JP4639756B2 - Aromatic liquid crystal polyester and film thereof and use thereof - Google Patents

Description

  The present invention relates to an aromatic liquid crystal polyester and a film thereof and uses thereof.

  Aromatic liquid crystalline polyesters are widely used in electronic parts such as connectors obtained by injection molding because of their low water absorption and excellent heat resistance, thin moldability and the like. In addition, since it is a material with low dielectric loss and excellent electrical properties, recently, methods for forming aromatic liquid crystal polyester into a film by T-die extrusion method, inflation method, solution casting method, etc. have been studied. Laminates with layers have been proposed for use as multilayer printed boards and the like, for example, aromatic polyesters mainly composed of repeating structural units derived from parahydroxybenzoic acid have been proposed (Patent Document 1). ).

JP 2002-359145 A

  Conventionally known aromatic liquid crystal polyesters are often inferior in film processability, and those having good film processability often have insufficient basic physical properties such as heat resistance. Under such circumstances, the film described in Patent Document 1 was excellent in balance between heat resistance and film processability, but the dielectric loss was not sufficiently small. An object of the present invention is to provide an aromatic liquid crystal polyester film having an excellent balance between heat resistance and film processability and low dielectric loss, an aromatic liquid crystal polyester used for the preparation thereof, and uses thereof.

（ここで、Ar₁およびAr₂はそれぞれ独立に１,４−フェニレン、またはパラ位でつながるフェニレン数２以上の二価の残基から選ばれる基である。）
〔２〕前記の〔１〕に記載の芳香族液晶ポリエステルを溶融成形して得られる芳香族液晶ポリエステルフィルムを提供するものであり、
〔３〕前記の〔２〕に記載の芳香族液晶ポリエステルフィルムからなる絶縁層と金属層とを含む積層体を提供するものであり、
〔４〕前記の〔１〕に記載の芳香族液晶ポリエステル１００重量部と充填剤１０〜４００重量部とを含む芳香族液晶ポリエステル樹脂組成物を提供するものであり、
〔５〕前記の〔４〕に記載の芳香族液晶ポリエステル樹脂組成物を射出成形して得られる成形体を提供するものである。 The present invention
[1] Consists of repeating structural units represented by the following formulas (I), (II), (III) and (IV), and (I) with respect to the total of repeating structural units of these (I) to (IV) The repeating structural unit is 40 to 74.8 mol%, the repeating structural unit (II) is 12.5 to 30 mol%, the repeating structural unit (III) is 12.5 to 30 mol% and the repeating unit (IV) The structural unit is 0.2 to 15 mol%, and the molar ratio of the repeating structural units represented by (III) and (IV) is (III) / {(III) + (IV)} ≧ 0.5 An aromatic liquid crystal polyester that satisfies the relationship is provided.

(Here, Ar ₁ and Ar ₂ are each independently 1,4-phenylene, or a group selected from divalent residues having 2 or more phenylenes connected at the para position.)
[2] An aromatic liquid crystal polyester film obtained by melt-molding the aromatic liquid crystal polyester according to the above [1] is provided.
[3] A laminate including an insulating layer and a metal layer made of the aromatic liquid crystal polyester film according to [2] is provided.
[4] An aromatic liquid crystal polyester resin composition comprising 100 parts by weight of the aromatic liquid crystal polyester according to the above [1] and 10 to 400 parts by weight of a filler,
[5] A molded article obtained by injection molding the aromatic liquid crystal polyester resin composition described in [4] is provided.

  According to the present invention, it is possible to provide an aromatic liquid crystal polyester having a small dielectric loss and excellent workability into a film shape.

（ここで、Ar₁およびAr₂はそれぞれ独立に１,４−フェニレン、またはパラ位でつながるフェニレン数２以上の二価の残基から選ばれる基である。） The aromatic liquid crystal polyester of the present invention is an aromatic liquid crystal polyester composed of repeating structural units represented by the following formulas (I), (II), (III) and (IV).

(Here, Ar ₁ and Ar ₂ are each independently 1,4-phenylene, or a group selected from divalent residues having 2 or more phenylenes connected at the para position.)

  In the aromatic liquid crystalline polyester of the present invention, the repeating structural unit of (I) is 40 to 74.8 mol% based on the total of repeating structural units of the above formulas (I) to (IV), and the repeating structure of (II) The unit is 12.5 to 30 mol%, the repeating structural unit (III) is 12.5 to 30 mol% and the repeating structural unit (IV) is 0.2 to 15 mol%, and (III) and (III) The molar ratio of the repeating structural unit represented by IV) satisfies the relationship of (III) / {(III) + (IV)} ≧ 0.5.

The aromatic liquid crystalline polyester of the present invention more preferably has 40 to 64.5 mol% of the repeating structural unit of (I) based on the total number of repeating structural units of the above formulas (I) to (IV), (II) 17.5-30 mol% of the repeating structural unit of (III), 17.5-30 mol% of the repeating structural unit of (III) and 0.5-12 mol% of the repeating structural unit of (IV), and (III ) And (IV) satisfying the molar ratio of repeating structural units of (III) / {(III) + (IV)} ≧ 0.6 is preferable because of excellent heat resistance and film processability.
More preferably, the repeating structural unit of (I) is 50 to 58 mol%, the repeating structural unit of (II) is 20 to 25 mol%, based on the total of repeating structural units of the formulas (I) to (IV). The repeating structural unit (III) is 20 to 25 mol% and the repeating structural unit (IV) is 2 to 10 mol%, and the molar ratio of the repeating structural units represented by (III) and (IV) is ( III) / {(III) + (IV)} ≧ 0.6.
When the repeating structural unit of (I) is less than 40 mol%, the aromatic liquid crystal polyester tends not to exhibit optical anisotropy at the time of melting, and when it exceeds 74.8 mol%, the aromatic liquid crystal polyester at the time of melting. Viscosity tends to increase and processability tends to decrease. Further, when the repeating structural unit (II) exceeds 30 mol%, the aromatic liquid crystal polyester tends not to exhibit optical anisotropy at the time of melting, and when it is less than 12.5 mol%, the aromatic liquid crystal polyester There is a tendency that the viscosity at the time of melting increases and the processability decreases. Further, when the repeating structural unit of (III) exceeds 30 mol%, the aromatic liquid crystal polyester tends not to exhibit optical anisotropy at the time of melting, and when it is less than 12.5 mol%, the aromatic liquid crystal polyester There is a tendency that the viscosity at the time of melting increases and the processability decreases. Further, when the repeating structural unit (IV) exceeds 12 mol% or less than 0.5 mol%, the dielectric loss of the aromatic liquid crystal polyester tends to increase. Further, when the value of (III) / {(III) + (IV)} is less than 0.5, the dielectric loss of the aromatic liquid crystal polyester tends to increase.

  Examples of the raw material for obtaining the repeating structural unit represented by the formula (I) include 2-hydroxy-6-naphthoic acid and ester-forming derivatives thereof. These may be used alone or in combination of two or more.

Ar ₁ in the repeating structural unit represented by the formula (II) is a group selected from 1,4-phenylene or a divalent residue having 2 or more phenylenes connected at the para position. Examples of the raw material for obtaining the repeating structural unit represented by the formula (II) include aromatic diols such as hydroquinone, 4,4′-dihydroxybiphenyl, 1,4-bis (4-hydroxyphenyl) benzene, and the like. Examples thereof include ester-forming derivatives. These may be used alone or in combination of two or more.
Examples of ester-forming derivatives of aromatic diols include esters with carboxylic acids, which are derivatives that form polyesters by transesterification.
Among these, hydroquinone and 4,4′-dihydroxybiphenyl are more preferable because the heat resistance of the obtained aromatic liquid crystal polyester is improved.

  Examples of the raw material for obtaining the repeating structural unit represented by the formula (III) include 2,6-naphthalenedicarboxylic acid which is an aromatic dicarboxylic acid, and ester-forming derivatives thereof. These may be used alone or in combination of two or more.

Ar ₂ in the repeating structural unit represented by the formula (IV) is a group selected from 1,4-phenylene or a divalent residue having 2 or more phenylenes connected at the para position. Examples of the raw material for obtaining the repeating structural unit represented by the formula (IV) include terephthalic acid, aromatic dicarboxylic acids such as 4,4′-biphenyldicarboxylic acid, and ester-forming derivatives thereof. These may be used alone or in combination of two or more.
Among these, terephthalic acid is preferable because the heat resistance of the aromatic liquid crystal polyester is enhanced, the tension in the molten state during film processing is improved, and the moldability is excellent.

  Examples of the ester-forming derivatives of the above aromatic dicarboxylic acids include derivatives that have a high reaction activity such as acid chlorides and acid anhydrides and that promote the reaction to produce polyester, alcohols, ethylene glycol, etc. Which are derivatives that form a polyester by transesterification.

Next, a method for producing the aromatic liquid crystal polyester of the present invention will be described.
Among the raw materials of the aromatic liquid crystal polyester of the present invention, the molar ratio of the aromatic dicarboxylic acid and the aromatic diol is preferably in the range of 85/100 to 100/85.
Within this range, the degree of polymerization of the obtained aromatic liquid crystal polyester is increased, and the mechanical strength of the molded product obtained from the aromatic liquid crystal polyester is preferably improved.

When producing the aromatic liquid crystalline polyester of the present invention, an ester-forming derivative obtained by acylating the phenolic hydroxyl group of 2-hydroxy-6-naphthoic acid and aromatic diol with a fatty acid anhydride is usually used as a raw material.
Examples of the fatty acid anhydride to be used for acylation of the phenolic hydroxyl group of such 2-hydroxy-6-naphthoic acid and aromatic diol, for example, acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, Gil Herbic acid, pivalic anhydride, 2-ethylhexanoic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, Examples include glutaric anhydride, maleic anhydride, succinic anhydride, and β-bromopropionic anhydride. You may use these in mixture of 2 or more types.

  Of the above fatty acid anhydrides, acetic anhydride, propionic anhydride, butyric anhydride, and isobutyric anhydride are preferably used, and acetic anhydride is more preferably used from the viewpoints of price and handleability.

  The usage-amount of this fatty acid anhydride with respect to the total mole number of the phenolic hydroxyl group of 2-hydroxy-6-naphthoic acid and aromatic diol is 1.0-1.2 times equivalent normally.

  From the viewpoint of reducing outgas from the molded article, the amount used is more preferably in the range of 1.0 to 1.05 times equivalent, and more preferably in the range of 1.03 to 1.05 times equivalent. Moreover, from a viewpoint of impact strength, 1.05-1.17 times equivalent is preferable and 1.05-1.15 times equivalent is further more preferable.

  When the amount of the fatty acid anhydride used is less than 1.0 equivalent to the phenolic hydroxyl group, the equilibrium during the acylation reaction is shifted to the fatty acid anhydride side, and an unreacted fragrance is produced during polymerization into the polyester. The aromatic diol or aromatic dicarboxylic acid tends to sublimate and the reaction system tends to be blocked, and when it exceeds 1.2 times the equivalent, the resulting aromatic liquid crystal polyester tends to be highly colored.

  The acylation reaction is preferably performed at 130 ° C. to 180 ° C. for 30 minutes to 20 hours, and more preferably 140 to 160 ° C. for 1 to 5 hours. As such reaction conditions, the methods described in JP-A Nos. 2002-220444 and 2002-146003 are recommended.

The aromatic liquid crystalline polyester of the present invention comprises an acyl group of an ester-forming derivative obtained by acylating the phenolic hydroxyl group of the above-mentioned 2-hydroxy-6-naphthoic acid and aromatic diol with a fatty acid anhydride,
Those acylating phenolic hydroxyl groups of 2-hydroxy-6-naphthoic acid with a fatty acid anhydride and the like, 2,6-naphthalene dicarboxylic acid, and a carboxyl group of the aromatic dicarboxylic acid and 2-hydroxy-6-naphthoic acid, It can be obtained by a step of transesterification.
Next, the transesterification reaction will be described.

  The transesterification (polycondensation) reaction is preferably carried out while raising the temperature at a rate of 0.1 to 50 ° C./min in the range of 130 to 330 ° C., and 0.3 to 5 ° C. in the range of 150 to 320 ° C. It is more preferable to carry out the reaction while raising the temperature at a rate of / min. It is not preferable to carry out the reaction at 330 ° C. or higher because the high melt viscosity and high melting point of the aromatic liquid crystal polyester are promoted and it becomes difficult to discharge the entire prepolymer from the reaction apparatus.

  In the transesterification reaction between the acyl group of the acylated ester-forming derivative and the carboxyl group derived from 2-hydroxy-6-naphthoic acid and the carboxyl group of dicarboxylic acid, a by-product is generated to shift the equilibrium. It is preferable that the fatty acid and unreacted fatty acid anhydride are evaporated and distilled out of the system. Further, by refluxing a part of the distilled fatty acid and returning it to the reactor, it is possible to condense or reverse sublimate the raw materials that evaporate or sublimate with the fatty acid and return them to the reactor. In this case, it is possible to return the precipitated carboxylic acid together with the fatty acid to the reactor.

  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 organic compound catalysts such as N, N-dimethylaminopyridine and 1-methylimidazole.

  The catalyst is usually added at the time of adding monomers, and it is not always necessary to remove it after acylation. If the catalyst is not removed, transesterification can be carried out as it is.

Among these catalysts, heterocyclic organic base compounds containing two or more nitrogen atoms such as N, N-dimethylaminopyridine and 1-methylimidazole are preferably used.
As a method for producing an aromatic liquid crystal polyester using a heterocyclic compound containing two or more nitrogen atoms, a method described in JP-A No. 2002-146003 is recommended.

  In the present invention, the melt polycondensation step is preferably performed by a batch-type repetitive polymerization method from the viewpoint of improving productivity.

  The prepolymer obtained by melt polycondensation is subjected to solid phase polymerization for the purpose of obtaining an aromatic liquid crystal polyester having a high degree of polymerization. In order to perform solid phase polymerization, the obtained prepolymer may be powdered and heated. By heating, the polymerization of the aromatic liquid crystal polyester proceeds in a fine powder state, and the degree of polymerization increases.

  In order to make the prepolymer obtained by melt polycondensation into powder, for example, the prepolymer may be cooled and solidified and then pulverized. The particle diameter of the powder is preferably 0.05 mm or more and about 3 mm or less, and more preferably 0.05 mm or more and about 1.5 mm or less because the degree of polymerization of the aromatic liquid crystal polyester is promoted more preferably. If it is about 0.0 mm or less, it is more preferable because the degree of polymerization of the aromatic liquid crystal polyester is promoted without causing sintering between powder particles.

  Heating in solid phase polymerization is usually performed while increasing the temperature, for example, from room temperature to a temperature that is 20 ° C. or more lower than the flow initiation temperature of the prepolymer. The temperature raising time at this time is not particularly limited, but is preferably within 1 hour from the viewpoint of shortening the reaction time.

  In the solid phase polymerization, it is preferable to raise the temperature from a temperature 20 ° C. or more lower than the flow start temperature of the prepolymer to a temperature of 300 ° C. or more at a rate of temperature increase of 0.3 ° C./min or less. The temperature rising rate is preferably 0.1 to 0.15 ° C./min. If the rate of temperature rise is 0.3 ° C./min or less, sintering between powder particles is less likely to occur, which makes it easy to produce an aromatic liquid crystal polyester having a high degree of polymerization.

In the production of the aromatic liquid crystalline polyester of the present invention, it is preferable to raise the temperature of the reaction mixture from a temperature 20 ° C. or more lower than the flow start temperature of the prepolymer to a temperature of 300 ° C. or more. In order to increase the degree of polymerization of the aromatic liquid crystal polyester, it varies depending on the monomer type of the aromatic diol or aromatic dicarboxylic acid component of the obtained aromatic liquid crystal polyester, but at a temperature of 300 ° C. or higher, preferably in the range of 300 to 400 ° C. It is preferable to react for 30 minutes or more.
In particular, from the viewpoint of the thermal stability of the aromatic liquid crystalline polyester, it is preferable to react at a reaction temperature of 300 to 350 ° C. for 30 minutes to 30 hours, and it is more preferable to react at a reaction temperature of 300 to 340 ° C. for 30 minutes to 20 hours. .

Here, the flow temperature, the inner diameter 1 mm, using a capillary rheometer fitted with a die length of ^{10mm, 9.8MPa (100kg / cm 2} ) aromatic polyester at a Atsushi Nobori rate of 4 ° C. / min under a load of Is a temperature at which the melt viscosity shows 4800 Pa · s (48,000 poise) when the material is extruded from the nozzle.

  The flow start temperature of the aromatic liquid crystalline polyester of the present invention is preferably in the range of 300 to 400 ° C. from the viewpoint of improving heat resistance, and particularly when it is 320 ° C. or more and 380 ° C. or less, the heat resistance is high and the polymer at the time of molding. It is preferable because decomposition degradation of the resin can be suppressed, and more preferably 330 ° C. or higher and 360 ° C. or lower.

  The aromatic liquid crystal polyester film of the present invention is formed into a film shape using the aromatic liquid crystal polyester thus obtained. As a molding method, for example, it is specifically melted to form a film. The method etc. are mentioned.

  As an aromatic liquid crystal polyester film formed by melting, for example, an aromatic liquid crystal polyester is melt kneaded with an extruder, and the molten resin extruded through a T die is wound while being stretched in the direction of the winder (longitudinal direction). Examples thereof include a uniaxially oriented film obtained by taking the film, a biaxially stretched film, and an inflation film in which a melt sheet extruded from a cylindrical die is formed by an inflation method.

The set temperature of the extruder during the production of the uniaxially oriented film varies depending on the monomer composition of the aromatic liquid crystal polyester, but is usually about 200 to 400 ° C, preferably about 230 to 380 ° C. It is preferable that the set temperature of the cylinder is within this range because thermal decomposition of the aromatic liquid crystal polyester is suppressed and film formation tends to be facilitated.
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 usually in the range of about 1.1 to 45. The draft ratio here refers to a value obtained by dividing the sectional area of the T-die slit by the film sectional area in the longitudinal direction. When the draft ratio is 1.1 or more, the film strength tends to be improved, and when the draft ratio is 45 or less, the surface smoothness of the film tends to be excellent. 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 usually about 200 to 400 ° C., preferably about 230 to 380 ° C., and the slit interval of the T die is Usually, melt extrusion is performed in the range of 0.1 to 2 mm.

  As the biaxial stretching method, the melt sheet extruded from the T die is stretched simultaneously in the longitudinal direction and the longitudinal direction (transverse direction), the melt sheet extruded from the T die is first stretched in the longitudinal direction, Next, a method of sequential stretching 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, and the like.

  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 within the above range, the strength of the resulting film tends to be excellent, and a film having a uniform thickness tends to be easily obtained.

Next, the manufacturing method of an inflation film is demonstrated.
The aromatic liquid crystalline polyester of the present invention is supplied to a melt-kneading extruder equipped with a die having an annular slit, and melt-kneading is performed at a cylinder set temperature of usually about 200 to 400 ° C., preferably about 230 to 380 ° C. The cylindrical aromatic polyester film is extruded upward or downward from the annular slit of the extruder. 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 1000 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 of the final tube diameter to the initial diameter) is usually 1.5-10.
The MD draw ratio is usually from 1.5 to 40, and a thickness within this range is preferable because it tends 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.
The thickness of the aromatic liquid crystal polyester film thus obtained is usually 0.5 to 500 μm from the viewpoint of film forming properties and mechanical properties, and preferably 1 to 100 μm from the viewpoint of handleability.

In the aromatic liquid crystal polyester film of the present invention, fillers, additives, and the like may be added within a range that does not impair the object of the present invention.
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 a coupling agent, an anti-settling agent, an ultraviolet absorber, and a heat stabilizer.

  In addition, the aromatic liquid crystal polyester film of the present invention includes polypropylene, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenyl ether and a modified product thereof, as long as the object of the present invention is not impaired. You may add 1 type, or 2 or more types, such as thermoplastic resins, such as polyetherimide, elastomers, such as a copolymer of glycidyl methacrylate and polyethylene.

Next, a laminate using the aromatic liquid crystal polyester film of the present invention will be described.
By laminating a metal layer on the aromatic liquid crystal polyester film of the present invention, a laminate composed of an insulating layer made of an aromatic liquid crystal polyester film and a metal layer can be obtained.

As a method of laminating a metal layer on the aromatic liquid crystal polyester film of the present invention, for example,
(1) A method of attaching an aromatic liquid crystal polyester film to a metal foil by thermocompression bonding,
(2) A method of attaching an aromatic liquid crystal polyester film and a metal foil with an adhesive,
(3) A method of forming a metal layer on the aromatic liquid crystal polyester film by vapor deposition, and the like.

  Among these, the laminating method (1) is a method of pressure bonding with a metal foil near the flow start temperature of the aromatic liquid crystal polyester film using a press or a heating roll, and is recommended because it can be easily carried out.

  Examples of the adhesive used in the lamination method (2) include a hot melt adhesive and a polyurethane adhesive. Among them, an epoxy group-containing ethylene copolymer is preferably used as an adhesive.

  Examples of the lamination method (3) 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.

  In laminating the metal layer, the surface of the aromatic liquid crystal polyester film on which the metal layer is laminated may be subjected to corona discharge treatment, ultraviolet irradiation treatment, or plasma treatment in order to increase the adhesive force.

  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.

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

Next, an aromatic liquid crystal polyester resin composition using the aromatic liquid crystal polyester of the present invention will be described.
This aromatic liquid crystal polyester resin composition contains the above aromatic liquid crystal polyester and a filler.
As the filler for use in the above aromatic liquid crystal polyester resin composition, for example, milled glass fiber, glass fibers such as chopped glass fibers, glass beads, hollow glass spheres, glass powder, mica, talc, clay, silica, alumina, potassium titanate, wollastonite, calcium carbonate (heavy, light, colloidal and the like), magnesium carbonate, basic magnesium carbonate, sodium sulfate, calcium sulfate, barium sulfate, calcium sulfite, aluminum hydroxide, magnesium hydroxide , Calcium hydroxide, calcium silicate, silica sand, silica, quartz, titanium oxide, zinc oxide, iron oxide graphite, molybdenum, asbestos, silica alumina fiber, alumina fiber, gypsum fiber, carbon fiber, carbon black, white carbon, Diatomaceous earth Bentonite, sericite, Shirasu, inorganic fillers such as graphite; potassium titanate whisker, alumina whisker, aluminum borate whisker, silicon carbide whisker, metallic or non-metallic whiskers such as silicon nitride-containing whisker, and the like. Of these, glass fiber, glass powder, mica, talc, carbon fiber and the like are preferable. Two or more kinds of the above fillers may be used in combination in the aromatic liquid crystal polyester resin composition.

  As a compounding quantity of the filler mix | blended with an aromatic liquid crystalline polyester resin composition, it is the range of 0.1-400 weight part normally with respect to 100 weight part of aromatic liquid crystalline polyester, Preferably, it is 10-400 weight part More preferably, it is in the range of 10 to 250 parts by weight.

The filler may be subjected to a surface treatment. Examples of the surface treatment method include a method of adsorbing the surface treatment agent on the surface of the filler, a method of adding the surface treatment agent when kneading the aromatic liquid crystal polyester and the filler, and the like.
Silane coupling agent as a surface treatment agent, titanate coupling agent, the reactive coupling agent, such as borane-based coupling agents, higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, lubricants such as fluorocarbon surfactant Agents and the like.

  A molded body made of the above aromatic liquid crystal polyester resin composition can be obtained by molding the above aromatic liquid crystal polyester resin composition. Such a molded body may contain a thermoplastic resin or an additive other than the aromatic liquid crystal polyester in addition to the aromatic liquid crystal polyester of the present invention and the filler. Examples of such additives include mold release improvers such as fluororesins and metal soaps, nucleating agents, antioxidants, stabilizers, plasticizers, lubricants, anti-coloring agents, coloring agents, ultraviolet absorbers, antistatic agents, and lubrication. Agents and flame retardants.

  Examples of the thermoplastic resin include polycarbonate resin, polyamide resin, polysulfone resin, polyphenylene sulfide resin, polyphenylene ether resin, polyether ketone resin, and polyetherimide resin.

As process for producing a molded article comprising the above aromatic liquid crystal polyester resin composition, for example, aromatic liquid crystal polyester, filler and single-screw extruder additives and the like, twin-screw extruder, Banbury mixer, roll, Brabender, A method of adding to a kneader such as a kneader, melting and kneading to obtain an aromatic liquid crystal polyester resin composition, and then supplying and molding to an molding machine such as an extrusion molding machine, an injection molding machine, a compression molding machine, or a blow molding machine ,
After premixing aromatic liquid crystal polyester, fillers and additives using a mortar, Henschel mixer, ball mill, ribbon blender, etc., as described above, addition, melt-kneading, molding method,
A method of adding and mixing aromatic liquid crystal polyester, fillers and additives into a reaction vessel,
Examples include a method in which aromatic liquid crystal polyester, a filler, an additive, and the like are supplied into a molding machine and molding is performed while melt-mixing.

  Among the molded products obtained by the above production method, a molded product obtained by injection molding is preferable because it has an excellent balance between heat resistance and melt moldability.

  Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and further includes meanings equivalent to the description of the claims and all modifications within the scope.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this.
[Flow start temperature measurement method]
Using a flow tester (manufactured by Shimadzu Corporation, “CFT-500 type”), a sample amount of about 2 g is filled into a capillary rheometer equipped with a die having an inner diameter of 1 mm and a length of 10 mm. When the aromatic polyester is extruded from the nozzle under a load of 9.8 MPa (100 kg / cm ² ) at a heating rate of 4 ° C./min, the temperature at which the melt viscosity is 4800 Pa · s (48000 poise) is defined as the flow start temperature. did.

Example 1
In a reactor equipped with a stirrer, a torque meter, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 940.90 g (5.0 mol) of 2-hydroxy-6-naphthoic acid, 4,4′-dihydroxybiphenyl 512 0.08 g (2.75 mol, used in excess of 0.25 mol), 2,6-naphthalenedicarboxylic acid 497.24 g (2.3 mol), terephthalic acid 33.23 g (0.2 mol), acetic anhydride 1179 .14 (11.5 mol) and 0.198 g of 1-methylimidazole as a catalyst were added, stirred at room temperature for 15 minutes, and then heated with stirring. When the internal temperature reached 145 ° C., the mixture was stirred for 1 hour while maintaining the same temperature, and 5.94 g of 1-methylimidazole as a catalyst was further added.

Next, the temperature was raised from 145 ° C. to 310 ° C. over 3 hours and 30 minutes while distilling off distilling by-product acetic acid and unreacted acetic anhydride. The mixture was kept at the same temperature for 2 hours and 10 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).
It was 273 degreeC when the flow start temperature was measured about this powder (aromatic liquid crystalline polyester) using the flow tester.

  The obtained powder was heated from 25 ° C. to 250 ° C. over 1 hour, then heated from the same temperature to 325 ° C. over 10 hours, and then kept at that temperature for 12 hours for solid phase polymerization. Thereafter, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (aromatic liquid crystal polyester) was measured using a flow tester.

Example 2
In the same reactor as in Example 1, 940.90 g (5.0 mol) of 2-hydroxy-6-naphthoic acid, 302.80 g of hydroquinone (2.75 mol, used in excess of 0.25 mol), 2, 6-naphthalenedicarboxylic acid 497.24G (2.3 mol), 33.23G terephthalic acid (0.2 mol), acetic anhydride 1232.74 (12.08 mol) and added 1-methylimidazole 0.17g as a catalyst The mixture was stirred at room temperature for 15 minutes and then heated while 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 and 30 minutes while distilling off distilling by-product acetic acid and unreacted acetic anhydride. The mixture was kept at the same temperature for 2 hours to obtain an aromatic liquid crystal polyester. The obtained aromatic liquid crystalline polyester was cooled to room temperature and pulverized with a pulverizer to obtain an aromatic liquid crystalline polyester powder (particle diameter of about 0.1 mm to about 1 mm).
This powder (aromatic liquid crystal polyester) was measured for flow start temperature using a flow tester and found to be 277 ° C.
The obtained powder was heated from 25 ° C. to 250 ° C. over 1 hour, then heated from the same temperature to 315 ° C. over 5 hours, and then kept at that temperature for 3 hours for solid phase polymerization. Thereafter, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (aromatic liquid crystal polyester) was measured using a flow tester.

Example 3
In the same reactor as in Example 1, 940.90 g (5.0 mol) of 2-hydroxy-6-naphthoic acid, 302.80 g of hydroquinone (2.75 mol, used in excess of 0.25 mol), 2, Add 43.2.38 g (2.0 mol) of 6-naphthalenedicarboxylic acid, 83.07 g (0.5 mol) of terephthalic acid, 1232.74 (12.08 mol) of acetic anhydride and 0.17 g of 1-methylimidazole as a catalyst. The mixture was stirred at room temperature for 15 minutes and then heated while 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 and 30 minutes while distilling off distilling by-product acetic acid and unreacted acetic anhydride. The mixture was kept at the same temperature for 2 hours and 15 minutes to obtain an aromatic liquid crystal polyester. The obtained aromatic liquid crystalline polyester was cooled to room temperature and pulverized with a pulverizer to obtain an aromatic liquid crystalline polyester powder (particle diameter of about 0.1 mm to about 1 mm).
It was 264 degreeC when the flow start temperature was measured about this powder (aromatic liquid crystalline polyester) using the flow tester.
The obtained powder was heated from 25 ° C. to 250 ° C. over 1 hour, then heated from the same temperature to 315 ° C. over 5 hours, and then kept at that temperature for 5 hours for solid phase polymerization. Thereafter, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (aromatic liquid crystal polyester) was measured using a flow tester.

Example 4
In the same reactor as in Example 1, 1023.499 g (5.5 mol) of 2-hydroxy-6-naphthoic acid, 272.52 g of hydroquinone (2.475 mol, used in 0.225 mol excess), 2, 443.19 g (2.05 mol) of 6-naphthalenedicarboxylic acid, 33.23 g (0.2 mol) of terephthalic acid, 1226.87 (12.1 mol) of acetic anhydride and 0.17 g of 1-methylimidazole as a catalyst were added. The mixture was stirred at room temperature for 15 minutes and then heated while 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 and 30 minutes while distilling off distilling by-product acetic acid and unreacted acetic anhydride. The mixture was kept at the same temperature for 3 hours to obtain an aromatic liquid crystal polyester. The obtained aromatic liquid crystalline polyester was cooled to room temperature and pulverized with a pulverizer to obtain an aromatic liquid crystalline polyester powder (particle diameter of about 0.1 mm to about 1 mm).
This powder (aromatic liquid crystal polyester) was measured for flow start temperature using a flow tester and found to be 282 ° C.
The obtained powder was heated from 25 ° C. to 250 ° C. over 1 hour, then heated from the same temperature to 315 ° C. over 5 hours, and then kept at that temperature for 3 hours for solid phase polymerization. Thereafter, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (aromatic liquid crystal polyester) was measured using a flow tester.

Example 5
In the same reactor as in Example 1, 1023.499 g (5.5 mol) of 2-hydroxy-6-naphthoic acid, 272.52 g of hydroquinone (2.475 mol, used in 0.225 mol excess), 2, 6-naphthalenedicarboxylic acid 378.33G (1.75 mol), 83.07G terephthalic acid (0.5 mol), acetic anhydride 1226.87 (11.9 mol) and adding 1-methylimidazole 0.17g as a catalyst The mixture was stirred at room temperature for 15 minutes and then heated while 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 and 30 minutes while distilling off distilling by-product acetic acid and unreacted acetic anhydride. The mixture was kept at the same temperature for 3 hours to obtain an aromatic liquid crystal polyester. The obtained aromatic liquid crystalline polyester was cooled to room temperature and pulverized with a pulverizer to obtain an aromatic liquid crystalline polyester powder (particle diameter of about 0.1 mm to about 1 mm).
It was 261 degreeC when the flow start temperature was measured about this powder (aromatic liquid crystalline polyester) using the flow tester.
The obtained powder was heated from 25 ° C. to 250 ° C. over 1 hour, then heated from the same temperature to 315 ° C. over 5 hours, and then kept at that temperature for 3 hours for solid phase polymerization. Thereafter, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (aromatic liquid crystal polyester) was measured using a flow tester.

Example 6
In the same reactor as in Example 1, 112.08 g (6.0 mol) of 2-hydroxy-6-naphthoic acid, 242.24 g of hydroquinone (2.2 mol, used in an excess of 0.2 mol), 2, Add 389.14 g (1.8 mol) of 6-naphthalenedicarboxylic acid, 33.23 g (0.2 mol) of terephthalic acid, 1221.00 (11.96 mol) of acetic anhydride and 0.17 g of 1-methylimidazole as a catalyst The mixture was stirred at room temperature for 15 minutes and then heated while 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 and 30 minutes while distilling off distilling by-product acetic acid and unreacted acetic anhydride. The mixture was kept at the same temperature for 3 hours to obtain an aromatic liquid crystal polyester. The obtained aromatic liquid crystalline polyester was cooled to room temperature and pulverized with a pulverizer to obtain an aromatic liquid crystalline polyester powder (particle diameter of about 0.1 mm to about 1 mm).
The flow starting temperature of this powder (aromatic liquid crystal polyester) was measured using a flow tester and found to be 272 ° C.
The obtained powder was heated from 25 ° C. to 250 ° C. over 1 hour, then heated from the same temperature to 315 ° C. over 5 hours, and then kept at that temperature for 3 hours for solid phase polymerization. Thereafter, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (aromatic liquid crystal polyester) was measured using a flow tester.

Example 7
In the same reactor as in Example 1, 112.08 g (6.0 mol) of 2-hydroxy-6-naphthoic acid, 242.24 g of hydroquinone (2.2 mol, used in an excess of 0.2 mol), 2, Add 324.29 g (1.5 mol) of 6-naphthalenedicarboxylic acid, 83.07 g (0.5 mol) of terephthalic acid, 1221.00 (11.96 mol) of acetic anhydride and 0.17 g of 1-methylimidazole as a catalyst The mixture was stirred at room temperature for 15 minutes and then heated while 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 and 30 minutes while distilling off distilling by-product acetic acid and unreacted acetic anhydride. The mixture was kept at the same temperature for 1 hour and 15 minutes to obtain an aromatic liquid crystal polyester. The obtained aromatic liquid crystalline polyester was cooled to room temperature and pulverized with a pulverizer to obtain an aromatic liquid crystalline polyester powder (particle diameter of about 0.1 mm to about 1 mm).
The flow starting temperature of this powder (aromatic liquid crystal polyester) was measured using a flow tester and found to be 263 ° C.
The obtained powder was heated from 25 ° C. to 250 ° C. over 1 hour, then heated from the same temperature to 315 ° C. over 5 hours, and then kept at that temperature for 3 hours for solid phase polymerization. Thereafter, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (aromatic liquid crystal polyester) was measured using a flow tester.

Comparative Example 1
The same reactor as in Example 1, p-hydroxybenzoic acid 911 g (6.6 mol), 4,4'-dihydroxybiphenyl 409 g (2.2 mol), 274 g of terephthalic acid (1.65 moles), isophthalic acid 91 g (0.55 mol) and 1235 g (12.1 mol) of acetic anhydride were charged. After stirring for 15 minutes at room temperature, the temperature was raised while stirring. When the internal temperature reached 145 ° C., the mixture was stirred for 1 hour while maintaining the same temperature.
Then, it heated up to 305 degreeC over 3 hours and 30 minutes, distilling off the byproduct acetic acid to distill and unreacted acetic anhydride. The mixture was kept at the same temperature for 1 hour to obtain an aromatic liquid crystal polyester. The obtained aromatic polyester was cooled to room temperature and pulverized by a pulverizer to obtain an aromatic liquid crystal polyester powder (particle diameter of about 0.1 mm to about 1 mm). This powder (aromatic liquid crystal polyester) was measured for flow start temperature using a flow tester and found to be 255 ° C.
The obtained powder was heated from 25 ° C. to 250 ° C. over 1 hour, then heated from the same temperature to 290 ° C. over 5 hours, and then kept at that temperature for 3 hours to obtain an aromatic liquid crystal polyester. . Solid phase polymerization was performed. Thereafter, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (aromatic liquid crystal polyester) was measured using a flow tester.

Comparative Example 2
In the same reactor as in Example 1, 987.95 g (5.25 mol) of 2-hydroxy-6-naphthoic acid and 486.47 g (2.612 mol, 0.237 mol excess) of 4,4′-dihydroxybiphenyl were added. use.), 2,6-naphthalene dicarboxylic acid 513.45G (2.375 mol), acetic anhydride 1174.04 (11.5 mol) and added 1-methylimidazole 0.194g as a catalyst for 15 minutes at room temperature After stirring, the temperature was raised while stirring. When the internal temperature reached 145 ° C., the mixture was stirred for 1 hour while maintaining the same temperature, and 5.83 g of 1-methylimidazole as a catalyst was further added.
Next, the temperature was raised from 145 ° C. to 310 ° C. over 3 hours and 30 minutes while distilling off distilling by-product acetic acid and unreacted acetic anhydride. The mixture was kept at the same temperature for 2 hours to obtain an aromatic liquid crystal polyester. The obtained aromatic liquid crystalline polyester was cooled to room temperature and pulverized with a pulverizer to obtain an aromatic liquid crystalline polyester powder (particle diameter of about 0.1 mm to about 1 mm).
It was 273 degreeC when the flow start temperature was measured about this powder (aromatic liquid crystalline polyester) using the flow tester.
The obtained powder was heated from 25 ° C. to 250 ° C. over 1 hour, then heated from the same temperature to 325 ° C. over 10 hours, and then kept at that temperature for 12 hours for solid phase polymerization. Thereafter, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (aromatic liquid crystal polyester) was measured using a flow tester.

Comparative Example 3
In the same reactor as in Example 1, 103.499 g (5.5 mol) of 2-hydroxy-6-naphthoic acid and 460.87 g (2.475 mol, 0.225 mol excess) of 4,4′-dihydroxybiphenyl were added. Use)), 486.43 g (2.25 mol) of 2,6-naphthalenedicarboxylic acid, 1174.04 (11.5 mol) of acetic anhydride and 0.194 g of 1-methylimidazole as catalyst and added at room temperature for 15 minutes. After stirring, the temperature was raised while stirring. When the internal temperature reached 145 ° C., the mixture was stirred for 1 hour while maintaining the same temperature, and 5.82 g of 1-methylimidazole as a catalyst was further added.
Next, the temperature was raised from 145 ° C. to 310 ° C. over 3 hours and 30 minutes while distilling off distilling by-product acetic acid and unreacted acetic anhydride. The mixture was kept at the same temperature for 2 hours to obtain an aromatic liquid crystal polyester. The obtained aromatic liquid crystalline polyester was cooled to room temperature and pulverized with a pulverizer to obtain an aromatic liquid crystalline polyester powder (particle diameter of about 0.1 mm to about 1 mm).
It was 273 degreeC when the flow start temperature was measured about this powder (aromatic liquid crystalline polyester) using the flow tester.
The obtained powder was heated from 25 ° C. to 250 ° C. over 1 hour, then heated from the same temperature to 325 ° C. over 10 hours, and then kept at that temperature for 12 hours for solid phase polymerization. Thereafter, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (aromatic liquid crystal polyester) was measured using a flow tester.

The aromatic liquid crystalline polyester powders obtained by solid-phase polymerization in Examples 1 to 7 and Comparative Examples 1 to 3 were each melted in a single screw extruder (screw diameter: 50 mm), and a T die (at the tip of the extruder) (A lip length of 300 mm, a lip clearance of 1 mm, a die temperature of 360 ° C.) was extruded into a film under a draft ratio of 4 and cooled to obtain an aromatic liquid crystal polyester film having a thickness of 250 μm. In this film processing step, when the melt tension was excellent and the film was continuously obtained, ○, the film was obtained, but the film tension was low during film processing, so the film could not be obtained continuously Δ.
About each of the obtained film, the dielectric constant and the dielectric loss were measured with the impedance material analyzer by Hewlett-Packard Co., Ltd.
Each of the obtained films was immersed in 280 ° C. H60A solder (tin 60%, lead 40) for 120 seconds, and the foam resistance (blister) of the film was examined. The case where no foaming was observed was marked as ◯.
The conditions and results of Examples 1 to 7 and Comparative Examples 1 to 3 are summarized in Table 1.

Explanation of abbreviations in Table 1 POB: p-hydroxybenzoic acid BON: 2-hydroxy-6-naphthoic acid DOD: 4,4'-dihydroxybiphenyl HQ: hydroquinone NDCA: 2,6-naphthalenedicarboxylic acid TPA: terephthalic acid IPA : Isophthalic acid NI: 1-methylimidazole

Since the aromatic liquid crystal polyester of the present invention has an excellent balance between heat resistance and film processability and a film having a small dielectric loss can be obtained, an aromatic liquid crystal polyester film obtained by melt-molding the aromatic liquid crystal polyester is suitable. In addition, it is used for flexible printed wiring boards, rigid printed wiring boards, substrate materials for electronic substrates such as module substrates, interlayer insulating materials and surface protective films. The laminate of the aromatic liquid crystal polyester film and the metal layer is used as a capacitor or an electromagnetic shielding material.

Claims (5)

It consists of repeating structural units represented by the following formulas (I), (II), (III) and (IV), and the repeating structure of (I) with respect to the total of these repeating structural units of (I) to (IV) 40 to 74.8 mol% of units, 12.5 to 30 mol% of repeating structural units of (II), 12.5 to 30 mol% of repeating structural units of (III) and repeating structural units of (IV) The molar ratio of the repeating structural units represented by (III) and (IV) satisfies the relationship of (III) / {(III) + (IV)} ≧ 0.5. An aromatic liquid crystal polyester having a flow start temperature of 300 to 400 ° C.

(Here, Ar ₁ and Ar ₂ are each independently 1,4-phenylene or 4,4′-biphenylylene.) An aromatic liquid crystal polyester film obtained by melt-molding the aromatic liquid crystal polyester according to claim 1 . The laminated body containing the insulating layer and metal layer which consist of an aromatic liquid-crystal polyester film of Claim 2 . An aromatic liquid crystal polyester resin composition comprising 100 parts by weight of the aromatic liquid crystal polyester according to claim 1 and 10 to 400 parts by weight of a filler. The molded object obtained by injection-molding the aromatic liquid-crystal polyester resin composition of Claim 4 .