JPH10237286A - Liquid crystal resin and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the color tone, residence stability during molding, thermal characteristics such as dry heat deterioration resistance, and hydrolysis resistance and reduce the generation of acetic acid by producing a liquid crystal resin which contains a liquid crystal polymer capable of forming an anisotropic melt phase and whose solution in a solvent mixture comprising pentafluorophenol and chloroform has a specified absorbance. SOLUTION: This liquid crystal resin comprises at least one polymer selected from among liquid crystal polyesters and liquid crystal polyester-amides capable of forming an anisotropic melt phase. Examples of the liquid crystal polyester used include those consisting of structural units of formula I to formula IV (wherein R1 is at least one group selected from those of formulas V to XIV; R2 is at least one group selected from those of formulas XV to XX; and X is H or Cl). The liquid crystal polyester-amid used contains at least one kind of structural units selected from among aromatic iminocarbonyl units, aromatic diimino units, etc. The solvent mixture used comprises pentafluorophenol and chloroform at a weight ratio of 1:1. The 0.5wt.% solution of the liquid crystal resin in this solvent mixture has an absorbance at 380nm, measured along an optical path of 10mm, of at most 0.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modification of a liquid crystalline resin, and more particularly, to an improvement in color tone, hydrolysis resistance, and heat resistance, and further reduces the amount of acetic acid generated during heat retention. Liquid crystal resin and molded articles.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for higher performance of plastics, and a number of polymers having various new properties have been developed and marketed. Among them, optics characterized by a parallel arrangement of molecular chains. Attention is paid to the fact that anisotropic liquid crystalline polymers have excellent fluidity and mechanical properties,
In particular, due to its high rigidity, demand for small molded products in the fields of electric / electronics and office equipment is increasing.

Further, liquid crystalline polymers obtained by copolymerizing p-hydroxybenzoic acid and polyethylene terephthalate (Japanese Patent Publication No. 56-18016), p-hydroxybenzoic acid and polyethylene terephthalate and aromatic compounds such as 4,4′-dihydroxybiphenyl and the like. Liquid crystalline polymer having improved fluidity and heat resistance by adding a copolymer component such as an aromatic diol and an aromatic dicarboxylic acid (JP-A-63-3052)
No. 3), a liquid crystalline polymer obtained by copolymerizing p-hydroxybenzoic acid with 4,4′-dihydroxybiphenyl, t-butylhydroquinone and terephthalic acid (JP-A-62-1)
No. 64719), p-hydroxybenzoic acid has 4,
Liquid crystalline polymer obtained by copolymerizing 4'-dihydroxybiphenyl, isophthalic acid and terephthalic acid (JP-B-57-24)
407, JP-A-60-25046), p-
Liquid crystalline polymer obtained by copolymerizing 6-hydroxy-2-naphthoic acid with hydroxybenzoic acid (JP-A-54-77691).
Publication), and the like.

[0004] However, since these have a higher melting point than ordinary polyesters such as polyethylene terephthalate and polybutylene terephthalate, there is a problem in that they are colored during polymerization and molding, and deteriorate in mechanical properties due to thermal deterioration. there were. 2-51
No. 524 proposes a method of improving the long-term heat resistance by adding a heat stabilizer such as an organic phosphorus compound or a hindered phenol during polymerization. Further, Japanese Unexamined Patent Publication No.
JP-A-53605 discloses that a liquid crystal polyester and / or a liquid crystal polyesteramide contain phosphorous acid, hypophosphorous acid, a metal salt thereof and the like.
JP-A-32880 discloses that a phosphoric acid compound is added while the reaction system is in a molten state.
No. 43 describes that a phosphorus compound is added to a resin comprising a non-liquid crystalline polyester and a liquid crystalline polyester.

[0005]

Problems to be Solved by the Invention However, Japanese Patent Publication No. 2-5
It has been found that the heat-resistant agent described in Japanese Patent No. 1524 does not always have sufficient effects on the thermal stability during staying and the coloring due to thermal deterioration. Further, the liquid crystalline polymer described in JP-A-63-30523 has a slight coloring due to the residual acetylating agent because the acetylating agent is added in an excess of 1.1 mole times the amount of the hydroxy terminal during polymerization. Also, in the method described in JP-A-8-53605, an excessive amount of an acetylating agent is added at the time of polymerization similarly to the liquid crystal polymer described in JP-A-63-30523, so that a particular color tone is required. It may not be enough for the application. Further, JP-A-6-32880 discloses that an excess acetylating agent is added and an organic phosphorus compound is added. In JP-A-7-179743, an organic phosphorus-based compound is added to a resin component so that the color tone is reduced. It turned out that the improvement effect was not enough.

Accordingly, the present invention solves the above-mentioned problems, is excellent in color tone, is excellent in thermal characteristics such as retention stability during drying and dry heat deterioration characteristics, and is resistant to hydrolysis, and has an extruder and a molding machine. It is an object of the present invention to obtain a resin composition and a molded product to which new characteristics such as a reduction in the amount of acetic acid which causes corrosion of a screw such as a screw are imparted.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention.

That is, the present invention relates to (1) a liquid crystalline resin containing at least one liquid crystalline polymer selected from a liquid crystalline polyester and a liquid crystalline polyesteramide which form an anisotropic molten phase; In a mixed solvent in which the weight ratio of fluorophenol and chloroform is 1 so that the concentration of the liquid crystalline resin is 0.5% by weight, the absorbance at 380 nm measured with a 10 mm optical path length is 0.5%.
The following liquid crystal resin, (2) the liquid crystal resin according to the above (1), wherein the liquid crystal resin contains an inorganic phosphorus compound, and (3) 100 parts by weight of the liquid crystal polymer, Liquid crystalline resin according to (1) or (2), wherein 0.001 to 5 parts by weight of at least one compound selected from hypophosphorous acid and metal salts thereof are added; The liquid crystalline resin according to the above (3), wherein the at least one compound selected from phosphoric acid, hypophosphorous acid and a metal salt thereof is phosphorous acid and / or a sodium metal salt of hypophosphorous acid, 5) A liquid crystalline polymer in which the liquid crystalline polymer comprises the following structural units (I), (II) and (IV) or a liquid crystal comprising the structural units (I), (II), (III) and (IV) Any of the above (1) to (4), which is a water-soluble polyester Liquid-crystalline resin according,

Embedded image (However, R ₁ in the formula is

Embedded image R ₂ represents one or more groups selected from

Embedded image Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. (6) a liquid crystal resin composition obtained by adding 5 to 300 parts by weight of an inorganic filler to 100 parts by weight of the liquid crystal resin according to any one of the above (1) to (5), (7) hydroxycarboxylic acid, 1 selected from dihydroxy compounds and dicarboxylic acids
When a liquid crystalline polyester and / or a liquid crystalline polyesteramide-forming raw material containing at least one species is reacted in the presence of an acylating agent to polymerize the liquid crystalline polyester and / or the liquid crystalline polyesteramide, At least one compound of phosphorous acid and a metal salt thereof is added at the time of polymerization, and the molar equivalent of the acylating agent (the hydroxyl group of the acylating agent can be acylated with respect to the amount (mol) of the hydroxy group in the raw material monomer) (8) a method for producing a liquid crystalline resin, characterized in that an acylating agent is present so that the amount (molar ratio) of the functional group is less than 1.1.
The method for producing a liquid crystalline resin according to the above (7), wherein the liquid crystalline polyester and / or the liquid crystalline polyester amide-forming raw material further contains at least one selected from polyalkylene terephthalates and amino group-containing monomers.
(9) A liquid crystalline resin molded article obtained by molding the liquid crystalline resin according to any one of the above (1) to (5) or the liquid crystalline resin composition according to the above (6), (10) a liquid crystalline resin molded article Is a liquid crystal resin molded product according to the above (9), which is a small molded product.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The liquid crystalline polymer used in the present invention is at least one selected from liquid crystalline polyesters and liquid crystalline polyester amides which form an anisotropic molten phase. Oxycarbonyl units such as carbonyl units, aromatic dioxy units,
A liquid crystalline polyester forming an anisotropic molten phase comprising at least one structural unit selected from dioxy units such as alkylenedioxy units such as ethylenedioxy units, dicarbonyl units such as aromatic dicarbonyl units, etc. Examples of the liquid crystalline polyesteramide include a structural unit selected from one or more of the above units and one or more structural units selected from an aromatic iminocarbonyl unit, an aromatic diimino unit, an aromatic iminooxy unit, and the like. And liquid crystalline polyesteramides that form an anisotropic molten phase composed of units.

Examples of the liquid crystalline polyester forming the anisotropic molten phase include a liquid crystalline polyester having the following structural units (I), (II), (III) and (IV), or
And liquid crystalline polyesters forming an anisotropic molten phase composed of the structural units of (I), (III) and (IV).

[0011]

Embedded image (However, R ₁ in the formula is

Embedded image R ₂ represents one or more groups selected from

Embedded image Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. The total of the above structural units (II) and (III) and the structural unit
(IV) is preferably substantially equimolar.

The structural unit (I) is a structural unit formed from p-hydroxybenzoic acid, and the structural unit (II) is 4,4′-dihydroxybiphenyl, 3,3 ′, 5,
5'-tetramethyl-4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane And 4,4'-
A structural unit generated from an aromatic dihydroxy compound selected from dihydroxydiphenyl ether, a structural unit (III) is a structural unit generated from ethylene glycol, and a structural unit (IV) is terephthalic acid, isophthalic acid,
4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-
4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,4'-dicarboxylic acid
The structural units generated from aromatic dicarboxylic acids selected from 4 ′ diphenyl ether dicarboxylic acids are shown below.

Examples of the liquid crystalline polyesteramide include 2,6-hydroxynaphthoic acid, a liquid crystalline polyesteramide formed from p-aminophenol and terephthalic acid, p-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl. And liquid crystalline polyesteramides produced from terephthalic acid, p-aminobenzoic acid and polyethylene terephthalate (see JP-A-64-33123).

The liquid crystalline polyester which can be preferably used in the present invention is a copolymer comprising the above structural units (I), (II) and (IV), or (I) or (I).
It is a copolymer composed of (I), (III) and (IV), and the copolymerization amount of the above structural units (I), (II), (III) and (IV) is arbitrary. However, the following copolymerization amount is preferred from the viewpoint of fluidity.

That is, when the above-mentioned structural unit (III) is contained, the total of the above-mentioned structural units (I) and (II) is the sum of the structural units (I) and (I) in view of heat resistance, flame retardancy and mechanical properties.
It is preferably from 35 to 95 mol%, more preferably from 40 to 93 mol%, based on the total of I) and (III). Further, the structural unit (III) is preferably 65 to 5 mol%, more preferably 60 to 7 mol%, based on the total of the structural units (I), (II) and (III).
Is more preferred. The molar ratio [(I) / (II)] between the structural units (I) and (II) is preferably 70/30 to 95/5, more preferably 75/30, from the viewpoint of the balance between heat resistance and fluidity. / 25 to 93/7. Further, it is preferable that the structural unit (IV) is substantially equimolar to the sum of the structural units (II) and (III).

On the other hand, when the structural unit (III) is not contained, the structural unit (I) is replaced with the structural unit (I) from the viewpoint of fluidity.
It is preferably from 40 to 90 mol%, more preferably from 60 to 88 mol%, based on the total of (II) and (II), and the structural unit (IV) is substantially equimolar to the structural unit (II). Preferably, there is.

In the polycondensation of the liquid crystalline polymer which can be preferably used in the present invention, the above structural units (I) to (I) are used.
In addition to the components constituting (IV), aromatic dicarboxylic acids such as 3,3'-diphenyldicarboxylic acid and 2,2'-diphenyldicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecandioic acid. Acid, alicyclic dicarboxylic acid such as hexahydroterephthalic acid, chlorohydroquinone, methylhydroquinone, 4,4 ′
Aromatic diols such as -dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxybenzophenone, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 1,4-cyclohexane Diols, aliphatic and alicyclic diols such as 1,4-cyclohexanedimethanol, and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid;
Aminophenol, p-aminobenzoic acid, derivatives thereof, and the like can be further copolymerized in a small proportion that does not impair the liquid crystallinity.

The liquid crystalline resin of the present invention contains the liquid crystalline polymer as described above, and the concentration of the liquid crystalline resin is 0.5% by weight in a mixed solvent of pentafluorophenol and chloroform at a weight ratio of 1. The absorbance at 380 nm measured with a 10 mm optical path length of the solution dissolved so as to be 0.5 or less, preferably 0.4 or less, particularly preferably 0.3 or less. If the absorbance exceeds 0.5, it means coloring due to oxidative deterioration, the color tone is not improved, and sufficient mechanical properties cannot be obtained.

The absorbance of the liquid crystalline resin is usually determined by dissolving the liquid crystalline resin in pentafluorophenol at 50 ° C. for 4 hours so that the concentration of the liquid crystalline resin is 1% by weight.
Further, a solution obtained by mixing chloroform with a liquid crystal resin concentration of 0.5% by weight was placed in a quartz glass cell having an optical path length of 10 mm, and a mixed solvent was used as a blank to make a spectrophotometer (UV-240, manufactured by Shimadzu Corporation). ) Using 380 nm
Can be obtained from the following equation measured with the following light:

Absorbance = -Log (transmitted light intensity / incident light intensity) In order to obtain such a liquid crystalline resin, it is preferable to contain an inorganic phosphorus compound.

The liquid crystalline resin containing the inorganic phosphorus compound can be obtained by adding at least one selected from phosphorous acid, hypophosphorous acid and metal salts thereof. Specific examples of such metal salts of phosphorous acid and hypophosphorous acid include the following. That is, for the metal species of the metal phosphite and the metal hypophosphite, lithium,
Alkali metals such as sodium and potassium, and alkaline earth metals such as magnesium, calcium and barium are preferable, and alkali metals are more preferable. More specifically, calcium hypophosphite, magnesium hypophosphite, barium hypophosphite, sodium hypophosphite, potassium hypophosphite, potassium phosphite, magnesium phosphite, barium phosphite, Sodium phosphate and the like. Most preferred are sodium metal salts such as sodium hypophosphite, sodium phosphite.

The addition amount of phosphorous acid, hypophosphorous acid and metal salts thereof is usually 0 to 100 parts by weight of the liquid crystalline resin in view of the color tone, heat resistance and mechanical properties of the resulting liquid crystalline resin. 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight.

It is preferable to add phosphorous acid, hypophosphorous acid and their metal salts before the completion of polymerization in view of the color tone of the resulting liquid crystalline resin.

The phosphorous acid, hypophosphorous acid and their metal salts can be added as a solid or as a liquid at a temperature equal to or higher than the melting point of phosphorous acid, hypophosphorous acid and their metal salts. If the compounding is performed at low temperature, phosphorous acid,
It is also possible to add hypophosphorous acid and their metal salts as a solution.

In the present invention, phosphoric acid and a metal salt other than hypophosphorous acid can be added to further improve the retention stability. Organic or inorganic metal salts other than phosphorous acid and hypophosphorous acid can be used, but sulfuric acid, hydrogen halide, nitric acid, boric acid, phosphoric acid, pyrophosphoric acid, acetic acid, oxalic acid, benzoic acid It is preferable to use an alkali metal salt or an alkaline earth metal salt. More specifically, potassium sulfate, sodium acetate, barium acetate, magnesium acetate, sodium benzoate,
Metal salts such as sodium hydrogen phosphate can be used.

The amount of the metal salt other than phosphorous acid and hypophosphorous acid is usually 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, per 100 parts by weight of the liquid crystalline polyester.

The metal salt other than phosphorous acid and hypophosphorous acid can be added as a solid or as a liquid at a temperature higher than its melting point. When the compounding is performed at a low temperature, it can be added as a solution.

The method for producing the liquid crystalline resin used in the present invention is as follows.
There is no particular limitation as long as a liquid crystalline resin satisfying the above absorbance range is obtained. However, from the viewpoint of color tone, heat resistance and hydrolysis resistance, it is preferable to produce the resin by the following method. That is, the raw materials necessary for constituting the liquid crystalline polymer, for example,
A liquid crystalline polyester containing one or more selected from hydroxycarboxylic acids, dihydroxy compounds, and dicarboxylic acids, and, if necessary, further containing one or more selected from polyalkylene terephthalates and amino group-containing monomers; and / or Alternatively, when a liquid crystalline polyesteramide-forming raw material is reacted in the presence of an acylating agent to polymerize a liquid crystalline polyester and / or a liquid crystalline polyesteramide, and the molar equivalent of the acylating agent (the amount of hydroxy group in the raw material monomer) In this method, the acylating agent is present in such a manner that the ratio of the amount (mol) of the functional group capable of acylating the hydroxy group of the acylating agent to the (mol) is relatively small.

Examples of the acylating agent include acetic anhydride, propionic anhydride, butyric anhydride, and benzoic anhydride. Among them, acetic anhydride is preferably used from the viewpoint of reactivity.

In order to reduce the amount of acetic acid generated during the heat retention, the molar equivalent of the acylating agent (the amount of the functional group capable of acylating the hydroxy group of the acylating agent (the molar amount relative to the amount (mol) of the hydroxy group in the starting monomer) is used. ) Is preferably relatively small, for example, less than 1.1, more preferably 1.090 or less, and particularly preferably 1.080 or less. The lower limit is not particularly limited, but is preferably 1.0 or more, more preferably 1.02 or more, from the viewpoint of the degree of polymerization of the obtained liquid crystalline polymer.
More preferably, it is 1.05 or more.

As described above, when the amount of the acylating agent used is small, the degree of polymerization of the polymer generally tends to be difficult to increase, but at least one of phosphorous acid, hypophosphorous acid, and metal salts thereof is used. By adding the above compound at the time of polymerization, the polymerization degree is sufficient even if the amount of the acylating agent used is reduced, and the amount of acetic acid generated during heat retention is small,
A liquid crystalline resin having an excellent color tone can be obtained.

When an acylating agent is added, it is preferable to carry out an acylation reaction prior to the polycondensation. The acylation reaction is carried out under a nitrogen stream at 80 to 300 ° C., preferably 100 ° C.
Perform at ~ 250 ° C.

Others are not particularly limited, and can be produced according to a known polyester polycondensation method.

For example, in the production of the liquid crystal polyester preferably used, the following production method is preferably mentioned.

(1) p-hydroxybenzoic acid, 4,4 '
Aromatic dihydroxy compounds such as dihydroxybiphenyl and hydroquinone; aromatic dicarboxylic acids such as acetic anhydride and terephthalic acid; polymers of polymers such as polyethylene terephthalate, oligomers and bis (β-hydroxyethyl) terephthalates; β-Hydroxyethyl) ester and the like are added, and esterification and / or transesterification are performed at 100 to 300 ° C. Thereafter, a catalyst is added, if necessary, to carry out an acylation reaction at 100 to 250 ° C. Then, a method of producing by a deacetic acid polycondensation reaction under vacuum or reduced pressure at 250 to 350 ° C.

As the catalyst used for the polycondensation reaction, those known as polymerization catalysts for liquid crystal polyester or liquid crystal polyesteramide can be used.

Some liquid crystal resins used in the present invention can measure the logarithmic viscosity in pentafluorophenol. In this case, the value measured at 60 ° C. at a concentration of 0.1 g / dl is 0%. 0.03 or more, preferably 0.05 to 1
0.0 dl / g is particularly preferred.

The melt viscosity of the liquid crystalline resin in the present invention is preferably from 1 to 2,000 Pa · s, particularly preferably from 2 to 1,
000 Pa · s is more preferable.

The melt viscosity is calculated as melting point (Tm) +10
It is a value measured by a Koka type flow tester under the condition of ° C and a shear rate of 1,000 (1 / second).

Here, the melting point (Tm) refers to an endothermic peak temperature (Tm) observed when a polymer that has been polymerized is measured from room temperature under a heating condition of 20 ° C./min.
After observation at m1), the temperature is maintained at a temperature of Tm1 + 20 ° C. for 5 minutes, cooled once to room temperature at a temperature lowering condition of 20 ° C./min, and then measured again at a temperature rising condition of 20 ° C./min. Refers to the endothermic peak temperature (Tm2).

The liquid crystalline resin of the present invention can be made into a liquid crystalline resin composition by incorporating an inorganic filler as necessary. The inorganic filler is not particularly limited, but a fibrous, plate-like, powder-like, or granular filler can be used. Specifically, for example, glass fiber, PAN-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber or brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia Fibrous, whisker-like filler, mica, talc, such as 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. Kaolin, silica, calcium carbonate, glass beads, glass flakes, glass microballoons,
Examples of the filler include powdery, granular and plate-like fillers such as clay, molybdenum disulfide, wollastenite, titanium oxide, zinc oxide, calcium polyphosphate, and graphite. Among the above fillers, glass fibers are preferably used. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and for example, it can be selected from long fiber type or short fiber type chopped strand, milled fiber and the like. Further, two or more of the above fillers can be used in combination. The filler used in the present invention may be used after its surface is treated with a known coupling agent (for example, a silane-based coupling agent, a titanate-based coupling agent, or the like) or another surface treatment agent. .

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 amount of the filler is 100
It is usually 300 parts by weight or less, preferably 5 to 300 parts by weight, particularly preferably 10 to 250 parts by weight, more preferably 20 to 150 parts by weight with respect to parts by weight.

The liquid crystalline resin of the present invention includes an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and the like) and an ultraviolet absorber (for example, resorcinol, salicylate,
Benzotriazole, benzophenone, etc.), lubricants and release agents (montanic acid and its salts, esters, half esters thereof, stearyl alcohol, stearamide, polyethylene wax, etc.), dyes (eg, nigrosine, etc.) and pigments (eg, cadmium sulfide, phthalocyanine) ), A general additive such as a coloring agent, a crystal nucleating agent, a plasticizer, a flame retardant, a flame retardant auxiliary, and an antistatic agent.

The method of adding these is preferably melt kneading, and a known method can be used for melt kneading. For example, Banbury mixer, rubber roll machine,
Using a kneader, single screw or twin screw extruder,
The composition can be melt-kneaded at a temperature of from about 370 ° C. to a composition.

In the present invention, when the absorbance of the liquid crystal resin is measured using the liquid crystal resin composition as described above, the components of the liquid crystal resin composition are determined in advance using GC-MS, LC-MS or other analytical instruments. Is analyzed, and additives and fillers other than the liquid crystalline resin are first separated, and thereafter, can be measured by the above-described method. Separation of the liquid crystalline resin from other additives and fillers can be performed as follows. That is, when the liquid crystal resin composition contains an additive and a filler which are insoluble in pentafluorophenol, a pentafluorophenol-insoluble matter is filtered from the liquid crystal resin composition with a 0.45 μm filter, and a filtrate (liquid crystal resin) is used. From the pentafluorophenol solution) using a poor solvent such as methanol. When the liquid crystal resin composition contains an additive that dissolves in pentafluorophenol, the liquid crystal resin composition is finely pulverized,
Toluene, acetone, benzene, methanol, DMF,
The additive is extracted and separated with a solvent selected from MNP. When both soluble and insoluble additives are added to pentafluorophenol, the above separation method is used in combination.
Then, as described above, the liquid crystal resin is obtained by separating the additive or filler from the liquid crystal resin composition, and as described above, the concentration of the liquid crystal resin in the mixed solvent in which the weight ratio of pentafluorophenol and chloroform is 1 is as follows. 0.5% by weight
, And the absorbance at 380 nm can be determined with an optical path length of 10 mm.

The liquid crystalline resin and the liquid crystalline resin composition thus obtained can be subjected to ordinary molding such as injection molding, extrusion molding, compression molding, etc., and used as various molded products for electric / electronic parts, precision parts, automobile parts and the like. Extremely useful.
In addition, since a color tone and retention stability are excellent, a colored molded article can be obtained by adding a coloring agent.

The molded article comprising the liquid crystalline resin and the liquid crystalline resin composition of the present invention has excellent heat resistance, excellent hydrolysis resistance,
Because of its excellent color tone, it can be processed into three-dimensional molded products, sheets, container pipes, etc. For example, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay case switch coil bobbins , Condenser, variable condenser 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, FDD Electric / electronic parts such as carriage, FDD chassis, motor brush holder, parabolic antenna, computer related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts,
Audio parts, audio equipment parts such as audio laser discs and compact discs, lighting parts, refrigerator parts,
Air conditioner parts, typewriter parts, word processor parts, and other household and office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, oilless bearings, stern bearings, Various bearings such as underwater bearings, motor parts, mechanical parts such as lighters, typewriters, etc., optical equipment such as microscopes, binoculars, cameras, watches, etc., precision mechanical parts; alternator terminals, alternator connectors, IC regulator, potentiometer base for light deer, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel,
Intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt Wear sensor, thermostat base for air conditioner, heating and hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related components, dust switcher, starter switch, starter relay, wire harness for transmission, window Osher nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, For automotive and vehicle-related parts such as fuse connectors, horn terminals, electrical component insulation boards, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, and other various applications Useful.

Among them, by taking advantage of the excellent characteristics of the liquid crystal resin or liquid crystal resin composition of the present invention, such as excellent color tone, heat resistance and hydrolysis resistance, small molded parts, for example, having a resin volume of 5 cc or less. It can be used very practically as a small molded product used for small parts. In particular, it is very practical for molded products that are small built-in parts such as connectors such as SIMM sockets, CD pickup lens holders and various small gears.

[0050]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the invention.

Comparative Example 1 LCP1: 11.05 kg of p-hydroxybenzoic acid,
1.40 kg of 4,4'-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and acetic anhydride 1
After charging 0.67 kg into a pressure vessel and reacting at 100 to 250 ° C. for 1.5 hours under a nitrogen gas atmosphere,
The pressure was reduced to 66 Pa in 1 hour at 66 ° C., and the reaction was further performed for 1.25 hours to complete the polycondensation. As a result, an almost theoretical amount of acetic acid was distilled out to obtain pellets. The absorbance at 380 nm of the liquid crystal resin (LCP1) measured at an optical path length of 10 mm is 1.1.
Met.

Comparative Example 2 LCP2: 11.05 kg of p-hydroxybenzoic acid,
1.40 kg of 4,4'-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and acetic anhydride 1
A 0.38 kg pressure vessel was charged and polymerization was carried out under the same conditions as for LCP1, but the degree of polymerization did not increase, and good pellets could not be obtained.

Example 1 LCP3: 11.05 kg of p-hydroxybenzoic acid,
1.40 kg of 4,4'-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and acetic anhydride 1
0.38 kg and 28.6 g of sodium hypophosphite were charged into a pressure vessel, and polymerization was carried out in the same manner as in LCP1, to obtain pellets. The absorbance at 380 nm of the liquid crystal resin (LCP3) measured at an optical path length of 10 mm was 0.1.

Example 2 LCP4: 11.05 kg of p-hydroxybenzoic acid,
1.40 kg of 4,4'-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and acetic anhydride 1
0.38 kg and 28.6 g of sodium phosphite were charged into a pressure vessel, and polymerization was carried out in the same manner as in LCP1, to obtain pellets. The absorbance at 380 nm of the liquid crystal resin (LCP4) measured at an optical path length of 10 mm was 0.2.

Example 3 LCP5: 11.05 kg of p-hydroxybenzoic acid,
1.40 kg of 4,4'-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and acetic anhydride 1
0.38 kg and 57.2 g of sodium hypophosphite were charged into a pressure vessel, and polymerization was carried out in the same manner as in LCP1, to obtain pellets. The absorbance at 380 nm of the liquid crystal resin (LCP5) measured at an optical path length of 10 mm was 0.1.

Comparative Example 3 LCP6: 11.05 kg of p-hydroxybenzoic acid,
1.40 kg of 4,4'-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and acetic anhydride 1
0.67 kg, MARK P manufactured by Adeka Argus Chemical Company
EP-36 (bis (4-methyl-2,6-t-butyl)
Pentaerythitol diphosphite)) 28.6 g
Was charged in a pressure vessel, and polymerization was carried out in the same manner as in LCP1, to obtain pellets. The absorbance at 380 nm of the liquid crystal resin (LCP6) measured at an optical path length of 10 mm was 0.9.

Comparative Example 4 LCP7: 11.05 kg of p-hydroxybenzoic acid,
1.40 kg of 4,4'-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and acetic anhydride 1
0.67 kg, MARK H manufactured by Adeka Argus Chemical Company
28.6 g of P-10 (2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite) was charged into a pressure vessel, and polymerized in the same manner as in LCP1 to obtain pellets. The absorbance at 380 nm of the liquid crystal resin (LCP7) measured at an optical path length of 10 mm was 0.8.

Comparative Example 5 LCP8: 11.05 kg of p-hydroxybenzoic acid,
1.40 kg of 4,4'-dihydroxybiphenyl, 1.25 kg of terephthalic acid, 2.40 kg of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and acetic anhydride 1
0.67 kg and 28.6 g of calcium hypophosphite were charged into a pressure vessel, and polymerized in the same manner as in LCP1, to obtain pellets. The absorbance at 380 nm of the liquid crystal resin (LCP8) measured at an optical path length of 10 mm was 0.55.

Each evaluation was measured according to the method described below.

(1) Absorbance A solution obtained by mixing a mixed solution of pentafluorophenol and chloroform (weight ratio: 1: 1) so that the concentration of the liquid crystal resin becomes 0.5% by weight is adjusted to an optical path length of 10 mm. The mixture was placed in a quartz glass cell, and the mixed solvent was used as a blank, using a spectrophotometer (UV-240, manufactured by Shimadzu Corporation) for 380.
It was determined from the following equation measured with light of nm.

Absorbance = −Log (transmitted light intensity / incident light intensity) (2) Whiteness (W value), Yellowness (YI value) A bending test piece of 127 mm × 12.7 mm × 3.12 mm was subjected to Sumitomo Heavy Industries Promat Cylinder temperature 32 at 25/40
The test piece was molded at 5 ° C. and a mold temperature of 90 ° C., and the whiteness (W value) of the test piece was measured using an SM color computer apparatus manufactured by Suga Test Instruments Co., Ltd.

(3) Retention stability The molding retention time was changed to 12 minutes under the two conditions of 4 minutes and 20 minutes.
A 7 mm × 12.7 mm × 3.12 mm bending test piece was subjected to a cylinder temperature of 330 using Sumitomo Heavy Industries Promat 25/40.
At a mold temperature of 90 ° C., and measuring the bending strength based on ASTM D790. The bending strength at a molding residence time of 20 minutes / the bending strength at a molding residence time of 4 minutes × 100.
Was determined as a flexural strength retention rate.

(4) Heat Aging Test An ASTM No. 1 tensile test piece was molded at 325 ° C. cylinder temperature and 90 ° C. mold temperature using Toshiba IS-55EPN, and the obtained test piece was treated in a hot air oven at 240 ° C. for 30 days. After that, the tensile strength was measured based on ASTM D638, and the tensile strength after treatment at 240 ° C. for 30 days / initial tensile strength × 100 was determined as the tensile strength retention.

(5) Hydrolysis test ASTM No. 1 tensile test piece was molded at 325 ° C. cylinder temperature and 90 ° C. mold temperature using Toshiba IS-55EPN, and the obtained test piece was charged into an autoclave together with water at 120 ° C.
, And the tensile strength was measured based on ASTM D638, and the tensile strength when treated at 120 ° C. for 3 days / initial tensile strength × 100 was defined as the tensile strength retention.

(6) Amount of acetic acid generated 0.3 g of resin was weighed into a test tube of 50 mmφ and 10
The pressure was reduced to rr, and the mixture was allowed to stand at 330 ° C. for 30 minutes in a sealed system. Thereafter, the pressure was returned to normal pressure with nitrogen, and the concentration of acetic acid in the test tube was measured using a detector tube for acetic acid (No. 81, manufactured by Gastech).

Examples 4-6, Comparative Examples 6-9 LCPs 1, 3 shown in Examples 1-3, Comparative Examples 1, 3-5
After dry-blending an inorganic filler (glass fiber having a diameter of 9 μm and a length of 3 mm) at a ratio shown in Table 1 with respect to ８100 parts by weight, the mixture was melt-kneaded with a 30 mmφ twin-screw extruder to obtain pellets. Then, a test piece was obtained from the pellet by a method for each evaluation item. The absorbance and the amount of acetic acid generated were measured for the liquid crystalline resin before kneading.

Table 1 shows the evaluation results.

[0068]

[Table 1] From the results shown in Table 1, the liquid crystal resin composition of the present invention can obtain a material having significantly improved color tone, improved heat resistance such as heat stability during stagnation and heat aging, and also improved hydrolysis resistance. Can be.

[0069]

As described above, the liquid crystalline resin composition and the molded article of the present invention have significantly improved color tone and excellent heat resistance and hydrolysis resistance. It is suitable for various other uses such as equipment for use, automobile and vehicle related parts, and the like.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI C09K 19/38 C09K 19/38 G02F 1/13 500 G02F 1/13 500

Claims (10)

[Claims] 1. A liquid crystalline resin containing at least one liquid crystalline polymer selected from a liquid crystalline polyester and a liquid crystalline polyester amide forming an anisotropic molten phase, wherein the weight ratio of pentafluorophenol to chloroform is Was measured with a 10 mm optical path length in a solution prepared by dissolving the liquid crystalline resin in a mixed solvent having a value of 1 such that the concentration of the liquid crystalline resin was 0.5% by weight.
A liquid crystalline resin having an absorbance at 80 nm of 0.5 or less. 2. The liquid crystalline resin according to claim 1, wherein the liquid crystalline resin contains an inorganic phosphorus compound. 3. A liquid crystal polymer, wherein 1001 parts by weight of a liquid crystalline polymer is added with 0.001 to 5 parts by weight of at least one compound selected from phosphorous acid, hypophosphorous acid and metal salts thereof. The liquid crystalline resin according to claim 1. 4. The method according to claim 3, wherein the at least one compound selected from phosphorous acid, hypophosphorous acid and metal salts thereof is a sodium metal salt of phosphorous acid and / or hypophosphorous acid. Liquid crystalline resin. 5. A liquid crystalline polyester wherein the liquid crystalline polymer comprises the following structural units (I), (II) and (IV), or structural units of (I), (II), (III) and (IV) The liquid crystalline resin according to any one of claims 1 to 4, which is a liquid crystalline polyester comprising: Embedded image (However, R ₁ in the formula is R ₂ represents one or more groups selected from Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. ) 6. A liquid crystalline resin composition comprising 100 parts by weight of the liquid crystalline resin according to claim 1 and 5 to 300 parts by weight of an inorganic filler. 7. A liquid crystalline polyester and / or a liquid crystalline polyesteramide-forming raw material containing at least one selected from hydroxycarboxylic acids, dihydroxy compounds and dicarboxylic acids is reacted in the presence of an acylating agent to give a liquid crystalline compound. When polymerizing a polyester and / or a liquid crystalline polyesteramide, at least one compound of phosphorous acid, hypophosphorous acid and a metal salt thereof is added at the time of polymerization, and a molar equivalent of an acylating agent (starting monomer Characterized in that the acylating agent is present in such a manner that the ratio of the amount (mol) of the functional group capable of acylating the hydroxy group of the acylating agent to the amount (mol) of the hydroxy group therein is less than 1.1. A method for producing a liquid crystalline resin. 8. The production of a liquid crystalline resin according to claim 7, wherein the raw material for forming a liquid crystalline polyester and / or a liquid crystalline polyester amide further contains at least one selected from polyalkylene terephthalates and amino group-containing monomers. Method. 9. A liquid crystalline resin molded article obtained by molding the liquid crystalline resin according to claim 1 or the liquid crystalline resin composition according to claim 6. 10. The liquid crystalline resin molded product according to claim 9, wherein the liquid crystalline resin molded product is a small molded product.