Liquid crystal polymer composition

Abstract

To provide a liquid crystal polymer composition having excellent dielectric properties and film forming properties, and a film comprising the same.SOLUTION: A liquid crystal polymer composition contains a liquid crystal polymer 100 pts.mass, and a polyarylate resin 0.1-20 pts.mass. The liquid crystal polymer composition has a molten tension of 3 mN or more, and a dielectric loss tangent of 0.0015 or less when measured at 1GHz using a stick-like test piece of 85 mm in length, 1.75 mm in width, and 1.75 mm in thickness.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a liquid crystal polymer composition having excellent dielectric properties and film-forming properties.

Background Art

[0002] Liquid crystal polymers are excellent in mechanical properties such as heat resistance and rigidity, chemical resistance, dimensional accuracy, etc., and thus their use is expanding not only in molded product applications but also in various applications such as fibers and films. Especially in the information and communication fields such as personal computers and mobile phones, the high integration, miniaturization, thinning, and low profile of components are rapidly progressing, and there are many cases where a very thin wall thickness part of 0.5 mm or less is formed. Taking advantage of the excellent moldability of liquid crystal polymers, that is, the characteristics of good fluidity and no flash, which are not found in other resins, the amount of their use is increasing significantly.

[0003] A liquid crystal polymer film made of such a liquid crystal polymer is excellent in electrical properties (low dielectric constant, low dielectric loss) in the high-frequency region (GHz band), and is attracting attention as a material for flexible printed wiring (FPC) substrates and the like because of characteristics such as less electrical transmission loss in a circuit.

[0004] However, since liquid crystal polymers have a rigid molecular structure, they tend to be oriented in the molding direction and show anisotropy, or tend to tear in the molding direction, so there has been a problem that film molding is difficult.

[0005] Therefore, various methods have been proposed to improve the film-forming properties of liquid crystal polymers. For example, Patent Document 1 discloses a film made of a blend resin of a liquid crystal polymer and an ethylene copolymer having a glycidyl group, and Patent Documents 2 and 3 disclose films formed from blends of liquid crystal polymers and thermoplastic resins such as polyarylate.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, since the film made of the blend resin described in Patent Document 1 has an ethylene copolymer as its basic skeleton, it has low heat resistance, and it has been difficult to produce a high-quality film.

[0008] In addition, the films described in Patent Documents 2 and 3 have insufficient film-forming properties and inferior dielectric properties, and are not suitable for use as circuit boards.

[0009] An object of the present invention is to provide a liquid crystal polymer composition excellent in dielectric properties and film-forming properties and a film composed of the same.

Means for Solving the Problems

[0010] As a result of intensive studies in view of the above problems, the present inventors have found that by blending a predetermined amount of polyarylate resin with a specific liquid crystal polymer, a liquid crystal polymer composition excellent in dielectric properties and film-forming properties can be obtained, and the present invention has been completed.

[0011] That is, the present invention includes the following preferred embodiments. 〔1〕A liquid crystal polymer composition containing 100 parts by mass of a liquid crystal polymer and 0.1 to 20 parts by mass of a polyarylate resin, having a melt tension of 3 mN or more, and having a dielectric loss tangent measured at 1 GHz using a stick-shaped test piece having a length of 85 mm, a width of 1.75 mm, and a thickness of 1.75 mm of 0.0015 or less. 〔2〕The difference ΔT (Tm - Tc) between the crystal melting temperature (Tm) and the crystallization temperature (Tc) is 40 °C or higher, the liquid crystal polymer composition according to claim 1. 〔3〕The liquid crystal polymer is represented by the formulas (I) to (III)

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0012] According to the present invention, it is possible to provide a liquid crystal polymer composition excellent in dielectric properties and film-forming properties and a film composed thereof.

Embodiments for Carrying Out the Invention

[0013] The liquid crystal polymer composition of the present invention contains a liquid crystal polymer and a polyarylate resin as essential components.

[0014] The liquid crystal polymer used in the present invention is a polyester or polyester amide that forms a mesomorphic molten phase, which is called a thermotropic liquid crystal polymer by those skilled in the art, and is not particularly limited as long as it is called a thermotropic liquid crystal polyester or thermotropic liquid crystal polyester amide in the technical field.

[0015] The properties of the mesomorphic molten phase can be confirmed by a conventional polarization inspection method using crossed polarizers. More specifically, the confirmation of the mesomorphic molten phase can be carried out by using a Leitz polarizing microscope and observing a sample placed on a Leitz hot stage at a magnification of 40 times in a nitrogen atmosphere. The liquid crystal polymer in the present invention exhibits optical anisotropy, that is, it transmits light when inspected between crossed polarizers. When the sample is optically anisotropic, the polarized light is transmitted even in a stationary state.

[0016] Examples of the polymerizable monomers constituting the liquid crystal polymer in the present invention include aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic aminocarboxylic acids, aromatic hydroxyamines, aromatic diamines, aliphatic diols, and aliphatic dicarboxylic acids. The polymerizable monomers constituting the liquid crystal polymer may be only one of these compounds, or a combination of two or more compounds, but it is desirable to include a polymerizable monomer having at least one hydroxy group and carboxyl group.

[0017] The polymerizable monomer constituting the liquid crystal polymer may be an oligomer formed by bonding one or more of the above compounds, that is, an oligomer composed of one or more of the above compounds.

[0018] Specific examples of the aromatic hydroxycarboxylic acid include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid, 7-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, and their alkyl, alkoxy or halogen substituents, and ester-forming derivatives such as their acylates, ester derivatives, acid halides, etc. Among these, from the viewpoint of easily adjusting the heat resistance, mechanical strength and melting point of the obtained liquid crystal polymer, one or more compounds selected from the group consisting of 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferable.

[0019] Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, 3,4'-dicarboxybiphenyl, and 4,4''-dicarboxytriphenyl, their alkyl, alkoxy, or halogen substituents, and their ester-forming derivatives such as ester derivatives and acid halides. Among these, from the viewpoint of effectively enhancing the heat resistance of the obtained liquid crystal polymer, one or more compounds selected from the group consisting of terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferable, and terephthalic acid and 2,6-naphthalenedicarboxylic acid are more preferable.

[0020] Specific examples of the aromatic diol include hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, and 2,2'-dihydroxybinaphthyl, their alkyl, alkoxy, or halogen substituents, and their ester-forming derivatives such as acylates. Among these, from the viewpoint of excellent reactivity during polymerization, one or more compounds selected from the group consisting of hydroquinone, resorcin, 4,4'-dihydroxybiphenyl, and 2,6-dihydroxynaphthalene are preferable, and one or more compounds selected from the group consisting of hydroquinone, 4,4'-dihydroxybiphenyl, and 2,6-dihydroxynaphthalene are more preferable.

[0021] Specific examples of the aromatic aminocarboxylic acid include 4-aminobenzoic acid, 3-aminobenzoic acid, 6-amino-2-naphthoic acid, their alkyl, alkoxy, or halogen substituents, and their ester-forming derivatives such as acylates, ester derivatives, and acid halides.

[0022] Specific examples of the aromatic hydroxyamine include 4-aminophenol, N-methyl-4-aminophenol, 3-aminophenol, 3-methyl-4-aminophenol, 4-amino-1-naphthol, 4-amino-4'-hydroxybiphenyl, 4-amino-4'-hydroxybiphenyl ether, 4-amino-4'-hydroxybiphenylmethane, 4-amino-4'-hydroxybiphenyl sulfide, 2,2'-diaminobinaphthyl, their alkyl, alkoxy or halogen substituents, and ester-forming derivatives such as their acylates. Among these, 4-aminophenol is preferred from the viewpoint of easily achieving a balance between the heat resistance and mechanical strength of the resulting liquid crystal polymer.

[0023] Specific examples of the aromatic diamine include 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, their alkyl, alkoxy or halogen substituents, and amide-forming derivatives such as their acylates.

[0024] Specific examples of the aliphatic diol include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and their acylates. Further, a polymer containing an aliphatic diol such as polyethylene terephthalate or polybutylene terephthalate may be reacted with the above-mentioned aromatic oxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol and their acylates, ester derivatives, acid halides, etc.

[0025] Specific examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, fumaric acid, maleic acid, 1,4-cyclohexanedicarboxylic acid, and hexahydroterephthalic acid. Among these, oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, and 1,4-cyclohexanedicarboxylic acid are preferred from the viewpoint of excellent reactivity during polymerization.

[0026] In the present invention, the liquid crystal polymer may contain, as polymerizable monomers, dihydroxyterephthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, trimellitic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, or their alkyl, alkoxy or halogen substituents, and their acylates, ester derivatives, acid halides and other ester-forming derivatives, as long as the object of the present invention is not impaired. The amount of these polymerizable monomers used is preferably 10 mol% or less based on the total amount of other polymerizable monomers.

[0027] In the present invention, the liquid crystal polymer may contain a thioester bond as long as the object of the present invention is not impaired. Examples of the polymerizable monomer that provides such a bond include mercaptoaromatic carboxylic acid, aromatic dithiol and hydroxyaromatic thiol. The content of these polymerizable monomers is preferably 10 mol% or less based on the total amount of other polymerizable monomers.

[0028] Among the polymers combining these repeating units, there are those that form a nematic molten phase and those that do not form a nematic molten phase, depending on the monomer constitution, composition ratio, and sequence distribution of each repeating unit in the polymer. However, the liquid crystal polymer used in the present invention is limited to those that form a nematic molten phase. Those skilled in the art can appropriately select and adjust the monomer constitution, composition ratio, and sequence distribution of each repeating unit in the polymer so as to obtain a liquid crystal polymer that forms a nematic molten phase.

[0029] In one embodiment of the present invention, as the liquid crystal polymer, formulas (I) to (III) [Chemical formula] [wherein, Ar1 and Ar2 each represent one or more divalent aromatic groups, and p, q, and r are the composition ratios (mol%) of each repeating unit in the liquid crystal polyester (A), respectively, and satisfy the following conditions: 35 ≤ p ≤ 90, 5 ≤ q ≤ 30, and 5 ≤ r ≤ 30] A liquid crystal polyester (A) containing a repeating unit represented by the formula is preferably used.

[0030] In another embodiment of the present invention, as the liquid crystal polymer, formulas (I) to (III) [Chemical formula] [In the formula, Ar1 and Ar2 each represent one or more divalent aromatic groups, and p, q, and r are respectively the composition ratios (mol%) of each repeating unit in the liquid crystal polyester (A), and satisfy the following conditions: 35 ≤ p ≤ 90, 5 ≤ q ≤ 30, and 5 ≤ r ≤ 30] A liquid crystal polyester (A) containing a repeating unit represented by the formula, and Formulas (IV) and (V) [Chemical formula] [In the formula, s and t are respectively the composition ratios (mol%) of each repeating unit in the liquid crystal polyester (B), and satisfy the following conditions: 80 / 20 ≤ s / t ≤ 60 / 40] A liquid crystal polyester (B) containing a repeating unit represented by the formula and are contained, A liquid crystal polyester in which the mass ratio [(A) / (B)] of the liquid crystal polyester (A) and the liquid crystal polyester (B) is 99 / 1 to 45 / 55 is preferably used. In this case, the mass ratio [(A) / (B)] of the liquid crystal polyester (A) and the liquid crystal polyester (B) is more preferably 90 / 10 to 50 / 50, and even more preferably 80 / 20 to 60 / 40.

[0031] In still another embodiment of the present invention, as the liquid crystal polymer, formulas (I) to (III) [Chemical formula] [In the formula, Ar1 and Ar2 each represent one or more divalent aromatic groups, and p, q, and r are each the composition ratio (mol %) of each repeating unit in the liquid crystal polyester (A), and satisfy the following conditions: 35 ≦ p ≦ 90, 5 ≦ q ≦ 30, and 5 ≦ r ≦ 30] A liquid crystal polyester (A) containing a repeating unit represented by Formula (IV) and Formula (V) [Chemical formula] [In the formula, s and t are each the composition ratio (mol %) of each repeating unit in the liquid crystal polyester (B), and satisfy the following conditions: 80 / 20 ≦ s / t ≦ 60 / 40] A liquid crystal polyester (B) containing a repeating unit represented by are composed of A liquid crystal polyester in which the mass ratio [(A) / (B)] of the liquid crystal polyester (A) and the liquid crystal polyester (B) is 99 / 1 to 45 / 55 is preferably used. In this case, the mass ratio [(A) / (B)] of the liquid crystal polyester (A) and the liquid crystal polyester (B) is more preferably 90 / 10 to 50 / 50, and even more preferably 80 / 20 to 60 / 40.

[0032] Examples of the monomer that gives the repeating unit represented by formula (I) include 6-hydroxy-2-naphthoic acid and ester-forming derivatives such as acylates, ester derivatives, and acid halides of this.

[0033] Specific examples of the monomer that provides the repeating unit represented by formula (II) include, for example, hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, etc., which are aromatic diols, and their alkyl, alkoxy or halogen substituents, and ester-forming derivatives such as their acylates, etc.

[0034] Specific examples of the monomer that provides the repeating unit represented by formula (III) include, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, etc., which are aromatic dicarboxylic acids, and their alkyl, alkoxy or halogen substituents, and ester-forming derivatives such as their ester derivatives and acid halides.

[0035] Examples of the monomer that provides the repeating unit represented by formula (IV) include 4-hydroxybenzoic acid and its acylates, ester derivatives, acid halides and other ester-forming derivatives.

[0036] Examples of the monomer that provides the repeating unit represented by formula (V) include 6-hydroxy-2-naphthoic acid and its acylates, ester derivatives, acid halides and other ester-forming derivatives.

[0037] Hereinafter, the method for producing the liquid crystal polymer used in the present invention will be described. There is no particular limitation on the method for producing the liquid crystal polymer used in the present invention. A liquid crystal polymer can be obtained by subjecting a polymerizable monomer to a known polycondensation method for forming an ester bond or an amide bond, such as a melt acidolysis method, a slurry polymerization method, etc.

[0038] The melt acidolysis method is a preferred method for producing the liquid crystal polymer used in the liquid crystal polymer composition of the present invention. In this method, the polymerizable monomer is first heated to form a molten solution of the reaction substance, and then the polycondensation reaction is continued to obtain a molten polymer. In addition, a vacuum may be applied to facilitate the removal of volatile substances (such as acetic acid, water, etc.) by-produced in the final stage of condensation.

[0039] The slurry polymerization method is a method of reacting a polymerizable monomer in the presence of a heat exchange fluid, and the solid product is obtained in a state of being suspended in the heat exchange medium.

[0040] In both the case of the melt acidolysis method and the slurry polymerization method, the polymerizable monomer used in producing the liquid crystal polymer can also be subjected to the reaction as a modified form (lower acyl group) obtained by acylating a hydroxyl group and / or an amino group, that is, a lower acyl compound, at normal temperature.

[0041] The lower acyl group preferably has 2 to 5 carbon atoms, and more preferably 2 or 3 carbon atoms. In a preferred embodiment of the present invention, the acetylated product of the polymerizable monomer is subjected to the reaction.

[0042] The lower acyl compound of the polymerizable monomer may be separately acylated and pre-synthesized, or an acylating agent such as acetic anhydride may be added to the polymerizable monomer during the production of the liquid crystal polymer to be generated in the reaction system.

[0043] In both the case of the melt acidolysis method or the slurry polymerization method, the polycondensation reaction is preferably carried out at a temperature of usually 150 to 400 °C, preferably 250 to 370 °C, under normal pressure and / or reduced pressure, and a catalyst may be used if necessary.

[0044] Specific examples of the catalyst include organotin compounds such as dialkyltin oxides (e.g., dibutyltin oxide), diaryltin oxides; titanium dioxide; antimony trioxide; organic titanium compounds such as alkoxytitanium silicates, titanium alkoxides; alkali and alkaline earth metal salts of carboxylic acids (e.g., potassium acetate); gaseous acid catalysts such as Lewis acids (e.g., boron trifluoride), hydrogen halides (e.g., hydrogen chloride), and the like.

[0045] When using the catalyst, the amount of the catalyst is preferably 1 to 1000 ppm, more preferably 2 to 100 ppm, based on the total amount of the polymerizable monomer.

[0046] The liquid crystal polymer thus obtained by the polycondensation reaction is usually processed into pellets, flakes, or powder after being withdrawn from the polymerization reaction tank in a molten state.

[0047] The pelletized, flaked, or powdered liquid crystal polymer may be heat-treated in a substantially solid state under reduced pressure, under vacuum, or in an inert gas atmosphere such as nitrogen or helium for the purpose of increasing the molecular weight and improving the heat resistance.

[0048] The temperature of the heat treatment carried out in the solid state is not particularly limited as long as the liquid crystal polymer does not melt, but it is usually carried out at 260 to 350 °C, preferably 280 to 320 °C.

[0049] The polyarylate resin used in the present invention is a resin having aromatic dicarboxylic acid or its derivative and divalent phenol or its derivative as structural units, and can be produced by methods such as solution polymerization, melt polymerization, interfacial polymerization, and the like.

[0050] Examples of the aromatic dicarboxylic acids that constitute the polyarylate resin include terephthalic acid and isophthalic acid. From the viewpoints of melt processability and overall performance, it is preferably a mixture of both. The blending ratio of terephthalic acid and isophthalic acid in the mixture is not limited, but in terms of mass ratio, terephthalic acid / isophthalic acid = 9 / 1 to 1 / 9 is preferred. Considering the balance of melt processability and performance, the blending ratio is preferably 7 / 3 to 3 / 7, and particularly preferably 1 / 1.

[0051] Examples of the dihydric phenols that constitute the polyarylate resin include, for example, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl methane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxydiphenyl, hydroquinone, etc. Among them, 2,2-bis(4-hydroxyphenyl)propane [bisphenol A] is preferred. These may be used alone or as a mixture. Further, a small amount of ethylene glycol, propylene glycol, etc. may be used in combination with these dihydric phenols.

[0052] The intrinsic viscosity of the polyarylate resin (A) is not particularly limited, but from the viewpoints of mechanical properties and fluidity, the intrinsic viscosity measured at a temperature of 25 °C using 1,1,2,2-tetrachloroethane as a solvent is preferably 0.4 to 0.8, and more preferably 0.5 to 0.7.

[0053] The liquid crystal polymer composition of the present invention contains 100 parts by mass of the above-described liquid crystal polymer and 0.1 to 20 parts by mass of a polyarylate resin. The content of the polyarylate resin in the liquid crystal polymer composition is preferably 0.2 to 18 parts by mass, more preferably 0.4 to 16 parts by mass.

[0054] The liquid crystal polymer composition of the present invention is characterized in that its melt tension is 3 mN or more. The melt tension is measured by a melt tension measuring device (Capirograph 1D manufactured by Toyo Seiki Co., Ltd.) using a capillary of 2.0 mmφ × 10 mm, under the condition that the piston extrusion speed is 5.0 mm / s and the winding speed is increased from 0 to 200 m / min over 5 minutes, at a temperature of the crystal melting temperature + 20°C. The melt tension of the liquid crystal polymer composition of the present invention is preferably 4 mN or more, more preferably 5 mN or more, and usually 100 mN or less. When the melt tension is less than 3 mN, the film-forming property deteriorates and it becomes difficult to obtain a high-quality film.

[0055] The liquid crystal polymer composition of the present invention is characterized in that the dielectric loss tangent measured at 1 GHz using a stick-shaped test piece having a length of 85 mm, a width of 1.75 mm, and a thickness of 1.75 mm is 0.0015 or less. The dielectric loss tangent is preferably 0.0013 or less, more preferably 0.001 or less. Also, the dielectric loss tangent is usually 0.0001 or more.

[0056] The liquid crystal polymer composition of the present invention preferably has a crystal melting temperature (Tm) of 310 to 350°C, more preferably 315 to 348°C, still more preferably 320 to 345°C, and a crystallization temperature (Tc) of preferably 230 to 310°C, more preferably 235 to 308°C, still more preferably 240 to 305°C.

[0057] In the liquid crystal polymer composition of the present invention, the difference ΔT (Tm - Tc) between the above-mentioned crystal melting temperature (Tm) and the crystallization temperature (Tc) is preferably 40 °C or higher, more preferably 42 °C or higher, still more preferably 45 °C or higher, and particularly preferably 50 °C or higher. The upper limit of ΔT is usually 120 °C. The larger the ΔT is, that is, the larger the difference between the crystal melting temperature (Tm) and the crystallization temperature (Tc), the better the film-forming property, and a uniform and high-quality film can be obtained.

[0058] The liquid crystal polymer composition of the present invention may further contain an inorganic and / or organic filler as an optional component.

[0059] Specific examples of the inorganic and / or organic filler include, for example, glass fiber, silica alumina fiber, alumina fiber, carbon fiber, potassium titanate fiber, aluminum borate fiber, aramid fiber, polyarylate fiber, polybenzimidazole fiber, talc, mica, graphite, wollastonite, dolomite, clay, glass flake, glass bead, glass balloon, calcium carbonate, barium sulfate, titanium oxide, etc., and they may be used alone or in combination of two or more.

[0060] Among these, talc is preferable in terms of excellent balance between physical properties and cost.

[0061] Further, the inorganic and / or organic filler may be surface-treated. Examples of the surface treatment method include a method of adsorbing a surface treatment agent on the filler surface and a method of adding a surface treatment agent during kneading.

[0062] Examples of the surface treatment agent include silane-based coupling agents, titanate-based coupling agents, borane-based coupling agents, etc., which are reactive coupling agents, and higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, fluorocarbon-based surfactants, etc., which are lubricants.

[0063] When blending inorganic and / or organic fillers, the content is preferably 1 to 150 parts by mass, more preferably 10 to 100 parts by mass, based on 100 parts by mass of the total amount of the liquid crystal polymer and the polyarylate resin.

[0064] When the content of the inorganic and / or organic filler is less than 1 part by mass, it is difficult to obtain the effect of improving the mechanical strength and heat resistance of the liquid crystal polymer composition by the inorganic and / or organic filler. When it exceeds 150 parts by mass, the fluidity tends to decrease.

[0065] In addition to the liquid crystal polymer and the polyarylate resin, other additives and resin components may be added to the liquid crystal polymer composition of the present invention within a range that does not impair the object of the present invention.

[0066] Specific examples of other additives include, for example, higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty acid metal salts (where the higher fatty acid means those having 10 to 25 carbon atoms) as lubricants, polysiloxanes, fluororesins as mold release improvers, dyes, pigments, carbon black as colorants, flame retardants, antistatic agents, surfactants, talc, organic phosphates, sorbitols as nucleating agents, antiblocking agents, phosphorus-based antioxidants, phenolic antioxidants, sulfur-based antioxidants as antioxidants, weathering agents, heat stabilizers, neutralizing agents, and the like. These additives can be used alone or in combination of two or more.

[0067] The total amount of other additives in the liquid crystal polymer composition is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total amount of the liquid crystal polymer and the polyarylate resin.

[0068] When the total amount of other additives is less than 0.01 part by mass, it is difficult to realize the function of the additives. When it exceeds 5 parts by mass, the thermal stability of the molding process of the liquid crystal polymer composition tends to deteriorate.

[0069] In addition, among the above-mentioned other additives, when using additives such as lubricants, mold release agents, and anti-blocking agents, they may be added when preparing the liquid crystal polymer composition, or adhered to the surface of the pellets of the liquid crystal polymer composition during molding.

[0070] Specific examples of other resin components include, for example, thermoplastic resins such as polyester, polyacetal, polyphenylene ether and its modified products, polysulfone, polyethersulfone, polyetherimide, polyamideimide, etc., and thermosetting resins such as phenol resin, epoxy resin, polyimide resin, etc. These resin components may be used alone or in combination of two or more.

[0071] When containing other resin components, the content is preferably 0.1 to 100 parts by mass, more preferably 0.2 to 80 parts by mass, based on 100 parts by mass of the total amount of the liquid crystal polymer and the polyarylate resin.

[0072] The liquid crystal polymer composition of the present invention can be obtained by mixing a liquid crystal polymer, a polyarylate resin, a compatibilizer, an inorganic and / or organic filler, other additives, and other resin components, and melt-kneading under temperature conditions between near the crystal melting temperature of the liquid crystal polymer and the crystal melting temperature + 40°C using a Banbury mixer, kneader, single-screw or twin-screw extruder, etc.

[0073] Other resin components and other additives may be previously blended with either the liquid crystal polymer or the polyarylate resin, or may be blended when molding the liquid crystal polymer composition obtained by melt-kneading the liquid crystal polymer and the polyarylate resin.

[0074] The liquid crystal polymer composition of the present invention can be processed into molded products such as injection molded products, films, sheets, and non-woven fabrics by conventionally known molding methods such as injection molding, compression molding, extrusion molding, and blow molding. Particularly, due to its excellent film-forming properties, it can be suitably processed into films and sheets.

[0075] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Example

[0076] The crystal melting temperature, crystallization temperature, load deflection temperature, and dielectric tangent in the examples were measured by the methods described below.

[0077] 〈Crystal melting temperature and crystallization temperature〉 Measurement was carried out using Exstar6000 manufactured by Seiko Instruments Inc. When measuring a sample of the liquid crystal polymer composition under the temperature rising condition of 20 °C / min from room temperature, an endothermic peak was observed, and the sample was held at a temperature 20 to 50 °C higher than that temperature for 10 minutes. Next, when the sample was cooled to room temperature under the temperature decreasing condition of 20 °C / min, an exothermic peak was observed, and the temperature indicating the peak top was defined as the crystallization temperature (Tc). After that, after the sample was cooled to room temperature, when the measurement was carried out again under the temperature rising condition of 20 °C / min, an endothermic peak was observed, and the temperature indicating the peak top was defined as the crystal melting temperature (Tm).

[0078] 〈Melt tension〉 Using a melt tension measuring device (Capirograph 1D manufactured by Toyo Seiki Seisaku-sho, Ltd.), with a capillary of 2.0 mmφ×10 mm, under the condition that the piston extrusion speed is 5.0 mm / s and the winding speed is increased from 0 to 200 m / min over 5 minutes, the melt tension at the crystal melting temperature +20 °C was measured.

[0079] 〈Load deflection temperature〉 Using an injection molding machine (UH1000-110 manufactured by Nissei Plastic Industrial Co., Ltd.), a strip-shaped test piece (length 127 mm×width 12.7 mm×thickness 3.2 mm) was molded, and using this, in accordance with ASTM D648, the temperature at which a predetermined deflection amount (0.254 mm) was reached under a load of 1.82 MPa and a temperature rising rate of 2 °C / min was measured.

[0080] 〈Dielectric tangent (tanδ)〉 Using an injection molding machine (UH1000-110 manufactured by Nissei Plastic Industrial Co., Ltd.), a stick-shaped test piece with a length of 85 mm, a width of 1.75 mm, and a thickness of 1.75 mm was prepared. Using this test piece, the dielectric tangent at 1 GHz and 10 GHz was measured by the cavity resonator perturbation method using a vector network analyzer (manufactured by Agilent Technologies).

[0081] In the examples, the following abbreviations represent the following compounds. POB: 4-Hydroxybenzoic acid BON6: 6-Hydroxy-2-naphthoic acid BP: 4,4'-Dihydroxybiphenyl HQ: Hydroquinone TPA: Terephthalic acid NDA: 2,6-Naphthalenedicarboxylic acid PAR: Polyarylate resin

[0082] [Synthesis Example 1 (LCP-1)] Into a reaction vessel equipped with a stirring device with a torque meter and a distillation tube, 660.5 g (54.0 mol%) of BON6, 254.2 g (21.0 mol%) of BP, 14.3 g (2.0 mol%) of HQ, and 248.3 g (23.0 mol%) of TPA were charged. Further, 1.03 times the molar amount of acetic anhydride based on the total amount of hydroxyl groups (mol) of all monomers was charged, and deacetic acid polymerization was carried out under the following conditions.

[0083] Under a nitrogen gas atmosphere, the temperature was raised from room temperature to 150 °C over 1 hour and held at 150 °C for 60 minutes. Then, while distilling off the by-produced acetic acid, the temperature was raised to 350 °C over 7 hours, and then the pressure was reduced to 10 mmHg over 90 minutes. The polymerization reaction was terminated when a predetermined torque was shown, and the contents were taken out from the reaction vessel, and pellets of liquid crystal polyester were obtained by a pulverizer. The amount of acetic acid distilled off during polymerization was almost the same as the theoretical value. The crystal melting temperature (Tm) of the obtained pellets was 338 °C, and the melt viscosity was 23 Pa·s.

[0084] [Synthesis Example 2 (LCP-2)] A stirring device equipped with a torque meter and a reaction vessel equipped with a distillation tube were charged with 655.4 g (73 mol%) of POB and 330.2 g (27 mol%) of BON6. Further, acetic anhydride in an amount 1.02 times the molar amount of the hydroxyl groups of all the monomers was charged, and deacetylation polymerization was carried out under the following conditions.

[0085] Under a nitrogen gas atmosphere, the temperature was raised from room temperature to 145 °C over 1 hour and held at 145 °C for 30 minutes. Next, while distilling off the by-produced acetic acid, the temperature was raised to 320 °C over 7 hours, and then the pressure was reduced to 10 mmHg over 80 minutes. When a predetermined torque was shown, the polymerization reaction was terminated, the content was taken out from the reaction vessel, and pellets of the liquid crystal polyester were obtained by a pulverizer. The amount of acetic acid distilled off during polymerization was almost the same as the theoretical value. The crystal melting temperature (Tm) of the obtained pellets was 279 °C, and the melt viscosity was 21 Pa·s.

[0086] [Synthesis Example 3 (LCP-3)] A stirring device equipped with a torque meter and a reaction vessel equipped with a distillation tube were charged with 641.9 g (71.5 mol%) of POB, 30.6 g (2.5 mol%) of BON6, 93.0 g (13 mol%) of HQ, and 182.7 g (13 mol%) of NDA. Further, acetic anhydride in an amount 1.03 times the molar amount of the hydroxyl groups of all the monomers was charged, and deacetylation polymerization was carried out under the following conditions.

[0087] Under a nitrogen gas atmosphere, the temperature was raised from room temperature to 145 °C over 1 hour and held at 145 °C for 30 minutes. Next, while distilling off the by-produced acetic acid, the temperature was raised to 345 °C over 7 hours, and then the pressure was reduced to 10 mmHg over 80 minutes. When a predetermined torque was shown, the polymerization reaction was terminated, the content was taken out from the reaction vessel, and pellets of the liquid crystal polyester resin were obtained by a pulverizer. The amount of acetic acid distilled off during polymerization was almost the same as the theoretical value. The crystal melting temperature (Tm) of the obtained pellets was 321 °C, and the melt viscosity was 23 Pa·s.

[0088] [Polyarylate resin] As the polyarylate resin, the following was used. Polyarylate resin: U Polymer (registered trademark) U-100 (manufactured by Unitika Ltd.)

[0089] Example 1 As 100 parts by mass of LCP-1 as a liquid crystal polymer and 3 parts by mass of a polyarylate resin, melt-kneading was performed at 350 °C using a twin-screw extruder (TEX-30 manufactured by Nippon Steel Corporation) to obtain pellets of the liquid crystal polymer composition. The crystallization melting temperature, crystallization temperature, deflection temperature under load, and dielectric tangent were measured by the above method. The results are shown in Table 1. Examples 2 to 6, Comparative Examples 1 to 6

[0090] LCP-1 to 3 and the polyarylate resin were blended so as to have the contents described in Table 1, and pellets were obtained in the same manner as in Example 1, and the crystallization melting temperature, crystallization temperature, deflection temperature under load, and dielectric tangent were measured. The results are shown in Table 1.

[0091]

Table 1

Claims

1. A liquid crystal polymer composition containing 100 parts by mass of a liquid crystal polymer and 0.1 to 20 parts by mass of a polyarylate resin, wherein the liquid crystal polymer contains a liquid crystal polyester (A) having repeating units represented by the formulas (I) to (III) 【Chemical 1】 [wherein, Ar １ and Ar ２ each represent one or more divalent aromatic groups, and p, q, and r are the composition ratios (mol%) of the respective repeating units in the liquid crystal polyester (A), satisfying the following conditions: 35 ≤ p ≤ 90, 5 ≤ q ≤ 30, and 5 ≤ r ≤ 30] and has a melt tension of 3 mN or more and a dielectric tangent measured at 1 GHz using a stick-shaped test piece having a length of 85 mm, a width of 1.75 mm, and a thickness of 1.75 mm of 0.0015 or less. A liquid crystal polymer composition.

2. The liquid crystal polymer composition according to claim 1, wherein the difference ΔT (Tm - Tc) between the crystal melting temperature (Tm) and the crystallization temperature (Tc) is 40°C or more.

3. The liquid crystal polymer is a liquid crystal polyester containing repeating units represented by the formulas (I) to (III) [wherein, 35 ≤ p ≤ 90, 5 ≤ q ≤ 30, and 【Chemical Formula 1】 5 ≤ r ≤ 30] Ar １ and Ar ２ each represent one or more divalent aromatic groups, and p, q, and r are the composition ratios (mol%) of the respective repeating units in the liquid crystal polyester (A), satisfying the following conditions: The liquid crystal polymer composition according to claim 1 or 2.

4. The liquid crystal polymer contains a liquid crystal polyester (A) having repeating units represented by the formulas (I) to (III) [wherein, 35 ≤ p ≤ 90, 5 ≤ q ≤ 30, and [Chemical 2] 5 ≤ r ≤ 30] Ar １ and Ar ２ each represent one or more divalent aromatic groups, and p, q, and r are the composition ratios (mol%) of each repeating unit in the liquid crystal polyester (A), respectively, and satisfy the following conditions: and a liquid crystal polyester (B) having repeating units represented by the formulas (IV) and (V) [wherein, s and t are the composition ratios (mol%) of the respective repeating units in the liquid crystal polyester (B), and satisfy the following conditions: 80 / 20 ≤ s / t ≤ 60 / 40] and the mass ratio [(A) / (B)] of the liquid crystal polyester (A) to the liquid crystal polyester (B) is 99 / 1 to 45 / 55. The liquid crystal polymer composition according to claim 1 or 2. 【Chemical 3】

5. The liquid crystal polymer composition according to claim 4, wherein the liquid crystal polyester (B) is a liquid crystal polyester composed of repeating units represented by the formulas (IV) and (V).

6. The liquid crystal polymer composition according to any one of claims 1 to 5, wherein the content of the polyarylate resin is 5 to 20 parts by mass.

7. A film composed of the liquid crystal polymer composition according to any one of claims 1 to 6. ​ ​ ​ ​ ​ ​

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