TWI586752B - Liquid crystal polyester composition - Google Patents

Description

Liquid crystal polyester composition

The present invention relates to a liquid crystal polyester composition and a molded body composed of the composition.

With the miniaturization and thinning of electronic and electrical products, the connectors used therein are miniaturized. As for the molding material of the connector, liquid crystal polyester is preferably used from the viewpoint of excellent melt fluidity, heat resistance and mechanical properties.

Since the molecular structure of the liquid crystal polyester is straight, the liquid crystal polyester in a molten state does not cause inter-molecular entanglement to form a polycrystalline domain, and as a result, it shows that the molecular chain is clearly aligned in the flow direction by the low shear rate. . Therefore, the liquid crystal polyester is excellent in flow characteristics and heat resistance.

In the use in a high-temperature environment in which the heat resistance of the liquid crystal polyester is utilized, in order to prevent discoloration, carbon black is generally added to the liquid crystal polyester. For example, JP-A-2001-279066 or JP-A-2011-157422 discloses a composition in which a liquid crystal polyester and carbon black are blended. Further, in order to impart a new pattern or design property to the liquid crystal polyester, the liquid crystal polyester may be colored with a coloring material. For example, Japanese Laid-Open Patent Publication No. Hei-4-4253 discloses a composition in which a liquid crystal polyester and an inorganic fired pigment are blended.

[Summary of the Invention]

However, since the liquid crystal polyester is aligned during molding, the color (especially brightness) of the molded body composed of the liquid crystal polyester colored with the coloring material of the carbon black or the inorganic fired pigment significantly changes depending on the thickness difference of the portion. . Therefore, there is a problem in that color unevenness occurs in the entire molded body, and the appearance defect is easily noticeable. In order to improve the change of the color, if a large amount of coloring material is added to the liquid crystal polyester, the mechanical strength of the liquid crystal polyester is lowered, or bubbles are generated in the formed body by the gas generated from the colored material (foaming property) ) The problem.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal polyester composition and a molded body comprising the liquid crystal polyester composition, which can reduce the thickness difference of the molded body due to the thickness of the portion. The color changes, and the mechanical strength is maintained, and the molded body having high foaming resistance is obtained.

The inventors of the present invention have completed the present invention by focusing on the results of such research. That is, the liquid crystal polyester composition of the present invention contains 100 parts by mass of the following components (1), and 0.01 to 5 parts by mass of the component (2) and/or the component (3) and the component (4) 0.01 to 3 Parts by mass; (1) liquid crystal polyester; (2) titanium oxide; (3) containing titanium oxide as a main component, and containing ruthenium, nickel, chromium, a compound of one or more metal elements selected from the group consisting of iron, zinc, molybdenum and tungsten (hereinafter referred to as "metal element compound") as a secondary metal oxide as a subcomponent; and, (4) ultramarine blue .

In the present invention, the metal element is preferably nickel or chromium.

In the present invention, the liquid crystal polyester composition further preferably contains 0.01 to 3 parts by mass of the coloring material.

In the present invention, the coloring material is preferably carbon black, cobalt green, iron oxide or phthalocyanine blue.

In the present invention, the liquid crystal polyester composition further preferably contains 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.

In the present invention, the fibrous filler is preferably a glass fiber.

Further, the present invention is a molded body comprising the liquid crystal polyester composition, wherein a ratio of a thickness of a maximum thickness portion of the molded body to a thickness of a minimum thickness portion is 3 or more.

In the present invention, the above shaped body is preferably a connector.

When the liquid crystal polyester composition of the present invention is used, a molded article which can reduce the color change due to the difference in the thickness of the molded body, can maintain mechanical strength, and has high foaming resistance can be obtained.

1‧‧‧Slab test piece

D1‧‧‧Maximum meat thick

D2‧‧‧Minimum meat thick

Fig. 1 is a schematic view showing a differential-plate test piece composed of the liquid crystal polyester composition of the present invention.

The liquid crystal polyester of the present invention is a liquid crystal polyester which exhibits liquid crystallinity in a molten state, and is preferably a liquid crystal polyester which is melted at a temperature of 450 ° C or lower. The liquid crystal polyester may be a liquid crystal polyester decylamine, a liquid crystal polyester ether, a liquid crystal polyester carbonate, or a liquid crystal polyester quinone. The liquid crystal polyester uses an aromatic compound as a raw material monomer.

Typical examples of the liquid crystal polyester include the following (I), (II), (III), and (IV): (I) an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and an aromatic a liquid crystal polyester obtained by polymerizing (polycondensing) at least one compound selected from the group consisting of a diol, an aromatic hydroxylamine, and an aromatic diamine; (II) polymerizing a plurality of aromatic hydroxycarboxylic acids Liquid crystal polyester; (III) a liquid crystal polyester obtained by polymerizing an aromatic dicarboxylic acid and at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxylamine, and an aromatic diamine; And (IV) a liquid crystal polyester obtained by polymerizing a polyester of polyethylene terephthalate with an aromatic hydroxycarboxylic acid.

Some or all of the above-mentioned aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxylamine, and aromatic diamine may be independently polymerizable derivatives thereof.

Such as aromatic hydroxycarboxylic acid and aromatic dicarboxylic acid having a carboxyl group The polymerizable derivative of the polymer is exemplified by an ester obtained by converting a carboxyl group into an alkoxycarbonyl group or an aryloxycarbonyl group, an oxyhalide obtained by converting a carboxyl group into a halomethyl group, and converting a carboxyl group into a fluorenylcarbonyl group. An anhydride.

A polymerizable derivative of a compound having a hydroxyl group of an aromatic hydroxycarboxylic acid, an aromatic diol, and an aromatic hydroxyamine is exemplified by a hydrazine which is converted into an oxiranyl group by deuteration of a hydroxy group.

The polymerizable derivative of the amine group-containing compound of the aromatic hydroxylamine and the aromatic diamine is a telluride which is obtained by deuteration of an amine group and conversion into a mercapto group.

The liquid crystal polyester is preferably a repeating unit having the following formula (1) (hereinafter sometimes referred to as "repeating unit (1)"), and more preferably having a repeating unit (1) and the following formula (2) The repeating unit (hereinafter referred to as "repetitive unit (2)") and the repeating unit shown in the following formula (3) (hereinafter, sometimes referred to as "repetitive unit (3) ").

(1)-O-Ar ¹ -CO-

(2)-CO-Ar ² -CO-

(3)-X-Ar ³ -Y-

(4)-Ar ⁴ -Z-Ar ⁵ - wherein Ar ¹ represents a phenylene group, an extended naphthyl group or a stretched biphenyl group; and the Ar ² and Ar ³ groups independently represent a phenylene group, an anthranyl group or A biphenyl group or a group represented by the above formula (4), wherein X and Y each independently represent an oxygen atom or an imido group (-NH-), and one or more of Ar ¹ , Ar ² or Ar ³ The atomic system may be independently substituted with a halogen atom, an alkyl group or an aryl group; the Ar ⁴ and Ar ⁵ systems each independently represent a phenyl or anthracene group; and the Z system represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group or Alkylene.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The alkyl group may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-hexyl, 2-ethylhexyl or n-octyl And the base. Its carbon number should be 1~10. The aryl group may, for example, be a phenyl group, an o-xylylene group, a m-xylylene group, a p-xylylene group, a 1-naphthyl group or a 2-naphthyl group, and the carbon number thereof is preferably from 6 to 20. When one or more hydrogen atoms of Ar ¹ , Ar ² and Ar ³ are substituted by such a group, the number of substitutions constitutes each of Ar ¹ , Ar ² or Ar ³ , and each of them is preferably 2 or 1 independently. One, more preferably one.

The alkylene group may, for example, be a methylene group, an ethylene group, an isopropylidene group, a n-butylene group or a 2-ethylhexylene group, and the carbon number thereof is preferably from 1 to 10.

The repeating unit (1) is a repeating unit derived from a compound of an aromatic hydroxycarboxylic acid. As the repeating unit (1), Ar ^{1 which} is derived from p-hydroxybenzoic acid is preferably a repeating unit derived from p-phenylene; or Ar ¹ derived from 6-hydroxy-2-naphthoic acid is 2,6-anthranyl Repeat unit.

The repeating unit (2) is a repeating unit derived from a compound of an aromatic dicarboxylic acid. The repeating unit (2) is derived from a repeating unit in which Ar ² is a para-phenylene group; the Ar ² derived from isophthalic acid is a repeating unit in which an exo-phenyl group is derived; and 2,6- Ar ² of naphthalene dicarboxylic acid is a repeating unit of 2,6-anthranyl; or Ar ² derived from diphenyl ether-4,4'-dicarboxylic acid is diphenyl ether-4,4'- A double-based repeating unit.

The repeating unit (3) is a repeating unit derived from a compound of an aromatic diol, an aromatic hydroxylamine or an aromatic diamine. The repeating unit (3) is preferably a repeating unit derived from hydroquinone, p-aminophenol or p-phenylenediamine, Ar ³ is a p-phenylene group; and is derived from 4,4'-dihydroxybiphenyl, 4 - amino-4'-hydroxy-biphenyl-4,4'-biphenyl group of ³ or Ar is 4,4'-biphenyl extending the repeating units.

The content of the repeating unit (1) is a total amount of the total repeating units (the mass of each of the overlapping units is divided by the amount of each of the overlapping units to determine the mass of each of the overlapping units) The equivalent amount (mole), the total value thereof is 100% by mole, generally preferably 30% by mole or more, more preferably 30 to 80% by mole, most preferably 40 to 70% by mole, particularly preferably 45~65% by mole. The content of the repetitive unit (2) is 100 mol% as the total unit of the full resurfacing unit, and is generally preferably 35 mol% or less, more preferably 10 to 35 mol%, and most preferably 15 to 30 m. %, especially 17.5~27.5 mol%. The content of the repetitive unit (3) is 100 mol% as the total amount of the full resurfacing unit, and is generally preferably 35 mol% or less, preferably 10 to 35 mol%, more preferably 15 to 30 mol%. It is especially suitable for 17.5~27.5 mol%. When the content of the repeating unit (1) is 30 mol% or more, the liquid crystal polyester tends to have high melt fluidity, heat resistance, strength, and rigidity. However, when it exceeds 80 mol%, the melting temperature or the melt viscosity of the liquid crystal polyester tends to be high, and as a result, the temperature necessary for molding tends to become high.

The ratio of the content of the repeating unit (2) to the content of the repeating unit (3) is generally 0.9/1 to 1/0.9, preferably 0.95/1 to 1/0.95, and most preferably 0.98/1 to 1/0.98.

The repetitive units (1) to (3) in the liquid crystal polyester may be independently a combination of one type of repetitive unit or two or more types of repetitive units. Liquid crystal The ester system may have a repeating unit other than the repeating units (1) to (3). The content of the other repeating unit is such that the total amount of all the repeating units in the liquid crystal polyester is 100 mol%, and is generally 10 mol% or less, preferably 5 mol% or less.

A part of the resurfacing unit (3) contained in the liquid crystal polyester is a repetitive unit in which both X and Y are oxygen atoms from the viewpoint of lowering the melt viscosity of the liquid crystal polyester (that is, a repeating from an aromatic diol) Unit), more preferably all of the repeating unit (3) is a repeating unit derived from an aromatic diol.

A preferred method for producing a liquid crystal polyester is to produce a polymer by melt-polymerizing the above-mentioned raw material monomers from the viewpoint of operability in producing a high-molecular-weight liquid crystal polyester having high heat resistance or strength/rigidity (hereinafter referred to as a "prepolymer" step; a manufacturing method comprising the step of solid phase polymerization of the prepolymer. The melt polymerization can be carried out in the presence of a catalyst. The catalyst may be exemplified by a metal compound such as magnesium acetate, first tin acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide; and, for example, 4-(dimethylamino)pyridine and A nitrogen-containing heterocyclic compound of 1-methylimidazole. Among them, a nitrogen-containing heterocyclic compound is preferred.

The flow starting temperature of the liquid crystal polyester is generally 270 ° C or higher, preferably 270 to 400 ° C, more preferably 280 to 380 ° C. When the flow start temperature is 270 ° C or more, the heat resistance, strength, and rigidity of the liquid crystal polyester are easily improved. When the flow initiation temperature exceeds 400 ° C, the melting temperature or melt viscosity of the liquid crystal polyester becomes high, and as a result, the molding temperature of the liquid crystal polyester tends to become high.

The flow initiation temperature is also referred to as the Flow temperature or the flow temperature, and is a standard temperature of the molecular weight of the liquid crystal polyester. The flow start temperature was obtained by using a capillary rheometer to raise the temperature of the liquid crystal polyester at a rate of 9.8 MPa (100 kg/cm ² ) at a rate of 4 ° C /min while melting, and ejecting from a nozzle having an inner diameter of 1 mm and a length of 10 mm. The temperature at which the viscosity of 4800 Pa ‧ (48000 poise) is displayed (refer to the book, "Liquid Crystal Polymer - Synthesis, Forming, Application -", company CMC, June 5, 1987, p. 95). The flow initiation temperature of the liquid crystal polymer other than the liquid crystal polyester or the composition containing the liquid crystal polymer can also be measured in the same manner as described above.

As the titanium oxide of the present invention, titanium oxide which is commercially available as a resin filler can be used as it is. If necessary, it can also be used after removing the impurities contained in it. The titanium oxide can also be used after surface treatment as described later.

The crystal form of titanium oxide is not particularly limited. The crystal form is a rutile type, an anatase type, or a combination of both. Among them, from the viewpoint of reducing the color change due to the difference in the thickness of the molded body of the present invention, it is preferable to use a titanium oxide having a rutile crystal shape, and more preferably a titanium oxide having a rutile crystal shape.

The average particle diameter of the titanium oxide is not particularly limited, and the average particle diameter is preferably 0.10 to 0.50 μm, more preferably 0.15 to 0.40 μm, and most preferably 0.18 to 0.30 μm from the viewpoint of allowing the titanium oxide to be well dispersed in the molded body. .

The average particle diameter is obtained by a method consisting of (1) measuring the appearance of titanium oxide by a scanning electron microscope (SEM), and (2) using, for example, a SEM photograph obtained by a company, Nireco Co., Ltd. The image analysis device "Luzex III U" calculates the distribution curve by plotting the amount of particles (%) in each particle size section of the primary particles; (3) the volume obtained from the distribution curve by the cumulativeity of 50%. The average particle size As the average particle diameter.

The titanium oxide is also subjected to surface treatment for improving the properties such as dispersibility. The method of the surface treatment is not particularly limited, and from the viewpoint of improving the dispersibility and weather resistance of the titanium oxide, it is preferred to treat the surface of the inorganic metal oxide. The inorganic metal oxide is preferably alumina. When the titanium oxide is not aggregated and it is easy to handle, it is preferable that the titanium oxide is not subjected to surface treatment from the viewpoint of heat resistance and strength of the composition of the liquid crystal polyester.

The method for producing titanium oxide is preferably a sulfuric acid method or a chlorine method, and particularly preferably a chlorine method. The sulfuric acid method is a production method consisting of the following steps.

(1) a step of reacting an ore as a titanium source (for example, ilmenite or titanium slag obtained by treating ilmenite) with sulfuric acid; (2) a step of extracting a reactant by water to obtain an aqueous solution of a sulfate; 3) a step of cooling the aqueous solution; (4) a step of removing the iron component in the aqueous solution and then hydrolyzing to obtain titanium oxide. The chlorine method is a manufacturing method consisting of the following steps.

(1) a step of reacting a source of titanium source (for example, synthetic rutile obtained from rutile or ilmenite) with chlorine at 1000 ° C to form crude titanium tetrachloride; (2) refining crude four by distillation a step of forming titanium chloride; (3) a step of oxidizing the purified titanium tetrachloride with oxygen to obtain titanium oxide.

The titanium oxide obtained by the chlorine method is excellent in whiteness because of the high purity in the step (2), and is preferably a rutile type in the present invention. The whiteness of the titanium oxide can be improved by optimizing the oxidation conditions of the step (3). The formation of coarse particles can be suppressed, and titanium oxide having an appropriate average particle diameter can be easily obtained.

For the commercially available product of the titanium oxide which can be used, TIPAQUE CR-58 and TIPAQUE CR-60 of the Ishihara Industry Co., Ltd. manufactured by the chlorine method, and SR-based by the sulfuric acid method can be exemplified. 1.

The total content of the titanium oxide in the composite metal oxide and the content of the metal element compound is 100% by mass, the content of the titanium oxide is preferably 50 to 95% by mass, and the content of the metal element compound is preferably 5 to 50% by mass. The combination of the metal elements is not particularly limited, and examples of the combination include a combination of a bismuth-nickel system, a combination of a bismuth-chromium system, and a combination of an iron-zinc system. The titanium oxide in the composite metal oxide is preferably the aforementioned titanium oxide. Examples of the compound of ruthenium, nickel, chromium, iron, zinc, molybdenum and tungsten in the composite metal oxide include oxides, hydroxides, chlorides, sulfates and metal salts. Chlorides, sulfates and metal salts are compounds which form oxides or hydroxides by neutralization or hydrolysis.

The composite metal oxide containing nickel is exemplified by a TiO ₂ -BaO-NiO-based compound and a TiO ₂ -Sb ₂ O ₃ -NiO-based compound.

The composite metal oxide containing chromium is exemplified by a TiO ₂ -Sb ₂ O ₃ -Cr ₂ O ₃ -based compound.

A preferred method for producing the composite metal oxide is a production method comprising a step of thermally diffusing nickel and ruthenium atoms in a crystal lattice of rutile-type titanium oxide (TiO ₂ ).

A commercially available composite metal oxide system which can be used is exemplified by TIPAQUE YELLOW TY-50, TIPAQUE YELLOW of Ishihara Industry Co., Ltd. TY-70, and TIPAQUE YELLOW TY-100.

The content of the titanium oxide and/or the composite metal oxide 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, based on 100 parts by mass of the liquid crystal polyester. It is 0.5 to 3 parts by mass. When the content is less than 0.01 parts by mass, the color of the obtained molded article is insufficient, and if it exceeds 5 parts by mass, the molded article is likely to be foamed, and the properties of the liquid crystal polyester and the heat resistance are not sufficiently maintained.

The ultramarine blue used in the present invention is a synthetic blue inorganic pigment containing, as a main component, cerium oxide, aluminum oxide, sodium oxide and sulfur as a main component, and containing a compound of sodium sulfate, second iron oxide and free sulfur as impurities. The molecular structure of ultramarine can be exemplified by Na ₈ (Al ₆ Si ₆ O ₂₄ )S (2~4).

The method for producing ultramarine blue can be exemplified by a step of pulverizing and mixing kaolin, soda lime glass, sulfur and a reducing agent (for example, charcoal, charcoal, and rosin), and a step of firing the mixture at 750 to 850 ° C for 40 to 50 hours. A known manufacturing method.

The average particle size of ultramarine blue is preferably 0.1 to 50 μm, particularly preferably 0.2 to 10 μm. When the average particle diameter is less than 0.1 μm, the color of the blue color may be insufficient. When the average particle diameter exceeds 50 μm, the color may be dark due to scattering, and as a result, the original color of the ultramarine may be damaged.

The content of ultramarine in the liquid crystal polyester composition of the present invention is preferably 0.01 to 3 parts by mass, more preferably 0.01 to 0.28 parts by mass, most preferably 0.01 to 0.15 parts by mass, per 100 parts by mass of the liquid crystal polyester.

As a commercially available ultramarine, the general-purpose ultramarine particles (for example, No. 300, No. 1500, and No.) manufactured by Dai-ichi Kogyo Co., Ltd. can be exemplified. 2000) or ceria-coated green particles (for example, AP 31, AP 201, AP 205, and AP 151), and ultramarine made by Nubiola Co., Ltd. or Holiday Pigment Co., Ltd.

The coloring material used in the present invention is exemplified by carbon black, iron oxide (red iron oxide), cobalt green, and phthalocyanine blue. Among them, carbon black, cobalt green or a combination of the two is excellent from the viewpoint of color or weather resistance.

The cobalt green can be exemplified by a compound of CoO-Al ₂ O ₃ or CoO-Al ₂ O ₃ -Cr ₂ O ₃ . The iron oxide system can be exemplified by FeOOH or Fe ₂ O ₃ . A hydroxide of iron as indicated by H ₂ O.

The content of the coloring material in the liquid crystal polyester composition of the present invention is preferably 0.01 to 3 parts by mass, more preferably 0.01 to 0.2 parts by mass, most preferably 0.01 to 0.1 parts by mass, per 100 parts by mass of the liquid crystal polyester.

The bulk density of the coloring material is preferably 0.4 to 1.0 g/cm ³ , more preferably 0.5 to 0.8 g/cm ³ . When the bulk density is less than 0.4 g/cm ³ , the dispersion in the molded body of the coloring material is a cause, and the molded body is easily broken. When it exceeds 1.0 g/cm ³ , the heat of the coloring material is agglomerated, and the molded body is formed. Foreign matter has become more and more, so it is not good.

When the coloring material is heated to have a large amount of moisture or decomposition products, the foaming resistance or mechanical strength of the liquid crystal polyester composition is lowered.

The water content of the coloring material is preferably 1000 ppm. When it exceeds 1000 ppm, the granulation workability of the liquid crystal polyester composition may deteriorate, or the molded body tends to be foamed.

In the thermogravimetric analysis (TGA) method, the heating loss at the temperature increase rate of 10 ° C /min from the normal temperature to 400 ° C is preferably 0.05 parts by mass. under.

The color material used in the present invention is not a color material of a surface or a color material which is surface-treated with an inorganic substance or a hydroxide thereof. The surface of the surface-treated coloring material is preferably previously coated with an inorganic material of alumina, cerium oxide, calcium oxide, and zirconia or water and water from the viewpoint of improving the light stability or dispersibility of titanium oxide.

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 may be a fibrous filler, a plate filler, a spherical filler, or a particulate filler. The fibrous filler is preferably a fibrous filler having a number average fiber diameter of 5 to 20 μm and a number average fiber length of 500 μm or less. When the average fiber length exceeds 500 μm, the fluidity of the liquid crystal polyester composition may be deteriorated even if the blending amount of the fibrous filler is reduced. When the average fiber diameter exceeds 20 μm, the moldability of the liquid crystal polyester composition is deteriorated, and if it is less than 5 μm, the molded body is easily broken when the liquid crystal polyester composition is formed, or the mechanical strength of the molded body is poorly improved. .

The number average fiber diameter and the number average fiber length can be measured by the following method.

(1) 2 g of the liquid crystal polyester composition was heated in an electric furnace at 600 ° C for 3 hours to be ashed;

(2) The ash is sufficiently dispersed in the polyethylene glycol.

(3) moving the dispersion to the watch glass with a pipette;

(4) Digital Microscope VHX- made by Keyence 1000 observations;

(5) arbitrarily selecting 100 fibers from the observed fibers;

(6) measuring the fiber length and the fiber diameter for each of the 100 fibers;

(7) The average measured fiber diameter and the number average fiber length were determined by the average measured value.

Further, the filler is an inorganic filler or an organic filler. The fibrous inorganic filler may be exemplified by glass fibers; carbon fibers of PAN-based carbon fibers and Pitch-based carbon fibers; ceramic fibers of cerium oxide fibers, alumina fibers, and yttria-alumina fibers; metal fibers of stainless steel fibers; and potassium titanate Whiskers, barium titanate whiskers, ettringite whiskers, aluminum borate whiskers, tantalum nitride whiskers and whiskers of tantalum carbide whiskers. The fibrous organic filler may be exemplified by polyester fibers and linaloamide fibers. The plate-like inorganic filler may be exemplified by talc, mica (for example, muscovite, phlogopite, fluorophlogopite, and sphagnum), graphite, ettringite, glass flakes, barium sulfate, and calcium carbonate. Examples of the particulate inorganic fillers include cerium oxide, aluminum oxide, glass beads, hollow glass beads, boron nitride, cerium carbide, and calcium carbonate. The content of the filler in the liquid crystal polyester composition is usually 5 to 100 parts by mass, preferably 5 to 80 parts by mass, particularly preferably 50 to 70 parts by mass, per 100 parts by mass of the liquid crystal polyester.

The above additives are exemplified by an antioxidant, a thermal stabilizer, an ultraviolet absorber, an antistatic agent, a surfactant, and a flame retardant. The content of the additive in the liquid crystal polyester composition is usually from 0 to 5 parts by mass based on 100 parts by mass of the liquid crystal polyester.

The resin other than the above liquid crystal polyester may, for example, be a polyester other than polypropylene, polyamine or liquid crystal polyester, polyfluorene, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene ether and polyether quinone. Thermoplastic resin; and, such as phenolic A thermosetting resin of a grease, an epoxy resin, a polyimide resin, and a cyanate resin. The content of the resin in the liquid crystal polyester composition is usually from 0 to 20 parts by mass based on 100 parts by mass of the liquid crystal polyester.

A preferred method for producing a liquid crystal polyester composition is a method comprising the steps of a step of laminating a liquid crystal polyester, a titanium oxide, and/or a composite metal oxide, ultramarine, and an optional component in an extruder by melt-kneading into a pellet. The extruder is preferably an extruder having a cylinder, one or more screws disposed in the cylinder, and a supply port provided at one or more cylinders, and more preferably having one or more exhausts provided in the cylinder Department of the extruder.

The liquid crystal polyester composition of the present invention may also be produced by the following steps.

(1) a step of producing a color masterbatch containing a liquid crystal polyester, a titanium oxide and/or a composite metal oxide and a cyanine; and (2) using the masterbatch and the plastic particles of the liquid crystal polyester to produce the liquid crystal polymerization of the present invention The step of the ester composition.

The "masterbatch" of the step (1) means that the content (concentration) of the titanium oxide and/or the composite metal oxide and the ultramarine in the plastic particles is larger than that of the liquid crystal polyester composition of the present invention and/or composite. A composition of a metal oxide and a content (concentration) of ultramarine blue.

The step (2) is a step of diluting the content (concentration) of the component in the masterbatch with the plastic particles of the liquid crystal polyester.

A preferred method of forming the liquid crystal polyester composition is a melt forming method. The melt molding method can be exemplified by an injection molding method, a T-die method, a blow molding method, a compression molding method, a blow molding method, a vacuum molding method, and a press forming method. law. Among them, injection molding is preferred.

In the molding system of the present invention, the ratio of the thickness of the minimum meat thickness (D2) to the thickness of the maximum meat thickness portion (D1) is preferably 3 or more in the plate-shaped test piece having a poor adhesion as shown in Fig. 1.

The products and parts of the molded body can be exemplified as the frame of the optical pickup frame and the transformer frame; the relay case, the relay base, the relay bobbin and the relay pivot type relay parts; RIMM; DDR; CPU socket; S/O; DIMM; Connector to board connector, FPC connector and card connector; reflector for lamp reflector and LED reflector; support for lamp support and heater support; vibration plate for horn vibration plate; photocopying machine Separating claws for separation claws for separation claws and printers; camera module parts; switch parts; motor parts; sensor parts; hard disk drive parts; oven foods; vehicle parts; aircraft parts; A sealing member for the sealing member and the sealing member for a coil.

Among the above-mentioned products and parts, the molding system of the present invention is particularly useful as a connector.

Example

The invention will be more specifically described below by way of examples, but the invention is not limited to the examples.

Manufacturing example 1

In a reactor equipped with a stirring device, a torque meter, a nitrogen gas introduction tube, a thermometer and a reflux cooler, a p-hydroxybenzoic acid 994.5 g (7.2 mol) was placed. Ear), 299.1g (1.8 moles) of citric acid, 99.7g (0.6 moles) of isophthalic acid, 446.9g (2.4 moles) of 4,4'-dihydroxybiphenyl, 1347.6g of acetic anhydride (13.2 moles) The ear and 0.2 g of 1-methylimidazole were heated at room temperature to 150 ° C for 30 minutes while stirring under a nitrogen gas stream, and refluxed at 150 ° C for 1 hour. Then, 0.9 g of 1-methylimidazole was added, and while acetic acid and unreacted acetic anhydride were distilled off, the temperature was raised from 150 ° C to 320 ° C for 2 hours and 50 minutes, and the temperature was maintained at 320 ° C. The reaction mixture was taken out from the reactor and cooled to room temperature. The obtained solid matter was pulverized by a pulverizer to obtain a powdery prepolymer. The prepolymer was heated in a nitrogen atmosphere for 1 hour from room temperature to 250 ° C, heated from 250 ° C to 285 ° C for 5 hours, and maintained at 285 ° C for 3 hours to solid phase polymerization, followed by cooling to obtain a powdery form. Liquid crystal polyester (described as "LCP1" in the table to be described later). The liquid crystal polyester had a flow initiation temperature of 327 °C.

The above-mentioned flow initiation temperature was carried out using a flow tester CFT-500 manufactured by Shimadzu Corporation, and about 2 g of liquid crystal polyester was filled in a cylinder in which a die having a nozzle having an inner diameter of 1 mm and a length of 10 mm was mounted, 9.8 MPa (100 kg/ Under the load of cm ² ), the temperature was raised at a rate of 4 ° C /min, and the liquid crystal polyester was melted and extruded from the nozzle, and the temperature at which the viscosity of 4800 Pa ‧ (48,000 poise) was measured was measured. This temperature is taken as the flow start temperature.

Examples 1 to 8 and Comparative Examples 1 to 8

The liquid crystal polyester obtained in Production Example 1 was blended with the fillers and coloring materials shown below at the ratios shown in Tables 1 and 2, and used by Ikei Iron Works Co., Ltd. A two-axis extruder PCM 30 type was produced and granulated at a cylinder temperature of 340 ° C to obtain a liquid crystal polyester composition. The obtained composition was molded at 350 ° C using an injection molding machine Model PS40E5ASE manufactured by Nissei Resin Co., Ltd. to obtain a size of 40 mm (short side) × 60 mm (long and short sides) × thickness (maximum meat thickness portion D1 = 3 mm). The minimum thickness portion D2 = 1 mm) is a molded body of a plate-shaped test piece having a poor section as shown in Fig. 1 . The color tone was measured for the minimum thickness portion D2 (thickness: 1 mm) and the maximum thickness portion D1 (thickness: 3 mm) of the molded body, and the results are shown in Tables 1 and 2.

Glass fiber: Nitto's fiber (PF) PF 70E-001 with an average fiber diameter of 10 μm and a number average fiber length of 70 μm

Talc: Talc X-50 of Talc (Japan)

Titanium oxide: Titanium oxide of TIPAQUE CR-60 of Ishihara Industry Co., Ltd.

Titanium yellow: Titanium yellow of TIPAQUE TY-70 of Ishihara Industry Co., Ltd.

Ultramarine: The first Huacheng Industry (shares) of the ultramarine No 2000

Carbon Black: Mitsubishi Chemical Corporation's Mitsubishi Carbon Black #960

Cobalt Green: Coa Green Green 2040 from Asahi Chemical Industry Co., Ltd.

The tensile strength of Tables 1 and 2 was such that the liquid crystalline polyester composition was injected under the conditions of a cylinder temperature of 350 ° C, a mold temperature of 130 ° C, and an injection speed of 60% using an injection molding machine PS 40 E1ASE of Nissei Resin Industrial Co., Ltd. It was molded into an ASTM No. 4 dumbbell test piece (thickness: 3.2 mm), and the test piece was measured in accordance with ASTM D638.

The foaming properties of Tables 1 and 2 were determined by the following methods.

(1) The liquid crystalline polyester composition was injection-molded under the same conditions as above to prepare 10 pieces of a JIS K 7113 (1/2) dumbbell test piece (thickness: 1.2 mm);

(2) Ten test pieces were immersed in a solder bath heated to 280 ° C for 60 seconds.

(3) taking out the test pieces from the solder bath and observing the presence or absence of blistering (expansion) on the surface of the test piece;

(4) When the foaming was not observed in all of the test pieces, it was good (the symbol ○ in the table), and even if one of the ten test pieces was observed to have foaming, it was defective (the X symbol in the table).

The color difference between Table 1 and Table 2 was determined by using a color difference meter cd-3600 manufactured by Konical Minolta Co., Ltd., by measuring the brightness index L of a 10 degree field isochromatic function of the CIE 1976 (L*a*b*) color system. * and find it. In order to quantify the color change of the molded body due to the difference in the thickness of the portion, the measurement condition was such that the light source was D65, the measurement diameter was 4 mm, and the measurement mode was SCI. When the value (ΔL*) of the L* value of the maximum thickness (3 mm) of the maximum thickness (3 mm) of the plate-shaped test piece was 2 or less, it was judged to be good (symbol of ○ in the table), and more than 2 The time is judged to be bad (the X symbol in the table).

Claims (8)

A liquid crystal polyester composition comprising the following components (1): 100 parts by mass, component (2), component (3) or both: 0.01 to 5 parts by mass and component (4): 0.01 to 0.28 parts by mass (1) liquid crystal polyester; (2) titanium oxide; (3) containing titanium oxide as a main component, and containing one selected from the group consisting of ruthenium, nickel, chromium, iron, zinc, molybdenum, and tungsten or A compound metal oxide having a compound of two or more kinds of metal elements as a subcomponent; and (4) ultramarine blue. The liquid crystal polyester composition of claim 1, wherein the metal element is nickel or chromium. The liquid crystal polyester composition of claim 1, which further contains 0.01 to 3 parts by mass of the coloring material, and the coloring material is carbon black, cobalt green, iron oxide or phthalocyanine blue. The liquid crystal polyester composition of claim 1, which further comprises 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 crystal polyester composition of claim 4, wherein the fibrous filler is glass fiber. The liquid crystal polyester composition of claim 1, wherein the total content of the titanium oxide in the composite metal oxide and the content of the compound of the metal element is 100% by mass, and the content of the titanium oxide is 50 to 95% by mass, the metal The content of the elemental compound is 5 to 50% by mass. A molded body obtained from the liquid crystal polyester composition of claim 1, wherein the ratio of the thickness of the largest thickness portion of the molded body to the thickness of the minimum thickness portion is 3 or more. The shaped body of claim 7, wherein the shaped body is a connector.