Liquid crystalline polymer composition

Abstract

The present invention provides a liquid crystal polymer composition which maintains mechanical strength and heat resistance possessed by a liquid crystal polymer, and which is excellent in thin-wall flowability and blister resistance. The present invention relates to a liquid crystal polymer composition which contains 0.1 to 150 parts by mass of talc having a quartz content of 0 to 0.25% by mass, relative to 100 parts by mass of a liquid crystal polymer.

Description

Technical Field

[0001] This patent application claims priority under the Paris Convention to Japanese Patent Application No. 2024-207683 (filed on November 28, 2024) and Japanese Patent Application No. 2024-207690 (filed on November 28, 2024), the entire contents of which are incorporated herein by reference.

[0002] This invention relates to a liquid crystal polymer composition that maintains the mechanical strength and heat resistance of liquid crystal polymers, and exhibits excellent thin-wall flowability and foam resistance. Background Technology

[0003] Liquid crystal polymers possess excellent moldability and high heat resistance, making effective use of these properties in electronic components such as connectors, relays, and spools. In recent years, electronic components have seen continuous development towards higher integration, miniaturization, thinner walls, and thinner profiles, with miniaturization and thinner walls being particularly evident in connector components.

[0004] Examples of such thin-walled connectors include board-to-board connectors for bonding printed wiring substrates to each other, and connectors for FPCs for connecting flexible printed circuit boards (FPCs) to printed wiring substrates.

[0005] In addition to heat resistance to withstand reflow soldering, board-to-board connectors or FPC connectors also require miniaturization of the components themselves due to the miniaturization of electronic devices using printed circuit boards. For example, narrow-pitch connectors with a spacing of 0.3mm to 0.4mm between the metal terminals are provided. Additionally, thin connectors with a stacking height of 0.6mm when embedded are also provided.

[0006] However, to meet the requirements of miniaturization and thinning, short shots may occur during connector molding due to insufficient resin flowability. Therefore, it is necessary to further improve the resin flowability in the thin-walled portion of the molded product (thin-wall flowability).

[0007] Additionally, when molded parts are placed in a high-temperature atmosphere for extended periods or subjected to welding, an expansion known as blistering sometimes occurs on the surface. While the cause of this phenomenon is unclear, it is speculated that air trapped during liquid crystal polymer molding or oligomer components from the resin are carried into the molded part. During subsequent high-temperature heat treatment, the expansion of this air or the vaporization of the oligomer components pushes up the softened surface of the molded part, resulting in blistering.

[0008] As described above, liquid crystal polymers used as forming materials for thin-walled connectors, such as board-to-board connectors or FPC connectors, are required to maintain the properties of liquid crystal polymers, such as mechanical strength and heat resistance, as well as excellent thin-wall flowability and excellent foaming resistance.

[0009] Patent Document 1 discloses a liquid crystal polyester composition that, by containing specific terphenyl and liquid crystal polyester, can produce a molded article with high fluidity of liquid crystal polyester, moderate anisotropy, and sufficiently reduced gas generation to suppress abnormal foaming. However, the fluidity of this resin composition is insufficient and there is room for improvement.

[0010] Patent Document 2 discloses a liquid crystal polyester resin composition that, by containing a specific liquid crystal polyester and a plate-like filler in a prescribed ratio, maintains high fluidity while exhibiting excellent rigidity at high temperatures, thereby reducing foaming. However, the foaming resistance of this resin composition is insufficient and there is room for improvement.

[0011] To improve thin-wall flowability, methods exist to reduce resin viscosity; however, this can easily introduce air into the molded part during molding, resulting in foaming. As mentioned above, various studies have been conducted on liquid crystal polymer compositions, but it is considered difficult to achieve a high level of both thin-wall flowability and foaming resistance.

[0012] Existing technical documents

[0013] Patent documents

[0014] Patent Document 1: Japanese Patent Application Publication No. 2009-30015;

[0015] Patent Document 2: Japanese Patent Application Publication No. 2016-89154. Summary of the Invention

[0016] The problem that the invention aims to solve

[0017] The present invention was made in view of the above circumstances, and its object is to provide a liquid crystal polymer composition that maintains the mechanical strength and heat resistance of liquid crystal polymers, and has excellent thin-wall flowability and foaming resistance.

[0018] Methods for solving problems

[0019] The inventors conducted in-depth research on the above-mentioned issues and discovered that by adding a specific amount of a particular talc to the liquid crystal polymer, a liquid crystal polymer composition that maintains the mechanical strength and heat resistance of the liquid crystal polymer and has excellent thin-wall flowability and foaming resistance can be obtained, thus completing the present invention.

[0020] That is, the present invention includes the following suitable solutions.

[0021] [1] A liquid crystal polymer composition, wherein, relative to 100 parts by weight of liquid crystal polymer, it contains 0.1 to 150 parts by weight of talc, wherein the talc contains 0 to 0.25 parts by weight of quartz.

[0022] [2][1] The liquid crystal polymer composition further comprises, relative to 100 parts by weight of liquid crystal polymer, 0.1 to 100 parts by weight of glass fiber.

[0023] The liquid crystal polymer composition described in [3][1] or [2], wherein the liquid crystal polymer comprises repeating units represented by formula (I) and / or formula (II),

[0024]

[0025] [4][3] The liquid crystal polymer composition, wherein the liquid crystal polymer further comprises repeating units represented by formula (III) and formula (IV),

[0026]

[0027] In the formula, Ar1 and Ar2 each independently represent a divalent aromatic group.

[0028] [5][4] The liquid crystal polymer composition wherein the repeating units represented by formulas (III) to (IV) are: Ar1 and Ar2 are each independently selected from one or more repeating units of the aromatic groups represented by formulas (1) to (4).

[0029]

[0030] The liquid crystal polymer composition described in any one of [6][1] to [4], wherein the liquid crystal polymer comprises repeating units represented by formula (I) and formula (II),

[0031]

[0032] [7][6] The liquid crystal polymer composition wherein the repeating units represented by formulas (III) to (IV) are: Ar1 and Ar2 are each independently selected from one or more repeating units of the aromatic groups represented by formulas (1) to (4).

[0033]

[0034] The liquid crystal polymer composition described in any one of [8][1] to [7], wherein the crystal melting temperature of the liquid crystal polymer, as determined by differential scanning calorimetry, is 290 to 360 °C.

[0035] The liquid crystal polymer composition described in any one of [9][1] to [8], wherein the average particle size of talc is 0.1 to 100 μm.

[0036] The liquid crystal polymer composition described in any one of

[10] [1] to [9], wherein the Izod impact strength as determined according to ASTM D256 is 200 J / m or more.

[0037] The liquid crystal polymer composition described in any one of

[11] [1] to

[10] , wherein the content of quartz relative to the liquid crystal polymer composition is 0 to 0.040 by mass.

[0038]

[12] A molded article comprising any one of the liquid crystal polymer compositions described in [1] to

[11] .

[0039]

[13]

[12] The molded article, wherein the molded article constitutes a component selected from the following: connector, switch, relay, spool, capacitor, coil, motor, fan, test socket, transformer, camera module and antenna.

[0040] Invention Effects

[0041] The liquid crystal polymer composition of the present invention maintains the mechanical strength and heat resistance of liquid crystal polymers, and has excellent thin-wall flowability and foam resistance. Therefore, it is suitable for a wide variety of electrical and electronic components of various communication devices or electronic devices, such as connectors, switches, relays, spools, capacitors, coils, motors, fans, test sockets, transformers, camera modules and antennas. Attached Figure Description

[0042] Figure 1 It is an X-ray diffraction pattern that is used to determine the quartz content in each talc and serves as the basis for the standard curve.

[0043] Figure 2 It is an X-ray diffraction pattern used to determine the quartz content in each talc. Detailed Implementation

[0044] The liquid crystal polymer (hereinafter also referred to as LCP) used in the liquid crystal polymer composition of the present invention is a polyester or polyesteramide that forms an anisotropic molten phase, and is not particularly limited as long as it is referred to as thermotropic liquid crystal polyester or thermotropic liquid crystal polyesteramide in this technical field.

[0045] The properties of the anisotropic molten phase of liquid crystal polymers can be confirmed by conventional polarization testing using orthogonal polarizers, i.e., by observing the sample placed on a hot stage under a nitrogen atmosphere.

[0046] The crystal melting temperature of the liquid crystal polymer used in this invention, as measured by differential scanning calorimetry, is preferably 220–380°C, more preferably 260–370°C, even more preferably 290–360°C, and particularly preferably 310–350°C.

[0047] If the crystal melting temperature of the liquid crystal polymer is below 220°C, its heat resistance is poor; if it is above 380°C, its moldability tends to decrease, so it is not preferred.

[0048] It should be noted that in this specification and claims, "crystal melting temperature" refers to the temperature determined by a differential scanning calorimeter (DSC) from the peak temperature of the crystal melting temperature measured at a heating rate of 20°C / min. More specifically, a sample of the liquid crystal polymer was heated from room temperature at a rate of 20°C / min, and the endothermic peak temperature (Tm1) observed during this measurement was recorded. The sample was then held at a temperature 20–50°C higher than Tm1 for 10 minutes. Next, the sample was cooled to room temperature at a rate of 20°C / min, and the endothermic peak was observed again when the temperature was increased at a rate of 20°C / min. The temperature representing the peak is set as the crystal melting temperature (Tm) of the liquid crystal polymer. For example, a DSC7020 manufactured by Hitachi High-Tech Science Co., Ltd. can be used for this measurement.

[0049] Examples of polymerizable monomers constituting the constituent units of the liquid crystal polymer of the present invention include: aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic aminocarboxylic acids, aromatic hydroxylamines, aromatic diamines, aliphatic diols, and aliphatic dicarboxylic acids. Only one such polymerizable monomer may be used, or two or more polymerizable monomers may be combined. Polymerizable monomers having at least one hydroxyl and carboxyl group are suitable. Furthermore, the liquid crystal polymer of the present invention is more preferably a liquid crystal polymer composed only of aromatic monomers and free of aliphatic monomers.

[0050] Specific examples of aromatic hydroxycarboxylic acids 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-substituted derivatives, as well as their acylates, ester derivatives, acid halides, and other ester-forming derivatives. Among these, 4-hydroxybenzoic acid and / or 6-hydroxy-2-naphthoic acid are preferred from the viewpoint of heat resistance, mechanical strength, and ease of melting point adjustment of the resulting liquid crystal polymer.

[0051] Specific examples of aromatic dicarboxylic acids include: terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-dicarboxylic biphenyl, 3,4'-dicarboxylic biphenyl and 4,4'-dicarboxylic terphenyl, their alkyl, alkoxy or halogen substituted derivatives, and their ester derivatives, ester-forming derivatives of acyl halides, etc. Among these, from the viewpoint of effectively improving the heat resistance of the resulting liquid crystal polymer, compounds selected from one or more of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferred, and terephthalic acid and / or 2,6-naphthalenedicarboxylic acid are more preferred.

[0052] Specific examples of aromatic diols include: hydroquinone, resorcinol, 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'-dihydroxynaphthalene, their alkyl, alkoxy, or halogen-substituted derivatives, and their acylates, etc. Among these, from the viewpoint of excellent reactivity during polymerization, compounds selected from one or more of hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, and 2,6-dihydroxynaphthalene are preferred, and hydroquinone and / or 4,4'-dihydroxybiphenyl are more preferred.

[0053] Specific examples of aromatic aminocarboxylic acids include: 4-aminobenzoic acid, 3-aminobenzoic acid, 6-amino-2-naphthoic acid, their alkyl, alkoxy or halogen-substituted derivatives, and their acylates, ester derivatives, acyl halides, etc., which are ester-forming derivatives.

[0054] Specific examples of aromatic hydroxylamines 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, and 2,2'-diaminobinaphthyl, their alkyl, alkoxy, or halogen-substituted derivatives, and their acylates, etc. 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.

[0055] Specific examples of aromatic diamines include amide-forming derivatives of 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, their alkyl, alkoxy, or halogen-substituted derivatives, and their acylates.

[0056] Specific examples of aliphatic diols include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and their acylates. Additionally, polymers containing aliphatic diols, such as polyethylene terephthalate or polybutylene terephthalate, can be reacted with the aforementioned aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, and their acylates, ester derivatives, acyl halides, etc.

[0057] Specific examples of aliphatic dicarboxylic acids include: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, dodecanoic acid, tetradecanoic acid, fumaric acid, maleic acid, and hexahydroterephthalic acid. Among these, oxalic acid, succinic acid, adipic acid, octanoic acid, sebacic acid, and dodecanoic acid are preferred from the viewpoint of excellent reactivity during polymerization.

[0058] In this invention, without prejudice to the purpose of the invention, the polymerizable monomers forming the constituent units of the liquid crystal polymer may further include dihydroxyterephthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, trimellitic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, or their alkyl, alkoxy, or halogen-substituted derivatives, as well as their acylates, ester derivatives, acyl halides, etc., as other copolymerizable components. The amount of these polymerizable monomers used is preferably 10 mol% or less relative to the total constituent units constituting the liquid crystal polymer.

[0059] In this invention, without prejudice to the purpose of the invention, the liquid crystal polymer can be a polymer containing thioester bonds. Examples of polymerizable monomers that provide such bonds include mercaptoaromatic carboxylic acids, aromatic dithiols, and hydroxyaromatic thiols. The content of these polymerizable monomers is preferably 10 mol% or less relative to the total number of constituent units constituting the liquid crystal polymer.

[0060] Polymers containing these repeating units exist in polymers that form anisotropic molten phases and polymers that do not form anisotropic molten phases, depending on the composition or composition ratio of the monomers and the sequence distribution of the repeating units in the polymer. However, the liquid crystal polymers used in this invention are limited to polymers that form anisotropic molten phases.

[0061] Specific examples of combinations of polymerizable monomers that form the constituent units of the liquid crystal polymer used in this invention can be listed below.

[0062] 1) 4-Hydroxybenzoic acid / 6-Hydroxy-2-naphthoic acid;

[0063] 2) 4-Hydroxybenzoic acid / terephthalic acid / 4,4'-Dihydroxybiphenyl;

[0064] 3) 4-Hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4,4'-dihydroxybiphenyl;

[0065] 4) 4-Hydroxybenzoic acid / Terephthalic acid / Isophthalic acid / 4,4'-Dihydroxybiphenyl / hydroquinone;

[0066] 5) 4-Hydroxybenzoic acid / terephthalic acid / hydroquinone;

[0067] 6) 6-Hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone;

[0068] 7) 4-Hydroxybenzoic acid / 6-Hydroxy-2-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl;

[0069] 8) 6-Hydroxy-2-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl;

[0070] 9) 4-Hydroxybenzoic acid / 6-Hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone;

[0071] 10) 4-Hydroxybenzoic acid / 6-Hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone / 4,4'-dihydroxybiphenyl;

[0072] 11) 4-Hydroxybenzoic acid / 2,6-Naphthalenedicarboxylic acid / 4,4'-Dihydroxybiphenyl;

[0073] 12) 4-Hydroxybenzoic acid / Terephthalic acid / 2,6-Naphthalenedicarboxylic acid / hydroquinone;

[0074] 13) 4-Hydroxybenzoic acid / 2,6-Naphthalenedicarboxylic acid / hydroquinone;

[0075] 14) 4-Hydroxybenzoic acid / 6-Hydroxy-2-naphthoic acid / 2,6-Naphthoic acid / Hydroquinone;

[0076] 15) 4-Hydroxybenzoic acid / Terephthalic acid / 2,6-Naphthalenedicarboxylic acid / hydroquinone / 4,4'-Dihydroxybiphenyl;

[0077] 16) 4-Hydroxybenzoic acid / Terephthalic acid / 4-Aminophenol;

[0078] 17) 6-Hydroxy-2-naphthoic acid / terephthalic acid / 4-aminophenol;

[0079] 18) 4-Hydroxybenzoic acid / 6-Hydroxy-2-naphthoic acid / Terephthalic acid / 4-Aminophenol;

[0080] 19) 4-Hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / 4-aminophenol;

[0081] 20) 4-Hydroxybenzoic acid / terephthalic acid / ethylene glycol;

[0082] 21) 4-Hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / ethylene glycol;

[0083] 22) 4-Hydroxybenzoic acid / 6-Hydroxy-2-naphthoic acid / terephthalic acid / ethylene glycol;

[0084] 23) 4-Hydroxybenzoic acid / 6-Hydroxy-2-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / ethylene glycol;

[0085] 24) 4-Hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / 4,4'-dihydroxybiphenyl;

[0086] 25) 6-Hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone / 4,4'-dihydroxybiphenyl.

[0087] Among these, liquid crystal polymers composed of constituent units of polymeric monomers from 1), 2), 3), 7), 9), 10), 14), and 25) are preferred, liquid crystal polymers composed of constituent units of polymeric monomers from 9), 10), 14), and 25) are more preferred, and liquid crystal polymers composed of constituent units of polymeric monomers from 10) are even more preferred.

[0088] In a suitable embodiment, considering excellent flowability and mechanical properties, the liquid crystal polymer used in the liquid crystal polymer composition of the present invention comprises repeating units represented by formula (I) and / or formula (II).

[0089]

[0090] In the liquid crystal polymer comprising repeating units represented by formula (I) and / or formula (II), from the perspective of excellent flowability and heat resistance, it is preferable to further comprise repeating units represented by formula (III) and formula (IV).

[0091]

[0092] In the formula, Ar1 and Ar2 each independently represent a divalent aromatic group.

[0093] Here, the repeating unit represented by formula (III) can be multiple repeating units containing different Ar1, and the repeating unit represented by formula (IV) can also be multiple repeating units containing different Ar2. That is, the repeating unit represented by formula (III) can be multiple repeating units such as repeating units of one type of Ar1 and repeating units of another type of Ar1, and similarly, the repeating unit represented by formula (IV) can also be multiple repeating units such as repeating units of one type of Ar2 and repeating units of another type of Ar2. In addition, "aromatic group" refers to a six-membered monocyclic (including biphenyl) or bicyclic fused ring aromatic group.

[0094] From the perspective of excellent flowability and mechanical properties, the composition ratio (mol%) of the repeating units represented by formula (I) and / or formula (II) is preferably 30 to 80 mol%, more preferably 40 to 70 mol%. The repeating units represented by formula (III) and formula (IV) are preferably 10 to 35 mol%, more preferably 15 to 30 mol%. The repeating units represented by formula (III) and formula (IV) are preferably substantially equimolar.

[0095] As another preferred embodiment, in the liquid crystal polymer comprising repeating units represented by formulas (III) and (IV), from the perspective of excellent flowability and mechanical properties, it is preferable to also comprise repeating units represented by formulas (I) and (II).

[0096]

[0097] From the perspective of excellent flowability and mechanical properties, the total composition ratio (mol%) of the repeating units represented by formulas (I) and (II) is preferably 30 to 80 mol%, more preferably 35 to 60 mol%. The repeating unit represented by formula (II) is preferably 0.1 to 30 mol%, more preferably 0.5 to 25 mol%, and even more preferably 1 to 20 mol%. The repeating units represented by formulas (III) and (IV) are preferably 10 to 35 mol%, more preferably 20 to 32.5 mol%. The repeating units represented by formulas (III) and (IV) are preferably substantially equimolar.

[0098] From the perspective of excellent flowability and heat resistance, the repeating units represented by formulas (III) to (IV) are more preferably: Ar1 and Ar2 are each independently selected from one or more aromatic groups represented by formulas (1) to (4) below. Particularly preferred is that the repeating unit represented by formula (III) is a repeating unit in which Ar1 is an aromatic group represented by formula (1) and / or formula (3), and the repeating unit represented by formula (IV) is a repeating unit in which Ar2 is a repeating unit in which Ar2 is a repeating unit in which Ar2 is a repeating unit selected from one or more aromatic groups represented by formulas (1), (2), and (4).

[0099]

[0100] The manufacturing method of the liquid crystal polymer used in this invention will be described below.

[0101] There are no particular limitations on the manufacturing method of the liquid crystal polymer used in this invention. The liquid crystal polymer can be obtained by supplying polymeric monomers to known polycondensation methods, such as melt acid hydrolysis or slurry polymerization, to form ester or amide bonds.

[0102] The melt acid hydrolysis method is a preferred method for manufacturing the liquid crystal polymer used in the liquid crystal polymer composition of the present invention. This method involves first heating the polymerizable monomer to form a molten solution of the reactants, and then continuing the polycondensation reaction to obtain the molten polymer. It should be noted that a vacuum can also be applied to facilitate the removal of volatile byproducts (e.g., acetic acid, water, etc.) generated in the final stage of condensation.

[0103] Slurry polymerization refers to a method in which polymerizable monomers react in the presence of a heat exchange fluid, and the solid product is obtained in a state of suspension in the heat exchange medium.

[0104] In either the melt acid hydrolysis method or the slurry polymerization method, the polymerizable monomers used in the manufacture of liquid crystal polymers can be provided as modified forms for acylation of hydroxyl and / or amino groups at room temperature, i.e., as lower acylates for the reaction.

[0105] The lower acyl group is preferably a group having 2 to 5 carbon atoms, more preferably a group having 2 or 3 carbon atoms. In a preferred embodiment of the invention, the acetylation of the polymerizable monomer is used in the reaction.

[0106] The lower acylates of polymerizable monomers can be substances that are pre-synthesized using additional acylation, or they can be generated in the reaction system by adding acylation agents such as acetic anhydride to the polymerizable monomers during the manufacture of liquid crystal polymers.

[0107] In either the melt acid hydrolysis method or the slurry polymerization method, the polycondensation reaction can be carried out at a temperature of 150–400°C, preferably 250–370°C, under normal and / or reduced pressure, and a catalyst can be used as needed.

[0108] Specific examples of catalysts include: organotin compounds such as dialkyltin oxide (e.g., dibutyltin oxide) and diaryltin oxide; titanium dioxide; antimony trioxide; organotitanium compounds such as alkoxytitanium silicates and titanium alkoxides; alkali metal and alkaline earth metal salts of carboxylic acids (e.g., sodium acetate and potassium acetate); gaseous acid catalysts such as Lewis acids (e.g., boron trifluoride) and hydrogen halides (e.g., hydrogen chloride).

[0109] When using a catalyst, the amount of the catalyst is preferably 1 to 1000 ppm, more preferably 2 to 100 ppm, relative to the total amount of polymerizable monomers.

[0110] The liquid crystal polymer obtained through this polycondensation reaction is usually extracted from the polymerization tank in a molten state, and then processed into granules, flakes or powders, and melt-blended with other components.

[0111] To increase molecular weight and improve heat resistance, granular, flake, or powdered liquid crystal polymers can also be heat-treated in a substantially solid state under reduced pressure, vacuum, or in an atmosphere such as nitrogen or helium as an inert gas.

[0112] The temperature of the heat treatment is not particularly limited as long as it is within the range where the liquid crystal polymer does not melt, but it is preferably 260 to 350°C, and more preferably 280 to 320°C.

[0113] The melt viscosity of the liquid crystal polymer used in this invention (measured using a capillary rheometer, crystal melting temperature +10~30℃, 1000s) -1 The preferred value is 1 to 200 Pa·s, more preferably 3 to 100 Pa·s, further preferably 4 to 80 Pa·s, and particularly preferably 5 to 40 Pa·s.

[0114] If the melt viscosity is less than 1 Pa·s, there is a tendency for drooling or stringing to occur during injection molding. If it exceeds 200 Pa·s, there is a tendency for reduced fluidity.

[0115] The average particle size of the talc used in the liquid crystal polymer composition of the present invention is preferably 0.1 to 100 μm, more preferably 0.5 to 80 μm, and even more preferably 3 to 50 μm. It should be noted that, in this specification, the average particle size refers to the median diameter (median value) of a volume reference measured using a laser diffraction / scattering particle size distribution method.

[0116] The quartz content in the talc used in this invention, as determined by the method described later in the powder X-ray diffraction apparatus, is preferably 0 to 0.25% by mass, more preferably 0.20% by mass or less, further preferably 0.15% by mass or less, particularly preferably 0.10% by mass or less, and most preferably 0.05% by mass or less. The closer the quartz content is to 0% by mass, the better the foaming resistance and flowability; if it exceeds 0.25% by mass, there is a tendency for decreased foaming resistance or flowability. It should be noted that in this invention, quartz refers to silicon dioxide (crystalline silicon dioxide) with a crystalline structure, also known as quartz. The method described later for evaluating the quartz content in talc using a powder X-ray diffraction apparatus can also be applied to substances other than talc.

[0117] The talc mentioned above can also be used after being treated with known surface treatment agents.

[0118] In the liquid crystal polymer composition of the present invention, the talc content is 0.1 to 150 parts by weight, preferably 1 to 100 parts by weight, more preferably 5 to 80 parts by weight, and even more preferably 10 to 50 parts by weight, relative to 100 parts by weight of the liquid crystal polymer. When the talc content is less than 0.1 parts by weight, there is a tendency for insufficient foaming resistance; when it exceeds 150 parts by weight, there is a tendency for reduced fluidity.

[0119] The liquid crystal polymer composition of the present invention may further contain glass fibers. By further containing glass fibers, there is a tendency to increase the load flexural temperature. The number-average fiber diameter of the glass fibers used is preferably 0.1 to 50 μm, and the number-average fiber length is preferably 20 μm to 10 mm.

[0120] Examples of glass fibers used in this invention include glass fibers manufactured by various methods, such as long-fiber chopped glass fibers and short-fiber ground glass fibers. Two or more of these may also be used together.

[0121] Examples of glass fibers used in this invention include E-glass, A-glass, C-glass, D-glass, AR-glass, R-glass, S-glass, and mixtures thereof. Among these, E-glass is preferred due to its superior strength and ease of availability.

[0122] The glass fibers used in this invention can be treated with coupling agents such as silane-based coupling agents or titanium-based coupling agents as needed.

[0123] The glass fibers used in this invention can be coated with thermoplastic resins such as urethane resin, acrylic resin, and ethylene / vinyl acetate copolymer, or thermosetting resins such as epoxy resin, or can be treated with a bundling agent.

[0124] The number-average fiber diameter of the glass fibers used in this invention is preferably 3–20 μm, more preferably 5–16 μm, and even more preferably 7–13 μm. The number-average fiber diameter of the glass fibers in the resulting liquid crystal polymer composition does not undergo substantial change even after melt mixing.

[0125] The glass fibers used are preferably cut to a length of 10 mm or less. When the glass fibers are long-fiber chopped glass fibers, 1.5 to 6 mm is more preferred, and 2 to 4 mm is even more preferred. When the glass fibers are short-fiber ground glass fibers, 10 μm to 200 μm is more preferred, and 20 to 150 μm is even more preferred. From the viewpoint of ease of acquisition and ease of handling, long-fiber chopped glass fibers are preferred. The number-average fiber length of the glass fibers in the resulting liquid crystal polymer composition is preferably 10 to 600 μm, more preferably 30 to 500 μm, and even more preferably 50 to 450 μm. The glass fibers are typically broken or crushed during blending or mixing with the liquid crystal polymer, resulting in the number-average fiber length in the liquid crystal polymer composition. To obtain a liquid crystal polymer composition containing glass fibers of the desired fiber length, the melt-mixing conditions can be set and adjusted according to the cut fiber length of the glass fibers used.

[0126] It should be noted that the number-average fiber diameter and number-average fiber length of the glass fibers in the liquid crystal polymer composition can be determined by microscopic observation. First, 1.0 g of the liquid crystal polymer composition is collected in a crucible and ashed in an electric furnace at 500–600 °C for 5 hours. The residue is dispersed in methanol and spread on a glass slide as a sample. Next, in the projected image of the glass fibers within the microscope's field of view, the length along the longitudinal direction is read as the fiber length, and the length in the direction orthogonal to the longitudinal direction is read as the fiber diameter. The arithmetic mean is then calculated. The parameter for the average value is set to be 200 or higher.

[0127] In the liquid crystal polymer composition of the present invention, the content of glass fiber is 0.1 to 100 parts by weight, preferably 1 to 70 parts by weight, more preferably 3 to 50 parts by weight, further preferably 5 to 40 parts by weight, and particularly preferably 8 to 30 parts by weight, relative to 100 parts by weight of the liquid crystal polymer. When the glass fiber content is less than 0.1 parts by weight, there is a tendency not to obtain the strength improvement effect based on the use of glass fiber; when it exceeds 100 parts by weight, there is a tendency for reduced fluidity.

[0128] In the liquid crystal polymer composition of the present invention, the content ratio of talc to glass fiber is preferably 0.5 or more, more preferably 0.7 to 10, even more preferably 0.9 to 7, and particularly preferably 0.95 to 5. When the talc / glass fiber content ratio is less than 0.5, there is a tendency for reduced foaming resistance or flowability.

[0129] In addition, without prejudice to the purpose of the present invention, the liquid crystal polymer composition of the present invention may contain, in addition to the talc or optionally added glass fiber, other fibrous, plate-like, or granular inorganic or organic filler materials.

[0130] Other fibrous filler materials used in this invention include, for example: silica-alumina fibers, alumina fibers, carbon fibers, aramid fibers, polyarylate fibers, polybenzimidazole fibers, potassium titanate whiskers, aluminum borate whiskers, needle-shaped titanium dioxide, calcium silicate such as wollastonite, hard calcium silicate, calcium titanate, aluminum borate, needle-shaped calcium carbonate, basalt fibers, tetrapod zinc oxide, etc. These can be used alone or in combination of two or more.

[0131] Other plate-shaped filler materials used in this invention include, for example: silicates such as mica, kaolin, clay, vermiculite, calcium silicate, aluminum silicate, feldspar powder, acidic clay, waxy clay, sericite, sillimanite, bentonite, glass flake, slate powder, and silane; carbonates such as calcium carbonate, lead oxide, barium carbonate, magnesium carbonate, and dolomite; sulfates such as barite powder, precipitated calcium sulfate, calcined gypsum, and barium sulfate; hydroxides such as hydrated alumina; oxides such as alumina, antimony oxide, magnesium oxide, titanium oxide, zinc oxide, silicon dioxide, silica sand, white carbon, and diatomaceous earth; sulfides such as molybdenum disulfide; and plate-shaped wollastonite. These can be used alone or in combination of two or more.

[0132] Other granular filler materials used in this invention include, for example, silicon dioxide, aluminum oxide, titanium oxide, calcium carbonate, glass beads, glass spheres, barium sulfate, boron nitride, silicon carbide, and resin beads, which can be used alone or in combination of two or more.

[0133] Relative to 100 parts by weight of the liquid crystal polymer, the content of these other fibrous, plate-like, or granular inorganic or organic fillers is preferably 50 parts by weight or less, more preferably 30 parts by weight or less. When the content of these other fibrous, plate-like, or granular inorganic or organic fillers exceeds 50 parts by weight, there is a tendency for reduced flowability.

[0134] Furthermore, without compromising the effectiveness of the invention, the liquid crystal polymer composition of the present invention may contain other additives.

[0135] Other additives used in this invention include, for example: higher fatty acids, higher fatty acid esters, higher fatty acid amides, and higher fatty acid metal salts (where higher fatty acids refer to, for example, fatty acids with 10 to 25 carbon atoms) as lubricants; polysiloxanes and fluororesins as mold release modifiers; dyes, pigments, and carbon black as colorants; flame retardants; antistatic agents; surfactants; phosphorus-based antioxidants, phenolic antioxidants, and sulfur-based antioxidants as antioxidants; weathering agents; heat stabilizers; and neutralizing agents. These additives can be used alone or in combination of two or more.

[0136] The content of these other additives is preferably 10 parts by mass or less, more preferably 0.01 to 5 parts by mass, relative to 100 parts by mass of the liquid crystal polymer. If the content of these other additives exceeds 10 parts by mass, there is a tendency for the thermal stability to deteriorate.

[0137] For substances that have external lubricant effects, such as higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, and fluorocarbon surfactants, these substances can be pre-attached to the surface of the liquid crystal polymer composition particles during the molding of the liquid crystal polymer composition.

[0138] Furthermore, without prejudice to the purpose of this invention, the liquid crystal polymer composition of this invention may further contain other resin components. Examples of other resin components include, for instance, thermoplastic resins such as polyamides, polyesters, polyacetals, polyphenylene ethers and their modified forms, polysulfones, polyethersulfones, polyetherimides, polyamide-imides, elastomers, etc.; or thermosetting resins such as phenolic resins, epoxy resins, polyimide resins, etc.

[0139] Other resin components may be contained individually or in combination of two or more. The content of other resin components is not particularly limited and can be appropriately determined according to the intended use or purpose of the liquid crystal polymer composition. Typically, the total content of other resins is added in a range preferably less than 100 parts by weight, particularly less than 50 parts by weight, relative to 100 parts by weight of the liquid crystal polymer.

[0140] Liquid crystal polymer compositions can be prepared by blending liquid crystal polymers and talc, as well as other inorganic and / or organic fillers, other additives or other resin components as required, according to a specified composition, and by melt-blending using a Banbury mixer, kneader, single-shaft or twin-shaft extruder, etc.

[0141] The liquid crystal polymer composition of the present invention thus obtained is shaped or processed using known molding methods such as injection molding machines and extruders.

[0142] The liquid crystal polymer composition of the present invention uses a 3.2 mm thick ASTM No. 4 dumbbell test piece. In a tensile test according to ASTM D638, the tensile strength is preferably 80 MPa or more, more preferably 90 MPa or more, and even more preferably 100 MPa or more. If the tensile strength is less than 80 MPa, it tends to break easily when used as a small, thin-walled component. There is no particular limitation on the upper limit of the above tensile strength; for example, it is 250 MPa.

[0143] The liquid crystal polymer composition of the present invention uses a 3.2 mm thick ASTM No. 4 dumbbell test piece. In a tensile test according to ASTM D638, the elongation at break is preferably 1% or more, more preferably 2% or more, and even more preferably 3% or more. If the elongation at break is less than 1%, it tends to break easily when used as a small, thin-walled component. There is no particular limitation on the upper limit of the above-mentioned elongation at break, for example, it is 10%.

[0144] The liquid crystal polymer composition of the present invention uses a strip test piece with a notched length of 63.5 mm, a width of 12.7 mm, and a thickness of 3.2 mm. In the Izod impact test according to ASTM D256, the Izod impact strength is preferably 50 J / m or more, more preferably 100 J / m or more, further preferably 150 J / m or more, and particularly preferably 200 J / m or more. If the Izod impact strength is less than 50 J / m, it tends to break easily when used as a small, thin-walled component. There is no particular limitation on the upper limit of the above-mentioned Izod impact strength; for example, it is 600 J / m.

[0145] The liquid crystal polymer composition of the present invention uses a strip test piece (127 mm in length and 12.7 mm in width) with a thickness of 3.2 mm. The flexural temperature (DTUL, 1.82 MPa load) according to ASTM D648 is preferably 200°C or higher, more preferably 210°C or higher, further preferably 220°C or higher, and particularly preferably 230°C or higher. If the flexural temperature is below 200°C, deformation is likely to occur during the processing of electronic components, i.e., the reflow process, and there is a tendency for poor heat resistance. There is no particular limitation on the upper limit of the above-mentioned flexural temperature; for example, it is 320°C.

[0146] The melt viscosity of the liquid crystal polymer composition of the present invention, measured by a melt viscosity measuring device having a capillary tube of 1.0 mm φ × 10 mm at a crystal melting temperature of +10 to 30°C, is preferably 3 to 70 Pa·s, more preferably 5 to 50 Pa·s, and even more preferably 10 to 40 Pa·s. When the melt viscosity is less than 3 Pa·s, defects such as drooling are prone to occur during injection molding; when it exceeds 70 Pa·s, there is a tendency for insufficient flowability.

[0147] The liquid crystal polymer composition of the present invention, measured by the method described later, preferably has a flow length of 9 mm or more at a thickness of 0.1 mm, more preferably 10 mm or more, further preferably 11 mm or more, and particularly preferably 12 mm or more. When the flow length at a thickness of 0.1 mm is less than 7 mm, there is a tendency for defects such as short shots to occur during the molding process of small, thin-walled parts. There is no particular limitation on the upper limit of the above-mentioned flow length at a thickness of 0.1 mm; for example, it is 50 mm.

[0148] The foaming rate of the liquid crystal polymer composition of the present invention in the step-like foaming test determined by the method described later is preferably 15% or less, more preferably 10% or less, and even more preferably 5% or less. The lower the foaming rate and the closer it is to 0%, the better the foaming resistance. Since this test is a rigorous test, it is sufficiently practical as long as the foaming rate in this test is 15% or less. If the foaming rate exceeds 15%, foaming may occur in actual use depending on the molding conditions.

[0149] In the liquid crystal polymer composition of the present invention, the quartz content relative to the total liquid crystal polymer composition is preferably 0 to 0.040% by mass, more preferably 0.030% by mass or less, even more preferably 0.020% by mass or less, and particularly preferably 0.010% by mass or less. When the quartz content exceeds 0.040% by mass, there is a tendency for poor foaming resistance or poor flowability. By pre-determining the quartz content of each substance, such as talc or other inorganic fillers contained in the liquid crystal polymer composition, the quartz content in the liquid crystal polymer composition can be calculated based on the content ratio. Alternatively, as another method, 1.0 g of the liquid crystal polymer composition can be collected in a crucible, treated in an electric furnace at 500 to 600°C for 5 hours to ashed it, the mass of the resulting residue can be measured, and the residue can be measured using a powder X-ray diffraction apparatus by the method described later. The amount of quartz contained in the residue can then be calculated and evaluated.

[0150] The liquid crystal polymer composition of the present invention can be used as a molded article because it maintains the mechanical strength and heat resistance of liquid crystal polymers and has excellent thin-wall flowability and foam resistance. It is particularly suitable for electronic components such as connectors, switches, relays, spools, capacitors, coils, motors, fans, test sockets, transformers, camera modules and antennas.

[0151] Example

[0152] The present invention will be described below by way of examples, but the present invention is not limited to any of the following examples.

[0153] The determination and evaluation of crystal melting temperature, tensile strength, tensile elongation at break, Izod impact strength, load flexural temperature, melt viscosity, flow length at 0.1 mm thickness, step bubbling, and quartz content in talc in the embodiments were performed by the methods described below.

[0154] (1) Crystal melting temperature

[0155] Using a differential scanning calorimeter (DSC7020 manufactured by Hitachi High-Tech Science Co., Ltd.), after observing the endothermic peak temperature (Tm1) when measured at a heating rate of 20°C / min starting from room temperature, the sample was held at a temperature 20–50°C higher than Tm1 for 10 minutes. Next, the sample was cooled to room temperature at a cooling rate of 20°C / min, and the temperature of the peak observed at this point was set as the crystallization temperature (Tc) of the liquid crystal polymer. Then, the endothermic peak was observed again when measured at a heating rate of 20°C / min, and the temperature representing its peak was set as the melting temperature (Tm) of the liquid crystal polymer.

[0156] (2) Tensile strength

[0157] Dumbbell-shaped tensile test specimens (ASTM No. 4 thickness 3.2 mm) were obtained by injection molding using an injection molding machine (Nissei Resin Kogyo Co., Ltd. UH1000-110) at a cylinder temperature of +10 to 30°C from the crystal melting temperature and a mold temperature of 70°C. Tensile tests were performed using an Autograph AG-X plus instrument manufactured by Shimadzu Corporation, according to ASTM D638, at a span distance of 64.0 mm and a tensile speed of 5 mm / min.

[0158] (3) Elongation at break

[0159] The same test piece used in the tensile strength determination was used, and the determination was performed under the same conditions as the tensile strength determination.

[0160] (4) Izod impact strength

[0161] Using an injection molding machine (Nissei Resin Kogyo Co., Ltd. UH1000-110), strip test pieces with a length of 127 mm, a width of 12.7 mm, and a thickness of 3.2 mm were formed at a barrel temperature of 350°C and a mold temperature of 70°C. The test piece was then cut perpendicularly to its length at its center to obtain a strip test piece with a length of 63.5 mm, a width of 12.7 mm, and a thickness of 3.2 mm. After notching, the strip test pieces were measured according to ASTM D256.

[0162] (5) Load-induced flexural temperature (DTUL)

[0163] Using an injection molding machine (Nissei Resin Kogyo Co., Ltd. UH1000-110), a strip test piece with a length of 127 mm, a width of 12.7 mm, and a thickness of 3.2 mm was formed at a barrel temperature of +10 to 30°C from the crystal melting temperature and a mold temperature of 70°C. Using this strip test piece, measurements were performed according to ASTM D648 at a load of 1.82 MPa and a heating rate of 2°C / min.

[0164] (6) Melt viscosity

[0165] Using a melt viscosity measuring apparatus (Toyo Seiki Co., Ltd. Capillograph 1D) with a 1.0 mm φ × 10 mm capillary tube, the melt viscosity at a shear rate of 1000 seconds was measured. -1 Melt viscosity at 350℃.

[0166] (7) Flow length with a thickness of 0.1 mm

[0167] A rectangular bar mold with a length of 50 mm, a width of 2.0 mm, and a thickness of 0.1 mm was used. Injection molding was performed using an injection molding machine (NEX-15-1E manufactured by Nissei Resin Kogyo Co., Ltd.) under the molding conditions in Table 1, and the flow length when filled into the bar mold was measured.

[0168] [Table 1]

[0169] Molding machine NEX-15-1E manufactured by Nissei Resin Kogyo Co., Ltd. Barrel temperature 350-350-260℃ mold temperature 80℃ Injection speed 300mm / second Pressure holding 30MPa Injection time 2 seconds Cooldown time 5 seconds Screw speed 150rpm Screw back pressure 5MPa

[0170] (8) Stepped foaming

[0171] Using an injection molding machine (NEX-15-1E, Nissei Resin Co., Ltd.), plate-shaped test pieces were produced under the molding conditions specified in Table 2. These plate-shaped test pieces have a plate-shaped portion measuring 24 mm in length, 16 mm in width, and 0.3 mm in thickness. On one side of the flat portion, six protrusions (4 mm in length, 4 mm in width, 0.5 mm in height, total thickness 0.8 mm) are evenly spaced at 4 mm intervals on each side. Based on this shape, during injection molding, it is intentionally designed to easily entrain air into the resin, and foaming easily occurs upon heating, thus enabling rigorous testing.

[0172] After the plate-shaped test piece was left to stand for 24 hours at 23°C and 50% relative humidity, it was refluxed using an IR reflux apparatus (Senju Metal Industries, Ltd., SAI-2604) under the following conditions: preheating temperature 190°C, preheating time 30–50 seconds, formal heating temperature above 250°C, formal heating time 20–30 seconds, and peak temperature 260–265°C. The occurrence of surface expansion (bubbling) was then visually counted. Regarding the counting method, the plate-shaped test piece was divided into six sections centered on six raised areas. The presence or absence of bubbles in each of the six sections was checked. If bubbles occurred in any section, it was counted as 1; otherwise, it was counted as 0. In other words, the maximum bubble count for a single plate-shaped test piece was 6.

[0173] 15 test pieces (90 areas) were evaluated under one injection speed condition, and a total of 60 test pieces (360 areas) were evaluated under a total of 4 injection speed conditions. The occurrence rate of bubbling was marked as ◎ for 0-5%, 0 for 5%-15%, △ for 15%-25%, and × for 25%.

[0174] [Table 2]

[0175] Molding machine NEX-15-1E manufactured by Nissei Resin Kogyo Co., Ltd. Barrel temperature 350-350-260℃ mold temperature 80℃ Injection speed 100, 200, 300, 400 mm / s Pressure holding 30MPa Injection time 1 second Cooldown time 4 seconds Screw speed 200rpm Screw back pressure 3MPa

[0176] (9) Evaluation of the quartz content in talc

[0177] The quartz content in talc was determined using a powder X-ray diffractometer (Bruker D8 ADVANCE) as follows.

[0178] Talc with a quartz content extremely close to zero (TP-40B manufactured by Tamura Talc Industry, mentioned later) and quartz (JAWE4513 manufactured by the Japan Occupational Environment Testing Association, with a SiO2 content of 99.6%) were mixed in a certain proportion (6 points in total, with quartz ratios of 0.1%, 0.3%, 0.5%, 1.0%, 2.0%, and 3.0% by mass). The mixture was measured using powder X-ray diffraction, and a standard curve was constructed using the peak intensity of quartz-derived components observed at 2θ around 26.6–26.7°. Subsequently, the talc used in the liquid crystal polymer composition was measured separately using powder X-ray diffraction, and the quartz content was calculated by comparing it with the standard curve.

[0179] The measurements were performed under the following conditions.

[0180] X-ray generator: CuKα ray source, voltage 40kV, current 40mA

[0181] Slit: 0.3°

[0182] Scan step size: 0.02°

[0183] Scanning range: 25–28°

[0184] Scanning speed: 0.12 deg / min

[0185] Speed: 15 rpm

[0186] X-ray detector: One-dimensional semiconductor detector

[0187] Atmosphere being measured: Atmospheric atmosphere

[0188] Sample stage: Sample stage for powder analysis (made of PMMA)

[0189] As a talc with a quartz content extremely close to zero, TP-40B manufactured by Tamura Talc Industry was selected, as no quartz-originating peak was detected in the above measurements at a 2θ value of 26.6–26.7°. Since no quartz-originating peak was detected, the quartz content of TP-40B in this embodiment is 0.00%. Furthermore, due to the influence of low noise, it is assumed that talc with a lower peak intensity than TP-40B exists, and the quartz content of these talcs is also considered to be 0.00%.

[0190] Figure 1 The image shows X-ray diffraction patterns of 100% talc with a quartz content very close to zero, used to prepare the standard curve, and a mixture of 97% talc with 3% quartz. Additionally, Figure 2 The image shows an X-ray diffraction pattern used to determine the quartz content in each talc.

[0191] In the following experimental examples, the quartz content in the liquid crystal polymer composition was calculated from the quartz content in the talc obtained based on the above evaluation.

[0192] The following describes examples of the synthesis of liquid crystal polymers used in the embodiments and comparative examples. The abbreviations of the compounds used in the synthesis examples are as follows.

[0193] Monomers used in the synthesis of liquid crystal polymers (LCPs)

[0194] POB: 4-Hydroxybenzoic acid

[0195] BON6: 6-Hydroxy-2-naphthoic acid

[0196] BP: 4,4'-Dihydroxybiphenyl

[0197] HQ: Hydroquinone

[0198] TPA: Terephthalic acid

[0199] NDA: 2,6-Naphthalenedicarboxylic acid

[0200] Synthesis example 1 (LCP1)

[0201] In a reaction vessel equipped with a torque meter, a stirrer, and a distillation tube, POB, BON6, HQ, BP, and TPA were added according to the composition ratio shown in Table 3 to make the total amount 6.5 mol. Acetic anhydride with a molar amount of hydroxyl groups relative to all monomers of 1.03 times the total amount of hydroxyl groups was then added, and deacetic acid polymerization was carried out under the following conditions.

[0202] [Table 3]

[0203] POB BON6 HQ BP TPA Mass (g) 318.7 55.0 114.5 169.4 323.9 mole% 35.5 4.5 16 14 30

[0204] Under a nitrogen atmosphere, the temperature was increased from room temperature to 150°C within 1 hour and maintained at that temperature for 30 minutes. Then, while distilling off the byproduct acetic acid, the temperature was increased to 350°C over 7 hours, followed by a reduction in pressure to 5 mmHg over 80 minutes. The polymerization reaction was terminated at the specified torque point, and the contents of the reaction vessel were removed. Particles of the liquid crystal polymer (LCP1) were obtained using a pulverizer. The amount of acetic acid distilled during polymerization was almost consistent with the theoretical value. The crystal melting temperature (Tm) of the obtained particles was 340°C.

[0205] Synthesis Example 2 (LCP2)

[0206] In a reaction vessel equipped with a torque meter, a stirrer, and a distillation tube, POB, BON6, HQ, and TPA were added according to the composition ratio shown in Table 4 to make the total amount 6.5 mol. Acetic anhydride with a molar amount of hydroxyl groups relative to all monomers of 1.03 times the total amount of monomers was then added. Deacetic acid polymerization was carried out under the following conditions.

[0207] [Table 4]

[0208] POB BON6 HQ TPA Mass (g) 385.7 183.3 150.2 226.2 mole% 43 15 21 21

[0209] Under a nitrogen atmosphere, the temperature was raised from room temperature to 150°C within 1 hour and maintained at that temperature for 30 minutes. Then, while distilling off the byproduct acetic acid, the temperature was raised to 350°C over 7 hours, followed by a reduction in pressure to 5 mmHg over 80 minutes. The polymerization reaction was terminated at the time point exhibiting the specified torque, and the contents of the reaction vessel were removed. Particles of the liquid crystal polymer (LCP2) were obtained using a pulverizer. The amount of acetic acid distilled during polymerization was almost consistent with the theoretical value. The crystal melting temperature (Tm) of the obtained particles was 332°C.

[0210] Synthesis Example 3 (LCP3)

[0211] In a reaction vessel equipped with a torque meter, a stirrer, and a distillation tube, POB, BON6, HQ, and NDA were added according to the composition ratio shown in Table 5 to make the total amount 6.5 mol. Acetic anhydride was then added in a molar ratio of 1.03 times the total amount of hydroxyl groups of all monomers. Deacetic acid polymerization was carried out under the following conditions.

[0212] [Table 5]

[0213] POB BON6 HQ NDA Mass (g) 641.9 30.6 93.0 182.7 mole% 71.5 2.5 13 13

[0214] Under a nitrogen atmosphere, the temperature was raised from room temperature to 150°C within 1 hour and maintained at that temperature for 30 minutes. Then, while distilling off the byproduct acetic acid, the temperature was raised to 350°C over 7 hours, followed by a reduction in pressure to 5 mmHg over 80 minutes. The polymerization reaction was terminated at the specified torque point, and the contents of the reaction vessel were removed. Liquid crystal polymer particles (LCP3) were obtained using a pulverizer. The amount of acetic acid distilled during polymerization was almost consistent with the theoretical value. The crystal melting temperature (Tm) of the obtained particles was 321°C.

[0215] Synthesis Example 4 (LCP4)

[0216] In a reaction vessel equipped with a torque meter, a stirrer, and a distillation tube, BON6, BP, HQ, and TPA were added according to the composition ratio shown in Table 6 to make a total of 6.5 mol. Acetic anhydride with a molar amount of hydroxyl groups relative to all monomers of 1.03 times was then added. Deacetic acid polymerization was carried out under the following conditions.

[0217] [Table 6]

[0218] BON6 BP HQ TPA Mass (g) 660.5 254.2 14.3 248.3 mole% 54 21 2 23

[0219] Under a nitrogen atmosphere, the temperature was raised from room temperature to 150°C within 1 hour and maintained at that temperature for 60 minutes. Then, while distilling off the byproduct acetic acid, the temperature was raised to 350°C over 7 hours, followed by a reduction in pressure to 5 mmHg over 90 minutes. The polymerization reaction was terminated at the time point exhibiting the specified torque, and the contents of the reaction vessel were removed. Liquid crystal polymer particles (LCP4) were obtained using a pulverizer. The amount of acetic acid distilled during polymerization was almost consistent with the theoretical value. The crystal melting temperature (Tm) of the obtained particles was 338°C.

[0220] The following examples show the talc used in the embodiments and comparative examples.

[0221] Talc 1: Manufactured by TALC Corporation of Japan, talc "MS-SF" (average particle size: 16μm, quartz content: 0.02%)

[0222] Talc 2: (Available) Tamura Talc Industry Co., Ltd., Talc "TP-40B" (average particle size: 16μm, quartz content: 0.00%)

[0223] Talc 3: Manufactured by Fuji TALC Industries, Ltd., Talc "NK-64" (average particle size: 17μm, quartz content: 0.28%)

[0224] Talc 4: Manufactured by Fuji TALC Industries, Ltd., Talc "DS-34" (average particle size: 13μm, quartz content: 0.80%)

[0225] Glass fiber: CPIC, ECS3010A (number-average fiber diameter 10.5μm, number-average fiber length 3mm, quartz content: 0.00%)

[0226] Examples 1-10 and Comparative Examples 1-7

[0227] The synthesized LCP, the aforementioned talc, and glass fiber were blended according to the contents (parts by mass) listed in Table 7, and melt-blended using a twin-screw extruder (Nippon Steel Co., Ltd. TEX-30) at a barrel temperature of 350°C to obtain granules of the liquid crystal polymer composition.

[0228] Subsequently, using the methods described above, tensile strength, elongation at break, Izod impact strength, load flexural temperature, melt viscosity, flow length at 0.1 mm thickness, and step foaming were measured and evaluated. The results are shown in Table 7.

[0229] As shown in Table 7, the liquid crystal polymer compositions of Examples 1 to 10 all maintain the mechanical strength and heat resistance of the liquid crystal polymer at a certain level, and the flow length of 0.1 mm thickness is more than 10 mm, the step foaming evaluation is ◎ or ○, and the thin-wall flowability and foaming resistance are excellent.

[0230] In contrast, the liquid crystal polymer compositions of Comparative Examples 1 to 7 are poor in any of the following aspects: mechanical strength, heat resistance, thin-wall flowability, and foaming resistance, and cannot fully meet the balance of performance.

[0231] [Table 7]

[0232]

Claims

1. A liquid crystal polymer composition, wherein, The liquid crystal polymer contains 0.1 to 150 parts by mass of talc, with the talc containing 0 to 0.25% quartz by mass, relative to 100 parts by mass of talc.

2. The liquid crystal polymer composition of claim 1, wherein, Relative to 100 parts by weight of liquid crystal polymer, it also contains 0.1 to 100 parts by weight of glass fiber.

3. The liquid crystal polymer composition according to claim 1 or 2, wherein, The liquid crystal polymer comprises repeating units represented by formula (I) and / or formula (II).

4. The liquid crystal polymer composition of claim 3, wherein, The liquid crystal polymer also contains repeating units represented by formulas (III) and (IV). In the formula, Ar1 and Ar2 each independently represent a divalent aromatic group.

5. The liquid crystal polymer composition of claim 4, wherein, The repeating units represented by formulas (III) to (IV) are: Ar1 and Ar2 are each independently selected from one or more repeating units of the aromatic groups represented by formulas (1) to (4).

6. The liquid crystal polymer composition of claim 4, wherein, The liquid crystal polymer comprises repeating units represented by formulas (I) and (II).

7. The liquid crystal polymer composition of claim 6, wherein, The repeating units represented by formulas (III) to (IV) are: Ar1 and Ar2 are each independently selected from one or more repeating units of the aromatic groups represented by formulas (1) to (4).

8. The liquid crystal polymer composition according to claim 1 or 2, wherein, The crystal melting temperature of the liquid crystal polymer, as determined by differential scanning calorimetry, is 290–360 °C.

9. The liquid crystal polymer composition according to claim 1 or 2, wherein, The average particle size of talc is 0.1–100 μm.

10. The liquid crystal polymer composition of claim 1 or 2, wherein, According to ASTM D256, the Izod impact strength is above 200 J / m.

11. The liquid crystal polymer composition of claim 1 or 2, wherein, The content of quartz relative to the liquid crystal polymer composition is 0 to 0.040% by mass.

12. A molded article comprising the liquid crystal polymer composition of claim 1 or 2.

13. The molded article of claim 12, wherein, Molded parts are components selected from one of the following: connectors, switches, relays, spools, capacitors, coils, motors, fans, test sockets, transformers, camera modules, and antennas.

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