JP5262138B2 - Liquid crystalline resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystalline resin composition which exhibits excellent properties in both of measurement and mold release in precise injection molding, has low gas characteristics, and gives a low-blister molded product most suitable for a narrow-pitch connector and the like, and a method for producing it. <P>SOLUTION: The liquid crystalline resin composition comprises (A) 100 pts.wt. of liquid crystalline polyester, (B) 0.1-0.5 pts.wt. of fatty acid ester of pentaerythritol, (C) 30-100 pts.wt. of a filler, and (D) 0.01-0.05 pts.wt. of metallic salt of a fatty acid. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

The present invention relates to a liquid crystal polyester, fatty acid esters of pentaerythritol, fillers, liquid resin composition containing a fatty acid metal salt, and a manufacturing method and molded article formed therefrom.

  The demand for liquid crystalline polymers is growing mainly for electrical and electronic parts, but the low release from precision injection molds without punch taper due to low molding shrinkage is often a problem. ing. In recent years, due to advances in fluidity of liquid crystal polymers, molds have become thinner and more precise, and even with materials that have been released without any problem, the thin wall portion can be 0.1 mm or less. In molds such as connectors with a pitch interval of 0.2 mm or less, the protruding pins are thin, and the sprue and runner are also thin. Abnormalities that remain in the mold frequently occur, making mold release difficult.

Studies to improve the releasability have been made so far (for example, see Patent Documents 1 and 2 ).

  Patent Document 1 describes a liquid crystalline resin composition in which pentaerythritol fatty acid ester and a filler are blended with liquid crystalline polyester, and it is shown that the mold release property is improved. However, the mold release force is only reduced to about 2000 N, and the precision molding die as described above is not sufficient.

  Patent Document 2 describes a composition in which a multimer of a pentaerythritol compound and an inorganic compound are blended with a thermoplastic polyester resin. However, the number of continuous mold release in a tapered normal mold is about 20. And the precision molds as described above are not sufficient.

Further, in precision molding of a liquid crystalline resin composition, a measurement failure at the time of screw measurement due to the shear rate responsiveness of the melt viscosity due to liquid crystallinity frequently occurs, but this problem has been a problem. The method described in 2 was not improved.
JP-A-2-208353 (pages 1 and 2) JP 2006-117736 (pages 1 and 2)

  In view of the background of such prior art, the present invention is superior in both weighing and mold release at the time of precision injection molding, and has low gas properties, so that liquid crystal properties can be obtained that are optimal for narrow pitch connectors with little blistering. It is an object to provide a resin composition and a method for producing the resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have solved the above problems by blending a liquid crystalline resin with a filler, a fatty acid ester of pentaerythritol and a fatty acid metal salt in a specific ratio. The present inventors have found that a molded product with less blistering can be obtained.

That is, the present invention comprises (1) (A) 100 parts by weight of a liquid crystalline polyester composed of the following structural units (I), (II), (III), (IV) and (V) and (B) pentaerythritol. Liquid crystallinity characterized in that 0.1 to 0.5 part by weight of a fatty acid ester and (C) 30 to 100 parts by weight of a filler further contain 0.01 to 0.05 part by weight of (D) a fatty acid metal salt. Resin composition ,

( 2 ) The structural unit (I) is 65 to 80 mol% based on the total of the structural units (I), (II) and (III), and the structural unit (II) is the structural units (II) and (III). ( 1 ) above, wherein the structural unit (IV) is 60 to 92 mol% based on the total of the structural units (IV) and (V). The liquid crystalline resin composition according to the description,
(3) The liquid crystalline resin composition according to (1) or (2) above, wherein the fatty acid ester of (B) pentaerythritol contains at least pentaerythritol tetrastearate,
(4) The liquid crystalline resin composition according to any one of (1) to (3) above, wherein the (D) fatty acid metal salt contains at least lithium stearate,
( 5 ) Melting liquid crystalline resin composition comprising (A) 100 parts by weight of liquid crystalline polyester, (B) 0.1 to 0.5 parts by weight of fatty acid ester of pentaerythritol, and (C) 30 to 100 parts by weight of filler. the liquid-crystalline resin composition obtained by kneading, further (D) above, wherein the drive Ren dos Rukoto the 0.01-0.05 parts by weight fatty acid metal salt (1) to (4) to one A method for producing the liquid crystalline resin composition according to claim 1,
( 6 ) A molded article comprising the liquid crystalline resin composition according to any one of (1) to ( 4 ) is provided.

  It is possible to provide a liquid crystalline resin composition which is excellent in both weighing and mold release at the time of precision injection molding and has low gasity and less blistering, and a method for producing the same. The resin composition of the present invention can provide an optimal molded product for a narrow pitch connector or the like.

  The (A) liquid crystalline polyester of the present invention is a polyester capable of forming an anisotropic melt phase, for example, an aromatic oxycarbonyl unit, an aromatic and / or an aliphatic dioxy unit, an aromatic and / or an aliphatic dicarbonyl. It is a liquid crystalline polyester comprising a structural unit selected from units and forming an anisotropic melt phase.

  Examples of the aromatic oxycarbonyl unit include a structural unit generated from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and the like, and examples of the aromatic and / or aliphatic dioxy unit include 4,4′- Dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2, Structural units formed from 2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, aromatic and / or aliphatic di Examples of the carbonyl unit include te Phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 1,2-bis (2-chloro) Phenoxy) ethane-4,4′-dicarboxylic acid and 4,4′-diphenyl ether dicarboxylic acid, adipic acid, sebacic acid and the like.

  (A) Specific examples of the liquid crystalline polyester include a liquid crystalline polyester comprising a structural unit produced from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, a structural unit produced from p-hydroxybenzoic acid, 6- A structural unit produced from hydroxy-2-naphthoic acid, an aromatic dihydroxy compound, a liquid crystalline polyester comprising a structural unit produced from an aromatic dicarboxylic acid and / or an aliphatic dicarboxylic acid, a structural unit produced from p-hydroxybenzoic acid, A liquid crystalline polyester comprising a structural unit generated from 4,4′-dihydroxybiphenyl, an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid and / or a structural unit generated from an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, p -Structural units produced from hydroxybenzoic acid, 4 Consists of structural units generated from 4'-dihydroxybiphenyl, structural units generated from hydroquinone, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and / or structural units generated from aliphatic dicarboxylic acids such as adipic acid and sebacic acid Liquid crystalline polyester, structural unit produced from p-hydroxybenzoic acid, structural unit produced from ethylene glycol, liquid crystalline polyester comprising structural unit produced from terephthalic acid and / or isophthalic acid, structure produced from p-hydroxybenzoic acid A liquid crystalline polyester comprising a unit, a structural unit produced from ethylene glycol, a structural unit produced from 4,4′-dihydroxybiphenyl, a structural unit produced from an aliphatic dicarboxylic such as terephthalic acid and / or adipic acid, sebacic acid, -Generated from structural units generated from hydroxybenzoic acid, structural units generated from ethylene glycol, structural units generated from aromatic dihydroxy compounds, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid Examples thereof include liquid crystalline polyester composed of structural units.

  Particularly preferred are liquid crystalline polyesters composed of the following structural units (I), (II), (III), (IV) and (V).

  The structural unit (I) is a structural unit generated from p-hydroxybenzoic acid, the structural unit (II) is a structural unit generated from 4,4′-dihydroxybiphenyl, and the structural unit (III) is generated from hydroquinone. The structural unit, the structural unit (IV) represents a structural unit produced from terephthalic acid, and the structural unit (V) represents a structural unit produced from isophthalic acid.

  The structural unit (I) is 65 to 80 mol%, more preferably 68 to 75 mol%, based on the total of the structural units (I), (II) and (III). Moreover, structural unit (II) is 60 to 75 mol% with respect to the sum total of structural units (II) and (III), More preferably, it is 65 to 73 mol%. The structural unit (IV) is 60 to 92 mol%, preferably 60 to 70 mol%, more preferably 62 to 68 mol%, based on the total of the structural units (IV) and (V). .

  In particular, when the structural unit (IV) is 62 to 68 mol% with respect to the total of the structural units (IV) and (V), the moldability, which is a characteristic of the present invention, is preferably expressed in a balanced manner.

  The sum of structural units (II) and (III) and (IV) and (V) is substantially equimolar, but an excess of carboxylic acid component or hydroxyl component is added to control the end groups of the polymer. May be. That is, “substantially equimolar” means that the unit constituting the polymer main chain excluding the terminal is equimolar, but the unit constituting the terminal is not necessarily equimolar.

  There is no restriction | limiting in particular in the manufacturing method of said (A) liquid crystalline polyester used in this invention, It can manufacture according to the well-known polyester polycondensation method.

For example, in the production of the (A) liquid crystalline polyester, the following production method is preferably exemplified.
(1) A method for producing a liquid crystalline polyester from p-acetoxybenzoic acid and 4,4′-diacetoxybiphenyl, diacetoxybenzene, terephthalic acid and isophthalic acid by a deacetic acid condensation polymerization reaction.

  (2) p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone and terephthalic acid, isophthalic acid is reacted with acetic anhydride to acylate the phenolic hydroxyl group, and then the liquid crystalline polyester is subjected to deacetic acid polycondensation reaction. How to manufacture.

  (3) A method for producing a liquid crystalline polyester from a phenyl ester of p-hydroxybenzoic acid and 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, and diphenyl ester of isophthalic acid by a dephenol polycondensation reaction.

  (4) A predetermined amount of diphenyl carbonate is reacted with p-hydroxybenzoic acid and aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid to form a diphenyl ester, and then aromatics such as 4,4'-dihydroxybiphenyl and hydroquinone. A method for producing a liquid crystalline polyester by adding a group dihydroxy compound and dephenol polycondensation reaction.

  Among them, p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid are reacted with acetic anhydride to acylate the phenolic hydroxyl group, and then the liquid crystalline polyester is obtained by deacetic acid polycondensation reaction. The manufacturing method is preferred.

  Furthermore, the total amount of 4,4'-dihydroxybiphenyl and hydroquinone and the total amount of terephthalic acid and isophthalic acid are substantially equimolar. The amount of acetic anhydride used is preferably 1.15 equivalents or less, more preferably 1.10 equivalents or less of the total of the phenolic hydroxyl groups of p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl and hydroquinone. Preferably, the lower limit is 1.0 equivalent or more.

  When the (A) liquid crystalline polyester of the present invention is produced by a deacetic acid polycondensation reaction, a melt polymerization method in which the polycondensation reaction is completed by reacting under reduced pressure at a temperature at which the liquid crystalline polyester melts is preferable. For example, in a reaction vessel equipped with a predetermined amount of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid, acetic anhydride, a stirring blade, a distillation pipe, and a discharge port at the bottom. There is a method in which the reaction is completed after charging and heating under stirring in a nitrogen gas atmosphere to acetylate the hydroxyl group, raising the temperature to the melting temperature of the liquid crystalline polyester, and performing polycondensation under reduced pressure. The conditions for the acetylation are usually 130 to 300 ° C., preferably 135 to 200 ° C., usually 1 to 6 hours, preferably 140 to 180 ° C. for 2 to 4 hours. The polycondensation temperature is a melting temperature of the liquid crystalline polyester, for example, in the range of 250 to 350 ° C., and preferably a melting point of the liquid crystalline polyester + 10 ° C. or higher. The degree of vacuum during polycondensation is usually 0.1 mmHg (13.3 Pa) to 20 mmHg (2660 Pa), preferably 10 mmHg (1330 Pa) or less, more preferably 5 mmHg (665 Pa) or less. In addition, although acetylation and polycondensation may be performed continuously in the same reaction vessel, acetylation and polycondensation may be performed in different reaction vessels.

The obtained polymer is pressurized in the reaction vessel to, for example, approximately 1.0 kg / cm ² (0.1 MPa) at a temperature at which it melts, and discharged in a strand form from the discharge port provided in the lower portion of the reaction vessel. Can do. The melt polymerization method is an advantageous method for producing a uniform polymer, and an excellent polymer with less gas generation can be obtained, which is preferable.

  When the (A) liquid crystalline polyester of the present invention is produced, the polycondensation reaction can be completed by a solid phase polymerization method. For example, the polymer or oligomer of the liquid crystalline polyester (A) of the present invention is pulverized by a pulverizer, and the melting point of the liquid crystalline polyester is −5 ° C. to the melting point −50 ° C. (for example, 200 to 300) under a nitrogen stream or under reduced pressure. C.) for 1 to 50 hours, polycondensation to a desired degree of polymerization, and completion of the reaction. Solid phase polymerization is an advantageous method for producing polymers with a high degree of polymerization.

  (A) Although the polycondensation reaction of the liquid crystalline polyester proceeds even without catalyst, metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and magnesium metal can be used.

  The number average molecular weight of the (A) liquid crystalline polyester of the present invention is preferably 3,000 to 25,000, more preferably 5,000 to 20,000, more preferably 8,000 to 18,000. It is a range.

  The number average molecular weight can be measured by GPC-LS (gel permeation chromatography-light scattering) method using a solvent in which liquid crystalline polyester is soluble.

  Moreover, 1-200 Pa.s is preferable, as for the melt viscosity of (A) liquid crystalline polyester in this invention, 10-200 Pa.s is more preferable, Furthermore, 10-100 Pa.s is especially preferable.

  The melt viscosity is a value measured by a Koka flow tester under the condition of (A) melting point of liquid crystalline polyester + 10 ° C. and shear rate of 1,000 / s.

  In the present invention, the melting point (Tm) refers to the endothermic peak temperature (Tm1) observed when the polymer having been polymerized is measured under the temperature rising condition from room temperature to 20 ° C./min in differential calorimetry. , After being held at a temperature of Tm1 + 20 ° C. for 5 minutes, once cooled to room temperature under a temperature decrease condition of 20 ° C./min, and then endothermic peak temperature (Tm2) observed when measured again under a temperature increase condition of 20 ° C./min Point to.

  The fatty acid ester of (B) pentaerythritol of the present invention may be any of fatty acid monoesters, diesters, triesters and tetraesters of pentaerythritol or a mixture thereof, but fatty acid tetraesters are preferred. The fatty acid ester of (B) pentaerythritol of the present invention does not contain a multimer.

  As fatty acids, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, Icosanoic acid, docosanoic acid (behenic acid), tetradocosanoic acid, hexadocosanoic acid, octadocosanoic acid (montanic acid), octadocosanoic acid, etc. are preferred, octadecanoic acid, docosanoic acid, octadocosanoic acid and the like are more preferred, and octadecanoic acid (stearic acid) is particularly preferred preferable.

  (B) The compounding quantity of the fatty acid ester of pentaerythritol is 0.1-0.5 weight part with respect to 100 weight part of liquid crystalline polyester, More preferably, it is 0.3-0.5. (B) If the amount of the fatty acid ester of pentaerythritol is too large, problems such as mold contamination and blistering of the molded product are caused, and if it is too small, the release effect cannot be obtained sufficiently. A blending amount in a preferable range of the present application is preferable because it is possible to achieve both weighing and mold release, which are the effects of the present application.

  As the filler (C) of the present invention, fillers such as fibers, plates, powders, and granules can be used. Specifically, for example, glass fibers, PAN and pitch 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, gypsum fibers, ceramic fibers , 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, etc. Examples include powdered, granular or plate-like fillers such as wood, mica, talc, kaolin, silica, glass beads, glass flakes, clay, molybdenum disulfide, wollastonite, titanium oxide, zinc oxide, calcium polyphosphate and graphite. . The above-mentioned filler used in the present invention can be used by treating the surface thereof with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.) or other surface treatment agents. .

  Among these fillers, glass fiber is particularly preferably used from the viewpoint of balance between availability and mechanical strength. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing resin, and can be selected from, for example, long fiber type or short fiber type chopped strands and milled fibers. Two or more of these can be used in combination. As the glass fiber used in the present invention, a weakly alkaline glass fiber is excellent in terms of mechanical strength and can be preferably used. In particular, glass fibers having a silicon oxide content of 50 to 80% by weight are preferably used, and more preferably 65 to 77% by weight. The glass fiber is preferably treated with an epoxy-based, urethane-based, acrylic-based coating or sizing agent, and epoxy-based is particularly preferable. Further, it is preferably treated with a silane-based or titanate-based coupling agent or other surface treatment agent, and an epoxysilane or aminosilane-based coupling agent is particularly preferable.

  The glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

(C) The compounding quantity of a filler is 30-100 weight part normally with respect to 100 weight part of liquid crystalline polyester , Preferably it is 40-60 weight part.

  (C) If the amount of the filler is too large, there will be many interfaces between the resin and the filler in the resin composition, and the molded product will tend to bulge out. The mold effect cannot be obtained sufficiently. By making a filler into the scope of the present invention, it is preferable that both weighing and mold release, which are the effects of the present invention, are obtained.

  The fatty acid metal salt (D) of the present invention is a metal salt of a fatty acid such as calcium, lithium, sodium, magnesium, potassium, and aluminum. Examples of the fatty acid include butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid. , Nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid, docosanoic acid (behenic acid), tetradocosanoic acid, hexadocosanoic acid, octadocosanoic acid (Montanic acid), octadocosanoic acid and the like are preferable, octadecanoic acid, docosanoic acid, octadocosanoic acid and the like are more preferable, and octadecanoic acid (stearic acid) is particularly preferable.

  (D) The amount of fatty acid metal salt is 100 parts by weight of liquid crystalline polyester (A), 0.1 to 0.5 parts by weight of fatty acid ester of pentaerythritol (B), and 30 to 100 parts by weight of filler (C). It is 0.01-0.05 weight part with respect to a liquid crystalline resin composition, Preferably it is 0.01-0.03 weight part, More preferably, it is 0.01-0.02 weight part. (D) When the blending amount of the fatty acid metal salt is too small, the measurement effect cannot be obtained, and when it is too large, problems such as blistering of the molded product are caused. (D) When the amount of the fatty acid metal salt is within the range of the present invention, the effects of measurement and mold release are preferably obtained in a balanced manner.

  The thermoplastic resin composition of the present invention includes an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and substituted products thereof), an ultraviolet absorber (for example, resorcinol, salicylate), phosphorous acid Colorants including salts, anti-coloring agents such as hypophosphite, lubricants and mold release agents (such as montanic acid and its metal salts, its esters, their half esters, stearyl alcohol, stearamide and polyethylene wax), dyes and pigments Carbon black, crystal nucleating agent, plasticizer, flame retardant (bromine flame retardant, phosphorus flame retardant, red phosphorus, silicone flame retardant, etc.), flame retardant aid, antistatic agent, etc. The conventional additive and a polymer other than the thermoplastic resin can be blended to further impart predetermined characteristics.

  Although it does not specifically limit as a manufacturing method of the composition of this invention, (A) 100 weight part of liquid crystalline polyester and (B) 0.1-0.5 weight part of fatty acid ester of pentaerythritol, (C ) To the liquid crystalline resin composition obtained by melt-kneading the liquid crystalline resin composition comprising 30 to 100 parts by weight of the filler, (D) 0.01 to 0.05 part by weight of a fatty acid metal salt is further dry blended. It is preferable to manufacture.

A known method can be used for melt kneading. For example, using a Banbury mixer, rubber roll machine, kneader, single-screw or twin-screw extruder, etc., the liquid crystalline polyester can be melt kneaded at a liquid crystal starting temperature of −50 ° C. to a melting point + 50 ° C. to obtain a liquid crystalline resin composition. . Among these, a twin screw extruder is preferable.

  Here, the liquid crystal start temperature is a temperature at which flow starts under the condition of a shear rate of 1000 (1 / second). For example, the shear rate is 1,000 (1 / second) by a shear stress heating device (CSS-450), It is determined by measuring the temperature at a heating rate of 5.0 ° C./min at an objective lens of 60 times and measuring the temperature at which the entire field of view starts to flow.

  As the kneading method, 1) batch kneading method with liquid crystalline polyester, pentaerythritol fatty acid ester, filler, and other additives, 2) first liquid crystalline polyester containing high concentration of pentaerythritol fatty acid ester in liquid crystalline polyester A method of preparing a composition (master pellet) and then adding a liquid crystalline polyester, a filler and other additives to a prescribed concentration (master pellet method), 3) liquid crystalline polyester and other additives Any method may be used such as a partial addition method in which a part is kneaded once and then the remaining fatty acid ester of pentaerythritol, a filler, and other additives are added.

  The liquid crystalline resin composition of the present invention thus obtained is a fatty acid metal salt of a fatty acid that comes out on the surface by weighing and shows a lubricant effect, and a pentaerythritol fatty acid ester that shows a releasing effect more on the surface of the molded product in the mold. Is unevenly distributed inside and on the surface of the composition, so that both the measurement and mold release at the time of precision injection molding are excellent, and the effect is synergistic, so that the total amount of additives can be reduced and the gas is low.

  The liquid crystalline resin composition of the present invention is a molded article or sheet having excellent surface appearance (color tone) and mechanical properties, heat resistance, and flame retardancy by a molding method such as normal injection molding, extrusion molding or press molding. It can be processed into pipes, films, fibers and the like.

  The liquid crystalline resin composition thus obtained includes, for example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, and oscillations. Terminals, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystal display parts, FDD carriages, FDD chassis, HDD parts, Electric and electronic parts such as motor brush holders, parabolic antennas, computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio lasers Audio equipment parts such as discs and compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, home appliances, office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, Copier related parts, cleaning jigs, oilless bearings, stern bearings, underwater bearings and other bearings, motor related parts such as motor parts, lighters, typewriters, microscopes, binoculars, cameras, watches, etc. Optical equipment, precision machinery-related parts: alternator terminal, alternator connector, IC regulator, light meter potentiometer base, various valves such as exhaust gas valves, fuel-related / exhaust / intake system pipes, 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 butt wear sensor, air conditioner Thermostat base, Air conditioner motor insulator, Heating hot air flow control valve, Radiator motor brush holder, Water pump impeller, Turbine vane, Wiper motor related parts, Dust distributor, Starter switch, Starter relay, Transmission wire harness, Window washer nozzle, air conditioner panel switch board, fuel electromagnetic valve Used for automotive and vehicle-related parts such as motors, fuse connectors, horn terminals, electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, etc. be able to. When used as a film, magnetic recording media film, photographic film, capacitor film, electrical insulation film, packaging film, drafting film, ribbon film, and sheet use as automotive interior ceiling, door trim, instrument panel It is useful for pad materials, bumper and side frame cushioning materials, sound absorbing pads such as the back of bonnets, seat materials, pillars, fuel tanks, brake hoses, nozzles for window washer fluid, air conditioner refrigerant tubes and their peripheral components.

  Hereinafter, although an example explains the present invention still in detail, the gist of the present invention is not limited only to the following example.

  In the examples, low gas properties, meterability, releasability, blister generation rate, and molded product corner filling properties were measured by the following methods.

(1) Low gasity 20 mg of an arbitrary part of the molded product was cut out, dried with hot air at 150 ° C. for 3 hours, and then kept under nitrogen at a temperature of melting point of liquid crystalline polyester + 10 ° C. for 60 minutes using a thermogravimetric analyzer (TGA). The weight loss rate was measured.

(2) Meterability After the hot air drying, the average value and the maximum value of the metering time when it was subjected to a FANUC α30C injection molding machine (FANUC screw diameter 28 mm) and weighed 8 mm at a screw rotation speed of 150 rpm and a back pressure of 1.5 MPa, The minimum value was evaluated with 500 shots.

(3) Releasability After drying with the above hot air, it was supplied to a FANUC α30C injection molding machine, the injection pressure was set to 100 MPa, the speed was set to the minimum filling speed +10 mm / s, and the box connector mold with 0.2 mm pitch and 36 cores (one point Injection time 0.1 seconds, pressure holding time 1.2 seconds, cooling time 1 second, mold opening to ejection 2 seconds, ejection, air eject, mold closure 1000 shot molding was performed with a cycle time of 8.2 seconds of 4 seconds until the number of mold release defects (mold remaining, deformation, peeling) was evaluated.

(4) Swelling occurrence rate The presence or absence of blistering after molding and after a reflow test at a surface maximum temperature of 265 ° C. was evaluated for 500 of the wall portions of the connector molded in (3).

(5) Molded part corner fillability The number of unfilled occurrences regarding the fillability of the wall corner on the gate-facing side is the same. Evaluated. The corner portion is a portion where unfilling is likely to occur due to variations in filling amount or gasification of the release agent.

(A) Production of liquid crystalline polyester (Reference Example 1)
In a 5 L reaction vessel equipped with a stirring blade and a distilling tube, 870 g (6.300 mol) of p-hydroxybenzoic acid, 327 g of 4,4′-dihydroxybiphenyl (1.890 mol), 89 g of hydroquinone (0.810 mol) , 292 g (1.755 mol) of terephthalic acid, 157 g (0.945 mol) of isophthalic acid and 1367 g of acetic anhydride (1.03 equivalent of the total of phenolic hydroxyl groups) were added at 145 ° C. with stirring in a nitrogen gas atmosphere. After reacting for 4 hours, the temperature was raised to 320 ° C. over 4 hours. Thereafter, the polymerization temperature was maintained at 320 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction was continued for 90 minutes, and the polycondensation was completed when the torque reached 12 kg · cm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer was discharged to a strand-like material via a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  In this liquid crystalline polyester (A-1), the p-oxybenzoate unit was 70 mol% based on the total of the p-oxybenzoate unit, the 4,4′-dioxybiphenyl unit and the 1,4-dioxybenzene unit. , 4′-dioxybiphenyl units are 70 mol% based on the total of 4,4′-dioxybiphenyl units and 1,4-dioxybenzene units, and terephthalate units are based on the total of terephthalate units and isophthalate units. It consists of 65 mol%, Tm (melting point of liquid crystalline polyester) is 314 ° C., liquid crystal starting temperature is 295 ° C., number average molecular weight is 12,000, and Koka type flow tester (orifice 0.5φ × 10 mm) is used. The melt viscosity measured at a temperature of 324 ° C. and a shear rate of 1000 / s was 20 Pa · s.

  The melting point (Tm) is determined by differential calorimetry. After observing the endothermic peak temperature (Tm1) observed when the polymer is measured at room temperature to 20 ° C./minute, the temperature is maintained at Tm1 + 20 ° C. for 5 minutes. Then, after cooling to room temperature under a temperature drop condition of 20 ° C./minute, the endothermic peak temperature (Tm 2) observed when measured again under a temperature rise condition of 20 ° C./minute was used.

  The liquid crystal starting temperature was measured with a shear stress heating device (CSS-450) at a shear rate of 1,000 (1 / second), a heating rate of 5.0 ° C./min, and an objective lens of 60 times. The starting temperature was taken as the measurement.

  The molecular weight was measured by GPC-LS (gel permeation chromatography-light scattering) method using pentafluorophenol which is a solvent in which liquid crystalline polyester is soluble, and the number average molecular weight was determined.

(Reference Example 2)
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 994 g (7.20 mol) of p-hydroxybenzoic acid, 338.7 g (1.80 mol) of 6-hydroxy-2-naphthoic acid, and 965 g of acetic anhydride (1.05 equivalents of total phenolic hydroxyl groups) was added and reacted at 145 ° C. for 2 hours with stirring under a nitrogen gas atmosphere, and then heated to 330 ° C. over 4 hours. Thereafter, the polymerization temperature was maintained at 330 ° C., nitrogen was pressurized to 0.1 MPa, and the mixture was heated and stirred for 20 minutes. Thereafter, the pressure was released, the pressure was reduced to 133 Pa in 1.0 hour, and the reaction was continued for another 120 minutes. When the torque reached 12 kg · cm, the polycondensation was completed. Next, the inside of the reaction vessel was pressurized to 0.1 MPa, the polymer was discharged to a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  This liquid crystalline polyester (A-2) has 80 mol% of p-oxybenzoate units and 20 mol% of 6-oxy-2-naphthalate units, Tm (melting point of liquid crystalline polyester) is 320 ° C., liquid crystal starting temperature. It had a number average molecular weight of 11,100 at 298 ° C., a melt viscosity of 20 Pa · s measured using a Koka flow tester (orifice 0.5φ × 10 mm) at a temperature of 330 ° C. and a shear rate of 1000 / s. .

(Reference Example 3)
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 994 parts by weight of p-hydroxybenzoic acid (7.20 mol), 126 parts by weight of 4,4′-dihydroxybiphenyl (0.67 mol), 112 weights of terephthalic acid Parts (0.67 mol), 216 parts by weight (1.12 mol) of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 960 parts by weight of acetic anhydride (1.10 equivalents of total phenolic hydroxyl groups) The mixture was charged and reacted at 145 ° C. for 2 hours with stirring in a nitrogen gas atmosphere, and then heated to 325 ° C. in 4 hours. Thereafter, the polymerization temperature was maintained at 325 ° C., nitrogen was pressurized to 0.1 MPa, and the mixture was heated and stirred for 20 minutes. Thereafter, the pressure was released, the pressure was reduced to 133 Pa in 1.0 hour, and the reaction was continued for another 120 minutes. When the torque reached 12 kg · cm, the polycondensation was completed. Next, the inside of the reaction vessel was pressurized to 0.1 MPa, the polymer was discharged to a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  This liquid crystalline polyester (A-3) has a p-oxybenzoate unit of 74.4 mol%, a 4,4'-dioxybiphenyl unit of 7 mol%, a terephthalate unit of 7 mol% and an ethylenedioxy unit of 11. 6 mol%, Tm (melting point of liquid crystalline polyester) is 314 ° C., liquid crystal starting temperature is 292 ° C., number average molecular weight is 11,100, and Koka type flow tester (orifice 0.5φ × 10 mm) is used. The melt viscosity measured at a temperature of 325 ° C. and a shear rate of 1000 / s was 12 Pa · s.

  The raw materials used in the examples are described below.

(B) Fatty acid ester of pentaerythritol B-1 Pentaerythritol tetrastearate (LOXILVPG861 manufactured by Cognis Japan)
B-2 Pentaerythritol monostearate (EXOPARAL PE-MS manufactured by Kao)
B-3 Pentaerythritol tetrapalmitate (EXOPARAL PE-TP manufactured by Kao)
B-4 Pentaerythritol compound (molecular weight 50000) (Riken Vitamin Riquester EW250).

(C) Filler C-1 E Glass Chopped Strand (ECS-03T747GH) manufactured by Nippon Electric Glass.
C-2 Mica Yamaguchi Mica (NJ-030)
C-3 Talc (NK64) manufactured by Fuji Talc.

(D) Fatty acid metal salt D-1 Lithium stearate (Li-St manufactured by Nitto Kasei Kogyo)
D-2 Calcium stearate (Ca-St manufactured by Nitto Kasei Kogyo)
D-3 Calcium behenate (Cs-7 manufactured by Nitto Kasei Kogyo)
D-4 Lithium montanate (Ls-8 manufactured by Nitto Kasei Kogyo).

(E) Other additives E-1 Clariant Lycowax E (Montannic acid glycol ester)
E-2 Riken Maru SL-900 (stearyl stearate) manufactured by Riken Vitamin.

Examples 1 11 Comparative Example 1-15
A side feeder is installed in C3 part of cylinder C1 (former feeder side heater) to C6 (die side heater) in TEM35B type twin screw extruder (meshing type same direction) manufactured by Toshiba Machine, and a vacuum vent is provided in C5 part. installed.

  Using a screw arrangement in which kneading blocks were incorporated in C2 part and C4 part, 100 parts by weight of the liquid crystalline polyester (A-1 to A-3) obtained in the reference example was introduced from the hopper, and the blending amounts shown in Table 1 were used. Pentaerythritol fatty acid ester (B-1 to 4) and other additives (E-1 and 2), fillers (C-1 to 3) and optionally fatty acid metal salts (D-1 to D-4) Throw in from the side and adjust the heater setting temperature of the cylinder so that the resin temperature of the resin thermometer attached to C4 and C6 is the melting point of the liquid crystalline polyester, the rotation speed of the original feeder and side feeder, screw rotation The number was adjusted, and the components shown in Table 1 were melt-kneaded with the compositions shown in Table 1 to obtain pellets.

  In some cases, the resulting pellets were dry blended with fatty acid metal salts (D-1 to 4), dried with hot air, and then subjected to the evaluation described above using a FANUC α30C injection molding machine (manufactured by FANUC). The results are shown in Table 1.

  As is clear from Table 1, the liquid crystalline resin composition of the present invention has both the biting property at the time of metering and the releasability at the time of molding by blending the fatty acid ester of pentaerythritol and the metal salt of the fatty acid. In addition, since the total amount of additives can be reduced, the gas is low and blistering is difficult to occur.

  Moreover, it turns out that meterability and mold release property are improved more notably by presence of a filler. Further, as a secondary effect, it can be seen that the variation in the filling amount is reduced and the amount of gas is small, so that unfilling of the fluid end without the gas vent hardly occurs.

  Such an effect of the present invention is reduced when the fatty acid ester of pentaerythritol is a polymer or a multimer, and is not a metal salt of a fatty acid and cannot be obtained in combination with a fatty acid ester. It is apparent that this is an effect obtained only by the combined use of a specific amount of a fatty acid ester of pentaerythritol and a fatty acid metal salt since it cannot be obtained by using a fatty acid metal salt other than pentaerythritol, for example, other than a fatty acid ester of glycol. It is.

Claims (6)

(A) 100 parts by weight of a liquid crystalline polyester composed of the following structural units (I), (II), (III), (IV) and (V) and (B) fatty acid ester of pentaerythritol 0.1-0. A liquid crystalline resin composition comprising 5 parts by weight and (C) a filler of 30 to 100 parts by weight, and further (D) a fatty acid metal salt of 0.01 to 0.05 parts by weight.

The structural unit (I) is 65 to 80 mol% based on the total of the structural units (I), (II) and (III), and the structural unit (II) is added to the total of the structural units (II) and (III). The liquid crystal property according to claim 1, wherein the liquid crystallinity is 60 to 75 mol%, and the structural unit (IV) is 60 to 92 mol% based on the total of the structural units (IV) and (V) . Resin composition. (B) The liquid crystalline resin composition according to claim 1 or 2, wherein the fatty acid ester of pentaerythritol contains at least pentaerythritol tetrastearate . The liquid crystalline resin composition according to any one of claims 1 to 3, wherein the fatty acid metal salt (D) contains at least lithium stearate . A liquid crystalline resin composition comprising (A) 100 parts by weight of liquid crystalline polyester, (B) 0.1 to 0.5 parts by weight of fatty acid ester of pentaerythritol, and (C) 30 to 100 parts by weight of filler is melt-kneaded. The obtained liquid crystalline resin composition is further dry blended with 0.01 to 0.05 part by weight of (D) a fatty acid metal salt. Production method. A molded product comprising the liquid crystalline resin composition according to claim 1.