The film stretched and stretched is air-cooled or water-cooled, and then passed through a nip roll and taken off.

  In the inflation film formation, it is preferable to select conditions such that the cylindrical melt film expands to a smooth surface with a uniform thickness according to the composition of the aromatic liquid crystal polyester.

（Ｉ）
式中、Aはハロゲン原子を表わすか、トリハロゲン化メチル基を表わし、ｉは１〜５の整数を表わす。ｉが２以上の場合、複数あるＡは互いに同一でも異なっていてもよいが、同一であることが好ましい。 In the case of producing an aromatic liquid crystal polyester film by the solution casting method, the organic solvent to be used is not particularly limited as long as the aromatic liquid crystal polyester can be dissolved, but a halogen-substituted phenol compound represented by the following general formula (I) is used. A solvent containing 30% by weight or more is preferably used because it can dissolve the aromatic liquid crystal polyester at room temperature or under heating.
Further, since the aromatic liquid crystalline polyester can be dissolved at a relatively low temperature, a solvent containing 60% by weight or more of the halogen-substituted phenol compound (I) is more preferable, and it is not necessary to mix with other components. ) Is substantially preferably 100% by weight of solvent.

(I)
In the formula, A represents a halogen atom or a trihalogenated methyl group, and i represents an integer of 1 to 5. When i is 2 or more, a plurality of A may be the same or different from each other, but are preferably the same.

(II)
式中、A’は、水素原子またはハロゲン原子を表わすか、トリハロゲン化メチル基を表わし、ｉは１〜５の整数を表わす。ｉが２以上の場合、複数あるＡは互いに同一でも異なっていてもよいが、同一であることが好ましい。 Further, the organic solvent is preferably a solvent containing 30% by weight or more of the halogen-substituted phenol compound represented by the following general formula (II) because the aromatic liquid crystal polyester can be dissolved at a relatively low temperature. A solvent containing 60% by weight or more of II) is more preferable, and a substance containing substantially 100% by weight of the halogen-substituted phenol compound (II) is more preferable because it does not need to be mixed with other components.

(II)
In the formula, A ′ represents a hydrogen atom or a halogen atom, or a trihalogenated methyl group, and i represents an integer of 1 to 5. When i is 2 or more, a plurality of A may be the same or different from each other, but are preferably the same.

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.
Examples of the general formula (I) in which the halogen atom is a fluorine atom include pentafluorophenol and tetrafluorophenol.
Examples of the general formula (I) in which the halogen atom is a chlorine atom include o-chlorophenol and p-chlorophenol, and p-chlorophenol is preferred from the viewpoint of solubility.
Examples of the halogen of the trihalogenated methyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the general formula (I) in which the halogen of the trihalogenated methyl group is a fluorine atom include 3,5-bistrifluoromethylphenol.
As the solvent, a solvent containing 30% by weight or more of a chlorine-substituted phenol compound such as o-chlorophenol and p-chlorophenol is preferably used from the viewpoint of cost and availability, and p-chlorophenol is used from the viewpoint of solubility. A solvent containing 30% by weight or more is more preferably used.

p-Chlorophenol may further have a substituent, and the phenol compound represented by the above general formula (II) is preferable from the viewpoint of price and availability.
Examples of the halogen-substituted phenol compound (II) include 2,4-dichlorophenol, 3,4-dichlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol. Of these, 2,4-dichlorophenol and 3,4-dichlorophenol are preferably used.

The solvent used in the present invention may contain other components in addition to the halogen-substituted phenol compound as long as the aromatic liquid crystal polyester is not precipitated during storage of the solution or casting described later.
Other components that may be contained are not particularly limited, and examples thereof include chlorine compounds such as chloroform, methylene chloride, and tetrachloroethane.

  The aromatic liquid crystalline polyester is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the solvent containing 30% by weight or more of the halogen-substituted phenol compound, and from the viewpoint of workability or economy, 0.5 to The amount is more preferably 50 parts by weight, and further preferably 1 to 10 parts by weight. If the amount is less than 0.1 parts by weight, the production efficiency tends to decrease, and if it exceeds 100 parts by weight, dissolution tends to be difficult.

  In the solution casting method, a solution obtained by dissolving an aromatic liquid crystal polyester in an organic solvent is filtered through a filter as necessary, and after removing fine foreign matters contained in the solution, , Cast evenly and uniformly by various means such as roller coating, dip coating, spray coating, spinner coating, curtain coating, slot coating, and screen printing, and then remove the organic solvent Thus, an aromatic liquid crystal polyester film can be obtained.

  The method for removing the organic solvent is not particularly limited, but it is preferably performed by evaporation of the solvent. Examples of the method for evaporating the solvent include methods such as heating, reduced pressure, and ventilation. Among them, it is preferable to evaporate by heating from the viewpoint of production efficiency and handleability, and it is more preferable to evaporate by heating while ventilating. preferable. The heating conditions at this time preferably include a step of performing preliminary drying at 80 to 100 ° C. for 30 minutes to 2 hours and a step of performing heat treatment at 180 to 300 ° C. for 30 minutes to 4 hours.

  The thickness of the aromatic liquid crystal polyester film thus obtained is not particularly limited, but is preferably 0.5 to 500 μm from the viewpoint of film forming properties and mechanical properties, and 1 to 100 μm from the viewpoint of handleability. It is more preferable that

The aromatic liquid-crystalline polyester film, a laminated body by laminating a metal layer.
In laminating the metal layer, it is preferable to perform corona discharge treatment, ultraviolet irradiation treatment, or plasma treatment on the surface of the aromatic liquid crystal polyester film on which the metal layer is laminated in order to increase the adhesion.

As a method for laminating a metal layer on the aromatic liquid-crystalline polyester film, for example, it can be exemplified the following method.
(1) Aromatic liquid crystalline polyester is dissolved in an organic solvent to obtain an aromatic polyester solution. If necessary, this is filtered through a filter to remove fine foreign matters contained in the solution, and then the solution is converted to a metal. On the foil, the surface is evenly and uniformly cast by various means such as a roller coating method, a dip coating method, a spray coating method, a spinner coating method, a curtain coating method, a slot coating method, and a screen printing method. A method of laminating an aromatic polyester film obtained by removing a solvent and a metal foil.
(2) A method of attaching an aromatic polyester film obtained by the above-described melt casting method to a metal foil by thermocompression bonding.
(3) A method of sticking the aromatic polyester film obtained by the above-described melt casting method and a metal foil with an adhesive.
(4) A method of forming a metal layer by vapor deposition on the aromatic polyester film obtained by the melt casting method described above.

  The method (1) is preferable because a laminate having a uniform film thickness and high adhesion to the metal foil can be easily obtained.

  The method (2) is preferable because the aromatic liquid crystal polyester film can be easily pressure-bonded to the metal foil using a press or a heating roll near the flow start temperature of the film.

  In the method (3), the adhesive used is not particularly limited, and examples thereof include a hot melt adhesive and a polyurethane adhesive. Among them, an epoxy group-containing ethylene copolymer is preferably used as an adhesive.

  In the method (4), the method for depositing the metal is not particularly limited, and examples thereof include an ion beam sputtering method, a high frequency sputtering method, a direct current magnetron sputtering method, and a glow discharge method. Among these, a high frequency sputtering method is preferably used.

  Examples of the metal used for the metal layer in the present invention include gold, silver, copper, nickel, and aluminum. Copper is preferred for tab tape and printed wiring board applications, and aluminum is preferred for capacitor applications.

Examples of the structure of the laminate thus obtained include a two-layer structure of an aromatic liquid crystal polyester film and a metal layer, a three-layer structure in which a metal layer is laminated on both surfaces of an aromatic liquid crystal polyester film, and an aromatic liquid crystal polyester. Examples include a five-layer structure in which films and metal layers are alternately laminated.
Moreover, you may heat-process this laminated body as needed for the purpose of high intensity | strength expression.

  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.

Production Example 1
In a reactor equipped with a stirrer, a torque meter, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 752.72 g (4.00 mol) of 2-hydroxy-6-naphthoic acid and 220.22 g of hydroquinone (2.00 mol) ), 432.38 g (2.00 mol) of 2,6-naphthalenedicarboxylic acid, 986.19 (9.2 mol) of acetic anhydride and 0.143 g of 1-methylimidazole as a catalyst were added and stirred at room temperature for 15 minutes. Then, it heated up, stirring. When the internal temperature reached 145 ° C., the mixture was stirred for 1 hour while maintaining the same temperature.
Next, the temperature was raised from 145 ° C. to 310 ° C. over 3 hours while distilling off distilling by-product acetic acid and unreacted acetic anhydride. Thereafter, 1.427 g of 1-methylimidazole was further added, and the mixture was kept at the same temperature for 30 minutes to obtain an aromatic polyester. The obtained aromatic polyester was cooled to room temperature and pulverized by a pulverizer to obtain an aromatic polyester powder (particle diameter of about 0.1 mm to about 1 mm).
The powder obtained above was heated from 25 ° C. to 250 ° C. over 1 hour, then heated from the same temperature to 320 ° C. over 5 hours, and then kept at that temperature for 3 hours for solid phase polymerization. Thereafter, the solid-phase polymerized powder was cooled, and the cooled powder (aromatic polyester) was measured for flow start temperature using a flow tester (manufactured by Shimadzu Corporation, “CFT-500 type”). It was 333 ° C.

Production Example 2
In a reactor equipped with a stirrer, a torque meter, a nitrogen gas introduction tube, a thermometer and a reflux condenser, 191.8 g (1.02 mol) of 2-hydroxy-6-naphthoic acid and 4,4′-dihydroxybiphenyl 63. 3 g (0.34 mol), 56.5 g (0.34 mol) of isophthalic acid and 191 g (1.87 mol) of acetic anhydride 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, the temperature was raised to 320 ° C. over 170 minutes while distilling off the 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 obtained solid content was cooled to room temperature, pulverized with a coarse pulverizer, held at 250 ° C. for 10 hours in a nitrogen atmosphere, and the polymerization reaction was advanced in a solid layer. The obtained aromatic liquid crystalline polyester was dissolved in p-chlorophenol, and the intrinsic viscosity was measured at 60 ° C. to be 2.1.

Production Example 3
In a reactor equipped with a stirrer, a torque meter, a nitrogen gas introduction tube, a thermometer and a reflux condenser, 140.8 g (1.02 mol) of p-hydroxybenzoic acid, 63.3 g of 4,4′-dihydroxybiphenyl ( 0.34 mol), 56.5 g (0.34 mol) of isophthalic acid, and 191 g (1.87 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.
Thereafter, the temperature was raised to 320 ° C. over 170 minutes while distilling off the 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 obtained solid content was cooled to room temperature, pulverized with a coarse pulverizer, held at 250 ° C. for 10 hours in a nitrogen atmosphere, and the polymerization reaction was advanced in a solid layer. The obtained aromatic liquid crystalline polyester was dissolved in p-chlorophenol, and the intrinsic viscosity was measured at 60 ° C. and found to be 1.5.

Reference example 1
The resin powder obtained in Production Example 1 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. The dielectric constant and dielectric loss of the obtained test piece were measured with an impedance material analyzer manufactured by Hewlett-Packard Co., Ltd. The results are shown in Table 1.

Reference example 2
The resin powder obtained in Production Example 2 was pressed at 290 ° C. for 10 minutes under a load of 100 kgf to obtain a test piece having a thickness of 2 mm. The dielectric constant and dielectric loss of the obtained test piece were measured with an impedance material analyzer manufactured by Hewlett-Packard Co., Ltd. The results are shown in Table 1.

Reference example 3
The resin powder obtained in Production Example 3 was pressed at 290 ° C. for 10 minutes under a load of 100 kgf to obtain a test piece having a thickness of 2 mm. The dielectric constant and dielectric loss of the obtained test piece were measured with an impedance material analyzer manufactured by Hewlett-Packard Co., Ltd. The results are shown in Table 1.

Reference example 4
The aromatic liquid crystal polyester obtained in Production Example 1 was melted in a single screw extruder (screw diameter 50 mm), and from a T die (lip length 300 mm, lip clearance 1 mm, die temperature 360 ° C.) at the tip of the extruder. The film was extruded in the form of a film under a draft ratio of 4 and cooled to obtain a film having a thickness of 250 μm.

Reference Example 5
As a result of adding 1 g of the aromatic liquid crystalline polyester powder obtained in Production Example 2 to 9 g of p-chlorophenol and heating to 120 ° C., it was confirmed that a completely dissolved and transparent solution was obtained. This solution was stirred and degassed to obtain an aromatic liquid crystal polyester solution. The obtained solution was bar-coated on a glass plate and then heat-treated at 100 ° C. for 1 hour and at 250 ° C. for 1 hour. A film was obtained by peeling from the glass substrate.

Example 1
As a result of adding 1 g of the aromatic liquid crystalline polyester powder obtained in Production Example 2 to 9 g of p-chlorophenol and heating to 120 ° C., it was confirmed that a completely dissolved and transparent solution was obtained. This solution was stirred and degassed to obtain an aromatic liquid crystal polyester solution. The obtained solution was bar-coated on a matte surface of 18 μm copper foil and then heat-treated at 100 ° C. for 1 hour and at 250 ° C. for 1 hour. The 90 ° peel strength of the copper foil was measured and found to be 0.8 N / mm.

Claims (8)

30-60 mol% of repeating structural units derived from 2-hydroxy-6-naphthoic acid,
Hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, repeating structural units. 35 to 20 mol% derived from at least one compound selected from the group consisting of bisphenol A and bisphenol S,
And substantially consisting of 35 to 20 mol% of repeating structural units derived from at least one compound selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid , and an intrinsic viscosity of 0.3 to 5 A laminate of a film made of an aromatic liquid crystal polyester in a range of 5 and a metal layer . 2. The aromatic diol is 4,4′-dihydroxybiphenyl, and the aromatic dicarboxylic acid is at least one compound selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid. Laminated body . The laminate according to claim 1 or 2, wherein the aromatic diol is 4,4'-dihydroxybiphenyl and the aromatic dicarboxylic acid is isophthalic acid. It said film, to obtain a solution by dissolving the aromatic liquid crystalline polyester in an organic solvent, according to claim 1, characterized in that it is a film obtained by removing the organic solvent from the solution Laminated body . The organic solvent is represented by the following general formula (I)

(I)
(In the formula, A represents a hydrogen atom or a halogen atom, or represents a trihalogenated methyl group, and i represents an integer of 1 to 5)
The laminate according to claim 4, which is an organic solvent containing 30% by weight or more of the halogen-substituted phenol compound represented by the formula: The organic solvent is represented by the following general formula (II)

(II)
(In the formula, A ′ represents a hydrogen atom or a halogen atom, or a trihalogenated methyl group, and i represents an integer of 1 to 4)
The laminate according to claim 4, which is an organic solvent containing 30% by weight or more of the halogen-substituted phenol compound represented by the formula: Said film laminate according to claim 1, characterized in that it is a film obtained by melt extrusion of the aromatic liquid crystal polyester. It said film laminate according to any one of claims 1 to 3, characterized in that the aromatic liquid crystal polyester is a film obtained by inflation molding.