JP5924527B2 - Liquid crystal polyester composition, liquid crystal polyester molded body, and connector using liquid crystal polyester composition - Google Patents

Description

  The present invention relates to a liquid crystal polyester composition, a liquid crystal polyester molded article, and a connector using the liquid crystal polyester composition.

As electronic and electrical products become smaller and lighter, connectors used for them are becoming shorter and narrower. As the molding material, liquid crystal polyester is preferably used because of excellent melt fluidity, heat resistance, and mechanical properties.
Liquid crystalline polyester forms a polydomain having a molten state without causing entanglement even in the molten state due to its rigid molecule, and exhibits a behavior in which molecular chains are remarkably oriented in the flow direction at a low shear rate, and has flow characteristics and heat resistance. Is excellent.
Since liquid crystal polyester is excellent in heat resistance, carbon black is generally added for the purpose of preventing discoloration during use in a high temperature atmosphere. For example, Patent Documents 1 and 2 disclose compositions obtained by blending liquid crystal polyester and carbon black. In addition, for the purpose of imparting designability and designability to the liquid crystal polyester, a coloring material may be added and used for coloring. For example, Patent Document 3 discloses a composition comprising a liquid crystal polyester and an inorganic fired pigment.

JP 2001-279066 A JP 2011-157422 A JP-A-4-4253

  However, when a colorant is added to the liquid crystal polyester and colored, the liquid crystal polyester is oriented at the time of molding, so that the color (particularly lightness) of the molded body changes greatly due to the difference in thickness of the molded body. Therefore, there is a problem that color unevenness occurs in the entire molded body, and appearance defects tend to be manifested. Further, when a large amount of coloring material is added to improve the color change due to the difference in the thickness of the molded body, the mechanical strength of the liquid crystal polyester is lowered. Furthermore, there is a problem that gas is generated from the added coloring material and bubbles (blisters) are easily generated in the molded body.

  The present invention has been made in view of the above circumstances, and a liquid crystal polyester composition having high blister resistance, in which a change in color due to a difference in thickness of a molded article made of a liquid crystal polyester composition is reduced, mechanical strength is maintained, and It is an object of the present invention to provide a connector using a liquid crystal polyester molded body and a liquid crystal polyester composition.

  As a result of intensive studies to solve such problems, the present inventors have completed the present invention.

That is, the present invention is based on 100 parts by mass of the liquid crystalline polyester, with titanium oxide and / or titanium oxide as a main component and one or more selected from antimony, nickel, chromium, iron, zinc, molybdenum or tungsten. 0.01 to 5 parts by mass of a composite metal oxide containing a metal element (hereinafter, the composite metal oxide mainly composed of titanium oxide and / or titanium oxide is collectively referred to as “titanium oxide filler”) In addition, a liquid crystal polyester composition containing 0.01 to 0.28 parts by mass of ultramarine.

  In the present invention, the titanium oxide filler is preferably a composite metal oxide containing nickel or a composite metal oxide containing chromium.

  In the present invention, the liquid crystal polyester composition preferably contains 0.01 to 3 parts by mass of a colorant other than the titanium oxide filler and ultramarine blue.

  In the present invention, the colorant other than the titanium oxide filler and ultramarine is preferably carbon black, cobalt green, iron oxide or phthalocyanine blue.

  Moreover, this invention provides the molded object using said liquid crystal polyester composition, and the connector using said liquid crystal polyester composition.

  In the liquid crystal polyester composition of the present invention, the change in color due to the difference in thickness of the molded body made of the liquid crystal polyester composition is reduced, the mechanical strength is maintained, and the blister resistance is high.

It is a schematic diagram which shows the board test piece with a level | step difference using the liquid crystalline polyester composition of this invention.

  The liquid crystalline polyester is a liquid crystalline polyester that exhibits liquid crystallinity in a molten state, and is preferably melted at a temperature of 450 ° C. or lower. The liquid crystal polyester may be a liquid crystal polyester amide, a liquid crystal polyester ether, a liquid crystal polyester carbonate, or a liquid crystal polyester imide. The liquid crystal polyester is preferably a wholly aromatic liquid crystal polyester using only an aromatic compound as a raw material monomer.

  A typical example of the liquid crystal polyester is polymerization (polycondensation) of an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine, and an aromatic diamine. At least one compound selected from the group consisting of aromatic dicarboxylic acids and aromatic diols, aromatic hydroxyamines and aromatic diamines, And those obtained by polymerizing a polyester such as polyethylene terephthalate and an aromatic hydroxycarboxylic acid. Here, the aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, the aromatic diol, the aromatic hydroxyamine, and the aromatic diamine are each independently replaced with a part or all of the polymerizable derivative. Also good.

  Examples of polymerizable derivatives of a compound having a carboxyl group such as aromatic hydroxycarboxylic acid and aromatic dicarboxylic acid include those obtained by converting a carboxyl group into an alkoxycarbonyl group or an aryloxycarbonyl group (ester), carboxyl Examples include those obtained by converting a group into a haloformyl group (acid halide), and those obtained by converting a carboxyl group into an acyloxycarbonyl group (acid anhydride). Examples of polymerizable derivatives of hydroxyl group-containing compounds such as aromatic hydroxycarboxylic acids, aromatic diols and aromatic hydroxyamines include those obtained by acylating hydroxyl groups and converting them to acyloxyl groups (acylated products) ). Examples of polymerizable derivatives of amino group-containing compounds such as aromatic hydroxyamines and aromatic diamines include those obtained by acylating an amino group and converting it to an acylamino group (acylated product).

  The liquid crystalline polyester preferably has a repeating unit represented by the following formula (1) (hereinafter sometimes referred to as “repeating unit (1)”), and the repeating unit (1) and the following formula (2) A repeating unit represented (hereinafter sometimes referred to as “repeating unit (2)”) and a repeating unit represented by the following formula (3) (hereinafter sometimes referred to as “repeating unit (3)”). It is more preferable to have.

（Ａｒ^１は、フェニレン基、ナフチレン基又はビフェニリレン基を表す。Ａｒ^２及びＡｒ^３は、それぞれ独立に、フェニレン基、ナフチレン基、ビフェニリレン基又は下記式（４）で表される基を表す。Ｘ及びＹは、それぞれ独立に、酸素原子又はイミノ基（−ＮＨ−）を表す。Ａｒ^１、Ａｒ^２又はＡｒ^３で表される前記基にある水素原子は、それぞれ独立に、ハロゲン原子、アルキル基又はアリール基で置換されていてもよい。）

(Ar ¹ represents a phenylene group, a naphthylene group, or a biphenylylene group. Ar ² and Ar ³ each independently represent a phenylene group, a naphthylene group, a biphenylylene group, or a group represented by the following formula (4). X And Y each independently represents an oxygen atom or an imino group (—NH—), and each hydrogen atom in the group represented by Ar ¹ , Ar ² or Ar ³ is independently a halogen atom or an alkyl group. Alternatively, it may be substituted with an aryl group.)

（Ａｒ^４及びＡｒ^５は、それぞれ独立に、フェニレン基又はナフチレン基を表す。Ｚは、酸素原子、硫黄原子、カルボニル基、スルホニル基又はアルキリデン基を表す。）

(Ar ⁴ and Ar ⁵ each independently represent a phenylene group or a naphthylene group. Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylidene group.)

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-hexyl group, 2-ethylhexyl group, An n-octyl group and n-decyl group are mentioned, The carbon number is 1-10 normally. Examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group, and a 2-naphthyl group, and the number of carbon atoms is usually 6 to 20. . When the hydrogen atom is substituted with these groups, the number is usually 2 or less for each of the groups represented by Ar ¹ , Ar ² or Ar ³ , and preferably 1 It is as follows.

  Examples of the alkylidene group include a methylene group, an ethylidene group, an isopropylidene group, an n-butylidene group, and a 2-ethylhexylidene group, and the number of carbon atoms is usually 1 to 10.

The repeating unit (1) is a repeating unit derived from a predetermined aromatic hydroxycarboxylic acid. As the repeating unit (1), Ar ¹ is a p-phenylene group (repeating unit derived from p-hydroxybenzoic acid), and Ar ¹ is a 2,6-naphthylene group (6-hydroxy-2). -Repeating units derived from naphthoic acid) are preferred.

The repeating unit (2) is a repeating unit derived from a predetermined aromatic dicarboxylic acid. As the repeating unit (2), Ar ² is a p-phenylene group (a repeating unit derived from terephthalic acid), Ar ² is an m-phenylene group (a repeating unit derived from isophthalic acid), Ar ² Is a 2,6-naphthylene group (a repeating unit derived from 2,6-naphthalenedicarboxylic acid), and Ar ² is a diphenyl ether-4,4′-diyl group (diphenyl ether- 4,4′-dicarboxylic acid-derived repeating units) are preferred.

The repeating unit (3) is a repeating unit derived from a predetermined aromatic diol, aromatic hydroxylamine or aromatic diamine. As the repeating unit (3), Ar ³ is a p-phenylene group (a repeating unit derived from hydroquinone, p-aminophenol or p-phenylenediamine), and Ar ³ is a 4,4′-biphenylylene group. Those (4,4′-dihydroxybiphenyl, 4-amino-4′-hydroxybiphenyl or repeating units derived from 4,4′-diaminobiphenyl) are preferred.

  The content of the repeating unit (1) is the total amount of all repeating units (the mass equivalent amount of each repeating unit (moles by dividing the mass of each repeating unit constituting the liquid crystal polyester by the formula amount of each repeating unit). ) And the total value thereof) is usually 30 mol% or more, preferably 30 to 80 mol%, more preferably 40 to 70 mol%, still more preferably 45 to 65 mol%. The content of the repeating unit (2) is usually 35 mol% or less, preferably 10 to 35 mol%, more preferably 15 to 30 mol%, still more preferably 17.5 to the total amount of all repeating units. 27.5 mol%. The content of the repeating unit (3) is usually 35 mol% or less, preferably 10 to 35 mol%, more preferably 15 to 30 mol%, still more preferably 17.5 to the total amount of all repeating units. 27.5 mol%. The higher the content of the repeating unit (1), the easier it is to improve the melt fluidity, heat resistance, strength and rigidity. However, if it is too much, the melting temperature and melt viscosity are likely to increase, and the temperature required for molding increases. easy.

  The ratio between the content of the repeating unit (2) and the content of the repeating unit (3) is expressed as [content of repeating unit (2)] / [content of repeating unit (3)] (mol / mol). The ratio is usually 0.9 / 1 to 1 / 0.9, preferably 0.95 / 1 to 1 / 0.95, and more preferably 0.98 / 1 to 1 / 0.98.

  In addition, liquid crystalline polyester may have 2 or more types of repeating units (1)-(3) each independently. Further, the liquid crystalline polyester may have a repeating unit other than the repeating units (1) to (3), but the content thereof is usually 10 mol% or less with respect to the total amount of all repeating units, preferably 5 mol% or less.

  Since the liquid crystal polyester has a repeating unit (3) in which X and Y are each an oxygen atom, that is, having a repeating unit derived from a predetermined aromatic diol, the melt viscosity tends to be low. It is more preferable that the repeating unit (3) has only those in which X and Y are each an oxygen atom.

  The liquid crystalline polyester can be produced by melt polymerizing raw material monomers corresponding to the repeating units constituting the liquid crystalline polyester and solid-phase polymerizing the obtained polymer (hereinafter sometimes referred to as “prepolymer”). preferable. Thereby, high molecular weight liquid crystal polyester having high heat resistance, strength and rigidity can be produced with good operability. Melt polymerization may be carried out in the presence of a catalyst. Examples of this catalyst include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide, And nitrogen-containing heterocyclic compounds such as 4- (dimethylamino) pyridine and 1-methylimidazole, and nitrogen-containing heterocyclic compounds are preferably used.

  The liquid polyester has a flow starting temperature of usually 270 ° C. or higher, preferably 270 to 400 ° C., more preferably 280 to 380 ° C. As the flow start temperature is higher, the heat resistance, strength, and rigidity are more likely to be improved.

The flow start temperature is also called flow temperature or flow temperature, and the temperature is raised at a rate of 4 ° C./min under a load of 9.8 MPa (100 kg / cm ² ) using a capillary rheometer while the liquid crystalline polyester is used. Is a temperature showing a viscosity of 4800 Pa · s (48000 poise) when extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm, and is a measure of the molecular weight of the liquid crystalline polyester (Naide Koide, “ "Liquid Crystal Polymer -Synthesis / Molding / Application-", see CMC Corporation, June 5, 1987, p. 95).

(Titanium oxide)
Titanium oxide can use what is marketed as a resin filler. In addition, what is called a titanium oxide and marketed as a resin filler can be used as it is, and does not exclude the impurity contained unintentionally. Further, titanium oxide that has been subjected to a surface treatment as described later can be used.

  The crystal form of titanium oxide itself contained in titanium oxide is not particularly limited, and a rutile type, anatase type, or a mixture of both may be used. From the viewpoint that the color unevenness of the molded article made of the liquid crystal polyester composition becomes good, it is preferable to use titanium oxide containing a rutile crystal form, and more preferably to use titanium oxide consisting only of a rutile crystal form. preferable.

  The average particle diameter of titanium oxide is not particularly limited, but from the viewpoint of dispersibility of titanium oxide in a molded article made of a liquid crystal polyester composition, the average particle diameter is preferably 0.10 to 0.50 μm, It is more preferably 0.15 to 0.40 μm, and further preferably 0.18 to 0.30 μm. The average particle diameter is measured by measuring the appearance of titanium oxide with a scanning electron microscope (SEM), and using the obtained SEM photograph using an image analyzer (for example, “Luzex IIIU” manufactured by Nireco Corporation). It is a volume average particle size obtained by plotting the particle amount (%) in each particle size interval to obtain a distribution curve, and obtaining a cumulative degree of 50% (average particle size) from the accumulated distribution curve.

  Titanium oxide may be subjected to surface treatment for the purpose of improving properties such as dispersibility. Such surface treatment is not particularly limited, but from the viewpoint of improving dispersibility and weather resistance, surface treatment with an inorganic metal oxide is preferable, and aluminum oxide (alumina) is preferable as the inorganic metal oxide. However, if there is no aggregation or the like and the handling is easy, titanium oxide not subjected to surface treatment is preferable from the viewpoint of heat resistance and strength.

  The method for producing titanium oxide is preferably titanium oxide containing titanium oxide produced by the sulfuric acid method or chlorine method, and particularly preferably titanium oxide containing titanium oxide produced by the chlorine method. Here, the sulfuric acid method and the chlorine method will be briefly described. In the sulfuric acid method, ore (titanium slag obtained by treating ilmenite or ilmenite ore), which is a titanium source, is reacted with sulfuric acid and extracted with water, and then the resulting solution is cooled. In this method, the iron content in the sulfate is removed and then hydrolyzed to obtain titanium oxide. In the chlorine method, ore that is a titanium source (synthetic rutile obtained from rutile or ilmenite ore) is reacted with chlorine at around 1000 ° C to obtain crude titanium tetrachloride, and this crude titanium tetrachloride is purified by rectification. The obtained titanium tetrachloride is oxidized with oxygen to obtain titanium oxide. According to this chlorine method, titanium oxide having a high purity can be obtained by distilling titanium chloride, so that titanium oxide excellent in white color can be obtained, and further, a rutile type of a suitable crystal type. Titanium oxide is easily obtained. And, by optimizing the conditions in the step of oxidizing with oxygen (oxidation step), titanium oxide having relatively excellent whiteness can be easily obtained. Further, by optimizing the conditions in the oxidation step, there is an advantage that it is easy to suppress the generation of coarse particles and to obtain titanium oxide having a suitable average particle diameter.

  Examples of the commercially available titanium oxide that can be used include “TIPAQUE CR-58, CR-60” manufactured by Ishihara Sangyo Co., Ltd. and “SR-1” manufactured by Sakai Chemical Co., Ltd. The “TIPAQUE CR-58, CR-60” is made of titanium oxide manufactured by a chlorine method, and “SR-1” is made of titanium oxide manufactured by a manufacturing method called a sulfuric acid method. Is.

(Titanium oxide filler)
The titanium oxide filler is a composite composed of titanium oxide and / or titanium oxide as a main component and containing one or more metal elements selected from antimony, nickel, chromium, iron, zinc, molybdenum or tungsten. It is a metal oxide.

  The composition of the titanium oxide filler other than titanium oxide used in the present invention is 50 to 95% by mass of titanium oxide as a main component, and the subcomponent is selected from antimony, nickel, chromium, iron, zinc, molybdenum, and tungsten. A composite oxide composed of 5 to 50% by mass of two metal oxides, and there are no particular limitations on the combination of subcomponents, such as antimony-nickel, antimony-chromium, and iron-zinc. The titanium oxide as the main component is preferably the titanium oxide described above. These oxides or hydroxides can be used for antimony, nickel, chromium, iron, zinc, molybdenum, and tungsten. Furthermore, any of chlorides, sulfates, and metal acid salts that generate oxides and hydroxides by neutralization and hydrolysis may be used.

Composite metal oxide containing nickel _may be exemplified TiO 2 -BaO-NiO _system, TiO ₂ -Sb ₂ O 3 -NiO system.

The composite metal oxide containing chromium can be exemplified by a TiO ₂ —Sb ₂ O ₃ —Cr ₂ O ₃ system.

The titanium oxide filler is preferably produced by thermally diffusing nickel and antimony atoms in the crystal lattice of rutile type titanium oxide (TiO ₂ ).

  Examples of commercially available titanium oxide fillers that can be used include “TIPAQUE YELLOW TY-50, TY-70, TY-100” manufactured by Ishihara Sangyo Co., Ltd.

  The content of the titanium oxide filler in the liquid crystal polyester composition of the present invention is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal polyester. 5-3 mass parts is more preferable. If it is less than 0.01 part by mass, the resulting molded product is insufficiently colored, and if it exceeds 5 parts by mass, blistering of the molded product tends to occur. The properties such as mechanical properties and heat resistance of the liquid crystal polyester are not sufficiently maintained. In addition, when both a titanium oxide and a titanium oxide filler are contained, the total amount should just be the said range with respect to liquid crystalline polyester.

(Ultramarine)
Ultramarine used in the present invention is a synthetic blue inorganic pigment mainly composed of silicon dioxide, alumina, sodium oxide and bonded sulfur, and containing sodium sulfate, ferric oxide, free sulfur and the like as impurities. Examples of the molecular structure of ultramarine blue include Na ₈ (Al ₆ Si ₆ O ₂₄ ) S (2-4).

  Ultramarine can be produced by a known production method such as pulverizing and mixing kaolin, soda ash, sulfur, and a reducing agent (such as charcoal, coal, or rosin) and firing at 750 to 850 ° C. for 40 to 50 hours. it can.

  Ultramarine has an average particle diameter of 0.1 to 50 μm, particularly preferably 0.2 to 10 μm. When the average particle diameter is less than 0.1 μm, blue coloration may be insufficient, and when the average particle diameter exceeds 50 μm, a dark color may occur due to scattering, and the original color of ultramarine blue may be impaired.

  Ultramarine is preferably 0.01 to 3 parts by mass, more preferably 0.01 to 0.28 parts by mass, and 0.01 to 0.15 parts by mass with respect to 100 parts by mass of the liquid crystalline polyester. It is particularly preferred that

  Examples of commercially available ultramarine products that can be used include “general-purpose types (No. 300, 1500, 2000, etc.)” and “silica-coated types (AP31, 201, 205, 151, etc.) manufactured by Daiichi Kasei Kogyo Co., Ltd. ) "Or the like. Further, ultramarine manufactured by Nubiola and Holdigy pigment can be used.

  Examples of the colorant other than the titanium oxide filler and ultramarine used in the present invention include carbon black, iron oxide (valve), cobalt green, and phthalocyanine blue. In particular, the use of one or more colorants selected from the group consisting of carbon black and cobalt green is excellent in terms of color and weather resistance.

Examples of cobalt green include CoO—Al ₂ O ₃ and CoO—Al ₂ O ₃ —Cr ₂ O ₃ . Iron oxide, and the like iron oxyhydroxide represented by FeOOH or _{Fe 2 O 3 · H 2 O} .

  The coloring material other than the titanium oxide filler and ultramarine blue is preferably 0.01 to 3 parts by mass, more preferably 0.01 to 0.2 parts by mass with respect to 100 parts by mass of the liquid crystalline polyester. It is especially preferable that it is 01-0.1 mass part.

The bulk density of the colorant other than the titanium oxide filler and ultramarine is preferably 0.4 to 1.0 g / cm ³ , more preferably 0.5 to 0.8 g / cm ³ . If it is less than 0.4 g / cm ³ , the molded product tends to become brittle due to poor dispersion, and if it exceeds 1.0 g / cm ³ , thermal aggregation occurs and foreign matter increases in the molded product, which is not preferable.

  When the colorant used in the present invention has a large amount of moisture and decomposition products generated when heated, the blister resistance and mechanical strength of the liquid crystal polyester are lowered.

  The water content of the coloring material is preferably 1000 ppm. When it exceeds 1000 ppm, there is a tendency that the granulation workability is deteriorated or foaming occurs in the molded product.

  The heating loss from normal temperature to 400 ° C. according to the thermogravimetric analysis (TGA) method of the colorant is preferably 0.05 parts by mass. The loss on heating can be determined as a decrease in the amount of heat until reaching 400 ° C. by heating at a rate of temperature increase of 10 ° C. per minute from room temperature by thermogravimetric analysis (TGA).

  As the coloring material used in the present invention, any of those which are surface-treated with an inorganic substance or a hydroxide thereof and those which are not surface-treated can be used. As a surface treatment method, for example, in order to improve the light stability or dispersibility of the above titanium dioxide, the surface thereof is previously coated with an inorganic substance such as aluminum oxide, silicon oxide, calcium oxide, zirconium oxide or a hydrate thereof. Preferably it has been treated.

  The liquid crystal polyester composition of the present invention may contain one or more other components such as a filler, an additive, and a resin other than the liquid crystal polyester.

  The filler that may be contained in the liquid crystal polyester composition of the present invention may be a fibrous filler, a plate-like filler, or other than the fibrous and plate-like, spherical or other The granular filler may be used. The fibrous filler preferably has a number average fiber diameter of 5 to 20 μm and a number average fiber length of 500 μm or less. If the number average fiber length exceeds 500 μm, the fluidity may deteriorate even if the blending amount is reduced. If the fiber diameter is too large, the moldability may be deteriorated. If the fiber diameter is too small, the fiber is likely to be broken during the molding process, and the effect of improving the mechanical strength may be inferior.

  In addition, the number average fiber diameter and number average fiber length of the fibrous filler in this invention can be measured with the following method, for example. 2 g of the resin composition is heated for 3 hours using an electric furnace at 600 ° C. to be incinerated. After the incineration residue was sufficiently dispersed in the polyethylene glycol solution, it was transferred onto a slide glass with a dropper, and observed with “VHX-1000” manufactured by Keyence Digital Microscope Co., Ltd. The fiber length and fiber diameter were measured, and the number average fiber diameter and number average fiber length were determined.

  The filler may be an inorganic filler or an organic filler. Examples of fibrous inorganic fillers include glass fibers; carbon fibers such as pan-based carbon fibers and pitch-based carbon fibers; ceramic fibers such as silica fibers, alumina fibers and silica-alumina fibers; and metal fibers such as stainless steel fibers. It is done. In addition, whiskers such as potassium titanate whisker, barium titanate whisker, wollastonite whisker, aluminum borate whisker, silicon nitride whisker, and silicon carbide whisker are also included. Examples of fibrous organic fillers include polyester fibers and aramid fibers. Examples of the plate-like inorganic filler include talc, mica, graphite, wollastonite, glass flake, barium sulfate, and calcium carbonate. Mica may be muscovite, phlogopite, fluorine phlogopite, or tetrasilicon mica. Examples of the particulate inorganic filler include silica, alumina, glass beads, glass balloons, boron nitride, silicon carbide and calcium carbonate. Content of a filler is 5-100 mass parts normally with respect to 100 mass parts of liquid crystalline polyester, 5-80 mass parts is preferable and 50-70 mass parts is especially preferable.

  Examples of the additive that may be contained in the liquid crystal polyester composition of the present invention include an antioxidant, a heat stabilizer, an ultraviolet absorber, an antistatic agent, a surfactant, and a flame retardant. The content of the additive is desirably 0 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal polyester.

  Examples of resins other than liquid crystal polyester include polypropylene, polyamide, polyester other than liquid crystal polyester, thermoplastic resin other than liquid crystal polyester such as polysulfone, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene ether, and polyetherimide; and phenol resin And thermosetting resins such as epoxy resins, polyimide resins, and cyanate resins. The content of the resin other than the liquid crystal polyester is usually preferably 0 to 20 parts by mass with respect to 100 parts by mass of the liquid crystal polyester.

  The liquid crystal polyester composition is preferably prepared by melt-kneading the liquid crystal polyester, titanium oxide filler, ultramarine blue, and other components used as needed using an extruder and extruding them into pellets. As the extruder, one having a cylinder, one or more screws arranged in the cylinder, and one or more supply ports provided in the cylinder is preferably used, and further one place provided in the cylinder What has the above vent part is used more preferably.

  It is also possible to use a method in which liquid crystal polyester and pigment are blended to prepare master batch pellets, which are dry blended with natural pellets during molding to obtain a product having a predetermined content.

  As a molding method of the liquid crystal polyester composition, a melt molding method is preferable, and examples thereof include an injection molding method, an extrusion molding method such as a T-die method and an inflation method, a compression molding method, a blow molding method, a vacuum molding method, and a press. Examples include molding. Of these, the injection molding method is preferable.

When the molded body using the liquid crystal polyester composition of the present invention obtained a plate test piece with a step as shown in FIG. 1, the thickness of the minimum thickness portion (D2) and the thickness of the maximum thickness portion (D1). The ratio preferably satisfies the following formula.
D1 / D2 ≧ 3

  Examples of products and parts that are molded products of liquid crystal polyester compositions include bobbins such as optical pickup bobbins and transformer bobbins; relay parts such as relay cases, relay bases, relay sprues, and relay armatures; RIMM, DDR, and CPU sockets. , S / O, DIMM, Board to Board connector, FPC connector, card connector, etc .; Lamp reflector, LED reflector, etc .; Lamp holder, heater holder, etc .; Speaker diaphragm, etc. Separation claws, separation claws for printers, etc .; camera module parts; switch parts; motor parts; sensor parts; hard disk drive parts; tableware such as ovenware; And a sealing member such as a coil sealing member.

  The liquid crystal polyester composition obtained by the present invention can be applied to the products and parts described above, but is particularly useful for connectors.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example.

[Measurement of flow start temperature of liquid crystalline polyester]
Using a flow tester (“CFT-500 type” manufactured by Shimadzu Corporation), about 2 g of liquid crystalline polyester was filled into a cylinder attached with a die having a nozzle having an inner diameter of 1 mm and a length of 10 mm, and 9.8 MPa (100 kg). The liquid crystalline polyester was melted while being heated at a rate of 4 ° C./min under a load of / cm ² ), extruded from a nozzle, and a temperature showing a viscosity of 4800 Pa · s (48000 poise) was measured.

[Production of liquid crystalline polyester]
In a reactor equipped with a stirrer, torque meter, nitrogen gas introduction tube, thermometer and reflux condenser, 994.5 g (7.2 mol) of p-hydroxybenzoic acid and 299.1 g (1.8 mol) of terephthalic acid were added. Mol), 99.7 g (0.6 mol) of isophthalic acid, 446.9 g (2.4 mol) of 4,4′-dihydroxybiphenyl, 1347.6 g (13.2 mol) of acetic anhydride, and 1-methylimidazole Was added while stirring under a nitrogen gas stream from room temperature to 150 ° C. over 30 minutes and refluxed at 150 ° C. for 1 hour. Next, 0.9 g of 1-methylimidazole was added, the temperature was raised to 320 ° C. over 2 hours and 50 minutes while distilling out by-product acetic acid and unreacted acetic anhydride, and an increase in torque was observed at 320 ° C. The contents were removed from the reactor and cooled to room temperature. The obtained solid was pulverized with a pulverizer to obtain a powdery prepolymer. Next, the prepolymer was heated from room temperature to 250 ° C. over 1 hour in a nitrogen gas atmosphere, heated from 250 ° C. to 285 ° C. over 5 hours, and held at 285 ° C. for 3 hours, After solid phase polymerization, the mixture was cooled to obtain a powdery liquid crystal polyester. The liquid crystal polyester had a flow initiation temperature of 327 ° C.

[Measurement of color tone]
A 40 mm × 60 mm × 3 mm stepped plate test piece was measured with a color difference meter (Konica Minolta, Inc., “cd-3600”) with a 10-degree visual field color matching function using the CIE 1976 (L * a * b *) color system. A certain lightness index L * was measured. In order to quantify the change in color due to the difference in thickness of the molded product, the light source was D65, the measurement diameter was 4 mm, and the measurement mode was SCI. {L * value of the maximum thickness (3 mm) of the plate-shaped test piece}-{L * value of the maximum thickness (1 mm) of the plate-shaped test piece} is 2 or less; Is shown in Tables 1 and 2.

[Measurement method of tensile strength]
ASTM 4 dumbbell test piece (thickness) using a liquid crystalline polyester composition at a cylinder temperature of 350 ° C., a mold temperature of 130 ° C., and an injection speed of 60% using an injection molding machine (Nissei Plastic Industries, Ltd. “PS40E1ASE”). 3.2 mm).
Tables 1 and 2 show the results obtained by measuring the tensile strength of ASTM No. 4 dumbbell test pieces in accordance with ASTM D638.

[Blister measurement method]
JIS K7113 (1/2) is applied to the liquid crystalline polyester composition using an injection molding machine (Nissei Plastic Industries, Ltd. “PS40E1ASE”) at a cylinder temperature of 350 ° C., a mold temperature of 130 ° C., and an injection speed of 60%. A dumbbell specimen (thickness 1.2 mm) was formed. Ten test specimens obtained were immersed in a solder bath heated to 280 ° C. for 60 seconds, and observed whether blisters (blowing) were generated on the surface of the test specimens after removal, and blisters were formed on all ten test specimens. The results are shown in Tables 1 and 2 when no occurs, and when one of the 10 test pieces occurs, x.

[Examples 1-8, Comparative Examples 1-8]
The liquid crystal polyester obtained in Production Example 1 was blended according to the following table, and granulated at a cylinder temperature of 340 ° C. using a twin-screw extruder (manufactured by Ikekai Tekko Co., Ltd., PCM30 type) to obtain a liquid crystal polyester composition. The obtained resin composition was molded at 350 ° C. with an injection molding machine (PS40E5ASE type manufactured by Nissei Plastic Industry Co., Ltd.) to obtain a stepped plate test piece (FIG. 1) having dimensions of 40 mm × 60 mm × 3 mm. Then, the color tone was measured about the minimum thickness part (1 mmt) and the maximum thickness part (3 mmt) of a molded object, and the result was shown in Table 1 and 2. FIG.
The following fillers and coloring materials were used.
Glass fiber: Nitto Boseki Co., Ltd. PF70E-001 (number average fiber diameter 10 μm, number average fiber length 70 μm)
Talc: Nippon Talc Co., Ltd. X-50
Titanium oxide: Ishihara Sangyo Co., Ltd. Taipei CR-60
Titanium Yellow: Ishihara Sangyo Co., Ltd. Taipei TY-70
Ultramarine: Daisei Kasei Kogyo Co., Ltd. Ultramarine No2000
Carbon Black: Mitsubishi Chemical Corporation Mitsubishi Carbon Black # 960
Cobalt Green: Asahi Chemical Industry Co., Ltd. Green 2040

DESCRIPTION OF SYMBOLS 1 ... Plate-shaped test piece, D1 ... Maximum thickness part, D2 ... Minimum thickness part.

Claims (8)

Consists of one or more metal elements selected from antimony, nickel, chromium, iron, zinc, molybdenum or tungsten, with titanium oxide and / or titanium oxide as the main component with respect to 100 parts by mass of liquid crystal polyester 0.01 to 5 parts by mass of the composite metal oxide (hereinafter, the composite metal oxide mainly composed of titanium oxide and / or titanium oxide is referred to as “titanium oxide filler”) and 0.01% of ultramarine blue. -0.28 mass part liquid crystal polyester composition characterized by the above-mentioned.   The liquid crystal polyester composition according to claim 1, wherein the titanium oxide filler is a composite metal oxide containing nickel or a composite metal oxide containing chromium.   The liquid-crystal polyester composition of Claim 1 or 2 which contains 0.01-3 mass parts of coloring materials other than a titanium oxide filler and ultramarine.   The liquid crystal polyester composition according to any one of claims 1 to 3, wherein the colorant other than the titanium oxide filler and ultramarine blue is carbon black, cobalt green, iron oxide, or phthalocyanine blue.   The liquid crystal polyester composition according to any one of claims 1 to 4, further comprising 5 to 100 parts by mass of a fibrous filler having an average fiber diameter of 5 to 20 µm and a fiber length of 500 µm or less.   The liquid crystalline polyester composition according to any one of claims 1 to 5, wherein the fibrous filler is a glass fiber. It is a molded object using the liquid-crystal polyester composition of any one of Claims 1-6, Comprising: Ratio of the thickness (D1) of the largest thickness part of a molded object, and the thickness (D2) of a minimum thickness part Satisfy | fills following formula, The liquid crystalline polyester molded object characterized by the above-mentioned.
D1 / D2 ≧ 3   The connector using the liquid crystalline polyester composition of any one of Claims 1-6, or the molded object of Claim 7.

Images