JP5098521B2 - Method for producing liquid crystalline resin - Google Patents

Description

  The present invention can completely suppress the formation of a hydroquinone complex during slurry mixing, thereby completely suppressing the sublimation of hydroquinone accompanied by a rapid exotherm during the polymerization temperature rising process, and improving the continuous batch productivity. The present invention relates to a method for polymerizing a liquid crystalline resin.

  Demand for liquid crystalline resins is growing, mainly for small precision molded products for electrical and electronic applications, taking advantage of their excellent heat resistance, fluidity, and electrical properties. In recent years, attention has been paid to its thermal stability and high thermal dimensional accuracy, and studies have been made on use as a support base for heat-generating components, such as a liquid crystal display support base for OA devices and mobile phones, and structural parts for lamps.

  As a raw material for the liquid crystalline resin, p-hydroxybenzoic acid or 6-hydroxy-2-naphthoic acid is a main component, and hydroquinone, 4,4′-dihydroxybiphenyl, 2,6-naphthalenediol, aliphatic as a copolymerization component Diols such as diol, dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and aliphatic dicarboxylic acid, and amino group-containing monomers such as p-aminobenzoic acid and aminophenol are used.

Among these, liquid crystalline polyesters using p-hydroxybenzoic acid and hydroquinone are known (see Patent Documents 1 to 3).
JP 2006-89714 A (Claims) Japanese Patent Laying-Open No. 2005-213418 (Claims) JP 2000-511220 A (Claims)

  According to the descriptions in these patent documents, when the raw material monomer is charged into the system and mixed with acetic anhydride, it is performed at room temperature. However, it is known that the system using hydroquinone has many sublimates. It was. As a result of intensive studies on the cause, among these monomers, hydroquinone, p-hydroxybenzoic acid, and acetic anhydride form a complex (complex) to make the system heterogeneous. As a result, it was revealed that a heterogeneous reaction was caused, and that intense exotherm during the temperature increase of the polymerization caused monomer sublimation.

  The present invention can completely suppress complex formation at the time of slurry mixing, thereby completely suppressing sublimation of hydroquinone monomer due to sudden exotherm during polymerization temperature rising process and improving continuous batch productivity. It is an object of the present invention to provide a method for polymerizing a liquid crystal resin.

  As a result of intensive studies to solve the above problems, the inventors of the present invention separately made hydroquinone and p-hydroxybenzoic acid as a slurry of acetic anhydride. It has been found that a completely homogeneous slurry can be formed.

That is, the present invention
(1) The monomer mixture is reacted with acetic anhydride, acetylated, and further polymerized to produce a liquid crystalline resin, which contains hydroquinone and does not contain p-hydroxybenzoic acid before the acetylation reaction. A monomer acetic anhydride slurry and a monomer containing acetic anhydride containing p-hydroxybenzoic acid and no hydroquinone are prepared separately, and one or both of them are mixed so that the temperature after mixing is 70 ° C. or higher. A method for producing a liquid crystalline resin comprising a step of adjusting the temperature of the slurry and mixing the slurry;
(2) Acetic anhydride slurry containing hydroquinone and not containing p-hydroxybenzoic acid is adjusted to 100 to 130 ° C, and acetic anhydride slurry containing p-hydroxybenzoic acid and not containing hydroquinone is adjusted to 20 to 40 ° C. A method for producing a liquid crystalline resin as described in (1) above, wherein
(3) An acetic anhydride slurry of the monomer containing hydroquinone and not containing p-hydroxybenzoic acid and / or an acetic anhydride slurry of monomer containing p-hydroxybenzoic acid and containing no hydroquinone are further added to 4,4′-dihydroxybiphenyl. , A method for producing a liquid crystalline resin according to the above (1) or (2), which contains any one or more of terephthalic acid and isophthalic acid,
(4) hydroquinone unrealized p - acetic anhydride slurry containing no hydroxybenzoic acid, further, 4,4'-dihydroxybiphenyl, (3) which comprises terephthalic acid and / or isophthalic acid described The present invention relates to a method for producing a liquid crystalline resin.

  According to the method for producing a liquid crystalline resin of the present invention, complex formation that causes sublimation of hydroquinone can be completely suppressed, and continuous batch productivity of the liquid crystalline resin can be improved.

  The method for producing a liquid crystalline resin of the present invention uses at least hydroquinone and p-hydroxybenzoic acid as monomers, adds these and other monomers, acetylates the hydroxyl group of the monomer by reaction with acetic anhydride, and then raises the system. Acetic anhydride slurry of monomer which is produced by deacetic acid polycondensation or dephenol polycondensation depending on conditions under temperature and reduced pressure, and containing hydroquinone and no p-hydroxybenzoic acid before performing acetylation reaction And the acetic anhydride slurry of the monomer containing p-hydroxybenzoic acid and no hydroquinone is prepared separately, and when mixing both, one or both of the slurries are adjusted so that the temperature after mixing is 70 ° C. or higher. And, more preferably, the temperature after mixing is 80. Or more, more preferably the temperature after mixing is 85 ° C. or higher.

A monomer acetic anhydride slurry containing hydroquinone and not containing p-hydroxybenzoic acid and / or a monomer acetic anhydride slurry containing p-hydroxybenzoic acid and containing no hydroquinone may further contain 4,4′-dihydroxybiphenyl, terephthalic acid. , Preferably containing any one or more of isophthalic acid, more preferably an acetic anhydride slurry of a monomer containing hydroquinone and no p-hydroxybenzoic acid and / or a monomer containing p-hydroxybenzoic acid and no hydroquinone The acetic anhydride slurry further contains 4,4′-dihydroxybiphenyl, terephthalic acid, and isophthalic acid.

  Specific combinations include hydroquinone, 4,4′-dihydroxybiphenyl, terephthalic acid, isophthalic acid acetic anhydride slurry and p-hydroxybenzoic acid acetic anhydride slurry, hydroquinone and isophthalic acid acetic anhydride slurry and p. -Hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, a combination of terephthalic acid and acetic anhydride slurry.

  As a preferable method for increasing the temperature after mixing to 70 ° C. or higher, an acetic anhydride slurry containing hydroquinone and not containing p-hydroxybenzoic acid is adjusted to 100 to 130 ° C., and containing hydroquinone containing p-hydroxybenzoic acid. It is preferable to mix an acetic anhydride slurry that is not heated to 20 to 40 ° C.

  Similarly, the acetic anhydride slurry containing p-hydroxybenzoic acid and not containing hydroquinone was adjusted to 100 to 130 ° C, and the acetic anhydride slurry containing hydroquinone and not containing p-hydroxybenzoic acid was adjusted to 20 to 40 ° C. The system after mixing can also be adjusted to 70 ° C. or higher by mixing or adjusting the temperature to 70 ° C. or higher in advance, but the acetic anhydride slurry containing p-hydroxybenzoic acid is 70 ° C. or higher. When the temperature is raised to 1, the p-hydroxybenzoic acid is acetylated and further oligomerized, which is not preferable because the system is precipitated.

  By carrying out slurrying under the above conditions, the monomer mixture containing hydroquinone and p-hydroxybenzoic acid and acetic anhydride form a homogeneous slurry without completely forming a complex. At a temperature lower than the above temperature range, hydroquinone, p-hydroxybenzoic acid and acetic anhydride form a complex, and the slurry is consolidated or thickened. A temperature higher than the above temperature range is not preferable because the transpiration amount of acetic anhydride increases.

Oyo acetic anhydride slurry monomers without containing hydroquinone p- hydroxybenzoic acid beauty p - after mixing the acetic anhydride slurry monomers without hydroquinone as a hydroxy acid is rapidly raised, 120 to 150 ° C. It is preferred to initiate acetylation at The time until the internal temperature reaches 120 ° C. or higher after mixing is preferably within 30 minutes, more preferably within 20 minutes.

  Examples of monomers used in addition to hydroquinone and p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl, terephthalic acid, and isophthalic acid include aromatic hydroxycarboxylic acids such as 6-hydroxy-2-naphthoic acid, Examples of the aromatic dicarboxylic acid include 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 1,2-bis ( 2-chlorophenoxy) ethane-4,4′-dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid and the like. Examples of the aromatic diol include resorcinol, t-butylhydroquinone, phenylhydroquinone, chlorohydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 3,4'-dihydroxybiphenyl, 2,2-bis (4- Hydroxyphenyl) propane, 4,4′-dihydroxydiphenyl ether, and the like. Examples of the monomer having an amino group include p-aminobenzoic acid and p-aminophenol.

  Preferable combinations include p-hydroxybenzoic acid, hydroquinone, 4,4'-dihydroxybiphenyl, terephthalic acid and / or isophthalic acid.

  The liquid crystalline resin of the present invention is a resin that forms an anisotropic molten phase, and examples thereof include liquid crystalline resins having an ester bond such as liquid crystalline polyester and liquid crystalline polyester amide.

  Specific examples of the liquid crystalline polyester include a structural unit generated from p-hydroxybenzoic acid, a structural unit generated from 4,4′-dihydroxybiphenyl, a structural unit generated from hydroquinone, and generated from terephthalic acid and / or isophthalic acid. Liquid crystalline polyester composed of structural units, structural units generated from p-hydroxybenzoic acid, structural units generated from ethylene glycol, structural units generated from 4,4′-dihydroxybiphenyl, structural units generated from hydroquinone, terephthalic acid, and Liquid crystalline polyester comprising structural units produced from isophthalic acid, structural units produced from p-hydroxybenzoic acid, structural units produced from hydroquinone, structural units produced from 4,4′-dihydroxybiphenyl, 2,6- Naphtalica Structural unit derived from Bonn acid, such as liquid crystalline polyester consisting of structural units produced from terephthalic acid.

  Preferable examples of the liquid crystalline polyester forming the anisotropic molten phase include liquid crystalline polyesters comprising 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.

  Hereinafter, this liquid crystalline polyester will be described as an example.

  The amount of copolymerization of the structural units (I), (II), (III), (IV) and (V) is arbitrary. However, in order to make it the range prescribed | regulated by this invention and to exhibit the characteristic, it is preferable that it is the following copolymerization amount.

  That is, the structural unit (I) is preferably 40 to 85 mol%, more preferably 65 to 80 mol%, still more preferably based on the total of the structural units (I), (II) and (III). Is 68-75 mol%. Further, the structural unit (II) is preferably 60 to 90 mol%, more preferably 60 to 75 mol%, and still more preferably 65 to 73 mol, based on the total of the structural units (II) and (III). Mol%. The structural unit (IV) is preferably 40 to 95 mol%, more preferably 60 to 92 mol%, still more preferably 72 to 92 mol% based on the total of the structural units (IV) and (V). It is.

  The sum of structural units (II) and (III) and (IV) and (V) are substantially equimolar. Here, “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.

  The liquid crystal polyester preferably used includes aromatic dicarboxylic acids such as 3,3′-diphenyldicarboxylic acid and 2,2′-diphenyldicarboxylic acid, adipine, in addition to the components constituting the structural units (I) to (V). Acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acid such as dodecanedioic acid, alicyclic dicarboxylic acid such as hexahydroterephthalic acid, chlorohydroquinone, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylsulfone, Aromatic diols such as 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxybenzophenone, 3,4′-dihydroxybiphenyl, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol 1,4-cyclohexanedi Lumpur, aliphatic, such as 1,4-cyclohexane dimethanol, an alicyclic diol and m- hydroxybenzoic acid, can be allowed to further copolymerization in a range that does not impair the liquid crystalline and characteristics.

  The melt viscosity of the liquid crystalline resin in the present invention is preferably 10 to 500 Pa · s, more preferably 12 to 200 Pa · s. This melt viscosity is a value measured by a Koka flow tester under the condition of melting point (Tm) + 10 ° C. and shear rate of 1000 (1 / second).

  The melting point of the liquid crystalline resin in the present invention is not particularly limited, but it is preferable to combine the copolymer components so as to be 280 ° C. or higher for use in high heat resistance applications, and more preferably to be 300 ° C. or higher. Preferably, the combination is more preferably 310 ° C or higher, and most preferably the combination is 325 ° C or higher. As the upper limit, the decomposition temperature of the liquid crystalline resin is preferably −10 ° C. or lower, and since the decomposition temperature of the liquid crystalline polyester as described above is around 370 ° C., it is preferable to combine them so as to be 360 ° C. or lower.

  The basic production method of the liquid crystalline resin of the present invention is not particularly limited, but after passing through the slurrying step of the present invention, the phenolic hydroxyl group in the liquid crystalline resin raw material, such as aromatic hydroxycarboxylic acid or aromatic Acetylation of the phenolic hydroxyl group of the aromatic diol with acetic anhydride, followed by polycondensation with the remaining liquid crystalline resin raw material (aromatic dicarboxylic acid or other monomer) (preferably at a temperature at which the liquid crystalline resin melts under reduced pressure) A production method including a step of reacting and performing polycondensation) is preferable.

  The amount of acetic anhydride used is preferably 1.00 to 1.20 molar equivalents, more preferably 1.03 to 1.16 molar equivalents of the total of phenolic hydroxyl groups in the liquid crystalline resin raw material to be used. The acetylation reaction is performed at a temperature not lower than 125 ° C. and not higher than 150 ° C. until the residual amount of monoacetylated aromatic diol reaches a specific range (hereinafter also referred to as “acetylation step”). Is preferred. As an apparatus for the acetylation reaction, for example, a reaction vessel equipped with a return tube and a rectifying column can be used. The reaction time of acetylation is roughly 1 to 5 hours, but the time until the residual amount of monoacetylated aromatic diol reaches a specific range depends on the liquid crystalline resin raw material used and the reaction temperature. Different. Preferably, the time is 1.0 to 2.5 hours, and the shorter the reaction temperature, the shorter the time, and the shorter the molar ratio of acetic anhydride to the phenolic hydroxyl terminal, the shorter the time.

  For example, in the production of the liquid crystalline polyester, the following production method is preferred. The following is an example of the synthesis of a liquid crystalline polyester composed of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid, but the copolymer composition is limited to these. However, each can be replaced with other hydroxycarboxylic acid, aromatic diol or aromatic dicarboxylic acid, and can be produced according to the following method.

  For example, in a reaction vessel equipped with a stirring blade, a rectifying column, and a distillation pipe and having a discharge port at the bottom, a monomer mixture consisting of a predetermined amount of hydroquinone, 4,4′-dihydroxybiphenyl, terephthalic acid, and isophthalic acid Acetic anhydride (1.00 to 1.20 molar equivalents relative to the hydroxyl group in the liquid crystalline resin raw material) is stirred and mixed at 20 to 40 ° C. for 0.1 to 3 hours to make a slurry, which is 100 ° C. or higher and lower than 130 ° C. Adjust the temperature. In a separate container, p-hydroxybenzoic acid and acetic anhydride are stirred and mixed at 20 to 40 ° C. for 0.1 to 3 hours to form a slurry, and mixed with the acetic anhydride slurry containing hydroquinone adjusted to 100 ° C. or more and less than 130 ° C. Then, the temperature was raised to 140 ° C. in 20 minutes, heated with stirring in a nitrogen gas atmosphere, and reacted at 140 to 150 ° C. for 1.0 to 2.5 hours while refluxing to acetylate the hydroxyl group. Thereafter, the acetylation process was completed by switching to a distillation tube, and the temperature was raised in 2.5 to 6.5 hours from the melting point of the liquid crystalline resin to 5 to 40 ° C. while distilling acetic acid, and 0.2 to 1 After heating and stirring for about 5 hours, the pressure is then reduced to 665 Pa or less for 0.5 to 2 hours, and polycondensation is performed for about 0.1 to 3 hours to complete the reaction.

  Note that the same reaction vessel may be used for the slurrying step and the acetylation reaction step, but the slurrying and acetylation may be performed in different reaction vessels, and acetylation and polycondensation are the same. Although it may be carried out continuously in a reaction vessel, acetylation and polycondensation may be carried out in different reaction vessels. Preferably, an acetic anhydride slurry that contains hydroquinone and does not contain p-hydroxybenzoic acid is prepared in a container that performs a slurry process, moves to a container that performs acetylation, and then contains hydroquinone that contains p-hydroxybenzoic acid in a container that performs a slurry process. This is a case where the acetic anhydride slurry not containing water is prepared again and transferred to a container for acetylation, and more preferably, the container for preparing these two types of slurry is different.

  As conditions for polycondensation, the degree of vacuum is more preferably 133 Pa or less, and the final polymerization temperature is preferably about melting point + 20 ° C., and preferably 360 ° C. or less. The stirring speed is preferably 50 rpm or less.

  The polymerization time from when the degree of vacuum becomes 665 Pa or less until the predetermined torque is detected and the polymerization is completed is more preferably 0.5 to 1 hour.

  In order to take out the obtained polymer from the reaction vessel after completion of the polymerization, the inside of the reaction vessel is pressurized to, for example, about 0.02 to 0.5 MPa at a temperature at which the polymer melts, and is discharged from a discharge port provided at the lower portion of the reaction vessel. It is discharged in the form of a strand, and the strand is cooled in cooling water and cut into a pellet to obtain a resin pellet. The melt polymerization method is an advantageous method for producing a uniform polymer, and is preferable because an excellent polymer with less gas generation can be obtained.

  When the liquid crystalline resin 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 resin of the present invention is pulverized with a pulverizer and heated in a nitrogen stream or under reduced pressure for 1 to 50 hours in the range of the melting point of the liquid crystalline resin from -5 ° C to the melting point -50 ° C. And a method of polycondensation to a desired degree of polymerization to complete the reaction. Solid phase polymerization is an advantageous method for producing polymers with a high degree of polymerization.

  The polycondensation reaction of the liquid crystalline resin proceeds even without a catalyst, but metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and magnesium metal can also be used.

  The liquid crystalline resin of the present invention preferably has a number average molecular weight of 3,000 to 25,000, more preferably 5,000 to 20,000, and more preferably 8,000 to 18,000. .

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

  In the present invention, a filler can be further blended in order to impart mechanical strength and other characteristics of the liquid crystalline resin. The filler is not particularly limited, but fillers such as a fiber, a plate, a powder, and a granule 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, basalt fiber, titanium oxide whisker, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, etc. Fibrous, whisker-like filler, mica, talc, kaolin, silica, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, titanium oxide, zinc oxide, calcium polyphosphate and graphite Which powder include particulate or plate-like filler. 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. 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.

  The blending amount of the filler is usually 30 to 200 parts by weight, preferably 40 to 150 parts by weight with respect to 100 parts by weight of the liquid crystalline polyester.

  Further, the liquid crystalline resin of the present invention includes antioxidants and heat stabilizers (for example, hindered phenols, hydroquinones, phosphites and their substitutes), ultraviolet absorbers (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.

  The method of blending these additives is preferably by melt kneading, and known methods can be used for melt kneading. For example, using a Banbury mixer, rubber roll machine, kneader, single-screw or twin-screw extruder, etc., it can be melt kneaded at a temperature of 180 to 350 ° C., more preferably 250 to 320 ° C. to obtain a liquid crystalline resin composition. . In that case, 1) a batch kneading method with a liquid crystalline resin, optional fillers and other additives, 2) a liquid crystalline resin composition containing a high concentration of other additives in a liquid crystalline polyester ( Master pellet), and then adding other thermoplastic resins, fillers and other additives to the specified concentration (master pellet method), 3) one of liquid crystalline resin and other additives Any method may be used, such as a split addition method in which the part is kneaded once and then the remaining filler and other additives are added.

  The liquid crystalline resin of the present invention and the liquid crystalline resin composition containing the same are excellent in surface appearance (color tone) and mechanical properties, heat resistance, flame retardancy by a molding method such as normal injection molding, extrusion molding, and press molding. It can be processed into a three-dimensional molded product, a sheet, a container, a pipe, a film, etc. In particular, it is suitable for electrical and electronic parts obtained by injection molding.

  The liquid crystalline resin thus obtained and the liquid crystalline resin composition containing the same are, for example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, Variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display component, FDD carriage , FDD chassis, HDD parts, motor brush holder, parabolic antenna, electric and electronic parts represented by computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustics Products, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, home appliances, office computer parts, telephone 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 , Optical equipment such as watches, precision machinery related parts; alternator terminal, alternator connector, IC regulator, light meter potentiometer base, various valves such as exhaust gas valve, 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, separator, 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, Wire harness for transmission, window washer nozzle, air conditioner Panel switch board, coil for fuel related electromagnetic valve, connector for fuse, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, etc. It can be used for automobile and vehicle related parts. 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, each characteristic was evaluated by the following measuring method.

  Increase in liquid level: The liquid level trace remaining on the stirring blade shaft was observed, and the liquid level was calculated with the height corresponding to the theoretical liquid level at 280 to 310 ° C. where foaming occurred as 100%.

  Melt viscosity of liquid crystalline resin: measured using a Koka flow tester at a temperature of 330 ° C. and a shear rate of 1000 / s.

  Melting point (Tm): In differential calorimetry, after observing the endothermic peak temperature (Tm1) observed when the polymer was measured at room temperature to 20 ° C./min, after maintaining for 5 minutes at a temperature of Tm1 + 20 ° C. The temperature was once cooled to room temperature under a temperature drop condition of 20 ° C./min, and then the endothermic peak temperature (Tm 2) observed when measured again under a temperature rise condition of 20 ° C./min.

Example 1
An upper vessel (hereinafter referred to as vessel (1)) of two 5 L reactors connected via a transition tube having a stirring blade and a distillation tube and having valves on the upper and lower sides, 352 g of 4,4′-dihydroxybiphenyl, 89 g of hydroquinone 292 g of terephthalic acid, 157 g of isophthalic acid, and 596 g of acetic anhydride were charged and stirred for 60 minutes in a nitrogen gas atmosphere to homogenize the slurry.

  The slurry was transferred from the container (1) to the lower container (hereinafter referred to as container (2)), the container (1) was washed with 98 g of acetic anhydride, and the cleaning liquid was also transferred to the container (2). The container (2) was awaited by raising the temperature of the contents to 120 ° C. while stirring.

  The emptied container (1) was charged with 870 g of p-hydroxybenzoic acid and 583 g of acetic anhydride, and stirred for 60 minutes in a nitrogen gas atmosphere to homogenize the slurry.

  At a temperature of 120 ° C. of the contents of the container (2) and a slurry temperature of 30 ° C. of the container (1), the slurry of the container (1) was transferred to the container (2) while stirring. The container (1) was washed with 98 g of acetic anhydride, and the washing liquid was also transferred to the container (2). Acetic anhydride is charged in an amount of 1374 g (1.15 equivalents of total phenolic hydroxyl groups) including those used for washing. The temperature of the contents of the container (2) after mixing was 85 ° C. The container (2) was heated to 145 ° C. in 30 minutes and acetylated at 145 ° C. for 2.5 hours. Thereafter, the temperature was raised to 330 ° C. in 4 hours, and the pressure was reduced to 133 Pa in 1.0 hour. The polycondensation was completed when the torque reached 20 kgcm. The time required to reach the predetermined torque after reaching 133 Pa was 5 minutes. 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.

  The yield was 99.2% of the theoretical yield. When the continuous batch was continuously performed under the same conditions, the yield of the second batch relative to the theoretical yield obtained by adding the first can residue to the charged quantity is It was 98.8%.

  After the discharge, the inside of the polymerization can was observed. As a result, no increase in the liquid level resulting from complex formation was observed, and the liquid level was 100.5%. Further, the sublimate adhering to the gas phase part was recovered by eluting with acetone, and when acetone was distilled off and the amount of sublimate was measured, the amount of sublimate was 0.05 g.

The melting point of this liquid crystalline resin is 310 ° C., and ΔS (melting entropy) is 0.3 × 10 ⁻³ J / g · K, measured using a Koka flow tester at a temperature of 330 ° C. and a shear rate of 1000 / s. The melt viscosity was 23 Pa · s.

Example 2
In Example 1, “870 g of p-hydroxybenzoic acid and 583 g of acetic anhydride were charged into an empty container (1) and stirred for 60 minutes under a nitrogen gas atmosphere to homogenize the slurry. 870 g of p-hydroxybenzoic acid and acetic anhydride were added to a 5 L reaction vessel (hereinafter referred to as vessel (3)) having a stirring blade separate from 1) and connected to vessel (2) via a transition pipe having upper and lower valves. 583 g was charged, and the slurry was homogenized by stirring for 60 minutes under a nitrogen gas atmosphere. The polycondensation was completed in the same manner as in Example 1 and pelletized in the same manner as in Example 1.

  The yield was 99.7% of the theoretical yield. When the continuous batch was continuously performed under the same conditions, the yield of the second batch relative to the theoretical yield obtained by adding the remaining can of the first batch to the charged quantity was It was 99.2%.

  After the discharge, the inside of the polymerization can was observed. As a result, no increase in the liquid level resulting from complex formation was observed, and the liquid level was 100.2%. Further, the sublimate adhering to the gas phase part was recovered by eluting with acetone, and when acetone was distilled off and the amount of sublimate was measured, the amount of sublimate was 0.04 g.

This liquid crystalline resin has a melting point of 311 ° C. and ΔS (melting entropy) of 0.3 × 10 ⁻³ J / g · K, and measured using a Koka flow tester at a temperature of 330 ° C. and a shear rate of 1000 / s. The melt viscosity was 23 Pa · s.

Example 3
An upper vessel (hereinafter referred to as vessel (1)) of two 5 L reactors connected via a transition tube having a stirring blade and a distillation tube and having valves on the upper and lower sides, 352 g of 4,4′-dihydroxybiphenyl, 89 g of hydroquinone 292 g of terephthalic acid, 157 g of isophthalic acid, and 596 g of acetic anhydride were charged and stirred for 60 minutes in a nitrogen gas atmosphere to homogenize the slurry.

  The slurry was transferred from the container (1) to the lower container (hereinafter referred to as container (2)), the container (1) was washed with 98 g of acetic anhydride, and the cleaning liquid was also transferred to the container (2). The container (2) was awaited by raising the temperature of the contents to 100 ° C. while stirring.

  The emptied container (1) was charged with 870 g of p-hydroxybenzoic acid and 583 g of acetic anhydride, and stirred for 60 minutes in a nitrogen gas atmosphere to homogenize the slurry.

  At a temperature of the content of the container (2) of 100 ° C. and a slurry temperature of the container (1) of 30 ° C., the slurry of the container (1) was transferred to the container (2) while stirring. The container (1) was washed with 98 g of acetic anhydride, and the washing liquid was also transferred to the container (2). Acetic anhydride is charged in an amount of 1374 g (1.15 equivalents of total phenolic hydroxyl groups) including those used for washing. The temperature of the contents of the container (2) after mixing was 72 ° C. The container (2) was heated to 145 ° C. in 30 minutes and acetylated at 145 ° C. for 2.5 hours. Thereafter, the temperature was raised to 330 ° C. in 4 hours, and the pressure was reduced to 133 Pa in 1.0 hour. The polycondensation was completed when the torque reached 20 kgcm. The time required to reach the predetermined torque after reaching 133 Pa was 3 minutes. 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.

  The yield was 99.1% of the theoretical yield. When the continuous batch was continuously performed under the same conditions, the yield of the second batch relative to the theoretical yield obtained by adding the can of the first batch to the charged quantity is It was 98.7%.

  When the inside of the superposition | polymerization can was observed after discharge, the raise of the liquid level derived from complex production | generation was not seen, but the liquid level was 101.1%. Further, the sublimate adhering to the gas phase part was recovered by eluting with acetone, and the amount of sublimate was measured by distilling off acetone and the amount of sublimate was 0.10 g.

The melting point of this liquid crystalline resin is 310 ° C., and ΔS (melting entropy) is 0.3 × 10 ⁻³ J / g · K, measured using a Koka flow tester at a temperature of 330 ° C. and a shear rate of 1000 / s. The melt viscosity was 23 Pa · s.

Example 4
870 g of p-hydroxybenzoic acid and 583 g of acetic anhydride were added to the upper container (hereinafter referred to as “container (1)”) of two 5 L reactors connected via a transition pipe having a stirring blade and a distillation pipe and having valves at the top and bottom. The slurry was homogenized by stirring for 60 minutes under a nitrogen gas atmosphere.

  The slurry was transferred from the container (1) to the lower container (hereinafter referred to as container (2)), the container (1) was washed with 98 g of acetic anhydride, and the cleaning liquid was also transferred to the container (2). The container (2) was awaited by raising the temperature of the contents to 100 ° C. while stirring.

  An empty container (1) was charged with 352 g of 4,4′-dihydroxybiphenyl, 89 g of hydroquinone, 292 g of terephthalic acid, 157 g of isophthalic acid, and 596 g of acetic anhydride, and stirred for 60 minutes in a nitrogen gas atmosphere to homogenize the slurry. .

At a temperature of the content of the container (2) of 100 ° C. and a slurry temperature of the container (1) of 30 ° C., the slurry of the container (1) was transferred to the container (2) while stirring. The container (1) was washed with 98 g of acetic anhydride, and the washing liquid was also transferred to the container (2). Acetic anhydride is charged in an amount of 1374 g (1.15 equivalents of total phenolic hydroxyl groups) including those used for washing. The temperature of the contents of the container (2) after mixing was 70 ° C. The container (2) was heated to 145 ° C. in 30 minutes and acetylated at 145 ° C. for 2.5 hours. Then the temperature was raised at 4 hours 330 ° C., 1. The pressure was reduced to 133 Pa in 0 hours. The polycondensation was completed when the torque reached 20 kgcm. The time required to reach the predetermined torque after reaching 133 Pa was 10 minutes. 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.

  The yield was 98.5% of the theoretical yield. When the continuous batch was continuously performed under the same conditions, the yield of the second batch relative to the theoretical yield obtained by adding the first batch of cans to the charged quantity was It was 96.6%.

  After the discharge, the inside of the polymerization can was observed. As a result, no increase in the liquid level resulting from the complex formation was observed, and the liquid level was 100.9%. Further, the sublimate adhering to the gas phase part was eluted and recovered with acetone, and the amount of sublimate was measured by distilling off acetone, and the amount of sublimate was 0.21 g.

The melting point of this liquid crystalline resin is 309 ° C., ΔS (melting entropy) is 0.3 × 10 ⁻³ J / g · K, and measured using a Koka flow tester at a temperature of 330 ° C. and a shear rate of 1000 / s. The melt viscosity was 22 Pa · s.

Example 5
279 g of 4,4′-dihydroxybiphenyl and 55 g of hydroquinone were added to the upper container (hereinafter referred to as “container (1)”) of two 5 L reactors connected via a transition pipe having a stirring blade and a distillation pipe and having valves on the upper and lower sides. 306 g of terephthalic acid, 27 g of isophthalic acid and 446 g of acetic anhydride were charged and stirred for 60 minutes in a nitrogen gas atmosphere to homogenize the slurry.

  The slurry was transferred from the container (1) to the lower container (hereinafter referred to as the container (2)), the container (1) was washed with 110 g of acetic anhydride, and the cleaning liquid was also transferred to the container (2). The container (2) was awaited by raising the temperature of the contents to 120 ° C. while stirring.

  The empty container (1) was charged with 828 g of p-hydroxybenzoic acid and 554 g of acetic anhydride, and stirred for 60 minutes in a nitrogen gas atmosphere to homogenize the slurry.

  At a temperature of 120 ° C. of the contents of the container (2) and a slurry temperature of 30 ° C. of the container (1), the slurry of the container (1) was transferred to the container (2) while stirring. The container (1) was washed with 110 g of acetic anhydride, and the washing liquid was also transferred to the container (2). Acetic anhydride is charged in an amount of 1220 g (1.15 equivalents of total phenolic hydroxyl groups) including those used for washing. The temperature of the contents of the container (2) after mixing was 86 ° C. The container (2) was heated to 145 ° C. in 30 minutes and acetylated at 145 ° C. for 2.5 hours. Thereafter, the temperature was raised to 360 ° C. over 4 hours, and the pressure was reduced to 133 Pa over 1.0 hour. The polycondensation was completed when the torque reached 20 kgcm. The time required to reach the predetermined torque after reaching 133 Pa was 9 minutes. 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. The yield was 99.2% of the theoretical yield. When the continuous batch was continuously performed under the same conditions, the yield of the second batch relative to the theoretical yield obtained by adding the first can residue to the charged quantity is It was 98.9%.

  After the discharge, the inside of the polymerization can was observed. As a result, no increase in the liquid level resulting from complex formation was observed, and the liquid level was 100.5%. Further, the sublimate adhering to the gas phase part was recovered by eluting with acetone, and when acetone was distilled off and the amount of sublimate was measured, the amount of sublimate was 0.34 g.

The melting point of this liquid crystalline resin is 353 ° C., and ΔS (melting entropy) is 1.3 × 10 ⁻³ J / g · K, measured using a Koka flow tester at a temperature of 360 ° C. and a shear rate of 1000 / s. The melt viscosity was 25 Pa · s.

Comparative Example 1
In a 5 L reaction vessel equipped with a stirring blade and a distilling tube, 870 g of p-hydroxybenzoic acid, 327 g of 4,4′-dihydroxybiphenyl, 104 g of hydroquinone, 292 g of terephthalic acid, 156 g of isophthalic acid and 1374 g of acetic anhydride (total of phenolic hydroxyl groups) 1.15 equivalents), and slurrying was performed for 30 minutes with stirring in a nitrogen gas atmosphere at 40 ° C. Thereafter, the temperature was raised to 148 ° C. and reacted for 2.5 hours to complete acetylation, and then the temperature was raised to 330 ° C. in 4 hours. Thereafter, the pressure was reduced to 133 Pa in 1.0 hour. The polycondensation was completed when the torque reached 20 kgcm. The time required to reach the predetermined torque after reaching 133 Pa was 30 minutes. Next, the inside of the reaction vessel was pressurized to 0.1 MPa, the polymer was discharged to a strand through a die having a circular discharge port having a diameter of 10 mm, and pelletized by a cutter. When the continuous batch was continuously performed under the same conditions, the yield of the second batch was 93.9% with respect to the theoretical yield obtained by adding the first batch of cans to the charged quantity.

  When the inside of the superposition | polymerization can was observed after discharge, the rise trace of the liquid level derived from complex production | generation was seen, The liquid level was 145%. Further, the sublimate adhering to the gas phase part was eluted and recovered with acetone, and the amount of sublimate was measured by distilling off acetone, and the sublimate amount was 4.5 g.

The melting point of this liquid crystalline resin is 310 ° C., and ΔS (melting entropy) is 0.3 × 10 ⁻³ J / g · K, measured using a Koka flow tester at a temperature of 330 ° C. and a shear rate of 1000 / s. The melt viscosity was 23 Pa · s.

Comparative Example 2
An upper vessel (hereinafter referred to as vessel (1)) of two 5 L reactors connected via a transition tube having a stirring blade and a distillation tube and having valves on the upper and lower sides, 352 g of 4,4′-dihydroxybiphenyl, 89 g of hydroquinone 292 g of terephthalic acid, 157 g of isophthalic acid, and 596 g of acetic anhydride were charged and stirred for 60 minutes in a nitrogen gas atmosphere to homogenize the slurry.
The slurry was transferred from the container (1) to the lower container (hereinafter referred to as container (2)), the container (1) was washed with 98 g of acetic anhydride, and the cleaning liquid was also transferred to the container (2). The container (2) was awaited by raising the temperature of the contents to 90 ° C. while stirring.

  The emptied container (1) was charged with 870 g of p-hydroxybenzoic acid and 583 g of acetic anhydride, and stirred for 60 minutes in a nitrogen gas atmosphere to homogenize the slurry.

At a temperature of 90 ° C. of the contents of the container (2) and a slurry temperature of 30 ° C. of the container (1), the slurry of the container (1) was transferred to the container (2) while stirring. The container (1) was washed with 98 g of acetic anhydride, and the washing liquid was also transferred to the container (2). Acetic anhydride is charged in an amount of 1374 g (1.15 equivalents of total phenolic hydroxyl groups) including those used for washing. The temperature of the contents of the container (2) after mixing was 67 ° C. The container (2) was heated to 145 ° C. in 30 minutes and acetylated at 145 ° C. for 2.5 hours. Then the temperature was raised at 4 hours 330 ° C., 1. The pressure was reduced to 133 Pa in 0 hours. The polycondensation was completed when the torque reached 20 kgcm. The time required to reach the predetermined torque after reaching 133 Pa was 30 minutes. 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. The yield was 97.6% of the theoretical yield. When the continuous batch was continuously performed under the same conditions, the yield of the second batch with respect to the theoretical yield obtained by adding the can of the first batch to the charged quantity is It was 93.9%.

  When the inside of the polymerization can was observed after the discharge, a slight increase in the liquid level due to complex formation was observed, and the liquid level was 121.2%. Further, the sublimate adhering to the gas phase part was recovered by eluting with acetone, and when acetone was distilled off and the amount of sublimate was measured, the amount of sublimate was 2.8 g.

The melting point of this liquid crystalline resin is 309 ° C., ΔS (melting entropy) is 0.3 × 10 ⁻³ J / g · K, and measured using a Koka flow tester at a temperature of 330 ° C. and a shear rate of 1000 / s. The melt viscosity was 23 Pa · s.

Claims (4)

  When the monomer mixture is reacted with acetic anhydride, acetylated, and further polymerized to produce a liquid crystalline resin, the anhydrous monomer containing hydroquinone and no p-hydroxybenzoic acid is included before the acetylation reaction. Prepare acetic acid slurry and acetic anhydride slurry of monomer containing p-hydroxybenzoic acid and no hydroquinone separately, and adjust one or both of the slurry so that the temperature after mixing is 70 ° C or higher. The manufacturing method of the liquid crystalline resin characterized by including the process of heating and mixing. Acetic anhydride slurry containing hydroquinone and not containing p-hydroxybenzoic acid is adjusted to 100 to 130 ° C, and acetic anhydride slurry containing p-hydroxybenzoic acid and not containing hydroquinone is adjusted to 20 to 40 ° C and mixed. The method for producing a liquid crystalline resin according to claim 1. A monomer acetic anhydride slurry containing hydroquinone and not containing p-hydroxybenzoic acid and / or a monomer acetic anhydride slurry containing p-hydroxybenzoic acid and containing no hydroquinone may further contain 4,4′-dihydroxybiphenyl, terephthalic acid. The manufacturing method of the liquid crystalline resin of Claim 1 or 2 containing any one or more of isophthalic acid. Hydroquinone unrealized p - acetic anhydride slurry containing no hydroxybenzoic acid, further, 4,4'-dihydroxybiphenyl, the liquid-crystalline resin according to claim 3, characterized in that it comprises a terephthalic acid and / or isophthalic acid Production method.