TW201817788A - Liquid crystal polyester resin composition, molded article, and method for producing molded article - Google Patents

Abstract

Provided is a liquid crystal polyester resin composition that contains 3-25 parts by weight of (B) a metal-based additive relative to 100 parts by weight of (A) a fully aromatic liquid crystal polyester. The fully aromatic liquid crystal polyester (A) contains a total of 60-77 mol.% of structural units derived from hydroxybenzoic acid and structural units derived from terephthalic acid relative to 100 mol.% of all the structural units in the fully aromatic liquid crystal polyester. The metal-based additive (B) comprises a metal selected from among copper, tin, cobalt, nickel and silver, or a compound containing such a metal. Provided is the liquid crystal polyester resin composition which exhibits excellent moldability of a molded article surface to a metal part, excellent adhesion between a molded article and a metal part when the temperature changes, and excellent molded article surface hardness. Also provided is a molded article comprising same.

Description

   Liquid crystalline polyester resin composition, molded article, and method for manufacturing molded article   

The present invention relates to a liquid crystalline polyester resin composition and a molded article using the same.

The liquid crystalline polyester is excellent in heat resistance, fluidity, and dimensional stability. Therefore, demand for electrical / electronic parts that require these characteristics is expanding. However, with regard to the use of electrical / electronic parts, as the products become thinner and lighter, they are becoming smaller and thinner. In order to achieve further space saving and weight reduction, resin parts are expected. Development of three-dimensional circuit substrate forming technology for assembling electronic circuit substrates. By forming the electronic circuit pattern three-dimensionally on the surface of the resin molded product, it is possible to achieve circuit board design freedom, module miniaturization, reduction in the number of parts, and reduction in the number of assembly steps. Methods for forming a circuit in a resin molded product include, for example, a method of forming a mask by using secondary molding to shield the rest of the place other than where the circuit is formed, a method of drawing a circuit pattern by laser irradiation, and plating. The combination of metallization technologies is continuously expanding.

Among them, the circuit pattern drawing method performed by laser irradiation is continuously expanding because it can easily cope with the narrowing of the circuit. Therefore, the resin composition in which various additives are blended in order to provide the formation property of plating by laser irradiation is reviewed.

    [Prior technical literature]         [Patent Literature]    

For example, a polyamine resin composition (e.g., Patent Documents 1 and 2) having excellent solder heat resistance and a copper chromium oxide or antimony-doped tin oxide are proposed; and a polycarbonate resin composition (e.g., excellent impact strength) Patent Document 3); a liquid crystal polymer that is blended with copper-chromium oxide and has excellent mechanical strength such as elongation strength and flexural strength, as well as dielectric properties (for example, Patent Documents 4 and 5); blended with aluminum-doped zinc oxide, and Polycarbonate, polyamide, and polyester resin compositions that increase whiteness (for example, Patent Document 6); blending additives such as resins and core-shell structures covered with metal oxides, and suppressing defects in resins containing additives Affected substrate material (for example, Patent Document 7).

Patent Document 1: Japanese Patent Laid-Open No. 2014-240452

Patent Document 2: International Publication No. 2013/141157

Patent Document 3: Japanese Patent Laid-Open No. 2015-108124

Patent Document 4: Japanese Patent Publication No. 2015-502418

Patent Document 5: International Publication No. 2016/003588

Patent Document 6: Japanese Patent Laid-Open No. 2015-71739

Patent Document 7: Japanese Patent Publication No. 2016-507650

However, this conventional technique includes a molded article obtained from a liquid crystalline polyester resin composition, which has low adhesion between a metal and a molded article obtained from a resin composition containing a polyamide resin or the like as a main component. On the surface, the linear expansion ratio of the resin composition is larger than the linear expansion ratio of the metal on the surface of the molded product. Therefore, when the temperature around the product changes, the adhesion strength of the metal part on the surface of the molded product decreases, or the metal part comes off or peels off. In addition, when various additives are added to improve the formation of the metal part, the surface hardness of the molded product may be lowered because it affects the crystallinity and molecular chain alignment of the resin composition. Therefore, the surface of the molded product is deformed or damaged during product assembly. Therefore, the conventional resin composition that responds to the formation technology of the three-dimensional circuit board cannot meet the above problems, and further improvement is expected.

The object of the present invention is to provide a liquid crystalline polyester having excellent surface hardness of the formed part of the metal part, adhesion of the metal part when the temperature around the product changes, and the hardness of the surface of the formed product for ensuring reliability of the metal part during product assembly. A resin composition and a molded article using the same.

The liquid crystalline polyester resin composition of the present invention has the following structure in order to solve the above problems. That is, a liquid crystalline polyester resin composition is one in which 3 to 25 parts by weight of the metal-based additive (B) is contained with respect to 100 parts by weight of the wholly aromatic liquid crystalline polyester (A). (A) Based on 100 mol% of the total structural unit of the wholly aromatic liquid crystalline polyester described above, the total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid is 60 to 77 mol%; the above The metal-based additive (B) is composed of any one metal selected from copper, tin, cobalt, nickel, or silver, or a compound containing the metal.

The molded product of the present invention has the following configuration. That is, a molded article is composed of the liquid crystalline polyester resin composition.

The manufacturing method of the molded article of this invention has the following structures. That is, a method for manufacturing a molded article is a method for manufacturing a molded article having a metal portion on a surface, and includes a pattern drawing step of performing laser irradiation on the molded article, and a metallizing step performed by a plating process.

The liquid crystalline polyester resin composition of the present invention preferably has an average particle diameter of the metal-based additive (B) of more than 1 m.

The liquid crystalline polyester resin composition of the present invention is preferably such that the wholly aromatic liquid crystalline polyester (A) contains a structural unit derived from hydroquinone.

The liquid crystalline polyester resin composition of the present invention preferably contains 10 to 200 parts by weight of the filler (C) based on 100 parts by weight of the wholly aromatic liquid crystalline polyester (A).

The liquid crystalline polyester resin composition of the present invention is preferably such that the filler (C) is a plate-shaped filler having a Mohs hardness of 2.0 to 7.0.

The liquid crystal polyester resin composition of the present invention is preferably such that the average particle diameter of the filler (C) is 0.1 to 20 times the average particle diameter of the metal-based additive (B).

The liquid-crystalline polyester resin composition of the present invention is preferably a long-chain fatty acid containing a metal salt and / or an ester of a long-chain fatty acid with respect to 100 parts by weight of the wholly aromatic liquid-crystalline polyester (A). Compound (D) is 0.01 to 1 part by weight.

With the liquid crystalline polyester resin composition of the present invention, it is possible to obtain a molded product having excellent metal part formability of a molded product and excellent metal part adhesion and surface hardness during temperature changes. These molded articles are particularly suitable for use in electrical / electronic parts having metal parts on the surface.

The present invention is explained in detail below.

    [Fully aromatic liquid crystalline polyester]    

The wholly aromatic liquid crystalline polyester (A) used in the present invention is a polyester that exhibits optical anisotropy when it is melted and is called a "thermotropic liquid crystal polymer". For example, a liquid crystalline polyester composed of a structural unit selected from an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic dicarbonyl unit, and the like, and forming an anisotropic molten phase. The structural unit does not contain a structural unit produced from an aliphatic compound such as ethylene glycol.

The wholly aromatic liquid crystalline polyester (A) used in the present invention is 100 mol% of the total structural units of the wholly aromatic liquid crystalline polyester described above, and is a structural unit derived from hydroxybenzoic acid, which is an aromatic oxycarbonyl unit. A total of 60 to 77 mol% with the structural unit derived from terephthalic acid, which is an aromatic dicarbonyl unit. With respect to 100 mol% of the total structural unit of wholly aromatic liquid crystalline polyester, if the total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid is less than 60 mol%, it is fully aromatic The heat resistance of the liquid crystalline polyester decreases. Therefore, when the temperature of the molded product changes, the deformation of the molded product increases, and the adhesiveness of the metal portion decreases. Moreover, when it exceeds 77 mol%, since the crystallinity of a wholly aromatic liquid crystalline polyester is excessively increased, the metal part adhesiveness will fall when a molded product changes in temperature, or the surface hardness of a molded product will fall.

The total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid is preferably 65 mol% or more relative to 100 mol% of the total aromatic liquid crystalline polyester structural unit. More than 69 mol%. On the other hand, it is preferably 76 mol% or less. In addition, the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid may have only any one of the structural units, and the other structural unit is 0 mole%. The structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid are each preferably more than 0 mole%.

The wholly aromatic liquid crystalline polyester (A) used in the present invention preferably contains a structural unit derived from hydroquinone. By containing a structural unit derived from hydroquinone, the crystallinity of the wholly aromatic liquid crystalline polyester can be controlled, so that the toughness and rigidity of the molded product are excellent, and the surface hardness of the molded product is excellent. With respect to 100 mol% of the total aromatic liquid crystal polyester total structural unit, if the content of the structural unit derived from hydroquinone is more than 2.5 mol%, the crystallinity of the wholly aromatic liquid crystalline polyester will not be too high. It is preferable because it can improve the flexibility of the molded product and suppress the decrease in surface hardness. On the other hand, if it is 12 mol% or less, the crystallinity of the wholly aromatic liquid crystalline polyester is not too low, the rigidity of the molded article can be improved, and the reduction in surface hardness can be suppressed, which is preferable.

Each structural unit constituting the wholly aromatic liquid crystalline polyester (A) used in the present invention contains a structural unit derived from hydroxybenzoic acid as an aromatic oxycarbonyl unit, and may further contain, for example, 6-hydroxy-2 -A structural unit derived from naphthoic acid and the like. The hydroxybenzoic acid is preferably p-hydroxybenzoic acid. Examples of the aromatic dioxy unit system include 4,4'-dihydroxybiphenyl, hydroquinone, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, and The structural units derived from tributylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and the like are preferably 4,4'-dihydroxybiphenyl and hydroquinone. The aromatic dicarbonyl unit contains a structural unit derived from terephthalic acid, and may be used in combination with isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, and the like. The derived structural unit is preferably isophthalic acid.

Specific examples of the wholly aromatic liquid crystalline polyester (A) used in the present invention include, for example, a structural unit derived from p-hydroxybenzoic acid, a structural unit derived from 6-hydroxy-2-naphthoic acid, A structural unit derived from an aromatic dihydroxy compound and a wholly aromatic liquid crystal polyester composed of a structural unit derived from an aromatic dicarboxylic acid such as terephthalic acid; a structural unit derived from p-hydroxybenzoic acid, Fully aromatic liquid crystal polyester composed of a structural unit derived from 4,4'-dihydroxybiphenyl and a structural unit derived from aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; p-hydroxybenzene Structural units derived from formic acid, structural units derived from 4,4'-dihydroxybiphenyl, structural units derived from hydroquinone, structural units derived from aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid Fully aromatic liquid crystalline polyester composed; construction unit derived from parahydroxybenzoic acid, construction unit derived from aromatic dihydroxy compound, terephthalic acid, isophthalic acid, and 2,6-naphthalene dicarboxylic acid Constructed from structural units derived from aromatic dicarboxylic acids such as acids Fully aromatic liquid crystalline polyester; construction unit derived from p-hydroxybenzoic acid, construction unit derived from 6-hydroxy-2-naphthoic acid, construction unit derived from 4,4'-dihydroxybiphenyl, Fully aromatic liquid crystalline polyester composed of a structural unit derived from 2,6-naphthalenedicarboxylic acid.

Particularly preferred are: construction units derived from parahydroxybenzoic acid, construction units derived from 4,4'-dihydroxybiphenyl, construction units derived from hydroquinone, terephthalic acid and isophthalic acid, etc. A wholly aromatic liquid crystalline polyester composed of a structural unit derived from an aromatic dicarboxylic acid.

As the raw material monomers constituting each of the above-mentioned structural units, carboxylic acid derivatives such as a halogenated compound of a hydroxyl group of each structural unit, an esterified product of a carboxyl group of each structural unit, an acid halide, and an acid anhydride can also be used. Wait.

The wholly aromatic liquid crystalline polyester (A) used in the present invention is constituted by using the above-mentioned structural unit, so that the obtained liquid crystalline polyester resin composition is excellent in heat resistance and can suppress the amount of gas generated. Therefore, the molded article using the liquid crystalline polyester resin composition is excellent in the adhesion of the metal portion even when the temperature changes.

The total of the aromatic dioxy units and the total of the aromatic dicarbonyl units constituting the wholly aromatic liquid crystalline polyester (A) are substantially equal to each other. The "substantially isomorphic" herein means that the structural units constituting the polymer main chain except for the terminal are isomorphic. Therefore, if the structural unit constituting the end is also included, it may not necessarily be the equivalent of Morr, and it may satisfy the requirement of "substantially Morr".

The calculation method of the content of each structural unit of the wholly aromatic liquid crystalline polyester (A) of the present invention is shown below. First, weigh the wholly aromatic liquid crystalline polyester (A) in an NMR (nuclear magnetic resonance) test tube, and dissolve the solvent (for example, pentafluorophenol / heavy tetrachloroethane-d) in a solvent capable of dissolving the wholly aromatic liquid crystalline polyester. ₂ mixed solvents). Next, ¹ H-NMR mass spectrometry is performed on the obtained solution, and it can be calculated from the peak area ratio derived from each structural unit.

The melting point (Tm) of the wholly aromatic liquid crystalline polyester (A) of the present invention is, from the viewpoint of heat resistance, preferably 220 ° C or higher, more preferably 270 ° C or higher, and particularly preferably 300 ° C or higher. On the other hand, from the viewpoint of processability, the melting point (Tm) of the wholly aromatic liquid crystalline polyester is preferably 350 ° C or lower, more preferably 345 ° C or lower, and particularly preferably 340 ° C or lower.

The melting point (Tm) is measured by differential scanning calorimetry. Specifically, first, the polymer that has been polymerized is heated from room temperature under a temperature rising condition of 20 ° C / min, and an endothermic peak temperature (Tm ₁ ) is observed. After the endothermic spike temperature (Tm ₁ ) was observed, the polymer was maintained at the endothermic spike temperature (Tm ₁ ) + 20 ° C. for 5 minutes. Then, the polymer was cooled to room temperature under a temperature-lowering condition of 20 ° C / min. Next, the polymer was heated under a temperature rising condition of 20 ° C / min, and the endothermic peak temperature (Tm ₂ ) was observed. The "melting point (Tm)" refers to the endothermic peak temperature (Tm ₂ ).

From the viewpoint of mechanical strength, the melt viscosity of the wholly aromatic liquid crystalline polyester (A) of the present invention is preferably 1 Pa · s or more, more preferably 5 Pa · s or more, and particularly preferably 15 Pa · s or more. On the other hand, from the viewpoint of fluidity, the melt viscosity of the wholly aromatic liquid crystalline polyester is preferably 200 Pa · s or less, more preferably 100 Pa · s or less, and particularly preferably 50 Pa · s or less.

The melt viscosity is a value measured by a high-performance flow tester under the conditions of the melting point (Tm) of the wholly aromatic liquid crystalline polyester + 20 ° C and a shear rate of 1,000 / second.

The method for producing the wholly aromatic liquid crystalline polyester (A) used in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method. As a known polyester polycondensation method, a wholly aromatic liquid crystalline polyester is a structural unit derived from p-hydroxybenzoic acid, a structural unit derived from 4,4'-dihydroxybiphenyl, and a hydroquinone derived The structural unit, the structural unit derived from terephthalic acid, and the structural unit derived from isophthalic acid are examples of fully aromatic liquid crystal polyesters, which are described below.

(1) Fully aromatic from de-acetic acid polycondensation reaction from p-acetoxybenzoic acid, 4,4'-diethylacetoxybiphenyl, diethylacetoxybenzene, terephthalic acid, and isophthalic acid Group liquid crystal polyester method.

(2) p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid are reacted with anhydrous acetic acid to acetylate the phenolic hydroxyl group, and then A method for producing a wholly aromatic liquid crystalline polyester by performing deacetic acid polymerization.

(3) Production of fully aromatic liquid crystals from dephenol polycondensation reaction from phenylparaben, 4,4'-dihydroxybiphenyl, hydroquinone, diphenyl terephthalate, and diphenyl isophthalate Polyester method.

(4) Aromatic dicarboxylic acids such as p-hydroxybenzoic acid, terephthalic acid, and isophthalic acid are reacted with a predetermined amount of diphenyl carbonate to form phenyl esters, respectively, and then 4,4'-dihydroxy is added. A method for producing a wholly aromatic liquid crystal polyester by using an aromatic dihydroxy compound such as biphenyl and hydroquinone by a dephenolization polycondensation reaction.

Among them, from the viewpoint of superior industrial terminal structure control and polymerization degree control of wholly aromatic liquid crystalline polyester, it is preferable to use (2) p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, Hydroquinone, terephthalic acid, and isophthalic acid are reacted with anhydrous acetic acid to acetylate a phenolic hydroxyl group, and then a method for producing a wholly aromatic liquid crystal polyester by deacetic acid polymerization.

The method for producing a wholly aromatic liquid crystalline polyester (A) used in the present invention can also complete a polycondensation reaction by a solid-phase polymerization method. Examples of the treatment by the solid-phase polymerization method include the following methods. First, the polymer or oligomer of the wholly aromatic liquid crystalline polyester (A) is pulverized by a pulverizer. The pulverized polymer or oligomer is heated under a nitrogen stream or under reduced pressure, and the reaction is completed by performing polycondensation to a desired degree of polymerization. The heating system can be performed for 1 to 50 hours in the range of the melting point of -50 ° C to the melting point of -5 ° C (for example, 200 to 300 ° C) of the wholly aromatic liquid crystalline polyester.

The polycondensation reaction of the wholly aromatic liquid crystalline polyester (A) proceeds even without a catalyst, but it can also be used, for example: stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, metal Catalysts such as magnesium.

    [Metal additive]    

The liquid crystalline polyester resin composition of the present invention contains a metal-based additive (B). By blending a metal-based additive (B), when a laser product is irradiated to a molded product composed of a liquid crystalline polyester resin composition, the metal-based additive (B) is exposed on the surface of the molded product, and formed from this starting point By plating, a metal part can be formed in a laser irradiation part.

The metal additive (B) used in the present invention is composed of any one metal selected from copper, tin, cobalt, nickel, or silver, or a compound containing the metal. Since the metal additive (B) is composed of any one of the above-mentioned metals, it can be appropriately dispersed in the liquid crystalline polyester resin composition, and the formed metal part has excellent formability. In addition, when the liquid crystalline polyester resin composition is subjected to a molding process, it is possible to suppress the reaction and decomposition of the metal-based additive, and it is possible to achieve excellent adhesion of the metal portion of the molded article when the temperature changes.

When the metal-based additive (B) is a metal-based additive composed of a metal species other than the above, or two or more of the above-mentioned metals, the formation of a metal part having a laser irradiation part is insufficient, or the When the conductive parts are short-circuited or the metal parts of the molded product are short-circuited, or when the liquid crystalline polyester resin composition is subjected to molding processing, the amount of gas generated due to the reaction and decomposition of the metal-based additive increases. In addition, an increase in the amount of generated gas causes a decrease in the adhesion of the metal part of the molded product when the temperature changes.

The metal-based additive (B) -based metal monomer or metal-containing compound used in the present invention can be used as the metal-containing compound, such as oxide, sulfide, sulfate, nitride, nitrate, carbonate, phosphate, and halogenation. Compounds, hydroxides, organometallic compounds, complexes, etc. The metal-based additive (B) is preferably a metal monomer or an oxide. The metal species are, for example, copper, tin, cobalt, nickel, or silver. Among them, tin, nickel, silver, copper oxide, or cobalt oxide is preferred, and copper (II) oxide is more preferred.

The liquid crystalline polyester resin composition of the present invention contains 3 to 25 parts by weight of a metal-based additive (B) based on 100 parts by weight of the wholly aromatic liquid crystalline polyester (A). The blending amount of the metal-based additive is preferably 3.5 parts by weight or more, and more preferably 5 parts by weight or more. The blending amount of the metal-based additive is preferably 23 parts by weight or less, and more preferably 21 parts by weight or less.

If the blending amount of the metal-based additive (B) is less than 3 parts by weight, or the metal-based additive is not blended, the metal part is not formed or the formed amount is insufficient, so that the conductivity of the metal part cannot be obtained, and the temperature The adhesion of the metal part at the time of the change also decreases. On the other hand, if the blending amount of the metal-based additive exceeds 25 parts by weight, the mechanical strength of a molded article composed of a liquid crystalline polyester resin composition decreases, and the surface hardness of the molded article decreases. Moreover, the adhesiveness of the metal part of a molded article at the time of a temperature change falls. In addition, when the liquid crystalline polyester resin composition is subjected to extrusion manufacturing, strand breakage or the like occurs, which adversely affects productivity.

The average particle diameter of the metal-based additive (B) used in the present invention in the resin composition is preferably greater than 1 μm. The "average particle diameter" as used herein means a volume average particle diameter, and can be calculated | required by the following method. 50 g of the liquid crystalline polyester resin composition was heated at 550 ° C for 3 hours to remove the resin component, and the metal-based additive (B) was taken out. When a filler is contained in a resin composition, it can isolate | separate by a difference in specific gravity. For example, take out the resin-removed metal additive and the mixture with the filler and disperse it in diiodomethane (specific gravity 3.33), 1,1,2,2-tetrabromoethane (specific gravity 2.970), ethanol (specific gravity) 0.789) and other mixed liquids that are appropriately mixed according to the specific gravity between the metal-based additive and the filler. After centrifugation at 10,000 rpm for 5 minutes, the floating filler is removed by decantation, and the precipitated filler is removed by filtration. Metal additive (B). 100 mg of the obtained metal-based additive was weighed out, dispersed in water, and measured using a laser diffraction / scattering type particle size distribution measuring device ("LA-300" manufactured by Horiba, Ltd.).

When the average particle diameter of the metal-based additive (B) is larger than 1 μm, it is preferable to moderately disperse the liquid-crystalline polyester resin composition and improve the adhesion of the metal part of the molded product. In addition, when a filler is blended, during the production of the liquid crystalline polyester resin composition, metal additives and fillers during the molding process are promoted to be kneaded, so that each cohesion is suppressed. Excellent dispersibility. This is preferred because the adhesion of the metal part of the molded product is improved and the surface hardness of the molded product is increased. It is preferably 1.5 μm or more, and more preferably 2.0 μm or more.

On the other hand, the upper limit of the average particle diameter of the metal-based additive is preferably 350 μm or less, more preferably 100 μm or less, and particularly preferably 50 μm or less. This is preferable because it suppresses uneven distribution of the metal-based additive in the liquid crystalline polyester resin composition and is excellent in the formability of the metal part of the molded product. In addition, it is preferable to suppress a short circuit caused by the surface of the molded product being conducted to a place other than the metal portion. Further, it is preferable to reduce the strength of the molded product by reducing the coarse particles of the metal-based additive, and to improve the surface hardness of the molded product.

    [Filling material]    

The liquid crystalline polyester resin composition of the present invention preferably contains a filler (C). Examples of the filler (C) used in the present invention include fibrous, whisker-like, plate-like, powdery, and granular fillers. Specific examples of the fibrous and whisker-like filler materials include: glass fibers; PAN-based, pitch-based carbon fibers; stainless steel fibers; aluminum fibers, brass fibers; and other metal fibers; aromatic polyamide fibers, and liquid crystalline polymers. Organic fibers such as ester fibers; gypsum fibers, ceramic fibers, asbestos fibers, zirconia fibers, alumina fibers, silica fibers, titanium oxide fibers, silicon carbide fibers, mineral wool, potassium titanate whiskers, and barium titanate crystals Whiskers, aluminum borate whiskers, silicon nitride whiskers, wollastonite, and acicular titanium oxide. Examples of the plate-shaped filling material include: mica, talc, kaolin, glass fragments, clay, graphite, and molybdenum disulfide. Examples of powdery and granular fillers include silicon dioxide, glass beads, titanium oxide, zinc oxide, and calcium polyphosphate.

The surface of the above-mentioned filler which can be used in the present invention may be treated with a known coupling agent (for example, a silane-based coupling agent, a titanate-based coupling agent, etc.) or other surface treatment agents. Moreover, the said filler used by this invention may use 2 or more types together.

Among these fillers, particularly preferred is a plate-shaped filler. By using a plate-shaped filler, excellent dispersibility and reinforcement effect when kneaded with a metal-based additive are obtained, and the obtained liquid crystal polyester resin composition molded product has excellent metal part formability and metal part adhesion when temperature changes. , So it is better. Moreover, since the obtained liquid crystalline polyester resin composition is excellent in the shape retention property of the molded article at the time of heat processing, and the sliding property of a molded article, it is preferable.

The Mohs hardness of the filler is preferably in the range of 2.0 to 7.0. Mohs hardness can be judged by the presence or absence of scratches when rubbing against a standard substance with a Mohs hardness of 1-10. When the Mohs hardness of the filler is within the above range, during the manufacture and molding of the liquid crystalline polyester resin composition, by kneading with a metal additive, each dispersibility can be improved, and the obtained resin composition can be molded. The product has excellent metal part formability and adhesion under temperature changes, and the surface hardness of the molded product is also excellent. The Mohs hardness of the filler is preferably 2.5 or more from the viewpoint of improving the adhesion of the metal part when the temperature is changed by the reinforcement effect. On the other hand, from the viewpoint of suppressing wear of the extrusion barrel and the screw of the injection molding machine during the molding process, it is preferably 6.5 or less.

Examples of filler materials with a Mohs hardness of 2.0 to 7.0 include: mica, glass fragments, and the like. Among these, mica is preferred from the viewpoints of high reinforcing effect, excellent metal part formability of the obtained liquid crystal polyester resin composition molded product, adhesion of the metal part when temperature changes, and surface hardness of the molded product.

In the present invention, the blending amount of the filler (C) is preferably 10 to 200 parts by weight based on 100 parts by weight of the wholly aromatic liquid crystalline polyester (A). By setting the blending amount of the filler to 10 parts by weight or more, heat resistance and mechanical strength can be further improved, so that the adhesion of the metal part of the molded product at the time of temperature change can be improved, and the surface hardness of the molded product is excellent. The blending amount of the filler is more preferably 15 parts by weight or more, and particularly preferably 20 parts by weight or more. In addition, by setting the blending amount of the filler to 200 parts by weight or less, fluidity and flexibility can be improved, so the surface of the molded product is excellent in smoothness, and it can be suppressed from being removed when the metal part is formed on the molded product. The metal part may be formed in other places. The blending amount of the filler is more preferably 150 parts by weight or less, and particularly preferably 100 parts by weight or less.

The filler (C) usable in the present invention is preferably a filler having an average particle diameter of 10 to 1,000 μm in the resin composition. The "average particle diameter" referred to herein means a volume average particle diameter, which can be obtained by the aforementioned method. When the average particle diameter of the filler is 10 μm or more, the reinforcing effect is excellent. Therefore, the obtained molded article of the liquid crystalline polyester resin composition has improved metal part adhesiveness when the temperature changes, so it is preferable. It is more preferably 15 μm or more, and particularly preferably 20 μm or more. On the other hand, if the average particle diameter of the filler is 1000 μm or less, the dispersibility in the liquid crystalline polyester resin composition is improved, and thus the metal part formability of the obtained liquid crystalline polyester resin composition molded product is improved. It is better. It is more preferably 900 μm or less, and particularly preferably 700 μm or less.

The average particle diameter of the filler of the liquid crystalline polyester resin composition of the present invention is preferably 0.1 to 20 times the average particle diameter of the metal-based additive (B). When the relationship between the average particle diameter of the metal-based additive and the plate-shaped filler is within the above range, when the liquid crystalline polyester resin composition is manufactured, the metal-based additive and the plate-shaped filler are kneaded during the molding process. Each of them can suppress aggregation, and the metal-based additive and the plate-shaped filler are excellent in dispersibility in the obtained molded product, and are therefore preferable. From the viewpoint of improving the dispersibility of the metal-based additive and the plate-shaped filler, the average particle diameter of the plate-shaped filler is preferably 0.15 times or more, and more preferably 0.3 times or more the average particle diameter of the metal-based additive. On the other hand, from the viewpoint of enhancing the reinforcing effect of the plate-shaped filler, it is preferably 15 times or less, and more preferably 10 times or less.

    [Long-chain fatty acid compound]    

The liquid crystalline polyester resin composition of the present invention is preferably a long-chain fatty acid compound (D) containing a metal salt of a long-chain fatty acid and / or an ester of a long-chain fatty acid. When the long-chain fatty acid compound (D) is contained, the molded product of the liquid crystalline polyester resin composition is excellent in surface smoothness, and when a metal part is formed on the molded product, it is possible to suppress the formation of a metal part in a place other than a designed place. In addition, by suppressing the residence time during molding, thermal degradation of the liquid crystalline polyester resin composition can be suppressed. Therefore, both the adhesion of the metal part of the molded product and the surface hardness of the molded product at the time of temperature change are excellent, which is preferable.

In the present invention, it is preferred to use a long-chain fatty acid as a raw material component of the long-chain fatty acid compound (D), and more preferably a carboxylic acid having 10 to 32 carbon atoms. The long-chain fatty acid may be an unsaturated fatty acid or may have two or more double bonds. Among them, preferred are, for example, capric acid, dodecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid (stearic acid), undecanoic acid, Pinanoic acid, arsenic acid (normanthic acid), arsenic acid, arachidonic acid, octadecanoic acid (montanic acid), and the like, more preferable examples are octadecanoic acid (stearic acid), arsenic A particularly preferred example is octadecanoic acid (stearic acid), such as alkanoic acid (agolic acid), octadecanoic acid (montanic acid), and the like. By using the long-chain fatty acid based on the above-mentioned types, the melting point of the long-chain fatty acid compound (D) can be controlled, and a solid state is easily obtained. The liquid crystal polyester resin composition is excellent in operability during production and is easily dispersed in the liquid crystal polyester resin composition. Therefore, it is better.

Among metal salts of long-chain fatty acids, the metal species are preferably calcium, lithium, sodium, magnesium, potassium, aluminum, and the like. By containing these metals, the long-chain fatty acid compound (D) in the liquid crystalline polyester resin composition is excellent in dispersibility, so it is preferable. Particularly preferred is lithium.

The esters of long-chain fatty acids are the esters of the aforementioned long-chain fatty acids and alcohols, and the alcohols may be any of the primary, secondary, and tertiary alcohols, and may also be, for example, glycols such as ethylene glycol, glycerol, and the like. Polyhydric alcohols such as tetrahydric alcohols and pentaerythritol. It may also be a monoester, diester, triester, tetraester, or the like of a polyhydric alcohol and a long-chain fatty acid, and is particularly preferably a tetraester of pentaerythritol.

The long-chain fatty acid compound (D) used in the present invention may use only one of a metal salt of a long-chain fatty acid or an ester of a long-chain fatty acid, or may be used in combination. In addition, a metal salt of a long-chain fatty acid and an ester of a long-chain fatty acid may be used alone, or two or more kinds thereof may be used.

The blending amount of the long-chain fatty acid compound (D) used in the present invention is preferably 0.01 to 1 part by weight based on 100 parts by weight of the wholly aromatic liquid crystalline polyester (A). When the long-chain fatty acid compound is 0.01 parts by weight or more, the molded article of the liquid crystalline polyester resin composition is excellent in surface smoothness, and when a metal portion is formed on the molded article, a metal portion can be suppressed from being formed in a place other than the designed place. This situation is better. In addition, by suppressing the residence time during molding, thermal degradation of the liquid crystalline polyester resin composition can be suppressed. Therefore, the metal parts of the molded product at the time of temperature change and the surface hardness of the molded product are both excellent, which is preferable. More preferred is 0.02 parts by weight or more, and particularly preferred is 0.03 parts by weight or more. On the other hand, when the long-chain fatty acid compound is 1 part by weight or less, the mechanical strength of the molded product of the liquid crystalline polyester resin composition can be suppressed from being lowered. Therefore, the adhesion of the metal part of the molded product when the temperature changes, and the surface hardness of the molded product. Both are excellent and therefore better. It is more preferably 0.7 part by weight or less, and particularly preferably 0.4 part by weight or less.

In the liquid crystalline polyester resin composition of the present invention, antioxidants, heat stabilizers (such as hindered phenols, hydroquinones, phosphites, and the like) may be further blended within a range that does not impair the effects of the present invention. Etc.); UV absorbers (such as resorcinol, salicylate); anti-staining agents such as phosphite and hypophosphite; slippers and release agents (polysiloxane, higher fatty acid alcohols, Higher fatty acids like ammonium, polyethylene wax, etc. However, among the compounds with the effect of lubricants and release agents, the compounds belonging to the long-chain fatty acid compound (D) are classified as (D) components; those containing dyes or pigments Colorants; conductive agents, or carbon black as colorants; crystal nucleating agents, plasticizers, flame retardants (bromine flame retardants, phosphorus flame retardants, red phosphorus, polysiloxane flame retardants, etc.), Common additives selected among flame retardant additives and antistatic agents. Alternatively, a polymer other than the wholly aromatic liquid crystalline polyester (A) may be blended to further impart predetermined properties. When a polymer other than the wholly aromatic liquid crystalline polyester (A) is blended, it is desirable that the proportion of the wholly aromatic liquid crystalline polyester (A) is the largest among the resin types of the liquid crystalline polyester resin composition.

In the liquid crystalline polyester resin composition of the present invention, a method of blending a metal additive, a filler, a long-chain fatty acid compound, and other additives can be used, for example, in a wholly aromatic liquid crystalline polyester, Dry-type blending of solid fillers, metal additives, long-chain fatty acid compounds, and other additives; blending with fully aromatic liquid crystal polyesters, metal additives, fillers, and long-chain fatty acid compounds Solution mixing of other liquid additives, etc .; a method of adding a metal additive, a filler, a long-chain fatty acid compound, and other additives during polymerization of the wholly aromatic liquid crystal polyester; Melt kneading with metal additives, fillers, long-chain fatty acid compounds, and other additives. Among them, the method of melt-kneading is preferred. For the melt-kneading system, a known method can be used. For example, using Banbury mixer, rubber roller, kneader, uniaxial or biaxial extruder, etc., it can be melt-kneaded according to the melting point of fully aromatic liquid crystal polyester + 50 ° C or lower, which can be used as liquid crystal polyester resin.组合 物。 Composition. Among these, a biaxial extruder is preferred.

For biaxial extruder, in order to improve the dispersibility of fully aromatic liquid crystalline polyester, metal additives, fillers, and long-chain fatty acid compounds, it is preferred to provide a kneading section at one or more locations, and more preferably 2 More than. The place where the kneading part is installed, for example, when adding a filler from a side feeder, in order to promote the plasticization of the wholly aromatic liquid crystalline polyester, it is preferably set at a position upstream of the side feeder of the filler. Above, in order to improve the dispersibility between the wholly aromatic liquid crystalline polyester and the filler, it is preferable to install more than one place on the downstream side of the side feeder, and two or more places in total.

In addition, in order to remove moisture in the biaxial extruder and decomposition products generated during kneading, it is preferable to provide an exhaust portion, and more preferably, to provide two or more locations. The place where the exhaust part is installed, for example, when a filler is added from a side feeder, in order to remove the moisture attached to the wholly aromatic liquid crystalline polyester, it is installed on the upstream side of the side feeder where the filler is put. As mentioned above, in order to remove the decomposed gas components during melting and kneading, and the air entrained during the supply of the filler, it is preferable to install more than one place on the downstream side of the side feeder, and two or more places in total. The exhaust system can be set under normal pressure or under reduced pressure. The maximum shear stress during melt-kneading is preferably set to 5,000 to 20,000 Pa. The preferred range is 7,500-18,000Pa, and the more preferred range is 8,000-16,000Pa. The maximum shear stress is calculated using the high-speed flow tester at the maximum shear speed calculated during kneading from the resin temperature in the extruder, the extruder barrel diameter, the number of screw revolutions, and the kneading gap. CFT-500D (Erificent hole plate 0.5 × 10mm) (manufactured by Shimadzu Corporation) can be measured. By setting the maximum shear stress at the time of melt-kneading to the above range, the dispersibility of the metal-based additive and the filler can be improved, and the deterioration of the resin composition can be suppressed. Therefore, the metal part of the molded product is excellent in formability, the metal part adhesion strength at the time of temperature change, and the surface hardness of the molded product, which are preferable.

The kneading method can be arbitrarily adopted as follows: 1) All-aromatic liquid crystal polyester (A), metal additive (B), filler (C), and long-chain fatty acid compound ( D) and other additives, and the method of kneading (integrated kneading method); 2) throw in the aromatic liquid crystal polyester (A), metal additives (B), long chain fatty acid compounds ( D) and other additives, and kneading, and then adding the filler (C) and other additives from the side feeder, and kneading (side feeding method); 3) making high concentration containing fully aromatic liquid crystal Master batches of polyester (A), metal-based additive (B), long-chain fatty acid compound (D), and other additives, and the master batches are then mixed with the wholly aromatic liquid crystalline polyester (A) and A method of kneading the filler (C) (masterbatch method) and the like.

The liquid crystalline polyester resin composition of the present invention can be processed to have excellent melt molding such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, spinning, and other known melt molding. A molded article with surface appearance (hue), mechanical properties, heat resistance, and flame resistance. The "molded product" used herein includes, for example, various films such as injection molded products, extrusion molded products, press molded products, sheets, tubes, unstretched films, uniaxially stretched films, biaxially stretched films, unstretched yarns, Various fibers such as super stretched yarn. Especially from the viewpoint of workability, injection molding is preferred.

The molded article made of the liquid crystalline polyester resin composition obtained in this way can be used in, for example, various gears, various cases, sensors, LED lights, connectors, sockets, resistors, relay boxes, relays, etc. Base, bobbin for relays, switches, coil windings, capacitors, variable capacitor boxes, optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, joints between substrates, antennas, speakers , Microphone, earphone, small motor, head mount, power module, housing, semiconductor, LCD display parts, FDD bracket, FDD chassis, HDD parts, motor brush holder, dish antenna, thermal protector , Mobile phone built-in antenna, wearable terminal components, computer-related parts and other electrical / electronic parts; VTR parts, TV parts, electric irons, hair dryers, electric cooker parts, microwave oven parts, audio parts, laser video discs (registered trademarks) ) ‧Sound machine parts such as optical discs; lighting parts, refrigerator parts, air-conditioning parts, typewriter parts, word processor parts, etc. Electrical product parts; office computer related parts, telephone related parts, fax machine related parts, photocopier related parts, cleaning fixtures, oil-free bearings, stern bearings, submerged bearings and other bearings; motor parts, lighters, Mechanical related parts such as typewriters; camera module related parts such as lens holders, bases, lens barrels, covers, sensor covers, actuators; microscopes, binoculars, cameras, clocks, and medical appliances And other optical equipment; precision machinery related parts; alternator terminals, alternator connectors, IC adjusters, potentiometer bases for optical controllers; various valves such as exhaust valves; fuel related‧exhaust systems‧intake systems Pipe, air intake nozzle exhaust pipe, intake manifold, fuel pump, engine cooling water connector, carburetor body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor Sensors, throttle position sensors, crankshaft position sensors, air flow meters; brakes to wear film sensors, thermostats for air conditioners Motor insulators for air conditioners, motor insulators for vehicles, power windows, etc .; hot air flow control valves for greenhouses, brush holders for radiator motors, water pump impellers, turbine blades, wiper motor related parts, switchboards, start switches, starting relays, power transmission Wiring harnesses, window washer nozzles, air-conditioning panel switch substrates, coils for fuel-related solenoid valves, fuse connectors, handles, horn terminals, electronic equipment parts insulation boards, stepper motor rotors, lamp bezels (lamp bezel), lamp holder, light reflector, lamp housing, brake piston, solenoid bobbin, oil core, ignition box, sensor, and other automotive and vehicle-related parts.

The molded article of the present invention can be effectively used for providing metal on the surface of the molded article in the above-mentioned various applications, since the metal portion can be formed on the surface of the molded article, and the adhesion of the metal portion when the temperature changes and the surface hardness of the molded article are excellent. The small electrical / electronic parts of the conductive part can be used in, for example, connectors, sensors, LED light substrates, camera modules, mobile phone built-in antennas, wearable terminal components, etc.

The molded article of the present invention is preferably provided with a metal portion on the surface. Examples of a method for forming a metal portion on a surface include a method using various plating treatments including providing a catalyst to a molded product, and a mask that shields a place other than a circuit to be formed by a secondary molding. A forming method; a method of modifying and partially removing the surface of a molded product by laser irradiation; and a combination method of these. In particular, it is preferable that the method includes a step of patterning a molded product by laser irradiation, and a method of selectively forming a metal portion in the laser irradiation portion by a metallization step performed by a plating process. This has the advantages of being able to form a molded product by a single molding, easily narrowing the circuit pitch, and changing the circuit pattern without changing the mold and only changing the laser irradiation pattern, which is preferred.

There are no particular restrictions on the lasers applied to the place where the metal part is formed. For example, YVO4 laser, CO ₂ laser, Ar laser, and excimer laser can be used. In particular, Nd, YAG laser, YVO ₄ laser, and FAYb laser operating at a basic wavelength of 1064 nm or a second high wavelength of 532 nm are preferable because they have excellent formability of metal parts. In addition, the laser light may be oscillated in a continuous oscillation laser or a pulsed laser. From the viewpoint of suppressing thermal degradation of the surface of the molded product and burying the metal-based additive by the molten resin, it is preferable to use a pulsed laser that irradiates a strong laser output for a short period of time.

Examples of the metal species of the metal portion formed according to the method described above include gold, silver, copper, platinum, zinc, tin, nickel, cadmium, chromium, and alloys containing these metals. The metal portions are particularly formable and tightly adhered. From the viewpoint of sex, gold, copper, and nickel are preferred. In addition, from the viewpoint of stability of the metal part and improvement of continuity, a metal layer composed of different types of metal species can be further formed on the metal part of the molded product by a method such as plating.

Compared with the conventional technique of forming a circuit board and a circuit member made of a molded product holding a metal part on the surface, the molded product obtained by the method described above can save space and have simple manufacturing steps. It can be effectively used for small electrical / electronic parts.

    [Example]    

In the following, the present invention will be described in more detail using examples, but the gist of the present invention is not limited to the following examples.

The fully aromatic liquid crystalline polyester (A) used in each Example and Comparative Example is shown below.

The composition analysis and characteristic evaluation of the wholly aromatic liquid crystalline polyester were performed according to the following methods.

    (1) Composition analysis of wholly aromatic liquid crystalline polyester    

The composition analysis of the wholly aromatic liquid crystalline polyester was performed by ¹ H-nuclear magnetic resonance mass spectrometry ( ¹ H-NMR) measurement. 50 mg of fully aromatic liquid crystalline polyester was weighed in an NMR sample tube and dissolved in a solvent (pentafluorophenol / 1,1,2,2-tetrachloroethane-d ₂ = 65/35 (weight ratio) mixed solvent) 800 μL In this experiment, a UNITY INOVA 500-type NMR device (manufactured by Varian) was used to perform ¹ H-NMR measurement at an observation frequency of 500 MHz and a temperature of 80 ° C. The ^{ratio was} measured from the peak area ratio of each structural unit observed around 7 to 9.5 ppm. Composition analysis.

    (2) Measurement of melting point (Tm) of wholly aromatic liquid crystalline polyester    

Using a differential scanning calorimeter DSC-7 (manufactured by Perkinelmer), when the wholly aromatic liquid crystalline polyester was measured from room temperature under a temperature rising condition of 20 ° C / min, an endothermic peak temperature (Tm ₁ ) was observed After keeping at Tm ₁ + 20 ° C for 5 minutes, the temperature was temporarily cooled to room temperature under the cooling condition of 20 ° C / min, and then the measurement was performed again under the heating condition of 20 ° C / min, and the endothermic spike observed at this time was measured. The temperature (Tm ₂ ) is set to the melting point (Tm). In the following production examples, the melting point is referred to as "Tm".

    (3) Measurement of melt viscosity of wholly aromatic liquid crystalline polyester    

Use high-tech type flow tester CFT-500D (aperture plate 0.5 × 10mm) (manufactured by Shimadzu Corporation) in a high-temperature type flow tester furnace set at a melting point of fully aromatic liquid crystal polyester + 20 ° C. In order to melt the fully aromatic liquid crystal polyester, After being filled with the wholly aromatic liquid crystalline polyester, it was held for 5 minutes, and then the melt viscosity was measured at a shear rate of 1,000 / second.

    Production Example 1 Fully aromatic liquid crystalline polyester (A-1)    

In a 5L reaction vessel equipped with a stirring blade and a distilling tube, 932 parts by weight of p-hydroxybenzoic acid, 251 parts by weight of 4,4′-dihydroxybiphenyl, 99 parts by weight of hydroquinone, and 284 by weight of terephthalic acid were charged. Parts by weight, 90 parts by weight of isophthalic acid, and 1,252 parts by weight of anhydrous acetic acid (1.09 equivalents of total phenolic hydroxyl group). After stirring at 145 ° C for 1 hour under a nitrogen atmosphere, the jacket temperature was changed from 145 ° C over a period of time. The temperature was raised to 350 ° C in 4 hours. Then, the polymerization temperature was maintained at 350 ° C., and the pressure was reduced to 1.0 mmHg (133 Pa) for 1.0 hour, and the reaction was continued. The polymerization was terminated when the torque required for the stirring reached 20 kg · cm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), and the polymer was discharged into a strand through a spinneret having a circular discharge port with a diameter of 10 mm, and granulated by a cutter. To obtain a wholly aromatic liquid crystalline polyester (A-1).

A composition analysis was performed on the wholly aromatic liquid crystalline polyester (A-1). As a result, the ratio of the structural unit derived from p-hydroxybenzoic acid was 60.0 mol%, and the structure was derived from 4,4'-dihydroxybiphenyl. The proportion of units is 12.0 mole%, the proportion of structural units derived from hydroquinone is 8.0 mole%, the proportion of structural units derived from terephthalic acid is 15.2 mole%, and the proportion of structural units derived from isophthalic acid It is 4.8 mole%. With respect to 100 mol% of the total structural unit of wholly aromatic liquid crystalline polyester, the total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid is 75.2 mol%. The Tm is 330 ° C and the melt viscosity is 28Pa · s.

    Production Example 2 Fully aromatic liquid crystalline polyester (A-2)    

In a 5L reaction vessel provided with a stirring blade and a distilling tube, 870 parts by weight of p-hydroxybenzoic acid, 302 parts by weight of 4,4'-dihydroxybiphenyl, 119 parts by weight of hydroquinone, and 247 by weight of terephthalic acid were charged. Parts by weight, 202 parts by weight of isophthalic acid, and 1,302 parts by weight of anhydrous acetic acid (total of 1.09 equivalents of phenolic hydroxyl group). After stirring at 145 ° C for 1 hour under a nitrogen atmosphere, the jacket temperature was changed from 145 ° C over a period of time. The temperature was raised to 330 ° C in 4 hours. Then, the polymerization temperature was maintained at 330 ° C, and the pressure was reduced to 1.0 mmHg (133 Pa) for 1.0 hour, and the reaction was continued. The polymerization was terminated when the torque required for stirring reached 20 kg‧cm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), and the polymer was discharged into a strand through a spinneret having a circular discharge port with a diameter of 10 mm, and granulated by a cutter. To obtain a wholly aromatic liquid crystalline polyester (A-2).

A composition analysis was performed on the wholly aromatic liquid crystalline polyester (A-2). As a result, the proportion of the structural unit derived from p-hydroxybenzoic acid was 53.8 mol%, and the structure was derived from 4,4'-dihydroxybiphenyl. The proportion of units is 13.8 mole%, the proportion of structural units derived from hydroquinone is 9.2 mole%, the proportion of structural units derived from terephthalic acid is 12.7 mole%, and the proportion of structural units derived from isophthalic acid It is 10.4 mole%. With respect to 100 mol% of the total structural unit of the wholly aromatic liquid crystalline polyester, the total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid is 66.5 mol%. The Tm is 310 ° C and the melt viscosity is 30Pa · s.

    Production Example 3 Fully aromatic liquid crystalline polyester (A-3)    

In a 5L reaction vessel provided with a stirring blade and a distilling tube, 874 parts by weight of p-hydroxybenzoic acid, 498 parts by weight of 4,4'-dihydroxybiphenyl, 285 parts by weight of terephthalic acid, and isophthalic acid were charged. 159 parts by weight and 1,299 parts by weight of anhydrous acetic acid (total of 1.09 equivalents of phenolic hydroxyl group). After stirring at 145 ° C for 1 hour under a nitrogen atmosphere, the jacket temperature was raised from 145 ° C to 340 ° C over 4 hours. . Then, the polymerization temperature was maintained at 340 ° C, and the pressure was reduced to 1.0 mmHg (133 Pa) for 1.0 hour, and then the reaction was continued. When the torque required for stirring reached 20 kg‧cm, the polymerization was terminated. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), and the polymer was discharged into a strand through a spinneret having a circular discharge port having a diameter of 10 mm. Pellets to obtain a wholly aromatic liquid crystalline polyester (A-3).

A composition analysis was performed on the wholly aromatic liquid crystalline polyester (A-3). As a result, the proportion of the structural unit derived from p-hydroxybenzoic acid was 54.2 mol%, and the structure was derived from 4,4'-dihydroxybiphenyl. The proportion of units is 22.9 mole%, the proportion of structural units derived from terephthalic acid is 14.7 mole%, and the proportion of structural units derived from isophthalic acid is 8.2 mole% relative to the total aromatic liquid crystalline polyester The construction unit is 100 mol%, and the total of the construction unit derived from hydroxybenzoic acid and the construction unit derived from terephthalic acid is 68.9 mol%. The Tm is 321 ° C and the melt viscosity is 26Pa · s.

    Production Example 4 Fully aromatic liquid crystalline polyester (A-4)    

In a 5L reaction vessel provided with a stirring blade and a distilling tube, 1,057 parts by weight of p-hydroxybenzoic acid, 151 parts by weight of 4,4'-dihydroxybiphenyl, 59 parts by weight of hydroquinone, and 202 parts of terephthalic acid were charged. Parts by weight, 22 parts by weight of isophthalic acid, and 1152 parts by weight of anhydrous acetic acid (1.09 equivalents of total phenolic hydroxyl group). After stirring at 145 ° C for 1 hour under a nitrogen atmosphere, the jacket temperature was changed from 145 ° C over a period of time. The temperature was raised to 365 ° C in 4 hours. Then, the polymerization temperature was maintained at 365 ° C, and the pressure was reduced to 1.0 mmHg (133 Pa) for 1.0 hour, and the reaction was continued. The polymerization was terminated when the torque required for stirring reached 20 kg‧cm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), and the polymer was discharged into a strand through a spinneret having a circular discharge port with a diameter of 10 mm, and granulated by a cutter. To obtain a wholly aromatic liquid crystalline polyester (A-4).

A composition analysis was performed on this wholly aromatic liquid crystalline polyester (A-4). As a result, the proportion of the structural unit derived from p-hydroxybenzoic acid was 73.9 mol%, and the structure was derived from 4,4'-dihydroxybiphenyl. The proportion of units is 7.8 mole%, the proportion of structural units derived from hydroquinone is 5.2 mole%, the proportion of structural units derived from terephthalic acid is 11.7 mole%, and the proportion of structural units derived from isophthalic acid It is 1.3 mole%. With respect to 100 mol% of the total structural unit of wholly aromatic liquid crystalline polyester, the total amount of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid is 85.7 mol%. The Tm is 351 ° C and the melt viscosity is 31 Pa · s.

    Production Example 5 Fully aromatic liquid crystalline polyester (A-5)    

In a 5L reaction vessel equipped with a stirring blade and a distilling tube, 711 parts by weight of p-hydroxybenzoic acid, 47 parts by weight of 6-hydroxy-2-naphthoic acid, and 335 parts by weight of 4,4'-dihydroxybiphenyl Parts, 299 parts by weight of terephthalic acid, and 965 parts by weight of anhydrous acetic acid (1.05 equivalents of total phenolic hydroxyl group), and reacted at 145 ° C for 1 hour under stirring in a nitrogen environment, and then heated from 145 ° C to 355 in 4 hours ℃. Then, the polymerization temperature was maintained at 355 ° C, and the pressure was reduced to 1.0 mmHg (133 Pa) for 1.0 hour, and the reaction was continued. The polymerization was terminated when the torque required for stirring reached 20 kg‧cm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), and the polymer was discharged into a strand through a spinneret having a circular discharge port with a diameter of 10 mm, and granulated by a cutter. To obtain a wholly aromatic liquid crystalline polyester (A-5).

A composition analysis was performed on this wholly aromatic liquid crystalline polyester (A-5). As a result, the proportion of the structural unit derived from p-hydroxybenzoic acid was 57.2 mol%, and 6-oxy-2-naphthalenedicarboxylic acid ester was used. The proportion of the derived structural unit is 2.8 mol%, the proportion of the structural unit derived from 4,4'-dihydroxybiphenyl is 20 mol%, and the proportion of the structural unit derived from terephthalic acid is 20 mol%. With respect to 100 mol% of the total structural unit of the wholly aromatic liquid crystalline polyester, the total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid is 77.2 mol%. The Tm is 336 ° C and the melt viscosity is 27 Pa · s.

    Production Example 6 Liquid crystalline polyester (A-6)    

In a 5L reaction vessel provided with a stirring blade and a distilling tube, 994 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4'-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, and an intrinsic viscosity of about 216 parts by weight of 0.6 dl / g polyethylene terephthalate and 960 parts by weight of anhydrous acetic acid (total of 1.10 equivalents of phenolic hydroxyl group). Under a nitrogen environment, the reaction was performed at 145 ° C for 1 hour while stirring. The temperature was raised from 145 ° C to 320 ° C in 4 hours. Then, the polymerization temperature was maintained at 320 ° C., and the pressure was reduced to 1.0 mmHg (133 Pa) for 1.0 hour, and the reaction was continued. The polymerization was terminated when the torque required for the stirring reached 20 kg · cm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), and the polymer was discharged into a strand through a spinneret having a circular discharge port with a diameter of 10 mm, and granulated by a cutter. To obtain a liquid crystalline polyester (A-6).

A composition analysis was performed on the wholly aromatic liquid crystalline polyester (A-6). As a result, the proportion of the structural unit derived from p-hydroxybenzoic acid was 66.7 mol%, and the structure was derived from 4,4'-dihydroxybiphenyl. The proportion of the unit is 6.3 mole%, the proportion of ethylene dioxy units derived from polyethylene terephthalate is 10.4 mole%, and the proportion of the structural unit derived from terephthalic acid is 16.7 mole%. The Tm is 313 ° C and the melt viscosity is 13Pa · s.

The metal additive (B) used in each example and comparative example is shown below:

(B-1): Copper (II) oxide (manufactured by Wako Pure Chemical Industries, Ltd., average particle size: 3 μm)

(B-2): Silver-coated glass beads ES-6000-S7 (Made by Potters-Ballotini (strand), the average particle diameter of which is covered with silver is 6 μm)

(B-3): Tin (made by Wako Pure Chemical Industries, Ltd., with an average particle size of 75 μm)

(B-4): Nickel (made by Wako Pure Chemical Industries, Ltd., with an average particle size of 150 μm)

(B-5): Ferric tetroxide (manufactured by Kanto Chemical Co., Ltd., average particle size: 3 μm)

(B-6): Copper chrome oxide Black3702 (manufactured by ASAHI Kasei Kogyo Co., Ltd., average particle diameter: 0.6 μm).

The fillers (C) used in the examples and comparative examples are as follows:

(C-1): Glass ground fiber EPDE-40M-10A (manufactured by Japan Electric Glass Co., Ltd., Mohs hardness 6.5)

(C-2): Talc NK64 (made by Fuji Talc Industries Co., Ltd., Mohs hardness 1)

(C-3): Mica AB-25S (made by Yamaguchi Mica (stock), Mohs hardness 2.8)

(C-4): Mica A-41 (YAMAGUCHI MICA (stock), Mohs hardness 2.8)

(C-5): Glass fragments REFG-112 (manufactured by Nippon Plate Glass Co., Ltd., Mohs hardness 6.5).

The long-chain fatty acid compounds (D) used in the examples and comparative examples are shown below:

(D-1): lithium stearate Li-St (made by Shengyou Chemical Co., Ltd.)

(D-2): Pentaerythritol tetrastearate LOXIOL VPG861 (manufactured by Cognis Japan).

    [Examples 1 to 26, Comparative Examples 1 to 8]    

Using a TEM35B 2-shaft extruder made by Toshiba Machine Co., Ltd. with a side feeder, the fully aromatic liquid crystal polyester (A-1) ~ (A -6), and the metal-based additives (B-1) to (B-6) and the long-chain fatty acid compound (D, based on 100 parts by weight of the wholly aromatic liquid crystalline polyester, in the amounts shown in Tables 1 and 2 -1), (D-2), and throw in the filler (C-1) with the blending amount shown in Tables 1 and 2 relative to 100 parts by weight of the wholly aromatic liquid crystalline polyester from the side feeder. (C-5) The extrusion temperature is set to the melting point of the wholly aromatic liquid crystalline polyester (A) + 10 ° C, and the mixture is melt-kneaded to form pellets. The particles of the obtained liquid crystalline polyester resin composition were subjected to hot air drying, and then dried at 150 ° C. for 3 hours, and then the following evaluations (1) to (6) were performed. The results are shown in Tables 1 and 2.

    (1) Evaluation of metal part formation    

The liquid crystalline polyester resin composition obtained in each Example and Comparative Example was supplied to a FANUC α 30C injection molding machine (manufactured by FANUC Co., Ltd., screw diameter 28 mm), and the extrusion temperature was set to a wholly aromatic liquid crystalline polyester It has a melting point of + 20 ° C, a mold temperature of 90 ° C, and is formed into a square shaped product of 70 mm × 70 mm × 1 mm thick. On the surface of the obtained molded product, a LP-V10U FAYb laser device manufactured by Panasonic was used, with a wavelength of 1,064 nm and a frequency of 50 Hz, and the laser output was 1.2, 2.4, 3.6, 4.8, 6.0, 7.2 W, and scanning, respectively. Speeds of 1,000, 2,000, 3,000, 4,000, 5,000, and 6,000 mm / s were changed, and laser irradiation was performed on a range of 5 mm x 5 mm. This molded article was subjected to electroless copper plating treatment, and then the number of copper plating was formed in the laser irradiated portions of 36 places with different laser irradiation conditions. The larger the number of copper plating formations (the number of metal parts formed), the more excellent the metal part formation properties of the molded product were evaluated.

    (2) Evaluation of Adhesion of Metal Parts at Temperature Change    

The liquid crystalline polyester resin composition obtained in each Example, Comparative Example, and Reference Example was supplied to a FANUC α 30C injection molding machine (manufactured by FANUC Co., Ltd., screw diameter 28 mm), and the extrusion temperature was set to a wholly aromatic liquid crystal. The melting point of the polyester is + 20 ° C, the mold temperature is set to 90 ° C, and the molded product is formed into a square shaped product of 70 mm × 70 mm × 1 mm thick. The conditions were changed, and the surface of the obtained molded product was subjected to laser irradiation, plating treatment, and thermal shock test. Condition (1): Using the LP-V10U FAYb laser device manufactured by Panasonic Co., Ltd. on the surface of the obtained molded product, laser was performed under conditions of a wavelength of 1064 nm, a frequency of 50 Hz, a laser output of 6.0 W, and a scanning speed of 3,000 mm / s Irradiated, the molded product was subjected to electroless copper plating with a thickness of 6 μm. Then, using a hot and cold impactor (TSA-70L made by ESPEC), the temperature was lowered from room temperature to -40 ° C for 5 minutes and held for 30 minutes, and then the temperature was raised to 125 ° C for 5 minutes and held for 30 minutes. , Perform thermal shock test. Condition (2): Using the above-mentioned laser device on the surface of the obtained molded product, laser irradiation was performed under the conditions of a wavelength of 1,064 nm, a frequency of 50 Hz, a laser output of 5.0 W, and a scanning speed of 3,000 mm / s, and the molded product was applied 6 μm thick electroless copper plating. Then, using the hot and cold shock device, the temperature was lowered from room temperature to -40 ° C for 5 minutes and held for 30 minutes, and then heated to 150 ° C for 5 minutes and held for 30 minutes. This was set to 1 cycle, and the cycle was repeated 10 times. The test conditions were cold-heat treated. Using a commercially available "NT cutter" (registered trademark) (manufactured by NT (stock), width 9mm, blade slant 35 °) on the plated surface of the thermal shock-treated molded product obtained under conditions (1) and (2), In a manner of forming 100 checkerboards at an interval of 1 mm, a cut mark having a depth of up to a resin molded product is drawn. Make the checkerboard fully adhere to the adhesive tape ("saisai tape" (registered trademark) manufactured by NICHIBAN (stock) with an adhesive force of 3.4 to 3.9 N / cm, and the width is 18mm). The number of checkerboards left without the overlying surface peeling off. In addition, those who were not plated on the surface of the molded product were rated "×". The larger the number of checkerboard cells (the number of remaining plating surfaces) that remain without peeling off the plated surface, the better the metal part adhesion at the time of thermal shock.

    (3) Evaluation of the surface hardness of the molded product    

The liquid crystalline polyester resin composition obtained in each Example and Comparative Example was supplied to a FANUC α 30C injection molding machine (manufactured by FANUC Co., Ltd., screw diameter 28 mm), and the extrusion temperature was set to a fully aromatic liquid crystalline polyester It has a melting point of + 20 ° C, a mold temperature of 90 ° C, and is formed into a square shaped product of 70 mm × 70 mm × 1 mm thick. Using the obtained molded product, a Rockwell hardness on an R scale was evaluated using a hardness tester (made by Matsuzawa Seiki Co., Ltd., DRH-FA) in accordance with ASTM D785. The larger the obtained value, the more excellent the surface hardness of the molded product is.

    (4) Measurement of the average particle size of metal-based additives and plate-like fillers    

50 g of the particles of the liquid crystalline polyester resin composition obtained in each example were heated at 550 ° C. for 3 hours to remove the resin component, and a mixture of the metal additive and the plate-like filler in the liquid crystalline polyester resin composition was taken out. The obtained mixture was dispersed in diiodomethane (specific gravity 3.33), and centrifuged at 10,000 rpm for 5 minutes, and then the floating plate-shaped filler was taken out by decantation, and the precipitated metal-based additive was taken out by filtration. 100 mg of the obtained metal additive and plate-shaped filler were dispersed in water and measured using a laser diffraction / scattering type particle size distribution measuring device ("LA-300" manufactured by Horiba, Ltd.) to calculate the volume. The average particle size.

    (5) Sliding evaluation    

The liquid crystalline polyester resin composition obtained in each example was supplied to a FANUC α 30C injection molding machine (manufactured by FANUC Co., Ltd., screw diameter 28 mm), and the extrusion temperature was set to the melting point of the wholly aromatic liquid crystalline polyester + A 20 ° C and a mold temperature of 90 ° C were used to form a 30 mm × 30 mm × 3.2 mm square molded product. The obtained molded product used a thrust wear tester (Suzuki type wear tester), and the material of the counterpart was aluminum alloy (5056). The wear of the square plate was measured under the conditions of a load of P = 5kgf / cm ² and a speed of V = 20m / min. the amount. The test n number is 5, and the numerical value is an average value. The smaller the amount of wear, the better the sliding property is.

    (6) Evaluation of shape retention during heat treatment    

The liquid crystalline polyester resin composition obtained in each Example was supplied to a FANUC α 30C injection molding machine (manufactured by FANUC Co., Ltd., screw diameter 28 mm), and the extrusion barrel temperature was set to the melting point of the wholly aromatic liquid crystalline polyester + 20 ° C., the mold temperature was set to 90 ° C., and a 70 mm × 70 mm × 1 mm thick molded article was molded. The obtained test piece was heat-treated at 200 ° C for 1 hour, and then the amount of deformation was measured. In addition, the amount of deformation is statically placed on a horizontal fixed plate, and a universal projector (V-16A (Nikon)) is used to measure the horizontal and diagonal setting of the square plate while pressing any one of the four sides of the square plate. Floating amount of the disk. When the amount of floating is so small that it cannot be measured, it is set to 0.5 mm or less. The smaller the amount of deformation, the better the shape retention property at the time of heat treatment.

As can be seen from the results in Table 1, the liquid crystal polyester resin composition-based molded product according to the embodiment of the present invention has excellent metal part formability, and has excellent metal part adhesion and molded surface hardness when the temperature changes. . It is also known from the results in Table 2 that the liquid-crystalline polyester resin composition according to the embodiment of the present invention uses a plate-shaped filler having a specific Mohs hardness as the filler to remove the metal of the molded product when the temperature changes. In addition to excellent part adhesion, the sliding properties of the molded product and the shape retention of the molded product during heat treatment are also excellent. Therefore, it can be said that it is particularly suitable for use in electrical / electronic parts having metal parts on the surface.

    (Industrial availability)    

The liquid crystalline polyester resin composition-based molded article of the present invention is excellent in formability of metal parts and has excellent metal part adhesion and surface hardness of the molded product at a temperature change, so it can be effectively used for electrical / electronic parts Wait.

Claims (10)

    A liquid crystal polyester resin composition containing 100 parts by weight of a wholly aromatic liquid crystal polyester (A) and containing 3 to 25 parts by weight of a metal-based additive (B); the above wholly aromatic liquid crystal polyester (A ) Is 100 mol% relative to the total structural unit of the above wholly aromatic liquid crystalline polyester, and the total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid is 60 to 77 mol%; the above metal The system additive (B) is composed of a metal selected from copper, tin, cobalt, nickel, or silver, or a compound containing the metal.         The liquid crystalline polyester resin composition according to claim 1, wherein the average particle diameter of the metal-based additive (B) is greater than 1 μm.         The liquid crystalline polyester resin composition according to claim 1 or 2, wherein the wholly aromatic liquid crystalline polyester (A) contains a structural unit derived from hydroquinone.         The liquid crystalline polyester resin composition according to any one of claims 1 to 3, which contains 10 to 200 parts by weight of the filler (C) based on 100 parts by weight of the wholly aromatic liquid crystalline polyester (A).         The liquid crystalline polyester resin composition according to any one of claims 1 to 4, wherein the filler (C) is a plate-shaped filler having a Mohs hardness of 2.0 to 7.0.         The liquid crystalline polyester resin composition according to any one of claims 1 to 5, wherein the average particle diameter of the filler (C) is 0.1 to 20 times the average particle diameter of the metal-based additive (B).         The liquid crystalline polyester resin composition according to any one of claims 1 to 6, which contains a metal salt and / or a long chain fatty acid with respect to 100 parts by weight of the wholly aromatic liquid crystalline polyester (A). The long-chain fatty acid compound (D) of an ester of a chain fatty acid is 0.01 to 1 part by weight.         A molded article comprising the liquid crystalline polyester resin composition according to any one of claims 1 to 7.         The molded article according to claim 6, which has a metal portion on the surface.         A method for manufacturing a molded article, which is a method for manufacturing a molded article having a metal portion on a surface, comprising: a pattern drawing step of applying laser irradiation to the molded article of claim 8; and a metallizing step using a plating treatment. .