Liquid crystal resin composition

Abstract

To provide a liquid crystalline resin composition excellent in dielectric characteristics and heat resistance and good in fluidity.SOLUTION: The liquid crystalline resin composition according to the present invention contains (A) a liquid crystalline resin, (B) a cyclic olefin resin, and (C) a hollow filler. The liquid crystalline resin (A) has a melting point of 300°C or higher. The cyclic olefin resin (B) has a glass transition temperature of 100°C or higher. Based on 100 pts.vol. of the total of the liquid crystalline resin (A) and the cyclic olefin resin (B), the content of the liquid crystalline resin (A) is 55-85 pts.vol.; the content of the cyclic olefin resin (B) is 15-45 pts.vol.; and the content of the hollow filler (C) is 20-75 pts.vol. The liquid crystalline resin (A) is preferably an aromatic polyester or an aromatic polyester amide having a constituent unit derived from at least one selected from the group consisting of an aromatic hydroxycarboxylic acid and a derivative thereof as a constituent. The hollow filler (C) is preferably a glass balloon.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid crystalline resin composition. [Background technology]

[0002] Liquid crystalline resins, typified by liquid crystalline polyester resins, have a good balance of excellent mechanical strength, heat resistance, chemical resistance, electrical properties, etc., and also have excellent dimensional stability, and are therefore widely used as high-performance engineering plastics. Meanwhile, in recent years, remarkable technological developments have been made in the information and communications field, including mobile phones, wireless LANs, and ITS technologies such as GPS, VICS (registered trademark), and ETC. Accordingly, there is a growing need for high-performance electronic components that can be used in high-frequency ranges such as microwaves and millimeter waves. Materials constituting such electronic components are required to have appropriate dielectric properties depending on the design of each electronic component.

[0003] For example, Patent Document 1 discloses a molded article of a wholly aromatic liquid crystalline polyester resin composition having a relative dielectric constant of 3.0 or less and a dielectric dissipation factor of 0.04 or less, which is obtained by injection molding a composition containing 90 to 45% by weight of a wholly aromatic liquid crystalline polyester having a melting point of 320°C or more, 10 to 40% by weight of inorganic hollow spheres having an aspect ratio of 2 or less, and 0 to 15% by weight of an inorganic filler having an aspect ratio of 4 or more. The molded article has heat resistance such as resistance to solder reflow, excellent dielectric properties, and is used as a fixing or holding member for transmitting and receiving components of information and communication devices used in high frequency bands such as microwaves and millimeter waves. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-27021 Summary of the Invention [Problem to be solved by the invention]

[0005] However, according to the studies of the present inventors, it has been found that conventional liquid crystalline resin compositions containing hollow fillers such as inorganic hollow spheres have extremely high melt viscosity, poor fluidity, or room for improvement in dielectric properties or heat resistance.

[0006] The present invention has been made to solve the above problems, and an object of the present invention is to provide a liquid crystalline resin composition which is excellent in dielectric properties and heat resistance, and has good fluidity. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to solve the above problems. As a result, they have found that a liquid crystalline resin composition containing a liquid crystalline resin having a melting point of 300°C or higher and a cyclic olefin resin having a glass transition temperature of 100°C or higher in a predetermined amount has excellent dielectric properties and heat resistance, and good fluidity, and have completed the present invention. More specifically, the present invention provides the following.

[0008] (1) A liquid crystalline resin composition comprising (A) a liquid crystalline resin, (B) a cyclic olefin resin, and (C) a hollow filler, wherein the melting point of the (A) liquid crystalline resin is 300°C or higher, the glass transition temperature of the (B) cyclic olefin resin is 100°C or higher, and the content of the (A) liquid crystalline resin is 55 to 85 parts by volume, the content of the (B) cyclic olefin resin is 15 to 45 parts by volume, and the content of the (C) hollow filler is 20 to 75 parts by volume, relative to 100 parts by volume of the total of the (A) liquid crystalline resin and the (B) cyclic olefin resin.

[0009] (2) The liquid crystalline resin composition according to (1), wherein (A) the liquid crystalline resin is an aromatic polyester or aromatic polyester amide having, as a constituent component, a constituent unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof.

[0010] (3) The liquid crystal resin composition according to (1) or (2), wherein the hollow filler (C) is a glass balloon.

[0011] (4) The liquid crystal resin composition according to any one of (1) to (3), wherein (B) the cyclic olefin resin is an addition polymer of a cyclic olefin monomer and an α-olefin.

[0012] (5) The liquid crystal resin composition according to any one of (1) to (4), further comprising an inorganic filler. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a liquid crystalline resin composition having excellent dielectric properties, heat resistance, and good fluidity. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a top view showing the cutting positions of the test pieces for evaluating dielectric characteristics used in the examples and comparative examples. DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. Furthermore, the value of volume parts representing the content of a component in a liquid crystalline resin composition is a value calculated from the value of parts by mass of the component and the true specific gravity of the component. In this specification, the values ​​of volume parts and true specific gravity are used at room temperature (20 to 30°C).

[0016] <Liquid crystal resin composition> The liquid crystalline resin composition according to the present invention contains (A) a liquid crystalline resin, (B) a cyclic olefin resin, and (C) a hollow filler, and the melting point of the (A) liquid crystalline resin is 300°C or higher, and the glass transition temperature of the (B) cyclic olefin resin is 100°C or higher.

[0017] [(A) Liquid crystalline resin] The liquid crystalline resin (A) used in the present invention refers to a melt-processable polymer capable of forming an optically anisotropic molten phase. The properties of the anisotropic molten phase can be confirmed by a conventional polarization examination method using crossed polarizers. More specifically, the anisotropic molten phase can be confirmed by observing a molten sample placed on a Leitz hot stage at 40x magnification using a Leitz polarizing microscope under a nitrogen atmosphere. When examined between crossed polarizers, the liquid crystalline polymer applicable to the present invention normally transmits polarized light, even in a molten, stationary state, exhibiting optical anisotropy.

[0018] The melting point of the (A) liquid crystalline resin is 300° C. or higher, preferably 300 to 360° C., and more preferably 315 to 345° C. When the (A) liquid crystalline resin has a melting point of 300° C. or higher, it is easy to obtain a liquid crystalline resin composition having excellent heat resistance. When the (A) liquid crystalline resin has a melting point of 360° C. or lower, it is easy to obtain a liquid crystalline resin composition having good fluidity.

[0019] The type of the liquid crystalline resin (A) is not particularly limited, but is preferably an aromatic polyester and / or an aromatic polyester amide. Polyesters partially containing aromatic polyesters and / or aromatic polyester amides in the same molecular chain are also included. The liquid crystalline resin (A) preferably has an inherent viscosity (IV) of at least about 2.0 dL / g, more preferably 2.0 to 10.0 dL / g, when dissolved in pentafluorophenol at 60°C to a concentration of 0.1% by mass.

[0020] The aromatic polyester or aromatic polyesteramide as the (A) liquid crystalline resin applicable to the present invention is particularly preferably an aromatic polyester or aromatic polyesteramide having, as a constituent component, a constituent unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, aromatic diamines, and derivatives thereof.

[0021] More specifically, (1) A polyester mainly composed of structural units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof; (2) A polyester composed mainly of (a) structural units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof, and (b) structural units derived from at least one selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof; (3) A polyester mainly composed of (a) structural units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof, (b) structural units derived from at least one selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof, and (c) structural units derived from at least one selected from the group consisting of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof; (4) A polyesteramide mainly composed of (a) structural units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof, (b) structural units derived from at least one selected from the group consisting of aromatic hydroxyamines, aromatic diamines, and derivatives thereof, and (c) structural units derived from at least one selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof; (5) Polyesteramides mainly comprising (a) structural units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and their derivatives, (b) structural units derived from at least one selected from the group consisting of aromatic hydroxyamines, aromatic diamines, and their derivatives, (c) structural units derived from at least one selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives, and (d) structural units derived from at least one selected from the group consisting of aromatic diols, alicyclic diols, aliphatic diols, and their derivatives. Furthermore, a molecular weight modifier may be used in combination with the above structural components, if necessary.

[0022] Preferred examples of specific compounds constituting the (A) liquid crystal resin applicable to the present invention include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; aromatic diols such as 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, hydroquinone, resorcinol, compounds represented by the following general formula (I) and compounds represented by the following general formula (II); aromatic dicarboxylic acids such as 1,4-phenylenedicarboxylic acid, 1,3-phenylenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid and compounds represented by the following general formula (III); and aromatic amines such as p-aminophenol, p-phenylenediamine and N-acetyl-p-aminophenol. [ka] (X is a group selected from alkylene (C1 to C4), alkylidene, -O-, -SO-, -SO2-, -S-, and -CO-.) [ka] [ka] (Y:-(CH2) n -(n=1 to 4) and -O(CH2) n O-(n=1 to 4).

[0023] The liquid crystal resin (A) used in the present invention can be prepared from the above-mentioned monomer compound (or a mixture of monomers) by known methods such as direct polymerization or transesterification. Typically, melt polymerization, solution polymerization, slurry polymerization, solid-state polymerization, or a combination of two or more of these methods is used. Melt polymerization or a combination of melt polymerization and solid-state polymerization is preferred. The above-mentioned compounds capable of forming esters may be used in the polymerization in their original form, or may be modified from precursors to derivatives capable of forming esters prior to polymerization. Various catalysts can be used in these polymerizations. Representative examples include metal salt catalysts such as potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and tris(2,4-pentanedionato)cobalt(III), and organic compound catalysts such as N-methylimidazole and 4-dimethylaminopyridine. The amount of catalyst used is generally about 0.001 to 1% by mass, preferably about 0.01 to 0.2% by mass, based on the total mass of the monomers. If necessary, the molecular weight of the polymers produced by these polymerization methods can be increased by solid-phase polymerization, in which the polymers are heated under reduced pressure or in an inert gas.

[0024] The melt viscosity of the liquid crystalline resin (A) obtained by the above method is not particularly limited. Generally, the melt viscosity at the molding temperature is 1000 s -1 A liquid crystal resin having a viscosity of 3 Pa·s or more and 500 Pa·s or less can be used. However, a liquid crystal resin having a viscosity that is too high is not preferable because it will significantly deteriorate the flowability. The liquid crystal resin (A) may be a mixture of two or more types of liquid crystal resins.

[0025] The content of component (A) is 55 to 85 parts by volume, preferably 58 to 82 parts by volume, and more preferably 60 to 80 parts by volume, per 100 parts by volume of the total of the liquid crystal resin (A) and the cyclic olefin resin (B). When the content of component (A) is 55 parts by volume or more, a liquid crystal resin composition with excellent heat resistance is easily obtained. When the content of component (A) is 85 parts by volume or less, a liquid crystal resin composition with excellent dielectric properties is easily obtained.

[0026] [(B) Cyclic olefin resin] The form of the cyclic olefin resin (B) in the present invention is not particularly limited, and examples thereof include the following. (1) Addition polymer of a monomer having a ring structure and an olefin (2) Ring-opening polymers of a monomer having a ring structure and a monomer having a monocyclic structure

[0027] The number of types of the cyclic olefin resin (B) blended in the liquid crystal resin composition of the present invention may be one or two or more.

[0028] Whether the (B) cyclic olefin resin is an addition polymer or a ring-opening polymer, from the viewpoint of flexibility, etc., it is preferable that the monomers constituting the (B) cyclic olefin resin are selected so that the resulting (B) cyclic olefin resin contains an ethylene unit. Here, the ethylene unit refers to a structural unit derived from ethylene. Examples of the monomers constituting the (B) cyclic olefin resin will be described below.

[0029] (Monomers with ring structures) (B) Examples of the monomer having a ring structure that constitutes the cyclic olefin resin include cyclic olefin monomers, such as norbornene and polycyclic cyclic monomers represented by the following general formula (IV):

[0030] [ka]

[0031] In formula (I), R 1 ~R 12 may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of unsaturated hydrocarbon groups include vinyl groups. Examples of monomers having a ring structure containing a vinyl group include 5-vinyl-2-norbornene.

[0032] R 9 and R 10 , R 11 and R 12 may combine to form a divalent hydrocarbon group. R 9 or R 10 and R 11 or R 12 may form a ring together. n represents 0 or a positive integer, and when n is 2 or more, R 5 ~R 8 may be the same or different in each repeating unit. However, when n=0, R 1 ~R 4 and R 9 ~R 12 At least one of the is not a hydrogen atom.

[0033] R 9 and R 10 , or R 11 and R 12 Specific examples of the divalent hydrocarbon group formed by combining with each other include alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group.

[0034] R 9 or R 10 and R 11 or R 12 When these rings form a ring, the ring formed may be a monocyclic ring or a polycyclic ring, a polycyclic ring having a bridge, a ring having a double bond, or a ring formed by a combination of these rings. In addition, these rings may have a substituent such as a methyl group.

[0035] The monomer having a ring structure may or may not have a side chain.

[0036] Specific examples of the monomer having a ring structure include norbornene and tetracyclododecene. Norbornene is particularly preferred as the monomer having a ring structure from the viewpoint of high reactivity to a catalyst (such as a metallocene catalyst) in the reaction with an olefin.

[0037] In the (B) cyclic olefin resin, the content of structural units derived from monomers having a ring structure is not particularly limited. From the viewpoint of imparting heat resistance to the (B) cyclic olefin resin, the lower limit of the content of the structural units is preferably more than 0 mol%, more preferably 5 mol or more, relative to all structural units contained in the (B) cyclic olefin resin. From the viewpoint of easily imparting crosslinkability, the upper limit of the content of the structural units is preferably 55 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less, relative to all structural units contained in the (B) cyclic olefin resin.

[0038] The monomer having a ring structure that constitutes the (B) cyclic olefin resin may be one type alone or two or more types in combination.

[0039] (olefin) The olefin constituting the (B) cyclic olefin-based resin is not particularly limited, and examples thereof include α-olefins, preferably α-olefins having 2 to 10 carbon atoms.

[0040] Specific examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. Of the above, ethylene is particularly preferred.

[0041] In the (B) cyclic olefin resin, the content of the olefin is not particularly limited. From the viewpoint of easily imparting flexibility to the obtained crosslinked product, the lower limit of the content of the olefin is preferably 45 mol% or more, more preferably 50 mol% or more, and even more preferably 60 mol% or more, based on all structural units contained in the (B) cyclic olefin resin. From the viewpoint of easily obtaining a crosslinked product having an appropriate elastic modulus, the upper limit of the content of the olefin is preferably less than 100 mol%, more preferably 95 mol% or less, based on all structural units contained in the (B) cyclic olefin resin.

[0042] The olefin constituting the (B) cyclic olefin-based resin may be one type alone or two or more types in combination.

[0043] (Monomers having a monocyclic structure) The monomer having a monocyclic structure is not particularly limited as long as it is an olefin having only one cyclic structure, and the olefin is preferably an olefin having 3 to 10 carbon atoms.

[0044] Specific examples of monomers having a monocyclic structure include cyclic monoolefins (cyclopropene, cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, cyclooctene, etc.) and cyclic diolefins (cyclohexadiene, methylcyclohexadiene, cyclooctadiene, methylcyclooctadiene, etc.). Of these, cyclopentene is particularly preferred.

[0045] In the (B) cyclic olefin resin, the content of the monomer having a monocyclic structure is not particularly limited. From the viewpoint of easily imparting flexibility to the obtained crosslinked product, the lower limit of the content of the monomer having a monocyclic structure is preferably 40 mol% or more relative to all structural units contained in the (B) cyclic olefin resin. From the viewpoint of easily obtaining a crosslinked product having an appropriate elastic modulus, the upper limit of the content of the monomer having a monocyclic structure is preferably less than 100 mol% relative to all structural units contained in the (B) cyclic olefin resin. The monomer having a monocyclic structure constituting the (B) cyclic olefin resin may be one type alone or two or more types in combination.

[0046] (addition reaction) When the (B) cyclic olefin resin is an addition polymer of a monomer having a ring structure and an olefin, the (B) cyclic olefin resin can be produced using the above-mentioned monomer having a ring structure and an olefin by employing any method known as a method for producing an addition polymer.

[0047] As the addition polymerization catalyst, a metallocene catalyst can be particularly suitably used.Specific examples of metallocene catalysts include (t-butylamido)dimethyl-9-fluorenylsilane titanium dimethyl, racemic ethylidene-bis(indenyl)zirconium dichloride, racemic dimethylsilyl-bis(2-methyl-benzoindenyl)zirconium dichloride, racemic isopropylidene-bis(tetrahydroindenyl)zirconium dichloride, isopropylidene(1-indenyl)(3-isopropyl-cyclopentadienyl)zirconium dichloride, (t-butylamido)dimethyl-9-fluorenylsilane zirconium dichloride, dimethyl, (t-butylamido)dimethyl-9-fluorenylsilane zirconium dichloride, (t-butylamido)dimethyl-9-(3,6-dimethylfluorenyl)silane zirconium dimethyl, (t-butylamido)dimethyl-9-[3,6-di(i-propyl)fluorenyl]silane zirconium dimethyl, (t-butylamido)dimethyl-9-[3,6-di(t-butyl)fluorenyl]silane zirconium dimethyl, (t-butylamido)dimethyl-9-[2,7-di(t-butyl)fluorenyl]silane zirconium dimethyl, (t-butyl (t-butylamido)dimethyl-9-(2,3,6,7-tetramethylfluorenyl)silane zirconium dimethyl, racemic-ethylidene-bis(indenyl)titanium dichloride, racemic-dimethylsilyl-bis(2-methyl-benzoindenyl)titanium dichloride, racemic-isopropylidene-bis(tetrahydroindenyl)titanium dichloride, isopropylidene(1-indenyl)(3-isopropyl-cyclopentadienyl)titanium dichloride, (t-butylamido)dimethyl-9-fluorenylsilanetitanium dichloride, (t-butylamido)dimethyl Examples of silane titanium dimethyl include, but are not limited to, t-butylamido)dimethyl-9-[3,6-di(i-propyl)fluorenyl]silanetitanium dimethyl, (t-butylamido)dimethyl-9-[3,6-di(t-butyl)fluorenyl]silanetitanium dimethyl, (t-butylamido)dimethyl-9-[2,7-di(t-butyl)fluorenyl]silanetitanium dimethyl, and (t-butylamido)dimethyl-9-(2,3,6,7-tetramethylfluorenyl)silanetitanium dimethyl.The addition polymerization catalysts can be used singly or in combination of two or more.

[0048] (B) Cyclic olefin resins can be more easily obtained by using a co-catalyst together with the polymerization catalyst. The co-catalyst can be used alone or in combination of two or more. Examples of the co-catalyst include alkylaluminoxanes and alkylaluminums.

[0049] (Ring-opening reaction) When the (B) cyclic olefin resin is a ring-opening polymer of a monomer having a ring structure and a monomer having a monocyclic structure, it can be obtained by ring-opening polymerization using the above-mentioned monomer having a ring structure, monomer having a monocyclic structure, and chain transfer agent in the presence of a ring-opening polymerization catalyst, followed by hydrogenation as necessary.

[0050] There are no particular restrictions on the chain transfer agent as long as it can control the molecular weight and has one double bond between carbon atoms at the terminal, and examples thereof include the above-mentioned α-olefins (1-hexene, etc.).

[0051] The ring-opening polymerization catalyst may be any catalyst capable of ring-opening copolymerization of a monocyclic olefin and a norbornene compound, and is preferably a ruthenium carbene complex. Specific examples of the ruthenium carbene complex include bis(tricyclohexylphosphine)benzylidene ruthenium dichloride, bis(triphenylphosphine)-3,3-diphenylpropenylidene ruthenium dichloride, bis(tricyclohexylphosphine)t-butylvinylidene ruthenium dichloride, dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium, bis(1,3-diisopropylimidazolin-2-ylidene)benzylidene ruthenium dichloride, and bis(1,3-dicyclohexyl Examples of the ring-opening polymerization catalyst include (1,3-dimesitylimidazolin-2-ylidene)benzylidene ruthenium dichloride, (1,3-dimesitylimidazolin-2-ylidene)(tricyclohexylphosphine)benzylidene ruthenium dichloride, (1,3-dimesitylimidazolin-2-ylidene)(tricyclohexylphosphine)benzylidene ruthenium dichloride, bis(tricyclohexylphosphine)ethoxymethylidene ruthenium dichloride, and (1,3-dimesitylimidazolin-2-ylidene)(tricyclohexylphosphine)ethoxymethylidene ruthenium dichloride. The ring-opening polymerization catalyst can be used alone or in combination of two or more.

[0052] In the present invention, after the ring-opening polymerization, if necessary, a hydrogenation catalyst and hydrogen may be added to the reaction system in the ring-opening polymerization step to hydrogenate the double bonds between carbon atoms in the ring-opening polymer. The hydrogenation catalyst may be any catalyst that is generally used in hydrogenation reactions of olefins and aromatic compounds. Specific examples of the hydrogenation catalyst include the following: (1) Supported metal catalysts in which transition metals are supported on a support (carbon, alumina, silica, diatomaceous earth, etc.) (2) Homogeneous catalysts consisting of organic transition metal compounds (titanium, cobalt, nickel, etc.) and organic metal compounds (lithium, magnesium, aluminum, tin, etc.) (3) Metal complex catalysts (rhodium, ruthenium, etc.)

[0053] ((B) Glass transition temperature of cyclic olefin resin) The glass transition temperature (hereinafter also referred to as "Tg") of the (B) cyclic olefin resin is 100°C or higher. When the (B) cyclic olefin resin has a Tg of 100°C or higher, it is easy to obtain a liquid crystalline resin composition that has excellent heat resistance while maintaining good fluidity. The lower limit of the Tg of the (B) cyclic olefin resin is preferably 120°C or higher, more preferably 140°C or higher. The upper limit of the Tg of the (B) cyclic olefin resin is not particularly limited, and may be 200°C or lower, or may be 170°C or lower.

[0054] In the present invention, the Tg is a value measured by the DSC method (method described in JIS K 7121) under the condition of a temperature rise rate of 20° C. / min.

[0055] The content of component (B) is 15 to 45 parts by volume, preferably 18 to 42 parts by volume, and more preferably 20 to 40 parts by volume, per 100 parts by volume of the total of liquid crystal resin (A) and cyclic olefin resin (B). When the content of component (B) is 15 parts by volume or more, a liquid crystal resin composition with excellent dielectric properties is easily obtained. When the content of component (A) is 45 parts by volume or less, a liquid crystal resin composition with excellent heat resistance is easily obtained.

[0056] [(C) Hollow filler] (C) Hollow filler is generally called balloon, and examples of hollow sphere materials include inorganic materials such as alumina, silica, and glass; and organic materials such as urea resin and phenolic resin. Among these, glass is preferred from the viewpoint of heat resistance and strength. That is, glass balloons are preferably used as the hollow filler. (C) component may be used alone or in combination of two or more types.

[0057] From the viewpoints of suppressing an increase in melt viscosity and a deterioration in fluidity, as well as moldability, the aspect ratio of the (C) hollow filler is preferably 1.15 or more, more preferably 1.20 to 2.00, even more preferably 1.22 to 1.50, and even more preferably 1.25 to less than 1.30. In this specification, the aspect ratio is determined by measuring the maximum length L, which is the length of the longest part in the particle projection plane, and the maximum perpendicular length S, which is the length of the longest part in the particle projection plane in the direction perpendicular to the maximum length L, for 3,000 particles using a dynamic image analysis method / particle state analyzer, and repeating the measurement several times to obtain the average value of the ratio L / S calculated for each particle.

[0058] From the viewpoint of moldability, the median diameter of component (C) is preferably 5 μm or more, more preferably 10 μm or more, and from the viewpoint of suppressing breakage of component (C) and moldability, it is preferably 200 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less. In this specification, the median diameter refers to the volume-based median value measured by a laser diffraction / scattering particle size distribution measurement method.

[0059] The content of component (C) is 20 to 75 parts by volume, preferably 25 to 73 parts by volume, and more preferably 30 to 70 parts by volume, per 100 parts by volume of the total of the liquid crystal resin (A) and the cyclic olefin resin (B). When the content of component (C) is 20 parts by volume or more, a liquid crystal resin composition with excellent dielectric properties is easily obtained. When the content of component (C) is 75 parts by volume or less, a liquid crystal resin composition with good fluidity is easily obtained.

[0060] [(D)(C) Inorganic fillers excluding hollow fillers] The liquid crystalline resin composition according to the present invention may optionally contain (D) an inorganic filler other than the hollow filler (C). When the liquid crystalline resin composition contains the component (D), the mechanical strength of the molded article of the liquid crystalline resin composition, such as the flexural modulus, is likely to be improved. The component (D) may be used alone or in combination of two or more. Examples of the component (D) include a plate-like filler, a fibrous filler, and a granular filler.

[0061] (plate-like filler) When the liquid crystalline resin composition according to the present invention contains a plate-like filler, the molded article made of the liquid crystalline resin composition is likely to have improved mechanical strength such as flexural modulus, and warpage is likely to be suppressed. The plate-like filler may be used alone or in combination of two or more kinds.

[0062] The plate-like filler preferably has a median diameter of 15 to 50 μm. When the median diameter is 15 μm or more, the necessary mechanical strength is easily ensured, and the effect of suppressing warpage of the molded article is easily enhanced. When the median diameter is 50 μm or less, the fluidity of the composition when melted is easily improved. The preferred median diameter is 20 to 30 μm.

[0063] The plate-like filler is not particularly limited, and examples thereof include mica, talc, glass flakes, graphite, various metal foils (e.g., aluminum foil, iron foil, copper foil), etc. In the present invention, it is preferable to use mica as the plate-like filler.

[0064] (fibrous filler) When the liquid crystalline resin composition according to the present invention contains a fibrous filler, the molded article made of the liquid crystalline resin composition tends to have improved mechanical strength such as flexural modulus. The fibrous fillers can be used singly or in combination of two or more.

[0065] The average fiber length of the fibrous filler is not particularly limited and may be, for example, 250 μm or more, preferably 350 to 600 μm, and more preferably 450 to 500 μm. When the average fiber length is 250 μm or more, the molded article made from the liquid crystalline resin composition of the present invention is likely to have improved mechanical strength and heat resistance. When the average fiber length is 600 μm or less, the liquid crystalline resin composition is likely to have sufficient fluidity. In this specification, the average fiber length of the fibrous filler is defined as the average of the fiber lengths measured for 100 fibrous fillers per stereomicroscope image, i.e., a total of 1,000 fibrous fillers, obtained by importing 10 stereomicroscope images of the fibrous filler from a CCD camera into a PC and processing the images using an image measuring device. The average fiber length of the fibrous filler in the liquid crystalline resin composition is measured by the above-mentioned method using the remaining fibrous filler after heating the liquid crystalline resin composition to 600°C for 2 hours to incinerate it.

[0066] The average fiber diameter of the fibrous filler is not particularly limited and may be, for example, 20 μm or less, or may be 5 to 15 μm. In this specification, the average fiber diameter of the fibrous filler is determined by observing the fibrous filler with a scanning electron microscope and measuring the fiber diameters of 30 fibrous fillers. The average fiber diameter of the fibrous filler in the liquid crystalline resin composition is measured by the above-mentioned method using the fibrous filler remaining after heating the liquid crystalline resin composition to incinerate it at 600°C for 2 hours.

[0067] Any fiber can be used as long as it satisfies the above-mentioned shape requirements, but examples of fibrous fillers include inorganic fibrous materials such as glass fiber, milled fiber, carbon fiber, asbestos fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, and metal fibers such as stainless steel, aluminum, titanium, copper, brass, etc. In the present invention, from the viewpoint of mechanical strength, it is preferable to use glass fiber as the fibrous filler.

[0068] (granular filler) When the liquid crystalline resin composition according to the present invention contains a granular filler, the molded article made of the liquid crystalline resin composition is likely to have improved mechanical strength such as flexural modulus and is likely to be inhibited from surface whitening. The granular filler can be used singly or in combination of two or more.

[0069] The median diameter of the granular filler is preferably 0.3 to 5.0 μm. When the median diameter is 0.3 μm or more, the impact resistance of the molded article is likely to be maintained. When the median diameter is 5.0 μm or less, the effect of suppressing surface whitening of the molded article is likely to be enhanced. The median diameter is more preferably 0.5 to 5.0 μm, and even more preferably 0.5 to 4.0 μm. The median diameter of the granular filler in the liquid crystalline resin composition is a value measured for the granular filler remaining after the liquid crystalline resin composition is incinerated by heating at 600° C. for 2 hours.

[0070] Examples of granular fillers include metal oxides such as silica, quartz powder, glass beads, glass powder, potassium aluminum silicate, diatomaceous earth, iron oxide, titanium oxide, zinc oxide, and alumina; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; phosphates such as calcium pyrophosphate and anhydrous dicalcium phosphate; silicon carbide; silicon nitride; and boron nitride. In the present invention, from the viewpoints of suppressing surface whitening of the molded article and reducing dust generation of the molded article, it is preferable to use one or more selected from the group consisting of silica and barium sulfate as the granular filler, and it is more preferable to use silica.

[0071] The content of the component (D) is preferably 2 to 15 parts by volume, more preferably 5 to 12 parts by volume, and even more preferably 7 to 10 parts by volume, per 100 parts by volume of the total of the liquid crystal resin (A) and the cyclic olefin resin (B). When the content of the component (D) is within the above range, the fluidity of the liquid crystal resin composition is sufficiently ensured, and the mechanical strength of a molded article made of the liquid crystal resin composition is likely to be improved.

[0072] [Other ingredients] To the liquid crystalline resin composition according to the present invention, other polymers, other fillers, and known substances generally added to synthetic resins, i.e., stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, colorants such as dyes and pigments, lubricants, mold release agents, crystallization accelerators, crystal nucleating agents, etc., may be added as appropriate depending on the required performance, within the range not impairing the effects of the present invention.

[0073] The other polymers refer to polymers other than the (A) liquid crystal resin and the (B) cyclic olefin resin, such as an epoxy group-containing copolymer. The other fillers refer to fillers other than the (C) hollow filler and the (D) inorganic filler, such as an organic filler other than the (C) hollow filler; carbon black.

[0074] [Preparation of Liquid Crystalline Resin Composition] The liquid crystalline resin composition according to the present invention may be prepared by, for example, blending components (A), (B), (C), optionally (D), and optionally other components, and then melt-kneading the mixture using a single-screw or twin-screw extruder.

[0075] [Liquid crystal resin composition] The liquid crystalline resin composition according to the present invention obtained as described above preferably has a melt viscosity of 80 Pa·sec or less, more preferably 75 Pa·sec or less, and even more preferably 73 Pa·sec or less, from the viewpoint of fluidity during melting and moldability. In this specification, the melt viscosity is defined as the viscosity at a cylinder temperature 10 to 20°C higher than the melting point of the liquid crystalline resin, a shear rate of 1000 sec -1 The value obtained under the above conditions using a measurement method conforming to ISO 11443 is used.

[0076] The liquid crystal resin composition according to the present invention has a relative dielectric constant of preferably 2.75 or less, more preferably 2.73 or less, and even more preferably 2.7 or less. The liquid crystal resin composition according to the present invention has a dielectric loss tangent of preferably 0.005 or less, more preferably 0.004 or less, and even more preferably 0.003 or less. [Example]

[0077] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0078] <Liquid Crystalline Resin> Liquid crystalline polyester amide resin (LCP1) The following raw materials were charged into a polymerization vessel, and the reaction temperature was raised to 140°C and allowed to react at 140°C for 1 hour. The temperature was then raised further to 340°C over 4.5 hours, and the pressure was then reduced to 10 Torr (i.e., 1330 Pa) over 15 minutes. Melt polymerization was carried out while distilling off acetic acid, excess acetic anhydride, and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen was introduced to change the pressure from reduced pressure to normal pressure and then to pressurized pressure. The polymer was discharged from the bottom of the polymerization vessel, and the strands were pelletized to obtain pellets. The resulting pellets were heat-treated at 300°C for 2 hours under a nitrogen stream to obtain the desired polymer. The melting point of the resulting polymer was 336°C, the melt viscosity at 350°C was 19.0 Pa·s, and the true specific gravity was 1.4. The melt viscosity of the above polymer was measured using the same method as described below for measuring melt viscosity. 4-Hydroxybenzoic acid (HBA): 1380 g (60 mol%) 2-Hydroxy-6-naphthoic acid (HNA): 157 g (5 mol%) 1,4-phenylenedicarboxylic acid (TA): 484 g (17.5 mol%) 4,4'-dihydroxybiphenyl (BP); 388 g (12.5 mol%) N-acetyl-p-aminophenol (APAP): 126 g (5 mol%) Metal catalyst (potassium acetate catalyst): 110 mg Acylating agent (acetic anhydride); 1659g

[0079] Liquid crystalline polyester resin (LCP2) The following raw materials were charged into a polymerization vessel, and the reaction temperature was raised to 140°C and allowed to react at 140°C for 1 hour. The temperature was then raised further to 330°C over 3.5 hours, and the pressure was then reduced to 10 Torr (i.e., 1330 Pa) over 15 minutes. Melt polymerization was carried out while distilling off acetic acid, excess acetic anhydride, and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen was introduced to change the pressure from reduced pressure to normal pressure and then to pressurized pressure. The polymer was discharged from the bottom of the polymerization vessel, and the strands were pelletized to obtain the desired polymer as pellets. The melting point of the resulting polymer was 323°C, the melt viscosity at 340°C was 30 Pa·s, and the true specific gravity was 1.4. The melt viscosity of the above polymer was measured using the same method as described below for measuring melt viscosity. 4-Hydroxybenzoic acid (HBA): 2524 g (79.3 mol%) 6-Hydroxy-2-naphthoic acid (HNA): 867 g (20 mol%) 1,4-phenylenedicarboxylic acid (TA): 27 g (0.7 mol%) Metal catalyst (potassium acetate catalyst): 150 mg Acylating agent (acetic anhydride): 2336g

[0080] <Cyclic Olefin Resin (COC)> A 5-liter autoclave equipped with a heater, stirrer, and nitrogen supply was charged with toluene (4 liters) and a toluene solution (75 ml) of PMAO (manufactured by Tosoh Finechem Corporation) adjusted to a concentration of 2.2 mol / L. Then, norbornene (1650 g) was added, and the vessel was purged with nitrogen and reduced in pressure. Ethylene was then introduced from an ethylene cylinder to a gauge pressure of 10 atm. The vessel was then heated to 70°C and stirred for 5 minutes. A toluene solution (5 ml) of isopyridene(9-fluorenyl)-(1-(3-methyl)cyclopentadienyl)zirconium dichloride adjusted to 1 μmol / ml was added to the autoclave in a glove box, and the autoclave was left to react for 15 minutes. After the reaction, the contents were discharged, and 500 ml of distilled water and a filter agent were added, followed by pressure filtration. The filtrate was poured into 10 L of acetone, stirred, filtered, washed with the same amount of acetone, and then dried to obtain approximately 60 g of the target cyclic olefin resin, an addition polymer, as a white powder. The resulting cyclic olefin resin had a glass transition temperature of 155°C, an ethylene unit ratio of 40 mol%, and a true specific gravity of 1.02. The Tg and ethylene unit ratio of the cyclic olefin resin were measured as described below.

[0081] The cyclic olefin resin does not contain unsaturated bonds between carbon atoms in the main chain (i.e., the main chain contains only saturated bonds between carbon atoms), and the cyclic olefin resin does not contain unsaturated bonds between carbon atoms in the side chain (i.e., the side chain contains only saturated bonds between carbon atoms).

[0082] (glass transition temperature (Tg)) In accordance with JIS K 7121, the Tg (unit: ° C.) of the cyclic olefin resin was measured under the following conditions based on the DSC method. DSC device: Differential scanning calorimeter "DSC-7000X" (Hitachi High-Tech Science Corporation) Measurement atmosphere: Nitrogen Temperature increase condition: 20°C / min

[0083] (Measurement of the ratio of ethylene units) 13The ratio of ethylene units (unit: mol%) in the cyclic olefin resin was measured by a method using C-NMR. The apparatus and measurement conditions used were as follows:

[0084] [ 13 C-NMR measurement conditions] NMR device: "Bruker AVANCE600" (manufactured by Bruker) Measurement solvent: 1,1,2,2-tetrachloroethane-d2 Measured nuclides: 13 C Measurement temperature: 381K Sample concentration: 80mg / mL Sample tube diameter: 10 mm Accumulation count: 18,000 times Pulse repetition time: 3 seconds

[0085] [Calculation method for ethylene unit ratio] The norbornene ratio Nb (mol%) was calculated from the signal integral values ​​of norbornene-derived (C1 to C7) and ethylene-derived (E) using the following formula, and the ratio of ethylene units was calculated by subtracting this value from 100. The positions of C1 to C7 and E are as shown in the following formula (V).

[0086]

number

[0087] [ka]

[0088] <Materials other than resin> Glass balloon: Y12000 (Seishin Enterprise Co., Ltd., aspect ratio (average) 1.264, median diameter 35 μm, true specific gravity 0.6) Glass fiber: ECS03T-786H (Nippon Electric Glass Co., Ltd., chopped strand, fiber diameter 10 μm, length 3 mm, true specific gravity 2.6) Mica: AB-25S (Yamaguchi Mica Co., Ltd., mica, median diameter 25.0 μm, true specific gravity 2.8)

[0089] <Production of Liquid Crystalline Resin Composition> The above components were melt-kneaded in the proportions shown in Table 1 or Table 2 using a twin-screw extruder (TEX30α type, manufactured by The Japan Steel Works, Ltd.) at the cylinder temperature shown below to obtain liquid crystal resin composition pellets. [Manufacturing conditions] Cylinder temperature: 350°C: In the case of a liquid crystalline resin composition containing a liquid crystalline polyester amide resin (LCP1) 340°C: In the case of a liquid crystalline resin composition containing a liquid crystalline polyester resin (LCP2)

[0090] <Melt viscosity> The melt viscosity of the liquid crystalline resin composition was measured in accordance with ISO 11443 using a Capillograph 1B model manufactured by Toyo Seiki Seisakusho Co., Ltd. at a temperature 10 to 20°C higher than the melting point of the liquid crystalline resin, using an orifice with an inner diameter of 1 mm and a length of 20 mm, at a shear rate of 1000 / sec. The specific measurement temperatures were 350°C for the liquid crystalline resin composition containing the liquid crystalline polyesteramide resin (LCP1) and 340°C for the liquid crystalline resin composition containing the liquid crystalline polyester resin (LCP2). The results are shown in Tables 1 and 2.

[0091] <Bending test> The liquid crystalline resin composition was injection molded under the following molding conditions to obtain a molded article having a thickness of 0.8 mm, and the flexural strength, flexural modulus, and flexural strain were measured in accordance with ASTM D790. [Molding conditions] Molding machine: Sumitomo Heavy Industries, Ltd., SE100DU Cylinder temperature: 350°C (Examples 1 to 6 and 8 and Comparative Examples 1 to 7) 340°C (Example 7) Mold temperature: 90℃ Injection speed: 33mm / sec

[0092] <Dielectric properties> The pellets of the examples and comparative examples were molded using a molding machine ("SE-100DU" manufactured by Sumitomo Heavy Industries, Ltd.) under the following molding conditions to prepare flat test pieces measuring 80 mm x 80 mm x 1 mm. As shown in FIG. 1, a test piece measuring 80 mm x 1 mm x 1 mm was cut from the center of the flat test piece in the direction perpendicular to the flow, and this was used as a test piece for evaluating dielectric properties. The relative permittivity and dielectric loss tangent of this test piece at 1 GHz were measured using a cavity resonator perturbation method complex permittivity evaluation device manufactured by Kanto Electronics Application Development Co., Ltd., with the following configuration. Scalar Network Analyzer: Agilent Technologies 8757D Frequency synthesizer: Agilent Technologies 83650L Sweep CW Generator Fixed attenuator: Agilent Technologies 85025D detector Cavity resonator: Kanto Electronics Application Development CP431 Measurement program: Kanto Electronics Application Development CPMA-S2 / V2 [Molding conditions] Cylinder temperature: 350°C (Examples 1 to 6 and 8 and Comparative Examples 1 to 7) 340°C (Example 7) Mold temperature: 80℃ Injection speed: 33mm / sec Holding pressure: 60MPa

[0093] <Solder heat resistance> The liquid crystal resin composition was injection molded under the following molding conditions to obtain 1 / 8 combustion test pieces of 120 mm x 12.7 mm x 3.2 mm, which were subjected to reflow under the following conditions and evaluated according to the following criteria. ◯ (Good): There was no change in the appearance of the test piece before and after reflow. Δ (bad): The test piece lost its surface gloss or its surface roughness worsened due to reflow. × (very poor): The test piece was melted or significantly deformed by reflow. [Molding conditions] Molding machine: Sumitomo Heavy Industries, Ltd., SE100DU Cylinder temperature: 350°C (Examples 1 to 6 and 8 and Comparative Examples 1 to 7) 340°C (Example 7) Mold temperature: 90℃ Injection speed: 33mm / sec [Reflow conditions] Measuring device: Futaba Scientific Co., Ltd. conveyor-type hot air circulation dryer DFC-27-022S Sample feed speed: 0.45 m / min Reflow oven passage time: 4 minutes 44 seconds Preheat zone temperature: 185℃ Reflow zone temperature: 295℃ Peak temperature: 258℃ Time the temperature was above 255°C: 11 seconds

[0094] [Table 1]

[0095] [Table 2]

[0096] As is clear from the results shown in Table 1, the liquid crystal resin compositions of the examples were excellent in dielectric properties and heat resistance, and had good fluidity.

Claims

1. (A) a liquid crystalline resin, (B) a cyclic olefin resin, and (C) Hollow filler Contains (A) The melting point of the liquid crystal resin is 300°C or higher, (B) The glass transition temperature of the cyclic olefin resin is 100°C or higher, For a total of 100 parts by volume of the liquid crystal resin (A) and the cyclic olefin resin (B), (A) The content of the liquid crystal resin is 55 to 85 parts by volume, (B) The content of the cyclic olefin resin is 15 to 45 parts by volume, (C) The content of the hollow filler is 20 to 75 parts by volume. The liquid crystal resin composition is

2. A liquid crystalline resin composition according to claim 1 which does not contain a fluororesin.

3. 3. The liquid crystalline resin composition according to claim 1, wherein the liquid crystalline resin (A) is an aromatic polyester or aromatic polyester amide having, as a constituent component, a constituent unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof.

4. 4. The liquid crystal resin composition according to claim 1, wherein the hollow filler (C) is a glass balloon.

5. 5. The liquid crystal resin composition according to claim 1, wherein the cyclic olefin resin (B) is an addition polymer of a cyclic olefin monomer and an α-olefin.

6. The liquid crystal resin composition according to any one of claims 1 to 5, further comprising an inorganic filler.

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