KR102244483B1 - Liquid crystal polyester resin composition, molded article, and method of manufacturing molded article - Google Patents

Abstract

The present invention is a liquid crystalline polyester resin composition comprising 3 to 25 parts by weight of a metal additive (B) based on 100 parts by weight of the wholly aromatic liquid crystalline polyester (A), wherein the wholly aromatic liquid crystalline polyester (A) is , The total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid relative to 100 mol% of the total structural units of the wholly aromatic liquid crystalline polyester is 60 to 77 mol%, and the metallic additive (B) is copper , Tin, cobalt, nickel, or silver. It relates to a liquid crystal polyester resin composition comprising a metal selected from any one of or a compound containing the metal.
It is to provide a liquid crystalline polyester resin composition having excellent formability of a metal part on the surface of a molded product, adhesion to a metal part of a molded product upon temperature change, and a molded product made of the same.

Description

Liquid crystal polyester resin composition, molded article, and method of manufacturing molded article

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

Liquid crystalline polyester is excellent in heat resistance, fluidity, and dimensional stability. For this reason, the demand is expanding mainly for the use of electric/electronic parts for which these characteristics are required. However, in the use of electric and electronic parts, the miniaturization and thinning of electric and electronic parts are in progress as the product is light and thin, and to further reduce space and weight, a three-dimensional structure in which an electronic circuit board is incorporated into a resin part. There is a demand for development of circuit board formation technology. By forming an electronic circuit pattern three-dimensionally on the surface of a resin molded article, it becomes possible to liberalize circuit board design, to downsize modules, to reduce the number of parts, and to reduce the number of assembly steps. As a method of forming a circuit on a resin molded article, for example, a mask forming method in which masking is performed in addition to the circuit formation points by two-time molding, a circuit pattern drawing method by laser irradiation, and metallization techniques such as plating. The combination of, and continues to expand.

Among them, the method of drawing a circuit pattern by laser irradiation continues to expand from the point that it is easy to cope with the narrow pitch of the circuit. Therefore, in order to impart plating formability by laser irradiation, examination of a resin composition containing various additives is in progress.

For example, a polyamide resin composition excellent in solder heat resistance (for example, Patent Document 1, Patent Document 2) or a polycarbonate resin composition excellent in impact strength (for example, by blending copper chromium oxide or antimony-doped tin oxide) , Patent Literature 3), copper chromium oxide is blended, and a liquid crystal polymer having excellent mechanical strength and dielectric properties such as tensile strength and bending strength (for example, Patent Literature 4 and Patent Literature 5), and aluminum-doped zinc oxide are blended. , Polycarbonate, polyamide, polyester resin composition (for example, Patent Document 6) with improved whiteness, and additives having a core cell structure coated with a resin or the like with a metal oxide are mixed, and adverse effects on the resin containing the additive A substrate material (for example, Patent Document 7) having suppressed is proposed. Japanese Laid-Open Patent No. 2014-240452 International Publication No. 2013/141157 Japanese Laid-Open Patent No. 2015-108124 Japanese Patent Publication No. 2015-502418 International Publication No. 2016/003588 Japanese Laid-Open Patent No. 2015-71739 Japanese Patent Publication No. 2016-507650

However, in such a conventional technique, the adhesion between a molded article made of a liquid crystal polyester resin composition and a metal is low, or on the surface of a molded article made of a resin composition containing a polyamide resin or the like as a main component, the coefficient of linear expansion of the resin composition is In some cases, it was larger than the coefficient of linear expansion of. As a result, there is a problem in that the adhesion strength of the metal part on the surface of the molded product decreases, or the metal part detaches or peels when the temperature around the product is changed. In addition, when various additives for improving the metal part formation property are blended, the surface hardness of the molded article may be lowered, perhaps because it affects the crystallinity of the resin composition and the orientation of the molecular chains. As a result, deformation and defects in the surface of the molded product may occur during assembly of the product. Therefore, the resin composition corresponding to the conventional technique for forming a three-dimensional circuit board is not sufficiently satisfactory for the above problem, and further improvement is required.

The present invention provides a liquid crystalline polyester resin composition having excellent hardness on the surface of a molded article for securing the formability of a metal part to the surface of a molded product, adhesion of the metal part at a change in temperature around the product, and reliability of the metal part during product assembly, and It is an object to provide a molded article using it.

The liquid crystal polyester resin composition of the present invention has the following configuration in order to solve the above-described problem. In other words,

A liquid crystalline polyester resin composition comprising 3 to 25 parts by weight of a metal additive (B) with respect to 100 parts by weight of the wholly aromatic liquid crystalline polyester (A), wherein the wholly aromatic liquid crystalline polyester (A) is The total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid is 60 to 77 mol% with respect to 100 mol% of all structural units of the liquid crystalline polyester, and the metallic additive (B) is copper, tin, cobalt , A metal selected from any one of nickel, or silver, or a liquid crystalline polyester resin composition comprising a compound containing the metal.

The molded article of the present invention has the following configuration. In other words,

It is a molded article made of the said liquid crystalline polyester resin composition.

The method for manufacturing a molded article of the present invention has the following configuration. In other words,

It is a method for producing a molded article having a metal portion on its surface, including a pattern drawing step by laser irradiation on the molded article and a metallization step by plating treatment.

In the liquid crystalline polyester resin composition of the present invention, it is preferable that the average particle diameter of the metal additive (B) is greater than 1 µm.

In the liquid crystalline polyester resin composition of the present invention, it is preferable that the wholly aromatic liquid crystalline polyester (A) contains a structural unit derived from hydroquinone.

It is preferable that the liquid crystal polyester resin composition of the present invention contains 10 to 200 parts by weight of a filler (C) with respect to 100 parts by weight of the wholly aromatic liquid crystal polyester (A).

In the liquid crystalline polyester resin composition of the present invention, it is preferable that the filler (C) is a plate-like filler having a Mohs hardness of 2.0 to 7.0.

In the liquid crystalline polyester resin composition of the present invention, it is preferable that the average particle diameter of the filler (C) is 0.1 to 20 times the average particle diameter of the metallic additive (B).

The liquid crystal polyester resin composition of the present invention contains 0.01 to 1 weight of a long chain fatty acid compound (D), which is a metal salt of a long chain fatty acid and/or an ester of a long chain fatty acid, based on 100 parts by weight of the wholly aromatic liquid crystal polyester (A). It is preferable to include parts.

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

Hereinafter, the present invention will be described in detail.

[Whole aromatic liquid crystalline polyester]

The wholly aromatic liquid crystal polyester (A) used in the present invention is a polyester called a thermotropic liquid crystal polymer that exhibits optical anisotropy when melted. For example, it is a liquid crystalline polyester consisting 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 melted phase. The structural unit does not include 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 a structural unit derived from hydroxybenzoic acid, an aromatic oxycarbonyl unit, and an aromatic dicarboxylic acid based on 100 mol% of the total structural unit of the wholly aromatic liquid crystalline polyester. The total of structural units derived from terephthalic acid, which is a lebonyl unit, is 60 to 77 mol%. If the sum of the structural units derived from hydroxybenzoic acid and the structural units derived from terephthalic acid is less than 60 mol% with respect to 100 mol% of the total structural units of the wholly aromatic liquid crystalline polyester, the heat resistance of the wholly aromatic liquid crystalline polyester decreases. do. Therefore, the deformation of the molded article increases when the temperature of the molded article changes, so that the adhesion of the metal portion is deteriorated. In addition, when it exceeds 77 mol%, since the crystallinity of the wholly aromatic liquid crystalline polyester becomes excessively high, the adhesion of the metal portion at the time of temperature change of the molded article is lowered, and the surface hardness of the molded article is lowered.

The total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid relative to 100 mol% of the total structural units of the wholly aromatic liquid crystalline polyester is preferably 65 mol% or more, and more preferably 69 mol% or more. . On the other hand, 76 mol% or less is preferable. In addition, the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid may have one of the structural units, and the other structural unit may be 0 mol%. It is preferable that the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid each exceed 0 mol%.

It is preferable that the wholly aromatic liquid crystalline polyester (A) used in the present invention contains a structural unit derived from hydroquinone. By including the structural unit derived from hydroquinone, since the crystallinity of the wholly aromatic liquid crystalline polyester is controlled, the balance of toughness and rigidity of the molded article is excellent, and the surface hardness of the molded article is excellent, which is preferable. If the content of the structural unit derived from hydroquinone relative to 100 mol% of the total structural unit of the wholly aromatic liquid crystalline polyester is 2.5 mol% or more, the crystallinity of the wholly aromatic liquid crystalline polyester is not too high, and the flexibility of the molded article is improved. It is preferable because the reduction in surface hardness is suppressed. 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 is improved, and the decrease in the surface hardness is suppressed, so it is preferable.

Each structural unit constituting the wholly aromatic liquid crystalline polyester (A) used in the present invention includes, as an aromatic oxycarbonyl unit, a structural unit derived from hydroxybenzoic acid, for example 6-hydroxy-2 -Structural units derived from naphthoic acid and the like can be used in combination. As the hydroxybenzoic acid, p-hydroxybenzoic acid is preferred. As an aromatic dioxy unit, for example, 4,4'-dihydroxybiphenyl, hydroquinone, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, tert-butylhydroquinone , Structural units derived from phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and the like, and 4,4'-dihydroxybiphenyl and hydroquinone are preferable. As the aromatic dicarbonyl unit, structural units derived from terephthalic acid are included, and structural units derived from, for example, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, etc. are further used in combination. And isophthalic acid is preferred.

Specific examples of the wholly aromatic liquid crystalline polyester (A) used in the present invention include a structural unit derived from p-hydroxybenzoic acid, a structural unit derived from 6-hydroxy-2-naphthoic acid, and an aromatic dihydroxy compound. A wholly aromatic liquid crystalline polyester consisting of a structural unit derived from an aromatic dicarboxylic acid including a structural unit derived from and a structural unit derived from terephthalic acid, a structural unit derived from p-hydroxybenzoic acid, 4,4'-dihyd A wholly aromatic liquid crystalline polyester consisting of structural units derived from oxybiphenyl, structural units derived from aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, structural units derived from p-hydroxybenzoic acid, 4,4'-di Structural units derived from hydroxybiphenyl A wholly aromatic liquid crystalline polyester consisting of structural units derived from hydroquinone, structural units derived from aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and structural units derived from p-hydroxybenzoic acid , A wholly aromatic liquid crystalline polyester consisting of structural units derived from aromatic dihydroxy compounds, structural units derived from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, p-hydroxybenzoic acid Structural unit derived from, 6-hydroxy-2-naphthoic acid, structural unit derived from 4,4'-dihydroxybiphenyl, structural unit derived from 2,6-naphthalenedicarboxylic acid The wholly aromatic liquid crystalline polyester etc. which consist of are mentioned.

Particularly preferred are structural units derived from p-hydroxybenzoic acid, structural units derived from 4,4'-dihydroxybiphenyl, structural units derived from hydroquinone, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid. It is a wholly aromatic liquid crystalline polyester composed of structural units described above.

The raw material monomers constituting each of the above structural units are carboxylates such as an acylated product 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, which are structures capable of forming each structural unit. This acid derivative or the like may be used.

When the wholly aromatic liquid crystalline polyester (A) used in the present invention is constituted by the above structural units, the obtained liquid crystalline polyester resin composition has excellent heat resistance and the amount of gas generated is suppressed. Therefore, a molded article using the liquid crystalline polyester resin composition is excellent in adhesiveness of a metal part even at the time of temperature change.

The total of the aromatic dioxy units constituting the wholly aromatic liquid crystalline polyester (A) and the total of the aromatic dicarbonyl units are substantially equimolar. The term "substantially equimolar" as used herein indicates that the structural units constituting the polymer main chain excluding the terminal are equimolar. Therefore, when the structural unit constituting the terminal is also included, the requirement of "substantially equimolar" can be satisfied even in an aspect that is not necessarily equimolar.

About the wholly aromatic liquid crystalline polyester (A) of this invention, the content calculation method of each structural unit is shown below. First, the wholly aromatic liquid crystalline polyester (A) is weighed in an NMR (nuclear magnetic resonance) test tube, and a solvent in which the wholly aromatic liquid crystalline polyester is soluble (e.g., pentafluorophenol / tetrachloroethane-d ₂ Mixed solvent). ^{Next, 1} H-NMR spectrum measurement 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 preferably 220°C or higher, more preferably 270°C or higher, and still more preferably 300°C or higher from the viewpoint of heat resistance. 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 less, more preferably 345°C or less, and still more preferably 340°C or less.

The melting point (Tm) is measured by differential scanning calorimetry. _{Specifically, the endothermic peak temperature (Tm 1} ) is observed by first heating the polymer having completed polymerization from room temperature to a temperature increase of 20°C/min. After observation of an endothermic peak temperature (Tm _1), and the 5 minute hold the polymer at a temperature of endothermic peak temperature (Tm ₁₎ + 20 ℃. After that, the polymer is cooled to room temperature under the condition of temperature-falling at 20°C/min. _{Then, the endothermic peak temperature (Tm 2} ) is observed by heating the polymer under a temperature rising condition of 20°C/min. The melting point (Tm) refers to _{the endothermic peak temperature (Tm 2 ).}

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 even more preferably 15 Pa·s or more from the viewpoint of mechanical strength. 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 even more preferably 50 Pa·s or less.

In addition, the melt viscosity is a value measured by a solidification flow tester at a temperature of the wholly aromatic liquid crystalline polyester melting point (Tm) + 20°C and a shear rate of 1,000/sec.

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

(1) Method for producing wholly aromatic liquid crystalline polyester from p-acetoxybenzoic acid and 4,4'-diacetoxybiphenyl, diacetoxybenzene, terephthalic acid, and isophthalic acid by deacetic acid condensation reaction

(2) Reaction of acetic anhydride with p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl and hydroquinone, terephthalic acid, and isophthalic acid to acetylate a phenolic hydroxyl group, and then deacetic acid polymerization to achieve wholly aromatic liquid crystal properties. How to make polyester

(3) Method for producing wholly aromatic liquid crystalline polyester from phenyl p-hydroxybenzoate and 4,4'-dihydroxybiphenyl, hydroquinone and diphenyl terephthalate, and diphenyl isophthalate by dephenol polycondensation reaction

(4) P-hydroxybenzoic acid and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid are reacted with a predetermined amount of diphenyl carbonate to form phenyl esters, and then 4,4'-dihydroxybiphenyl, hydroquinone, etc. A method for producing a wholly aromatic liquid crystalline polyester by adding an aromatic dihydroxy compound of

Among them, (2) p-hydroxybenzoic acid and 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid were reacted with acetic anhydride to acetylate a phenolic hydroxyl group, followed by deacetic acid polycondensation reaction. The method of producing the wholly aromatic liquid crystalline polyester is preferably used from the viewpoint of industrially excellent control of the terminal structure and polymerization degree of the wholly aromatic liquid crystalline polyester.

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

Although the polycondensation reaction of the wholly aromatic liquid crystalline polyester (A) proceeds without a catalyst, stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, metallic magnesium, and the like can also be used as a catalyst.

[Metal additives]

The liquid crystal polyester resin composition of the present invention contains a metal additive (B). By blending the metal additive (B), the metal additive (B) is exposed on the surface of the molded article during laser irradiation to a molded article made of a liquid crystalline polyester resin composition, plating is formed as a starting point, and a metal part is formed in the laser irradiation portion. can do.

The metal additive (B) used in the present invention is made of a metal selected from any one of copper, tin, cobalt, nickel, or silver, or a compound containing the metal. When the metal additive (B) is composed of any one of the above metals, it is appropriately dispersed in the liquid crystalline polyester resin composition, and the metal part of the molded article is excellent in formability. In addition, reaction and decomposition of the metal-based additive during molding processing of the liquid crystal polyester resin composition are suppressed, and the adhesion of the metal part of the molded product at the time of temperature change is excellent.

When the metal additive (B) is a metal type other than the above, or a metal additive composed of two or more metals among the metal types, the formation of the metal part of the laser irradiation unit is insufficient, or the molded article is formed due to conduction between the metal additives. The amount of gas generated increases due to the occurrence of a short circuit to other than the metal part, or reaction and decomposition of the metal-based additive during molding processing of the liquid crystalline polyester resin composition. Further, due to the increase in the amount of generated gas, the adhesion of the metal part of the molded article at the time of temperature change decreases.

The metal additive (B) used in the present invention is a single metal or a compound containing a metal, and as a compound containing a metal, oxides, sulfides, sulfates, nitrides, nitrates, carbonates, phosphates, halides, hydroxides, organometallic compounds , Complexes, etc. can be used. The metal additive (B) is preferably a single metal or an oxide. The type of metal is copper, tin, cobalt, nickel, or silver. Among these, it is preferable that it is an oxide of tin, nickel, silver, copper, or an oxide of cobalt, and it is more preferable that it is copper (II) oxide.

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

If the amount of the metal-based additive (B) is less than 3 parts by weight, or if the metal-based additive is not mixed, the metal part of the molded product is not formed, or the metal part is not formed due to insufficient formation, so that the metal at the time of temperature change The negative adhesion is also lowered. On the other hand, when the blending amount of the metallic additive is more than 25 parts by weight, the mechanical strength of the molded article made of the liquid crystalline polyester resin composition decreases, and the surface hardness of the molded article decreases. In addition, the adhesion of the metal part of the molded article at the time of temperature change decreases. In addition, during extrusion production of the liquid crystalline polyester resin composition, strand breakage occurs, which adversely affects productivity.

The metal additive (B) used in the present invention preferably has an average particle diameter larger than 1 µm in the resin composition. The average particle diameter here is a volume average particle diameter, and can be calculated|required by the following method. The resin component is removed by heating 50 g of a liquid crystalline polyester resin composition at 550 degreeC for 3 hours, and the metallic additive (B) is taken out. When the resin composition contains a filler, it can be separated by a difference in specific gravity. For example, a mixture of metal additives and fillers from which the resin component has been removed is taken out, and this is methylene iodide (specific gravity 3.33), 1,1,2,2-tetrabromoethane (specific gravity 2.970), ethanol (specific gravity 0.789), etc. Disperse in the mixed solution properly mixed so as to have a specific gravity between the metal additive and the filler, and centrifuge for 5 minutes at a rotation speed of 10,000 rpm, and then the suspended filler is removed by decantation, and the precipitated metal additive (B) is removed. It is taken out by filtration. 100 mg of the obtained metallic additive is weighed, dispersed in water, and measured using a laser diffraction/scattering particle diameter distribution measuring device ("LA-300" manufactured by Horiba Seisakusho).

When the average particle diameter of the metal additive (B) is larger than 1 µm, it is suitably dispersed in the liquid crystalline polyester resin composition, and thus the adhesion of the metal part of the molded article is improved, which is preferable. In addition, when the filler is blended, the mixing of the metallic additive and the filler is promoted during the production of the liquid crystalline polyester resin composition and during the molding process, so that agglomeration of each is suppressed, and the dispersibility in the resulting molded product is excellent. Do. As a result, the adhesion of the metal part of the molded article is improved, and the surface hardness of the molded article is improved, which is preferable. 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 metallic additive is preferably 350 µm or less, more preferably 100 µm or less, and still more preferably 50 µm or less. As a result, it is preferable that the nonuniformity of distribution of the metal additive in the liquid crystalline polyester resin composition is suppressed, and the formation of the metal part of the molded article is excellent. Further, it is preferable because short circuit due to conduction to other than metal parts on the surface of the molded article is suppressed. In addition, the reduction in the coarse particles of the metal-based additive suppresses the decrease in the strength of the molded article and improves the surface hardness of the molded article, which is preferable.

[filling]

It is preferable that the liquid crystalline polyester resin composition of this invention contains a filler (C). The filler (C) used in the present invention includes, for example, a filler such as fibrous, whisker, plate, powder, and granular. Specifically, as fibrous and whisker-like fillers, glass fibers, PAN-based or pitch-based carbon fibers, stainless fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers and liquid crystalline polyester fibers, and gypsum Fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, wollastonite, and acicular titanium oxide, etc. Can be lifted. Examples of the plate-like filler include mica, talc, kaolin, glass flakes, clay, graphite, and molybdenum disulfide. Examples of powdery and granular fillers include silica, glass beads, titanium oxide, zinc oxide, and calcium polyphosphate.

The above filler that can be used in the present invention may have its surface treated with a known coupling agent (for example, a silane-based coupling agent, a titanate-based coupling agent, etc.) or other surface treatment agents. Further, the above fillers used in the present invention may be used in combination of two or more.

Among these fillers, plate-shaped fillers are particularly preferred. By using a plate-like filler, it is preferable because it is excellent in dispersibility and reinforcing effect at the time of kneading with a metal additive, and is excellent in the formability of the molded metal part of the resulting liquid crystalline polyester resin composition, and the adhesion of the metal part at a temperature change. Moreover, it is preferable because it is excellent in shape-retaining property of a molded article and the sliding property of a molded article at the time of heat treatment of the obtained liquid crystal polyester resin composition.

It is preferable that the said filler has a Mohs hardness in the range of 2.0-7.0. The Mohs hardness can be determined by the presence or absence of a scratch caused by a scratch with a standard substance having a Mohs hardness of 1 to 10. When the Mohs hardness of the filler is in the above range, by kneading with a metal additive in the production and molding processing of the liquid crystalline polyester resin composition, each dispersibility is improved, and the formability of the metal part of the obtained resin composition molded article, It has excellent adhesion at the time of temperature change, and has excellent surface hardness of molded products. The Mohs hardness of the filler is preferably 2.5 or more from the viewpoint of improving the adhesion of the metal part at the time of temperature change due to the improvement of the reinforcing effect. On the other hand, at the time of molding processing, 6.5 or less is preferable from the viewpoint of suppressing abrasion of the cylinders and screws of the injection molding machine.

Examples of the filler having a Mohs hardness of 2.0 to 7.0 include mica and glass flakes. Among them, mica is preferred in that the reinforcing effect is high, and the molded article metal portion of the obtained liquid crystalline polyester resin composition is excellent in the formability of the metal portion of the molded article, the adhesion of the metal portion upon temperature change, and the surface hardness of the molded article.

The blending amount of the filler (C) usable in the present invention is preferably 10 to 200 parts by weight based on 100 parts by weight of the wholly aromatic liquid crystalline polyester (A). When the blending amount of the filler is 10 parts by weight or more, the 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 is 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 even more preferably 20 parts by weight or more. In addition, since the fluidity and flexibility can be improved by setting the blending amount of the filler to 200 parts by weight or less, the surface smoothness of the molded product is excellent, and the formation of the metal part other than the intended location when forming the metal part into the molded product is not possible. Is suppressed. The blending amount of the filler is more preferably 150 parts by weight or less, and even more preferably 100 parts by weight or less.

It is preferable that the filler (C) usable in the present invention is a filler having an average particle diameter of 10 to 1,000 µm in the resin composition. The average particle diameter here is a volume average particle diameter, and can be calculated|required by the method mentioned above. When the average particle diameter of the filler is 10 µm or more, since the reinforcing effect is excellent, the adhesion of the metal portion of the obtained liquid crystalline polyester resin composition when the temperature of the molded article is changed is improved, which is preferable. It is more preferably 15 µm or more, and even more preferably 20 µm or more. On the other hand, when the average particle size of the filler is 1000 µm or less, the dispersibility in the liquid crystalline polyester resin composition is improved, and thus the formability of the metal part of the molded article of the obtained liquid crystalline polyester resin composition is improved, which is preferable. 900 µm or less is more preferable, and 700 µm or less is still more preferable.

In the liquid crystalline polyester resin composition of the present invention, it is preferable that the average particle diameter of the filler is 0.1 to 20 times the average particle diameter of the metal additive (B). When the relationship between the average particle diameter of the metal additive and the plate-like filler is within the above range, the metal-based additive and the plate-like filler are kneaded at the time of production of the liquid crystal polyester resin composition during molding processing, thereby suppressing respective aggregation, and in the obtained molded product. Metal additives and plate-like fillers are preferable because they each have excellent dispersibility. From the viewpoint of improving the dispersibility of the metal additive and the plate-like filler, the average particle diameter of the plate-like filler is preferably 0.15 times or more, more preferably 0.3 times or more of the average particle diameter of the metal additive. On the other hand, from the viewpoint of improving the reinforcing effect of the plate-shaped filler, 15 times or less is preferable, and 10 times or less is more preferable.

[Long-chain fatty acid compound]

It is preferable that the liquid crystalline polyester resin composition of this invention contains a long chain fatty acid compound (D) which is a metal salt of a long chain fatty acid and/or an ester of a long chain fatty acid. By including the long-chain fatty acid compound (D), the smoothness of the surface of the molded article of the liquid crystal polyester resin composition is excellent, and formation of the metal portion other than the intended portion at the time of forming the metal portion into the molded article is suppressed. In addition, since the residence time at the time of formation is suppressed, thermal deterioration of the liquid crystal polyester resin composition is suppressed, and since the adhesion of the metal part of the molded article at the time of temperature change and the surface hardness of the molded article are excellent, it is preferable.

The long-chain fatty acid which is a raw material component of the long-chain fatty acid compound (D) preferably used in the present invention is 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, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanic acid, docosanic acid (behenic acid), tetradocosanic acid , Hexadocoic acid, octadocoic acid (montanic acid), etc. are preferable, octadecanoic acid (stearic acid), docosanic acid (behenic acid), octadocoic acid (montanic acid) and the like are more preferable, and octadecanoic acid (stearic acid) Acid) is particularly preferred. When the long-chain fatty acid is of the above type, the melting point of the long-chain fatty acid compound (D) is controlled, so that it is easy to become a solid state, and it is excellent in handling properties when preparing a liquid crystal polyester resin composition, and is dispersed in a liquid crystal polyester resin composition. It is preferable because it becomes easy.

As the metal type in the metal salt of the long-chain fatty acid, calcium, lithium, sodium, magnesium, potassium, aluminum, and the like are preferable. By including these metals, since the dispersibility of the long-chain fatty acid compound (D) in the liquid crystalline polyester resin composition is excellent, it is preferable. Lithium is particularly preferred.

The ester of the long chain fatty acid is an ester of the above-described long chain fatty acid and an alcohol, and the alcohol may be any of primary, secondary, and tertiary alcohols, dihydric alcohols such as ethylene glycol, trihydric alcohols such as glycerol, pentaerythritol, etc. Polyhydric alcohols, such as tetrahydric alcohol, may be sufficient. Monoester, diester, tryester, tetraester of polyhydric alcohol and long-chain fatty acid may be sufficient, and tetraester of pentaerythritol is particularly preferable.

The long-chain fatty acid compound (D) used in the present invention may be used either alone or in combination of a metal salt of a long-chain fatty acid or an ester of a long-chain fatty acid. Further, the metal salt of the long-chain fatty acid and the ester of the long-chain fatty acid may each be used alone or in combination of two or more.

The 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 content of the long-chain fatty acid compound is 0.01 parts by weight or more, the surface smoothness of the molded article of the liquid crystal polyester resin composition is excellent, and formation of the metal portion other than the intended portion is suppressed when forming the metal portion into the molded article, which is preferable. In addition, since the residence time at the time of formation is suppressed, thermal deterioration of the liquid crystal polyester resin composition is suppressed, and since the adhesion of the metal part of the molded article at the time of temperature change and the surface hardness of the molded article are excellent, it is preferable. 0.02 parts by weight or more is more preferable, and 0.03 parts by weight or more is still more preferable. On the other hand, when the amount of the long-chain fatty acid compound is 1 part by weight or less, the decrease in the mechanical strength of the molded article of the liquid crystal polyester resin composition is suppressed, and therefore the adhesion of the molded article metal portion at the time of temperature change and the surface hardness of the molded article are excellent, which is preferable. 0.7 parts by weight or less is more preferable, and 0.4 parts by weight or less is still more preferable.

In the liquid crystalline polyester resin composition of the present invention, antioxidants, heat stabilizers (e.g., hindered phenol, hydroquinone, phosphites, and substituents thereof), ultraviolet absorbers ( For example, resorcinol, salicylate), phosphite, hypophosphite, and other anti-coloring agents, lubricants and release agents (silicone, higher fatty acid alcohol, higher fatty acid amide and polyethylene wax, etc., but lubricants and Among the compounds having the effect of a release agent, the compound corresponding to the long-chain fatty acid compound (D) is classified as component (D)], a colorant containing a dye or pigment, a carbon black as a conductive agent or colorant, a crystal nucleating agent, a plasticizer, and a flame retardant (Bromine-based flame retardant, phosphorus-based flame retardant, red phosphorus, silicone-based flame retardant, etc.), a conventional additive selected from a flame retardant aid and an antistatic agent can be further blended. Alternatively, a polymer other than the wholly aromatic liquid crystalline polyester (A) can be blended to further impart predetermined properties. In the case of blending a polymer other than the wholly aromatic liquid crystalline polyester (A), it is preferable that the proportion of the wholly aromatic liquid crystalline polyester (A) is the largest among the types of resins in the liquid crystalline polyester resin composition.

As a method of mixing a metal additive, a filler, a long chain fatty acid compound, and other additives in the liquid crystalline polyester resin composition of the present invention, for example, a solid filler, a metal additive, a long chain fatty acid compound and others in the wholly aromatic liquid crystalline polyester Dry blend method of blending additives, etc., or a solution blending method of blending wholly aromatic liquid crystalline polyester, metal additives, fillers and long chain fatty acid compounds with other liquid additives, metal additives, fillers, long chain fatty acid compounds, and others A method of adding an additive during polymerization of the wholly aromatic liquid crystalline polyester, a method of melt-kneading the wholly aromatic liquid crystalline polyester with a metal additive, a filler, a long-chain fatty acid compound, and other additives can be used. Among them, the method of melt-kneading is preferable. A known method can be used for melt-kneading. For example, a Banbury mixer, a rubber roll machine, a kneader, a single screw or twin screw extruder, or the like can be used and melt-kneaded at the melting point of the wholly aromatic liquid crystalline polyester +50° C. or lower to obtain a liquid crystalline polyester resin composition. Among them, a twin screw extruder is preferable.

For the twin-screw extruder, in order to improve the dispersibility of the wholly aromatic liquid crystalline polyester, the metal additive, the filler, and the long-chain fatty acid compound, it is preferable to form at least one kneading part, and to form at least two parts. It is more preferable. In order to promote plasticization of the wholly aromatic liquid crystalline polyester, for example, when the filler is added from the side feeder, the kneading part is formed at one or more places upstream of the side feeder of the filler, and wholly aromatic. In order to improve the dispersibility of the liquid crystalline polyester and the filler, it is preferable to provide at least one in total and at least two at the downstream side from the side feeder.

Further, in order to remove moisture in the twin-screw extruder or decomposition products generated during kneading, it is preferable to provide a vent part, and it is more preferable to form two or more places. For example, when the filler is added from the side feeder, the vent part is installed at least one place on the upstream side of the side feeder where the filler is introduced in order to remove adhering moisture from the wholly aromatic liquid crystalline polyester. In order to remove the decomposition gas component and the air carried in when the filler is supplied, it is preferable to install at least one at least two at the downstream side of the side feeder. The vent portion may be under normal pressure or under reduced pressure. In addition, it is preferable that the maximum shear stress at the time of melt-kneading is 5,000 to 20,000 Pa. It is preferably 7,500 to 18,000 Pa, more preferably 8,000 to 16,000 Pa. The maximum shear stress is calculated from the resin temperature in the extruder, the cylinder diameter of the extruder, the screw rotation speed, and the maximum shear rate at the time of kneading calculated from the clearance of the kneading part, the solidification flow tester CFT-500D (orifice 0.5 φ × 10 mm) (Shimazu Sei It can be measured using Sakusho). By setting the maximum shear stress at the time of melt-kneading into the above range, deterioration of the resin composition is suppressed while improving the dispersibility of the metal additive and the filler. Therefore, it is preferable because the moldability of the metal part of the molded product, the adhesion strength of the metal part when the temperature changes, and the surface hardness of the molded product are excellent.

As a kneading method, 1) a wholly aromatic liquid crystalline polyester (A), a metal additive (B), a filler (C), a long-chain fatty acid compound (D), and other additives are put in a batch from a thick feeder and kneaded. Kneading method), 2) Totally aromatic liquid crystalline polyester (A), metal additives (B), long chain fatty acid compounds (D) and other additives are added from the thick feeder and kneaded, and then fillers (C) and other additives are added. Method of kneading by adding from a side feeder (side feed method), 3) A master pellet containing a wholly aromatic liquid crystalline polyester (A), a metal additive (B), a long chain fatty acid compound (D) and other additives at a high concentration You may use any method, such as a method (master pellet method) of manufacturing, and then kneading the master pellet with the wholly aromatic liquid crystalline polyester (A) and the filler (C) so as to have a specified concentration.

The liquid crystal polyester resin composition of the present invention has excellent surface appearance (color tone) by performing known melt molding such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, spinning, etc. And it is possible to process into a molded article having mechanical properties, heat resistance, and flame retardancy. Examples of the molded products used herein include injection molded products, extrusion molded products, press-molded products, sheets, pipes, unstretched films, uniaxially oriented films, various films such as biaxially oriented films, and various fibers such as undrawn yarns and super-drawn yarns. have. In particular, injection molding is preferred from the viewpoint of processability.

Molded articles made of the liquid crystalline polyester resin composition thus obtained include, for example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, relay bases, relay spools, switches, coil bobbins, Capacitor, variable capacitor case, optical pickup, oscillator, various terminal boards, transformers, plugs, printed wiring boards, inter-board joint parts, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystal displays Electrical and electronic parts represented by parts, FDD carriages, FDD chassis, HDD parts, motor brush holders, parabolic antennas, thermal protectors, mobile phone internal antennas, wearable terminal members, computer-related parts, and the like; VTR parts, TV parts, irons, hair dryers, rice cookers parts, microwave parts, sound parts, audio equipment parts such as audio laser disc (registered trademark) and compact disc, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, Home and office electrical appliance parts represented by word processor parts and the like; Office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, oilless bearings, stern bearings, various bearings such as underwater bearings, motor parts, lighters, typewriters, and other machine-related parts and lenses Camera module-related parts represented by holders, bases, barrels, covers, sensor covers, actuators, etc., optical devices represented by microscopes, binoculars, cameras, watches, medical instruments, etc., and precision machinery-related parts; Alternator terminal, alternator connector, IC regulator, light dimer potentiometer base, various valves such as exhaust gas valves, various pipes for fuel, exhaust and intake systems, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint , Carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, motor insulator for air conditioner, power wind, etc. Motor insulators, heating air flow control valves, radiator motor brush holders, water pump impellers, turbine vanes, wiper motor related parts, distributors, starter switches, starter relays, transmission wire harnesses, window washers, air conditioner panel switch boards , Fuel-related solenoid valve coil, fuse connector, handle, horn terminal, electrical component insulation plate, step motor rotor, lamp bezel, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter It can be used for automobile/vehicle related parts, such as, ignition device case, sensor, etc.

Among the various uses described above, the molded article of the present invention is a compact electric device having a metal conductive portion on the surface of the molded article, taking advantage of the ability to form a metal portion on the surface of the molded article, the adhesion of the metal portion upon temperature change, and the excellent surface hardness of the molded article. It is useful for electronic parts, and is used, for example, for connectors and sensors, LED lamp boards, camera modules, antennas for built-in mobile phones, and wearable terminal members.

It is preferable that the molded article of the present invention has a metal part on its surface. As a method of forming a metal part on the surface, a method by various plating treatments including application of a catalyst to a molded article, a mask forming method in which masking is performed in addition to the circuit formation points by two-time shaping, the modification of the surface of the molded article by laser irradiation, The method by partial removal and the thing by the combination of these are mentioned. Particularly, a method of selectively forming a metal portion to a laser irradiation portion, including a pattern drawing step by laser irradiation on a molded article and a metallization step by plating treatment, is preferable. This is preferable because it has advantages such as that it is possible to create a molded product by one-time molding, that it is easy to reduce the pitch of the circuit, that a mold change is not required when changing the circuit pattern, and only the laser irradiation pattern is changed. .

There is no restriction|limiting in particular about the laser to be irradiated to a metal part formation location, YVO ₄ laser, CO ₂ laser, Ar laser, excimer laser, etc. are mentioned. In particular, Nd operating at a wavelength of a fundamental wavelength of 1064 nm or a second high wavelength of 532 nm; YAG lasers, YVO ₄ lasers, and FAYb lasers are preferable because they have excellent metal part formation properties. In addition, the laser beam oscillation system may be a continuous oscillation laser or a pulse laser. The laser irradiated to the metal part formation location is preferably a pulsed laser that irradiates a strong laser output for a short time from the viewpoint of suppressing thermal deterioration of the surface of the molded product and burial of the metal-based additive by the molten resin.

Metal types of the metal part formed by the above method include gold, silver, copper, platinum, zinc, tin, nickel, cadmium, chromium, and alloys containing them. In particular, gold, copper, nickel is the metal part. , It is preferable from the point of adhesiveness. Further, from the viewpoint of improving the stability and conductivity of the metal part, a metal layer made of different types of metal may be further formed on the metal part of the molded article by a method such as plating.

The molded article having a metal part on the surface obtained by the above method can save space and simplify the manufacturing process compared to a circuit member comprising a substrate for forming a circuit and a molded article holding the circuit in the prior art. It is useful for use as electric and electronic parts.

<Example>

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

The wholly aromatic liquid crystalline polyester (A) used in each example and comparative example is shown next.

The composition analysis and characteristic evaluation of the wholly aromatic liquid crystalline polyester were performed by the following method.

(1) Composition analysis of wholly aromatic liquid crystalline polyester

The composition analysis of the wholly aromatic liquid crystalline polyester is, was carried out by ¹ H- nuclear magnetic resonance spectra ⁽¹ H-NMR) measurement. Weigh 50 mg of wholly aromatic liquid crystalline polyester in an NMR sample tube, _{and dissolve in 800 μL of a solvent [pentafluorophenol/1,1,2,2-tetrachloroethane-d 2} =65/35 (weight ratio) mixed solvent] ^{, Using a UNITY INOVA500 type NMR device [manufactured by Varian], 1} H-NMR measurement was actually performed at an observation frequency of 500 MHz and a temperature of 80°C. The composition was analyzed from the peak area ratio.

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

_{After the observation of the endothermic peak temperature (Tm 1} ) observed when the wholly aromatic liquid crystalline polyester was measured at a temperature rising condition of 20°C/min from room temperature with a differential scanning thermal system DSC-7 (manufactured by Parkin Elmer), Tm ₁ After maintaining at a temperature of +20°C for 5 minutes, cooling down to room temperature at a temperature of 20°C/minute is performed once, and the endothermic peak temperature (Tm ₂ ) observed when measured under a temperature increase condition of 20°C/minute is determined as the melting point. It was set as (Tm). In the following production examples, the melting point is described as Tm.

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

Using a solidification flow tester CFT-500D (orifice 0.5φ×10mm) (manufactured by Shimadzu Seisakusho Co., Ltd.), in a solidification flow tester set to the melting point +20°C of the wholly aromatic liquid crystalline polyester, In order to melt the wholly aromatic liquid crystalline polyester, after loading the wholly aromatic liquid crystalline polyester and holding for 5 minutes, the melt viscosity was measured at a shear rate of 1,000/sec.

<Production Example 1 wholly aromatic liquid crystalline polyester (A-1)>

932 parts by weight of p-hydroxybenzoic acid, 251 parts by weight of 4,4'-dihydroxybiphenyl, 99 parts by weight of hydroquinone, and 284 parts by weight of terephthalic acid in a 5L reaction vessel equipped with a stirring blade and an outlet tube , 90 parts by weight of isophthalic acid and 1,252 parts by weight of acetic anhydride (1.09 equivalents of the total phenolic hydroxyl groups) were injected and reacted at 145° C. for 1 hour while stirring under a nitrogen gas atmosphere, and then the jacket temperature was increased from 145° C. to 350° C. 4 The temperature was raised over time. Thereafter, the polymerization temperature was maintained at 350°C, the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, and further reaction was continued, and polymerization was completed where the torque required for stirring reached 20 kg·cm. . Next, the inside of the reaction vessel is pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer is discharged to the strand-like material through a clasp having one circular discharge port with a diameter of 10 mm, and pelletized by a cutter to transfer. Aromatic liquid crystalline polyester (A-1) was obtained.

Composition analysis of the wholly aromatic liquid crystalline polyester (A-1) showed that the proportion of the structural unit derived from p-hydroxybenzoic acid was 60.0 mol%, and the structural unit derived from 4,4'-dihydroxybiphenyl The proportion of is 12.0 mol%, the proportion of the structural unit derived from hydroquinone was 8.0 mol%, the proportion of the structural unit derived from terephthalic acid was 15.2 mol%, and the proportion of the structural unit derived from isophthalic acid was 4.8 mol%. The sum of the structural units derived from hydroxybenzoic acid and the structural units derived from terephthalic acid was 75.2 mol% with respect to 100 mol% of the total structural units of the wholly aromatic liquid crystalline polyester. In addition, Tm was 330°C and melt viscosity was 28 Pa·s.

<Production Example 2 wholly aromatic liquid crystalline polyester (A-2)>

870 parts by weight of p-hydroxybenzoic acid, 302 parts by weight of 4,4'-dihydroxybiphenyl, 119 parts by weight of hydroquinone, 247 parts by weight of terephthalic acid, 202 parts by weight of isophthalic acid in a 5L reaction vessel equipped with a stirring blade and an outlet tube Parts and 1,302 parts by weight of acetic anhydride (1.09 equivalents of the total phenolic hydroxyl groups) were injected and reacted at 145°C for 1 hour while stirring under a nitrogen gas atmosphere, and then the jacket temperature was raised from 145°C to 330°C in 4 hours. After that, the polymerization temperature was maintained at 330°C, the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, and the reaction was continued, and polymerization was completed where the torque required for stirring reached 20 kg·cm. . Next, the inside of the reaction vessel is pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer is discharged as a strand-like material through a clasp having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter for transfer. Aromatic liquid crystalline polyester (A-2) was obtained.

Composition analysis of the wholly aromatic liquid crystalline polyester (A-2) showed that the proportion of the structural unit derived from p-hydroxybenzoic acid was 53.8 mol%, and the structural unit derived from 4,4'-dihydroxybiphenyl The proportion of is 13.8 mol%, the proportion of structural units derived from hydroquinone was 9.2 mol%, the proportion of structural units derived from terephthalic acid was 12.7 mol%, and the proportion of structural units derived from isophthalic acid was 10.4 mol%. The sum of the structural units derived from hydroxybenzoic acid and the structural units derived from terephthalic acid was 66.5 mol% with respect to 100 mol% of the total structural units of the wholly aromatic liquid crystalline polyester. In addition, Tm was 310°C and melt viscosity was 30 Pa·s.

<Production Example 3 wholly aromatic liquid crystalline polyester (A-3)>

874 parts by weight of p-hydroxybenzoic acid, 498 parts by weight of 4,4'-dihydroxybiphenyl, 285 parts by weight of terephthalic acid, 159 parts by weight of isophthalic acid, and 1,299 parts by weight of acetic anhydride in a 5 L reaction vessel equipped with a stirring blade and an outlet tube. After injecting a part by weight (1.09 equivalents of the total phenolic hydroxyl groups) and reacting at 145°C for 1 hour while stirring in a nitrogen gas atmosphere, the jacket temperature was raised from 145°C to 340°C in 4 hours. Thereafter, the polymerization temperature was maintained at 340°C, the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, and the reaction was continued, and polymerization was completed where the torque required for stirring reached 20 kg·cm. . Next, the inside of the reaction vessel is pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer is discharged as a strand-like material through a clasp having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter for transfer. Aromatic liquid crystalline polyester (A-3) was obtained.

Composition analysis of the wholly aromatic liquid crystalline polyester (A-3) showed that the proportion of the structural unit derived from p-hydroxybenzoic acid was 54.2 mol%, and the structural unit derived from 4,4'-dihydroxybiphenyl The ratio of was 22.9 mol%, the ratio of the structural unit derived from terephthalic acid was 14.7 mol%, and the ratio of the structural unit derived from isophthalic acid was 8.2 mol%. The sum of the structural units derived from hydroxybenzoic acid and the structural units derived from terephthalic acid was 68.9 mol% with respect to 100 mol% of the total structural units of the wholly aromatic liquid crystalline polyester. In addition, Tm was 321 degrees and melt viscosity was 26 Pa·s.

<Production Example 4 wholly aromatic liquid crystalline polyester (A-4)>

In a 5L reaction vessel equipped with a stirring blade and an outlet tube, 1,057 parts by weight of p-hydroxybenzoic acid, 151 parts by weight of 4,4'-dihydroxybiphenyl, 59 parts by weight of hydroquinone, 202 parts by weight of terephthalic acid, 22 parts by weight of isophthalic acid Parts and 1152 parts by weight of acetic anhydride (1.09 equivalents of the total amount of phenolic hydroxyl groups) were injected and reacted at 145° C. for 1 hour while stirring under a nitrogen gas atmosphere, and then the jacket temperature was raised from 145° C. to 365° C. in 4 hours. After that, the polymerization temperature was maintained at 365°C, the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, and the reaction was continued, and polymerization was completed where the torque required for stirring reached 20 kg·cm. . Next, the inside of the reaction vessel is pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer is discharged as a strand-like material through a clasp having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter for transfer. Aromatic liquid crystalline polyester (A-4) was obtained.

Composition analysis of the wholly aromatic liquid crystalline polyester (A-4) showed that the proportion of the structural unit derived from p-hydroxybenzoic acid was 73.9 mol%, and the structural unit derived from 4,4'-dihydroxybiphenyl The ratio of was 7.8 mol%, the proportion of the structural unit derived from hydroquinone was 5.2 mol%, the proportion of the structural unit derived from terephthalic acid was 11.7 mol%, and the proportion of the structural unit derived from isophthalic acid was 1.3 mol%. The sum of the structural units derived from hydroxybenzoic acid and the structural units derived from terephthalic acid was 85.7 mol% with respect to 100 mol% of the total structural units of the wholly aromatic liquid crystalline polyester. In addition, Tm was 351 degrees, and the melt viscosity was 31 Pa·s.

<Production Example 5 wholly aromatic liquid crystalline polyester (A-5)>

711 parts by weight of p-hydroxybenzoic acid, 47 parts by weight of 6-hydroxy-2-naphthoic acid, 335 parts by weight of 4,4'-dihydroxybiphenyl, terephthalic acid in a 5L reaction vessel equipped with a stirring blade and an outlet tube. 299 parts by weight and 965 parts by weight of acetic anhydride (1.05 equivalents of the total phenolic hydroxyl groups) were injected, and the mixture was reacted at 145°C for 1 hour while stirring in a nitrogen gas atmosphere, and then the temperature was raised from 145°C to 355°C in 4 hours. After that, the polymerization temperature was maintained at 355°C, the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, and the reaction was continued, and polymerization was completed where the torque required for stirring reached 20 kg·cm. . Next, the inside of the reaction vessel is pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer is discharged as a strand-like material through a clasp having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter for transfer. Aromatic liquid crystalline polyester (A-5) was obtained.

Composition analysis of the wholly aromatic liquid crystalline polyester (A-5) showed that the proportion of the structural unit derived from p-hydroxybenzoic acid was 57.2 mol%, and the proportion of the structural unit derived from 6-oxy-2-naphthalate The ratio of the structural unit derived from this 2.8 mol%, 4,4'-dihydroxybiphenyl was 20 mol%, and the ratio of the structural unit derived from terephthalic acid was 20 mol%. The sum of the structural units derived from hydroxybenzoic acid and the structural units derived from terephthalic acid was 77.2 mol% with respect to 100 mol% of the total structural units of the wholly aromatic liquid crystalline polyester. In addition, Tm was 336°C and melt viscosity was 27 Pa·s.

<Production Example 6 Liquid crystalline polyester (A-6)>

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 0.6 dl/g in a 5 L reaction vessel equipped with a stirring blade and an outlet tube. 216 parts by weight of polyethylene terephthalate and 960 parts by weight of acetic anhydride (1.10 equivalents of the total phenolic hydroxyl group) were injected and reacted at 145° C. for 1 hour while stirring under a nitrogen gas atmosphere, and then the temperature was raised from 145° C. to 320° C. for 4 hours. Made it. Thereafter, the polymerization temperature was maintained at 320° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, and further reaction was continued, and polymerization was completed where the torque required for stirring reached 20 kg·cm. . Next, the inside of the reaction vessel is pressurized to 1.0 kg/cm 2 (0.1 MPa), the polymer is discharged as a strand-like material through a clasp having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter to produce liquid crystal. The resulting polyester (A-6) was obtained.

Composition analysis of the liquid crystalline polyester (A-6) showed that the proportion of the structural unit derived from p-hydroxybenzoic acid was 66.7 mol%, and the proportion of the structural unit derived from 4,4'-dihydroxybiphenyl The ratio of this 6.3 mol%, the ethylenedioxy unit derived from polyethylene terephthalate was 10.4 mol%, and the ratio of the structural unit derived from terephthalic acid was 16.7 mol%. In addition, Tm was 313°C and melt viscosity was 13 Pa·s.

The metallic additive (B) used in each Example and a comparative example is shown next.

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

(B-2): Silver-coated glass beads ES-6000-S7 (manufactured by Porters Balotini Co., Ltd., glass beads having an average particle diameter of 6 μm coated with silver on the surface)

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

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

(B-5): triiron tetraoxide (manufactured by Kanto Chemical Co., Ltd., average particle diameter 3 µm)

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

The filler (C) used in each Example and Comparative Example is shown next.

(C-1): Glass milled fiber EPDE-40M-10A (manufactured by Nippon Denki Glass Co., Ltd., Mohs hardness 6.5)

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

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

(C-4): Mica A-41 (made by Yamaguchi Mica, Mohs hardness 2.8)

(C-5): Glass flake REFG-112 (manufactured by Nihon Itagarasu Co., Ltd., Mohs hardness 6.5)

The long-chain fatty acid compound (D) used in each Example and Comparative Example is shown below.

(D-1): Lithium stearate Li-St (manufactured by Katsuta Chemical Industries, Ltd.)

(D-2): Pentaerythritol tetrastearate LOXIOL VPG861 (manufactured by Gonix Japan Co., Ltd.)

<Examples 1 to 26, Comparative Examples 1 to 8>

A TEM35B twin-screw extruder manufactured by Toshiba Kikai Co., Ltd. equipped with a side feeder, and wholly aromatic liquid crystalline polyester (A-1) to (A-6) obtained in each production example, and wholly aromatic liquid crystalline polyester Metal additives (B-1) to (B-6), long chain fatty acid compounds (D-1), and (D-2) were added from the thick feeder in the amount shown in Tables 1 and 2 based on 100 parts by weight. , Fillers (C-1) to (C-5) were added from the side feeder in the amount shown in Tables 1 and 2 based on 100 parts by weight of the wholly aromatic liquid crystalline polyester, and the cylinder temperature was adjusted to the wholly aromatic liquid crystalline polyester. The melting point of the ester (A) was set at +10°C, and melt-kneaded to obtain a pellet. After drying the pellets of the obtained liquid crystalline polyester resin composition at 150° C. for 3 hours using after hot air drying, the following evaluations (1) to (6) were performed. The results are shown in Tables 1 and 2.

(1) Evaluation of metal part formability

The liquid crystalline polyester resin composition obtained by each Example and Comparative Example was supplied to a Fanuc α30C injection molding machine (manufactured by Fanak Co., Ltd., a screw diameter of 28 mm), and the cylinder temperature was supplied to the melting point of the wholly aromatic liquid crystalline polyester +20. The angular molded article having a thickness of 70 mm×70 mm×1 mm was formed at a temperature of 90°C and a mold temperature. On the surface of the obtained molded article, an LP-V10U FAYb laser device manufactured by Panasonic Corporation was used, and the laser output was 1.2W, 2.4W, 3.6W, 4.8W, 6.0W, 7.2W at a wavelength of 1,064 nm and a frequency of 50 Hz. The scanning speed was changed to 1,000, 2,000 mm/s, 3,000 mm/s, 4,000 mm/s, 5,000 mm/s, and 6,000 mm/s, and laser irradiation was performed in a range of 5 mm x 5 mm, respectively. The molded article was subjected to an electroless copper plating treatment, and after that, the number of copper plating formed among 36 laser irradiation portions having different laser irradiation conditions was determined. As the number of copper plating formations (number of formations of metal parts) increased, it was evaluated that the formation of metal parts into a molded article was excellent.

(2) Evaluation of adhesion to metal parts during temperature change

The liquid crystalline polyester resin composition obtained by each Example, Comparative Example, and Reference Example was provided to a Fanuc α30C injection molding machine (manufactured by Fanak Co., Ltd., screw diameter 28 mm), and the cylinder temperature was adjusted to that of the wholly aromatic liquid crystalline polyester. The melting point +20°C and the mold temperature were set to 90°C to form a rectangular molded article having a thickness of 70 mm×70 mm×1 mm. Laser irradiation, plating treatment, and heat shock tests on the surface of the obtained molded article were performed by changing conditions. As condition (1), the surface of the obtained molded article was irradiated with a laser under the conditions of a wavelength of 1,064 nm, a frequency of 50 Hz, a laser output of 6.0 W, and a scanning speed of 3,000 mm/s using an LP-V10U FAYb laser device manufactured by Panasonic Corporation. Then, the molded article was subjected to an electroless copper plating treatment having a thickness of 6 μm. Thereafter, with a cold and thermal shock machine (TSA-70L manufactured by SPEC Co., Ltd.), the temperature was lowered from room temperature to -40°C in 5 minutes and held for 30 minutes, and then the temperature was raised to 125°C in 5 minutes and maintained for 30 minutes. The heat shock test was performed. As condition (2), the surface of the obtained molded article was irradiated with the laser 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 using the above laser device, and the molded article was subjected to a thickness of 6 μm. The electroless copper plating treatment was performed. Thereafter, by the cold and heat shock device, the temperature was lowered from room temperature to -40°C in 5 minutes, maintained for 30 minutes, then heated to 150°C in 5 minutes, and maintained for 30 minutes as a test condition of repeating 10 times. Treatment was performed. The plated surface of the heat shock-treated molded article obtained under condition (1) and condition (2) is a commercially available "NT cutter" (registered trademark) (manufactured by NT Corporation, width 9 mm, 35° inclined blade). Then, a cut was put in the resin molded article so that 100 cells were formed at intervals of 1 mm. Sufficiently adhere the tape ["Cellotape" (registered trademark) manufactured by Nichiban Co., Ltd., with an adhesive strength of 3.4 to 3.9 N/cm, width 18 mm), hold both ends of the tape and instantly remove it in the vertical direction, The number of cells remaining without peeling off the plated surface was measured. In addition, it was set as "x" that plating was not formed on the surface of a molded article. It was evaluated that the greater the number of cells remaining without peeling of the plated surface (the number of remaining plated surfaces), the better the adhesion of the metal part during heat shock.

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

The liquid crystalline polyester resin composition obtained by each Example and Comparative Example was supplied to a Fanuc α30C injection molding machine (manufactured by Fanak Co., Ltd., a screw diameter of 28 mm), and the cylinder temperature was supplied to the melting point of the wholly aromatic liquid crystalline polyester +20. The angular molded article having a thickness of 70 mm×70 mm×1 mm was formed at a temperature of 90°C and a mold temperature. Using the obtained molded article, according to ASTM D785, the Rockwell hardness of the R scale was evaluated by a hardness tester (manufactured by Matsuzawa Seiki Co., Ltd., DRH-FA). The larger the obtained value, the better the surface hardness of the molded article was evaluated.

(4) Measurement of average particle diameter of metal additives and plate-shaped fillers

The resin component was removed by heating 50 g of the pellets of the liquid crystal polyester resin composition obtained by each example at 550°C for 3 hours, and a mixture of the metal additive and the plate-like filler in the liquid crystal polyester resin composition was taken out. The obtained mixture was dispersed in methylene iodide (specific gravity 3.33), centrifuged at a rotation speed of 10,000 rpm for 5 minutes, and then the floating plate-shaped filler was taken out by decantation, and the precipitated metallic additive was taken out by filtration. 100 mg of the obtained metal additive and plate-like filler were weighed, dispersed in water, and measured using a laser diffraction/scattering particle diameter distribution measuring device (manufactured by Horiba Seisakusho, "LA-300"), and volume average The particle diameter was calculated.

(5) Evaluation of sliding properties

The liquid crystalline polyester resin composition obtained by each example was provided to a Fanuc α30C injection molding machine (manufactured by Fanak Co., Ltd., screw diameter 28 mm), and the cylinder temperature was provided with the melting point of the wholly aromatic liquid crystalline polyester +20°C, and the mold At a temperature of 90°C, a rectangular molded article having a thickness of 30 mm×30 mm×3.2 mm was formed. The obtained molded product was subjected to a thrust abrasion tester (Suzuki-type abrasion tester), an aluminum alloy (5056) as an opposite material, and a load of P = 5 kgf/cm 2 and a speed of V = 20 m/min. The amount of wear was measured. The number of tests n was 5, and the value was measured as the average value. The smaller the amount of wear, the better the sliding property was evaluated.

(6) Evaluation of shape retention during heat treatment

The liquid crystalline polyester resin composition obtained by each example was provided to a Fanuc α30C injection molding machine (manufactured by Fanak Co., Ltd., screw diameter 28 mm), and the cylinder temperature was provided with the melting point of the wholly aromatic liquid crystalline polyester +20°C, and the mold At a temperature of 90°C, a rectangular molded article having a thickness of 70 mm×70 mm×1 mm was molded. The obtained test piece was heat-treated at 200° C. for 1 hour, and then the amount of deformation was measured. Then, the amount of deformation is placed on a horizontal platen, and using a universal projector (manufactured by Nikon, V-16A), press down any one of the four sides of the leg plate, and place it on a diagonal horizontal platen. It was measured as the amount of injuries relative to each other. When the floatation amount is small and cannot be measured, it was set to 0.5 mm or less. It was evaluated that the smaller the amount of deformation, the better the shape retention during heat treatment.

[Table 1]

Note 1) The amount of the metal additive (B), the filler (C) and the long-chain fatty acid compound (D) is based on 100 parts by weight of the wholly aromatic liquid crystalline polyester (A).

Note 2) “×” indicates that no plating was formed on the surface of the molded product.

[Table 2]

Note) The amount of the metal additive (B) and the filler (C) is based on 100 parts by weight of the wholly aromatic liquid crystalline polyester (A).

As a result of Table 1, the liquid crystal polyester resin composition of the embodiment of the present invention has excellent metal part formation to the surface of the molded product, and also has excellent adhesion of the metal part of the molded product to the temperature change, and the surface hardness of the molded product. Able to know. In addition, from the results of Table 2, the liquid crystal polyester resin composition of the embodiment of the present invention uses a plate-shaped filler having a specific Mohs hardness as a filler, in addition to the adhesion of the metal part of the molded product at a temperature change, and the sliding property of the molded product. , It can be seen that the shape retention of the molded article during heat treatment is excellent. Therefore, it can be said that it is particularly suitable for use in electric/electronic parts applications having a metal part on the surface.

<Industrial availability>

The liquid crystal polyester resin composition of the present invention is useful for electric/electronic parts and the like because it has excellent formability of a metal part of a molded article, and has excellent adhesion of a metal part of a molded article at a temperature change, and excellent surface hardness of a molded article.

Claims (10)

A liquid crystalline polyester resin composition comprising 3 to 25 parts by weight of a metal additive (B) based on 100 parts by weight of the wholly aromatic liquid crystalline polyester (A),
In the wholly aromatic liquid crystalline polyester (A), the sum of the structural units derived from hydroxybenzoic acid and the structural units derived from terephthalic acid is 60 to 77 with respect to 100 mol% of the total structural units of the wholly aromatic liquid crystalline polyester. Mol%, and the metal-based additive (B) is made of a metal selected from any one of copper, tin, cobalt, nickel, or silver, or a compound containing the metal,
A liquid crystal polyester resin composition for forming a metal part on a laser irradiation part. The method of claim 1,
The liquid crystalline polyester resin composition, wherein the average particle diameter of the metal additive (B) is larger than 1 μm. The method of claim 1,
The liquid crystalline polyester resin composition, wherein the wholly aromatic liquid crystalline polyester (A) contains a structural unit derived from hydroquinone. The method of claim 1,
A liquid crystalline polyester resin composition comprising 10 to 200 parts by weight of a filler (C) based on 100 parts by weight of the wholly aromatic liquid crystalline polyester (A). The method of claim 4,
The liquid crystal polyester resin composition, wherein the filler (C) is a plate-like filler having a Mohs hardness of 2.0 to 7.0. The method of claim 4,
The liquid crystalline polyester resin composition, wherein the filler (C) has an average particle diameter of 0.1 to 20 times the average particle diameter of the metallic additive (B). The method of claim 1,
A liquid crystalline polyester resin composition comprising 0.01 to 1 part by weight of a long-chain fatty acid compound (D), which is a metal salt of a long-chain fatty acid and/or an ester of a long-chain fatty acid, based on 100 parts by weight of the wholly aromatic liquid crystalline polyester (A). A molded article comprising the liquid crystalline polyester resin composition according to any one of claims 1 to 7. The method of claim 8,
A molded product having a metal part on its surface. A liquid crystalline polyester resin composition comprising 3 to 25 parts by weight of a metal additive (B) based on 100 parts by weight of the wholly aromatic liquid crystalline polyester (A),
In the wholly aromatic liquid crystalline polyester (A), the sum of the structural units derived from hydroxybenzoic acid and the structural units derived from terephthalic acid is 60 to 77 with respect to 100 mol% of the total structural units of the wholly aromatic liquid crystalline polyester. Laser irradiation of a molded article made of a liquid crystal polyester composition consisting of a metal selected from copper, tin, cobalt, nickel, or silver, or a compound containing the metal in mol%, and the metal additive (B) is selected from any one of copper, tin, cobalt, nickel, or silver A method for producing a molded article having a metal portion on its surface, including a pattern drawing step by means of a metallization step to a laser irradiation portion by a plating treatment.