WO2005123804A1 - 液晶性樹脂、その製造方法、液晶性樹脂組成物および成形品 - Google Patents
液晶性樹脂、その製造方法、液晶性樹脂組成物および成形品 Download PDFInfo
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- WO2005123804A1 WO2005123804A1 PCT/JP2004/017445 JP2004017445W WO2005123804A1 WO 2005123804 A1 WO2005123804 A1 WO 2005123804A1 JP 2004017445 W JP2004017445 W JP 2004017445W WO 2005123804 A1 WO2005123804 A1 WO 2005123804A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
Definitions
- Liquid crystalline resin Method for producing the same, liquid crystalline resin composition and molded article
- the present invention relates to a liquid crystalline resin most suitable for electric and electronic applications, a method for producing the same, a liquid crystalline resin composition, and a molded product.
- Patent Document 1 JP-A-2-16150 (pages 11 and 12)
- Patent Document 2 Japanese Patent No. 3309459 (pages 11 and 2)
- Patent Document 3 Japanese Patent Application Laid-Open No. 11-263829 (pages 11 and 2)
- Patent Document 1 The method described in Patent Document 1 is to increase the amount of carboxylic acid terminal groups of the liquid crystalline resin. However, it was found that in this method, the amount of carbon dioxide gas increased and the mechanical properties of the liquid crystalline resin also decreased.
- Patent Document 2 describes a method for reducing the amount of acetic acid gas generated by reducing the ratio of acetylated hydroxyl group terminals to carboxylic acid terminals of a liquid crystalline resin. However, according to the method described in the same document, the gas generation at about 200 ° C is certainly improved.If the improvement of gas generation at high temperatures that exceeds 330 ° C is required, Was not enough.
- Patent Document 3 describes that compounding liquid crystalline resin and water and hydrolyzing acetyl-terminated hydroxyl group terminals can increase the number of hydroxyl group terminals, thereby improving gas burning. ing.
- the ester bond in the polymer chain is also decomposed in addition to the hydrolysis of the terminal, so that the total amount of the terminal group is increased and the amounts of carbon dioxide gas and phenol gas are not sufficiently reduced. Also, the amount of oligomers increased, so that the cloudiness of the glass was not improved.
- the present invention provides a liquid crystalline resin in which all of such metal corrosion, glass fogging, and blistering of a molded product are reduced, a method for producing the same, a liquid crystalline resin composition, and a molded product thereof.
- the task is to
- the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found a liquid crystalline polyester exhibiting a specific low gas property.
- the present invention includes a structural unit derived from at least two types of aromatic diols, and has a melting point of + 10 ° C. (but 335 ° C. when the melting point is lower than 325 ° C.) in a helium gas atmosphere.
- a liquid crystalline resin in which acetic acid gas generated from the above liquid crystalline resin after being held for 10 minutes is less than 100 ppm, phenol gas is less than 20 ppm and carbon dioxide gas is less than 100 ppm.
- the present invention also includes a liquid crystalline resin composition obtained by mixing 30 to 200 parts by weight of a filler with respect to 100 parts by weight of the above liquid crystalline resin. [0013] The present invention also includes a molded article comprising the above liquid crystalline resin or liquid crystalline resin composition.
- the present invention also includes a film comprising the above liquid crystalline resin or liquid crystalline resin composition.
- the present invention also includes a fiber comprising the above liquid crystalline resin or liquid crystalline resin composition.
- the present invention uses a raw material containing at least two kinds of aromatic diols, and uses phenolic hydroxyl groups in the raw materials and acetic anhydride in an amount of 1.03 to 1.09 molar equivalents relative to the total of the phenolic hydroxyl groups.
- polycondensation is carried out.
- the reaction rate is the slowest, and the remaining amount of the monoacetyl ether is calculated from the following formula of the aromatic diol (A).
- the acetyl ester reaction is performed until the amount of the aromatic diol (A) reaches 0.8 to 5 mol%. This is a method for producing the above liquid crystalline resin.
- the liquid crystalline resin of the present invention generates a very small amount of gas and does not easily cause blistering on the surface when a molded article is formed using the resin. Further, when the molded article is used in combination with a transparent part made of glass or plastic, the transparent part does not become cloudy. Further, when the molded article is used in contact with metal parts, the metal parts do not corrode. Therefore, the liquid crystalline resin of the present invention is most suitable for electric and electronic applications.
- FIG. 1 is a cross-sectional view of one embodiment of a nozzle preferably used in the present invention.
- the liquid crystalline resin of the present invention has a structural unit derived from at least two kinds of aromatic diols as an essential structural unit, and has a melting point of + 10 ° C. in a helium gas atmosphere (provided that the melting point is less than 325 ° C.).
- Liquid crystalline resin with less than lOOppm of acetic acid gas, less than 20ppm of phenol gas and less than lOOppm of carbon dioxide gas when kept at 335 ° C) for 30 minutes. is there.
- the amount of acetic acid gas generated is preferably at most 80 ppm, more preferably at most 50 ppm, even more preferably at most 20 ppm.
- the amount of phenol gas is preferably 10 ppm or less, more preferably 8 ppm or less.
- the carbon dioxide content is preferably 80 ppm or less, more preferably 60 ppm or less.
- the melting point of the liquid crystalline resin is determined by measuring the endothermic peak temperature (endothermic peak temperature observed when the polymer after polymerization is measured from room temperature to 20 ° CZ in the temperature rising condition by differential calorimetry). (Tml), hold at Tml + 20 ° C for 5 minutes, cool down to room temperature under 20 ° CZ, then measure again at 20 ° CZ The measured endothermic peak temperature (Tm2).
- the amounts of acetic acid gas, phenol gas and carbon dioxide gas generated can be determined, for example, by a pyrolysis gas chromatograph mass spectrometer (TGZGC-MS) under a helium gas flow.
- TGZGC-MS pyrolysis gas chromatograph mass spectrometer
- the liquid crystalline resin of the present invention contains structural units derived from at least two types of aromatic diols.
- aromatic diol examples include 4,4′-dihydroxybiphenyl, hydroquinone, resorcinol, and the like. t-butylhydroquinone, phenylhydroquinone, black hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 3,4'-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, And 4,4'-dihydroxydiphenyl ether.
- Examples of the combination of two kinds of aromatic diols include a combination of 4,4'-dihydroxybiphenyl and hydroquinone, a combination of 4,4, dihydroxybiphenyl and 2,6-dihydroxynaphthalene, and hydroquinone.
- a combination of 2,4-dihydroxynaphthalene and 2,4-dihydroxynaphthalene is particularly preferred, and a combination of 4,4'-dihydroxybiphenyl and hydroquinone is particularly preferred.
- a phenolic hydroxyl group in a monomer used as a raw material to be used is reacted with an acetylating agent such as acetic anhydride to perform an acetylation reaction (hereinafter referred to as an "acetylation process"). )), Followed by polycondensation.
- the acetylation reaction is preferably performed at a temperature of 140 ° C. or more and 150 ° C. or less.
- a reaction vessel equipped with a distillation tube and a rectification column can be used as an apparatus for the acetyl-dani reaction.
- the reaction time of asetiluidani is roughly about 115 hours, but differs depending on the liquid crystalline resin raw material used and the reaction temperature.
- the reaction time is preferably 2.1 to 2.9 hours.
- one of the phenolic hydroxyl groups of the aromatic diol is usually acetylated to form a mono-acetylated product, and further acetylation proceeds to form a di-acetyl-terminated product.
- acetylacetyl indicates the concept of a reaction for converting a hydroxyl group to an acetyl group, and includes all of monoacetylation, diacetylylani, and the like.
- At least two kinds of diol components used in the present invention are subjected to a monoacetirido reaction.
- the reactivity is generally similar, it is preferable that the combination has a difference in reactivity between monoacetylated compound and diacetylated compound.
- 4,4'-dihydroxybiphenyl and hydroquinone have almost the same monoacetylation reaction rate, but when the reaction is carried out under the same conditions, hydroquinone has a higher monoacetylated compound than 4,4, dihydroxybiphenyl.
- the reaction rate of the compound to diacetyl compound (hereinafter, referred to as the diacetyl reaction rate) is low.
- the diacetylation reaction rate of the monoacetylated product is the slowest, and the residual amount of the monoacetylated product of the aromatic diol (A) is determined by the aromatic content.
- the concentration is preferably 0.8 to 5 mol%, more preferably 1 to 13 mol%. . 2 2. it forces more preferably carried out until the 4 Monore 0/0.
- the remaining amount of the monoacetyl terrestrial object is calculated by the following equation.
- the diacetylation reaction rate is the slowest!
- the reaction rate of diacetylation of aromatic diols other than diol (A), ie, monoacetylated product, is high, and the residual amount of monoacetylated aromatic diol is less than 0.5 mol% when the charged mole amount is 100 mol%. It is preferred that
- the composition ratio other aromatic diols is a 20-30 mol 0/0.
- the remaining amount of the monoacetili sword can be determined by the above-described formula. Specifically, for example, a part of the reaction mixture after the acetylation step is sampled, and the peak intensity force can be calculated as follows by nuclear magnetic resonance spectrum measurement. Here, the peak intensity corresponds to the area of the peak.
- acetylation is carried out with a sufficient molar ratio of acetic anhydride, reaction temperature, and reaction time, and the residual amount of the monoacetyl chloride is generally close to zero.
- the terminal of the obtained liquid crystalline resin has almost the same amount of the terminal of the acetyl group and the terminal of the carboxyl group, and it is considered that acetic acid gas, carbon dioxide gas and phenol gas are easily generated. It is.
- the acetylated hydroxyl terminal which causes acetic acid gas, and the generation of carbon dioxide gas and phenol gas are generated. It is thought that the carboxylic acid terminal derived from p-hydroxybenzoic acid can be reduced.
- the liquid crystalline resin of the present invention requires at least two types of structural units derived from an aromatic diol as essential structural units, but other structural units satisfy the gas amount defined by the present invention. There is no particular limitation as long as fat can be obtained.
- the liquid crystalline resin is a resin that forms an anisotropic molten phase, and examples thereof include a liquid crystalline resin having an ester bond such as a liquid crystalline polyester and a liquid crystalline polyesteramide.
- the liquid crystalline polyester includes, for example, structural units derived from at least two kinds of aromatic diols, ie, aromatic dioxy units, and aromatic carboxylic acid units, aromatic dicarbonyl units, and ethylenedioxy units. And polyesters that form an anisotropic molten phase consisting of structural units selected to form a liquid crystalline polyester.
- aromatic oxycarbol unit examples include structural units derived from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and the like. Among them, a structural unit derived from p-hydroxybenzoic acid is preferable.
- aromatic dicarbonyl unit examples include, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenediene Rubonic acid, 4,4, -diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4, dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'- Structural units derived from dicarboxylic acid, 4,4'-dietheretherdicarboxylic acid and the like are included. Among them, structural units derived from terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferred.
- ethylenedioxy unit preferably include structural units derived from ethylene glycol and the like.
- liquid crystalline polyester examples include a structural unit derived from p-hydroxybenzoic acid, a structural unit derived from 4,4'-dihydroxybiphenyl, a structural unit derived from hydroquinone, and terephthalic acid and Z or Liquid crystalline polyester consisting of structural units derived from isophthalic acid, structural units derived from p-hydroxybenzoic acid, structural units derived from ethylene glycol, structural units derived from 4,4'-dihydroxybiphenyl , A liquid crystalline polyester having a structural unit derived from terephthalic acid and Z or isophthalic acid, a structural unit derived from p-hydroxybenzoic acid, a structural unit derived from hydroquinone, 4, 4 'Structural unit derived from dihydroxybiphenyl, derived from 2,6-naphthalenedicarboxylic acid Structural unit and liquid crystalline polyester with structural unit strength derived from terephthalic acid, structural unit derived
- liquid crystal polyester forming the anisotropic molten phase include liquid crystal polyesters having the following structural units (1), (II), (III), (IV) and (V). Is mentioned.
- the structural unit (I) is a structural unit derived from ⁇ -hydroxybenzoic acid
- the structural unit (II) is a structural unit derived from 4,4 dihydroxybiphenyl
- the structural unit (III) is hydroquinone
- the structural unit (IV) represents a structural unit derived from terephthalic acid
- the structural unit (V) represents a structural unit derived from isophthalic acid.
- liquid crystalline polyester will be described as an example.
- copolymerization amount of the above structural units (1), ( ⁇ ), (III), (IV) and (V) is arbitrary. However, in order to exhibit the characteristics of the present invention, the following copolymerization amount is preferable.
- the copolymerization of the structural unit (I) is a structural unit (1), (II) and preferably from preferably instrument that is 40- 85 mol 0/0 of the total of (III) is 65- 80 mol 0/0, further preferred properly is 68- 75 mol%. Further, the copolymerization of the structural unit (II) is preferably from it preferably tool is 60- 90 mol 0/0 relative to the total amount of the structural units (II) and (III) at 60- 75 mole% And more preferably 65 to 73 mol%.
- the copolymerization of the structural unit (IV) is preferably 40- 95 mol% relative to the total amount of the structural units (IV) and (V), more preferably 60- 92 Monore 0/0, further preferably 72- 92 Monore 0/0.
- a liquid crystalline polyester having a melting entropy ( ⁇ S) within a preferable range as described later is obtained.
- the total of structural units (II) and (III) and the total of (IV) and (V) are substantially equimolar.
- substantially equimolar means that the units constituting the polymer main chain excluding the terminal are equimolar, and the units constituting the terminal are not necessarily equimolar. .
- liquid crystalline resin comprising the structural unit (I)-(V)
- a liquid crystalline resin using 2,6-dihydroxynaphthalene instead of hydroquinone to give the structural unit (III) is also used.
- the preferred ratio of the structural unit is the same as the ratio in which the above (III) is replaced with a structural unit derived from 2,6-dihydroxynaphthalene.
- liquid crystalline resin having the structural unit (I)-(V) power a liquid crystalline resin using 2,6-naphthalenedicarboxylic acid instead of isophthalic acid to give the structural unit (V) may be used.
- V a liquid crystalline resin using 2,6-naphthalenedicarboxylic acid instead of isophthalic acid to give the structural unit (V)
- the ratio of the structural unit is the same as the ratio of the above (V).
- the liquid crystal polyester preferably used includes, in addition to the component constituting the structural unit (I)-(V), 3,3'-difluorodicarboxylic acid and 2,2'-difluorodicarboxylic acid.
- Aromatic dicarboxylic acids such as aromatic dicarboxylic acids, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, etc .; alicyclic dicarboxylic acids such as hexahydroterephthalic acid;
- Aromatic diols such as enyl, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfide, 4,4'dihydroxybenzophenone, 3,4-dihydroxybiphenyl, propylene Glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexaned
- liquid crystal ⁇ of the present invention is preferably defined by the equation [1] delta S (entropy of fusion) is 0. 9 X 10- 3 jZg'K below.
- delta S entropy of fusion
- Such a liquid crystalline resin exhibits particularly high mechanical strength even in a state close to non-alignment.
- ⁇ S ⁇ / g ⁇ ⁇ ) ⁇ Hm Q / g) / [Tm (° C) + 273] — [1]
- Tml the endothermic peak temperature observed when the polymerized polymer was measured from room temperature to 20 ° C for 20 minutes in the differential calorimetry was measured.
- Tm2 the endothermic peak temperature observed when the sample is kept at the temperature for 5 minutes, cooled to room temperature under the temperature-lowering condition of 20 ° CZ, and cooled again under the temperature-raising condition of 20 ° CZ.
- ⁇ Hm is the heat of fusion ( ⁇ Hm2) for which the endothermic peak area force was also calculated.
- AS « is 0. 9 X 10- 3 jZg'K less, more preferably, 0. 7 X 10- 3 is a JZg'K less, more preferably 0. 5 X 10- 3 jZg'K or less.
- High crystallinity means a state in which the restraint of the amorphous part is small, and as a result, the ratio of the crystalline part is increased. In such a state, the restraint is weak at high density crystal parts and low density, and there is a large gap between the existence of molecular chains between the amorphous parts. Soft parts are scattered with great turbulence, and both mechanical strength and heat resistance are reduced.
- ⁇ S of the liquid crystalline resin is in the above-mentioned preferable range of U, the crystal and amorphous portions are not disordered, the molecules are arranged neatly, and all the molecules are totally formed.
- the chains are very ordered, close to the same, and exhibit high mechanical strength and heat resistance without orientation.
- the molecular chains are packed (the molecular chains are arranged at a high density), and the distance between the molecular chains is reduced. The difference is larger at larger parts.
- the distance between the molecular chains is in the middle.
- Such a liquid crystalline resin is preferable because it contains a moderate looseness.
- Crystallinity can be evaluated by evaluating the heat of fusion ( ⁇ ).
- the distance between the molecular chains can be evaluated, for example, by X-ray diffraction using ⁇ -alumina as an internal standard, based on the diffraction angle (2 °) of the peak.
- the melt viscosity of the liquid crystalline resin in the present invention is preferably from 10 to 500 Pa's, particularly preferably from 12 to 20 OPa's.
- the melt viscosity is a value measured by a Koka flow tester under the conditions of melting point (Tm) + 10 ° C. and a shear rate of 1000 (1Z seconds).
- the melting point of the liquid crystalline resin is controlled by combining the copolymer components.
- the melting point of the liquid crystalline resin in the present invention is not particularly limited, but is preferably 280 ° C or higher, more preferably 300 ° C or higher, for use in high heat resistance applications.
- the temperature is more preferably 310 ° C or more, and most preferably 325 ° C or more.
- the upper limit of the melting point is preferably not higher than the decomposition temperature of liquid crystalline resin—10 ° C. Since the decomposition temperature of the above-mentioned liquid crystalline polyester is around 370 ° C, the melting point is preferably 360 ° C or less.
- the basic method for producing the liquid crystalline resin of the present invention is not particularly limited as long as the liquid crystalline resin specified in the present invention can be obtained, but the liquid crystalline resin containing at least two kinds of aromatic diols is not limited.
- a raw material preferably further using an aromatic hydroxycarboxylic acid
- an acetic anhydride is reacted with phenolic hydroxyl groups in the liquid crystalline resin raw material, for example, the phenolic hydroxyl groups of aromatic hydroxycarboxylic acid or aromatic diol and acetic anhydride.
- a production method including a step and a step of performing polycondensation with the remaining liquid crystalline resin raw material (aromatic dicarboxylic acid or other monomer) thereafter is preferable.
- the polycondensation is preferably carried out under reduced pressure at a temperature at which the liquid crystalline resin melts.
- the amount of acetic anhydride used is preferably 0.001 to 1.10 monoequivalents of the total of phenolic hydroxyl groups in the liquid crystalline resin raw material to be used, and is preferably 1.03 to 1.09 monoequivalents. More preferable than S. 1.05-1.08 Mono-equivalent force is even more preferable! / ⁇ .
- the amount of acetic anhydride is in the above range, it is particularly preferable to easily control the residual amount of the monoacetylated aromatic diol in the acetylation step.
- the following production method is preferably exemplified.
- the following is an example of the synthesis of a liquid crystalline polyester consisting of p-hydroxybenzoic acid and 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid.
- the composition is not limited to these, and each may be replaced with other hydroxycarboxylic acids and aromatic diols! /, And can be produced according to the following method by replacing with aromatic dicarboxylic acids.
- the acetylation and polycondensation may be continuously performed in the same reaction vessel, but the acetylation and polycondensation may be performed in different reaction vessels.
- the degree of reduced pressure is more preferably 133 Pa or less.
- the final polymerization temperature is preferably 360 ° C. or less, which is preferably about melting point + 20 ° C.
- the stirring speed is preferably 50 rpm or less.
- the polymerization time from the detection of a predetermined torque to the end of polymerization is more preferably 0.5 to 1 hour.
- the obtained polymer is taken out of the reaction vessel by pressurizing the inside of the reaction vessel at a temperature at which the polymer melts, for example, to about 0.02 to 0.5 MPa, and placing the polymer in the lower part of the reaction vessel.
- the strands are discharged from the discharge port, and the strands are cooled in cooling water and cut into pellets to obtain resin pellets.
- the melt polymerization method is an advantageous method for producing a uniform polymer, and is preferable because an excellent polymer can be obtained with a smaller gas generation amount.
- the polycondensation reaction can be completed by a solid phase polymerization method.
- the polymer or oligomer of the liquid crystalline resin of the present invention is pulverized with a pulverizer, and is heated under a nitrogen stream or under reduced pressure in a temperature range of 5 ° C. to 50 ° C. of the liquid crystalline resin.
- Solid state polymerization is an advantageous method for producing polymers with a high degree of polymerization.
- the polycondensation reaction of the liquid crystalline resin proceeds without a catalyst
- metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and metallic magnesium may be used. it can.
- 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 even more preferably 8,000 to 18,000.
- the number average molecular weight can be measured by a GPC-LS (gel permeation chromatography-light scattering) method using a solvent in which a liquid crystalline resin is soluble.
- GPC-LS gel permeation chromatography-light scattering
- the liquid crystalline resin produced by deacetic acid polycondensation can be hydrolyzed by, for example, adding water to change the terminal acetyl group to a hydroxyl group.
- the liquid crystalline resin is used.
- Most of the terminal hydroxyl groups are hydroxyl groups derived from oxycarboxylic acid, and the molecular weight is reduced, which is not preferable because oligomers are generated.
- the terminal is a hydroxyl group derived from an aromatic oxycarboxylic acid, it is not preferable because carbon dioxide gas and phenol gas are generated by elimination and thermal decomposition of the aromatic oxycarboxylic acid having low heat stability and oxidation resistance. .
- a filler can be further blended in order to impart the mechanical strength and other properties of the liquid crystalline resin.
- the filler is not particularly limited, but a fibrous, plate-like, powdery, granular filler or the like can be used.
- the filler used in the present invention may be used by treating its surface with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent
- glass fiber is particularly preferably used in terms of balance between availability and mechanical strength.
- the type of glass fiber is not particularly limited as long as it is used for reinforcing a resin.
- a long fiber type or short fiber type chopped strand and milled fiber can also be selected and used. Two or more of these can be used in combination.
- a weakly alkaline glass fiber is excellent in mechanical strength and can be preferably used.
- an epoxy-based sizing agent which is preferably treated with a coating or sizing agent such as an epoxy-based, urethane-based, or acrylic-based glass, is particularly preferable.
- an epoxy silane or amino silane coupling agent which is preferably treated with a coupling agent such as a silane or titanate, or other surface treatment agent, is particularly preferable.
- the glass fiber may be coated with a thermoplastic resin such as an ethylene Z-vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or may be bundled.
- a thermoplastic resin such as an ethylene Z-vinyl acetate copolymer or a thermosetting resin such as an epoxy resin
- the compounding amount of the filler is preferably 30 to 200 parts by weight, more preferably 40 to 150 parts by weight, based on 100 parts by weight of the liquid crystalline polyester.
- 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, etc.) ), Phosphites, hypophosphites, etc., anti-coloring agents, lubricants and mold release agents (montanic acid and its metal salts, its esters, herfest, stearyl alcohol, stearamide and polyethylene wax, etc.), dyes And carbon black, crystal nucleating agent, plasticizer, flame retardant (bromine flame retardant, phosphorus flame retardant, red phosphorus, silicone flame retardant, etc.) And ordinary additives such as antistatic agents and polymers other than thermoplastic resins to further impart the specified properties.
- an antioxidant and a heat stabilizer for example, hindered phenol, hydroquinone, phosphites and the like
- an ultraviolet absorber for example, resorcinol, salicylate, etc
- the method of blending these additives is preferably melt kneading.
- the liquid crystalline resin composition is melt-kneaded at a temperature of 180 to 350 ° C, more preferably 250 to 320 ° C, using a Banbury mixer, a rubber roll machine, a kneader, a single screw or twin screw extruder, or the like. It can be.
- the liquid crystalline resin of the present invention and the liquid crystalline resin composition containing the same are excellent in low gas properties, and have excellent surface appearance by ordinary molding methods such as injection molding, extrusion molding, and press molding. It can be applied to three-dimensional molded products, sheets, containers, pipes, films, etc. having (color), mechanical properties, heat resistance and flame retardancy. Among them, it has excellent fluidity and low gas properties and is suitable for electric and electronic parts obtained by injection molding.
- liquid crystalline resin and the liquid crystalline resin composition containing the same according to the present invention can remarkably improve the productivity of precision molded articles, since blisters are very unlikely to occur.
- liquid crystalline resin of the present invention and the liquid crystalline resin composition containing the same are excellent in processability as a film due to high solidification rate and high homogeneity, and have small thickness unevenness. A film is obtained.
- a T-die method is preferable in order to minimize thickness unevenness and make use of characteristics.
- the channels from multiple holders are machined so that they gradually become oblique to the film discharge direction and become narrower as the channels become longer.
- Films having multiple layers of different orientations can be obtained.
- the film thus obtained has excellent mechanical properties and dimensional stability in all directions.
- the lip opening degree is preferably 0.3 mm or less, more preferably 0.2 mm or less, and the viewpoint force of thickness unevenness is preferably 0.1 mm or less.
- liquid crystalline resin of the present invention and the liquid crystalline resin composition containing the same have an appropriate margin for liquid crystal packing, and therefore, are subjected to solid-state polymerization when formed into fibers. Very high-strength fibers can be obtained.
- the obtained liquid crystal resin fiber is used for differential calorimetry!
- the heat of fusion (AHml) at the endothermic peak (Tml) observed when the temperature is measured from room temperature to 20 ° CZ is the temperature at Tml + 20 ° C after the observation of Tml.
- the heat of fusion (A Hm2) at the endothermic peak (Tm2) observed when the temperature is measured again under the temperature-raising condition of 20 ° CZ ) Is preferably less than 3 times, more preferably less than 2 times. This value indicates that the fiber has not been subjected to solid state polymerization.
- the fiber strength of the obtained liquid crystal resin fiber is preferably 12 cNZdtex or more.
- a tapered portion in which the diameter of the liquid crystalline resin of the present invention is continuously reduced toward the spinning hole is smaller than that when the liquid crystalline resin is spun by a normal spinning method. It is preferable that the liquid crystalline resin is melt-spun using a nozzle having a length of at least 80% of the total length of the nozzle hole and a total length of the nozzle hole of 10 to 20 mm.
- the nozzle may be configured as a single component, may have a plurality of component strengths, or may be formed by integrating the nozzle and other members.
- the portion treated as a nozzle refers to the portion where the inlet hole on the upstream side of the tapered portion and the spinning hole on the downstream side of the tapered portion are combined. If the inlet hole and Z or the spinning hole have a straight hole, the nozzle For the portion treated as, the total length of the nozzle and the tapered portion in addition to the straight hole portion of the introduction hole and Z or the spinning hole is the total nozzle length, and the other portions are not treated as nozzles.
- the length of the tapered portion is at least 85%, more preferably at least 90%, of the entire length of the nozzle hole.
- the most preferred nozzle for the inlet hole is a continuous taper up to the spinning hole.
- the total length of the nozzle hole is more preferably 10 to 15 mm, more preferably 10 to 12 mm.
- the fiber strength becomes 1.5 times or more as compared with the case where the spinning is performed using a normally used straight-hole nozzle.
- the rate of this increase is preferably 1.7 times or more, more preferably 2 times or more, than the force affected by the taper angle or the taper length.
- the melt spinning refers to a method of melting at a temperature higher than the melting point (Tm2) of the thermoplastic liquid crystalline resin, and processing into a thread through a nozzle.
- melt spinning unlike liquid spinning, in which a liquid crystalline resin is dissociated into a solvent, processed as a solution through a nozzle into a thread, and the solvent is removed by drying, a secondary substance such as a solvent is not used.
- the process is very simple.
- the fiber obtained by melt spinning does not require drying, a high-quality fiber can be obtained without causing defects such as voids due to evaporation of the solvent inside.
- the fiber strength can be increased by drawing.
- the draft ratio was increased because the liquid crystalline resin was already aligned without being stretched when it entered the nozzle introduction hole. Even so, the strength does not improve much.
- the liquid crystalline resin as described above is used, and the liquid crystalline resin fiber spun using the specific nozzle is heat-treated or solid-phase polymer irrespective of the draft ratio. Extremely high strength without passing. In addition, since the liquid crystal is already highly packed, there is no significant improvement in strength even after heat treatment or solid-phase polymerization, so it is possible to perform heat treatment or solid-phase polymerization if desired. From the viewpoint of strength, heat treatment or solid state polymerization is not usually required. [0111] If the taper angle is too steep, liquid crystal packing of the liquid crystalline resin fiber does not proceed, and the main flow of spinning is generated at the center of the tapered portion, and a stagnant portion is formed on the outer wall of the tapered portion. Therefore, a preferable taper angle is 1 to 20 °, more preferably 2 to 15 °, and further preferably 2.5 to 10 °.
- the taper angle is determined by the diameter of the spinning hole of the spinning nozzle, the diameter of the spinning hole from which the resin is discharged, and the length of the tapered portion in the nozzle length direction.
- the diameter of the introduction hole is preferably 0.5-3 mm ⁇ , more preferably 0.8-2. 5 ⁇ ⁇ , and still more preferably 1.0-2. Omm ⁇ .
- the spinning hole diameter is preferably 0.1-0.5 mm ⁇ , more preferably 0.12-0.3 mm ⁇ , and still more preferably 0.13-0.25 ⁇ ⁇ .
- a nozzle having a single hole for a single yarn or a nozzle having a plurality of holes for a multi-yarn may be used.
- the shape and dimensions of the holes may be the same for all the holes, but the holes have different or different force to adjust the discharge balance. It may be something! / ,.
- FIG. 1 is a cross-sectional view of one embodiment of a nozzle preferably used in the present invention.
- a nozzle hole 2 having a tapered portion 3 is provided in the nozzle 1, and an introduction hole 4 and a subsequent straight hole 6 on the introduction hole side, a straight hole 7 on the spinning hole side, and a subsequent spinning hole 5 are provided at one end thereof. Have been.
- La, Lt, and Lb respectively represent the length of the straight hole on the introduction hole side, the length of the tapered portion, and the length of the straight hole on the spinning hole side, and Da and Db represent the diameters of the introduction hole and the spinning hole, respectively.
- ⁇ indicates a taper angle.
- the (La + Lb + Lt) force represents the total length of the slip hole
- Lt represents the length of the tapered portion. For example, if (La + Lb + Lt) is 10 mm and the taper is 9.9 mm, the length of the taper is 99% (Lt / (La + Lb + Lt) x 100) of the total nozzle length. is there.
- the diameter of the inlet hole Da is 1.5 mm ⁇
- the diameter Db of the spinning hole is 0.15 mm ⁇
- the length of the inlet hole side is 0.09 mm
- the diameter of the straight hole is 1.5 ⁇
- the diameter of the discharge hole side is If there is a straight hole with a length of 01mm, the taper angle is 7.7 °.
- La is the force which is the length of the straight hole portion of the introduction hole. This may be 0.
- Lb is the length of the straight hole portion of the spinning hole. Is also good.
- the straight hole is generated due to a processing limit, and is preferably as small as possible.
- the length of the straight hole on the introduction hole side is preferably 2 mm or less in the nozzle length direction, more preferably 1 mm or less, and further preferably 0.5 mm or less.
- the length of the straight hole on the spinning hole side is preferably not more than 0.06 mm in the length direction of the nozzle, more preferably not more than 0.03 mm.
- the nozzle of the present invention is provided with at least one tapered portion, and the tapered portion preferably continuously occupies 80% of the entire nozzle length. From the viewpoint of improving the accuracy, the tapered portion may not be completely continuous, but may have an extremely short straight hole between the tapered portions.
- the number of the straight holes is preferably two or less, more preferably one or less, and most preferably none.
- the length of the straight hole portion in the taper is preferably 0.05 mm or less, more preferably 0.05 Olmm or less at each location.
- the straight hole portion in the taper is also treated as the taper length.
- the melting point of the liquid crystalline resin is higher than + 15 ° C, and the melting point is +40.
- the melting point is preferably lower than 20 ° C. and more preferably lower than 35 ° C.
- temperature refers to the extruder and compression melter used for plasticizing during spinning, all the devices from the filter to the nozzle through the sand pack, and the piping and nozzles that connect it. Refers to all the temperatures at each part.
- the liquid crystalline resin is sufficiently plasticized.
- the liquid crystal packing effect by the taper nozzle of the present invention is preferably increased.
- the liquid crystalline resin fiber of the present invention has high strength even when the draft ratio is not increased during spinning.
- the draft ratio is preferably set to 1 to 50, more preferably 2 to 35, and further preferably 3 to 15 It is.
- the ⁇ ⁇ ⁇ 2 of the fiber is almost the same as the ⁇ 2 of the liquid crystalline resin before spinning, and is a value specific to the composition of the liquid crystalline resin.
- the ⁇ Hml of the fiber is less than 3 times the ⁇ Hm2, it is easy to recycle because heat treatment or solid phase polymerization that greatly changes the ⁇ Hml has not been performed, and more preferably less than 2 times. Yes, and more preferably less than 1.5 times.
- the lower limit is preferably 0.1 times.
- the liquid crystalline resin fiber having the above heat of fusion has not been subjected to a heat treatment that greatly changes ⁇ Hml after spinning, and has not been subjected to heat treatment or solid-phase polymerization. Does not cause high crystallization or high melting point which is a side reaction of polymerization. For this reason, the liquid crystalline resin fiber can be recycled at a temperature lower than the melting point at which the liquid crystalline resin is usually processed plus 20 ° C.
- the fiber strength of the liquid crystalline resin fiber of the present invention is more preferably 14 cNZdtex or more, and further preferably 16 cNZdtex or more.
- An upper limit of 25 cNZdtex or less can be practically preferably used.
- the fiber strength refers to the strength of a single yarn.
- the fiber strength can be measured using, for example, Tensilon UCT-100 manufactured by Orientec, according to JIS L1013.
- the liquid crystalline resin of the present invention and the liquid crystalline resin composition containing the same include, for example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, and the like.
- VTR parts TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio 'laser disc' compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriters Household, office electrical product parts, office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, coilless bearings, stern bearings, such as parts, word processor parts, etc.
- audio equipment parts such as audio 'laser disc' compact discs
- lighting parts refrigerator parts, air conditioner parts, typewriters Household
- office electrical product parts office computer-related parts
- telephone-related parts facsimile-related parts
- copier-related parts copier-related parts
- cleaning jigs coilless bearings
- stern bearings such as parts, word processor parts, etc.
- Various bearings such as underwater bearings, Parts, such as motor parts, lighters, tie-writers, etc., optical equipment such as microscopes, binoculars, cameras, watches, etc., precision machinery parts, alternator terminals, alternator connectors, IC regulators, light regulators
- Various valves such as a potentiometer base, gas and gas valves, fuel-related exhaust systems, various intake systems pipes, 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, slot position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, air conditioner thermostat base, Motor insulators for air conditioners, separators, heating hot air flow controllers, rono levano levers, radiator motor brush honed ladders, water pump impellers, turbine vanes, wiper motor related parts, dust distributors, starter switches, starter relays, transmission wire harnesses, Window washer Nozzle,
- the film of the present invention includes films for magnetic recording media, films for photography, films for capacitors, films for electrical insulation, films for packaging, films for drafting, films for ribbons, Applications include automotive interior ceilings, door trims, padding for instrument panels, cushioning materials for bumpers and side frames, sound absorbing pads such as the back of bonnets, seating materials, pillars, fuel tanks, brake hoses, and window washer fluids. It is useful for nozzles for air conditioners, tubes for air conditioner refrigerants and their peripheral parts.
- the fibers of the present invention include screen gauze, combination ribbon, print base fabric, air bag, airship, dome, etc., rider suit, fishing line, various lines (yacht, paraglider, balloon). It is useful for PET chain substitute yarn, blind cord, screen door support cord, various cords in automobiles and aircrafts, and power transmission cords for electrical products and robots.
- the pressure was reduced to 133 Pa in 1.0 hour, and the reaction was continued for another 50 minutes.
- the torque reached 20 kgcm, the polycondensation was completed.
- the inside of the reaction vessel was pressurized to O.lMPa, the polymer was discharged into a strand through a die having one circular discharge port with a diameter of 10 mm, and pelletized with a cutter.
- the liquid crystal ⁇ (A- 1) is a structural unit derived from p- hydroxybenzoic acid (structural unit (1)) 60 mol 0/0, 4, 4, over-dihydroxy bi Hue - from Le structural unit (structural unit (II)) 14 mol 0/0, the structural unit derived from hydroquinone (structural unit (III)) 6 mole 0/0, structural units derived from terephthalic acid (structural unit (IV)) 18 ..
- structural unit of derived from isophthalic acid structural unit (V)
- structural unit (V) structural unit of derived from isophthalic acid
- l 6 mole 0/0 power et structural unit of derived from isophthalic acid
- the structural unit derived from the above was in a ratio of 70:30 (structural unit (II): structural unit (III)).
- Structural unit (I) is the sum of structural units (1), (II) and (III)
- structural unit (IV) is 92 mol% with respect to the total of the structural units (IV) and (V), and the total of the structural units (II) and (III) and (IV) And the sum of (V) was equimolar.
- the melting point of the liquid crystalline ⁇ at 348 ° C, delta S is 0. 6 X 10- 3 jZg'K, using Koka type flow one tester, temperature 360 ° C, shear rate 1000 / Melt viscosity measured in s is 20 Pa's.
- the melting point (Tm) was determined by measuring the endothermic peak temperature (Tml), which was observed when the polymer was measured from room temperature to 20 ° CZ for 20 minutes after the differential calorimetry. After holding at a temperature of 20 ° C for 5 minutes, once cooling to room temperature under a temperature-lowering condition of 20 ° CZ, the endothermic peak temperature (Tm2 ). The same applies to the following examples.
- lb Peak intensity attributable to the hydrogen atom bonded to the ⁇ -position carbon of the aromatic carbon in which the acetyl group of the aromatic diol is bonded to the monoacetylated compound or the diacetylated compound.
- a sample (150 mg) was preliminarily dried at 150 ° C. for 5 hours, and measured using a simultaneous measuring device combining a TG40M manufactured by Shimadzu Corporation and a GC / MS QP5050A manufactured by Shimadzu Corporation.
- the sample was kept in a helium atmosphere at a temperature of melting point + 10 ° C for 30 minutes. However, liquid crystalline resins having a melting point of less than 325 ° C were kept at 335 ° C.
- the generated gas is trapped by the adsorbent, and the adsorbent is reheated by a thermal desorption device (280 ° C, adsorbent C300).
- GC-MS measurement (column PTEM-5).
- the mass type power of the GC-MS measurement was specified, and the gas type was specified.
- the total loss on heating and the peak intensity were calculated for the amounts of acetic acid gas, phenol gas, and carbon dioxide gas generated.
- the liquid crystalline resin composition pellets are supplied to a FANUC 30a C injection molding machine, extruded at a cylinder melting point of + 10 ° C, and formed into a rod-like shape having a length of 150mm x a width of 12.7mm x a thickness of lmm.
- the product was molded. After performing a wet heat treatment at 120 RH% and 95 ° C for 8 hours, a heat treatment was performed in a reflow bath at 275 ° C for 10 minutes, and the number of blisters generated was evaluated for 1000 molded articles.
- the molded article molded in (3) and a 2 cm square 2 mm thick iron plate were placed in a glass Petri dish, covered, and treated in an oven at 150 ° C for 200 hours. Discoloration and corrosion of the iron plate were visually judged.
- A discoloration, no corrosion
- B discoloration, no corrosion
- C discoloration, corrosion.
- the molded article was placed in a glass petri dish in the same manner as in (4), covered, and allowed to stand on a hot plate at 270 ° C. The time until clouding of the top of the glass petri dish was determined (maximum 50 hours)
- the polymerization temperature was maintained at 350 ° C., and the mixture was heated with stirring for 1 hour. Thereafter, the pressure was reduced to 133 Pa in 1.0 hour, and the reaction was continued for another 42 minutes. When the torque reached 20 kgcm, the polycondensation was completed.
- the inside of the reaction vessel was pressurized to O.lMPa, the polymer was discharged into a strand through a die having one circular discharge port with a diameter of 10 mm, and pelletized with a cutter.
- This liquid crystalline resin (A-2) had a structural unit derived from p-hydroxybenzoic acid (structural unit (I)) of 54 mol%, and a structural unit derived from 4,4'-dihydroxybiphenyl (structure unit (II)) 16. 1 mole 0/0, the structural unit (structural unit (III) derived from hydroquinone) 6.9 mole 0/0, the structural unit (structural unit (IV) derived from terephthalic acid) 19.
- structural unit (V) ' structural unit derived from 2,6-naphthalenedicarboxylic acid
- structural unit (V) ' structural unit derived from 2,6-naphthalenedicarboxylic acid
- structural unit (V) ' structural unit derived from 2,6-naphthalenedicarboxylic acid
- structural unit (IV) structural unit (III)
- the structural unit (I) is 70 mol% with respect to the total of the structural units (1), (II) and (III)
- structural unit (IV) is the same as the structural unit (IV) and (V) ′. It was 83 mol% based on the total, and the total of the structural units (II) and (III) and the total of (IV) and (V) were equimolar.
- the melting point of the liquid crystalline ⁇ is delta S at 335 ° C was 0. 5 X 10- 3 jZg'K, using Koka type flow tester, the temperature 345 ° C, at a shear rate of 1000 / s
- the measured melt viscosity was 22 Pa's.o
- the polymerization temperature was maintained at 370 ° C, and the mixture was heated with stirring for 1 hour. Thereafter, the pressure was reduced to 133 Pa in 1.0 hour, and the reaction was continued for another 22 minutes. When the torque reached 20 kgcm, it was compressed. Completed. Next, the inside of the reaction vessel was pressurized to O.lMPa, the polymer was discharged into a strand through a die having one circular discharge port with a diameter of 10 mm, and pelletized with a cutter.
- the liquid crystal ⁇ (A- 3) is p- hydroxy structural unit derived from benzoic acid (structural unit (I)) 66. 8 mole 0/0, 4, 4, over-dihydroxy bi Hue - Le a structural unit derived from (structural unit (II)) 1 4. 8 mol 0/0, 2, structural units (structural units ( ⁇ ),) derived from the 6-dihydroxynaphthalene 1.8 mole 0/0, the terephthalic acid a structural unit derived from (structural unit (IV)) 10. 8 mole 0/0, structural units derived from isophthalic acid (structural unit (V)) 5.
- structural unit (II) structural unit (III), The structural unit (I) is 80 mol% with respect to the total of the structural units (1), (II) and (III), and the structural unit (IV) is the same as the structural unit (IV) and (V). The total was 65 mol%, and the total of structural units (II) and (III) and the total of (IV) and (V) were equimolar.
- the melting point of the liquid crystalline ⁇ is 355 ° C in AS is 0. 4 X 10- 3 jZg'K, using Koka type flow tester, the temperature 365 ° C, measured at a shear rate of 1000 / s The melt viscosity was 24 Pa's.o
- the polymerization temperature was maintained at 330 ° C, and the mixture was heated and stirred for 1 hour. Thereafter, the pressure was reduced to 133 Pa in 1.0 hour, and the reaction was continued for another 60 minutes. When the torque reached 20 kgcm, the polycondensation was completed.
- the inside of the reaction vessel was pressurized to O.lMPa, and the polymer was discharged into a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.
- the liquid crystal ⁇ (A- 4) is derived from p- structural units derived from hydroxybenzoic acid (structural unit (I)) 53. 8 mole 0/0, 4, 4 'over dihydroxy Biff enyl Structural unit (Structural unit (II)) 1 5 mole 0/0, the structural unit derived from hydroquinone (structural unit (III)) 8. 1 mole 0/0, structural units derived from terephthalic acid (structural unit (IV)) 15 mol%, derived from isophthalic acid consists structural unit of (structural unit (V)) 8.
- structure Unit (II) structural unit (III)
- the structural unit (I) is 70 mol% based on the total of the structural units (1), (II) and (III), and the structural unit (IV) is the total of the structural units (IV) and (V).
- the total of structural units (II) and (III) and the total of (IV) and (V) were equimolar.
- the melting point of the liquid crystalline ⁇ in the AS 310 ° C was 0. 3 X 10- 3 jZg'K, using Koka type flow tester, the temperature 320 ° C, measured at a shear rate of 1000 / s
- the melt viscosity was 20 Pa's.o
- Example 1 100 parts by weight of the liquid crystalline resin (A-1) obtained in Example 1 was mixed with 50 parts by weight of glass fiber (ECS03T-747H manufactured by Asahi Denki Glass) and kneaded at 350 ° C with a twin screw extruder. , Pelletized. Since the gas composition was measured using the resin composition as a sample, the gas generation amount was calculated by multiplying the measured gas generation amount by 3Z2 in order to evaluate the gas generation amount only by the liquid crystalline resin component force.
- ECS03T-747H manufactured by Asahi Denki Glass
- Example 1 was the same composition as in Example 1 except that the charged amount of acetic anhydride was changed to 1377 g (1.199 equivalents of the total phenolic hydroxyl group), and the acetyl violent conditions were performed at 170 ° C for 45 minutes. Polymerization was carried out under the same conditions as described above.
- the reaction was continued for 2 minutes at a final polymerization temperature of 360 ° C. and a reduced pressure of 133 Pa, and the polycondensation was completed when the torque reached 20 kgcm.
- the inside of the reaction vessel was pressurized to O.lMPa, the polymer was discharged into a strand through a die having one circular discharge port with a diameter of 10 mm, and pelletized by a cutter.
- the liquid crystal ⁇ (A- 5) is p- structural units derived from hydroxybenzoic acid (structural unit (I)) 60 mol 0/0, 4, 4, over-dihydroxy bi Hue - from Le structural unit (structural unit (II)) 14% by mole, the structural unit derived from hydroquinone (structural unit (III)) 6 mole 0/0, the terephthalic acid A structural unit derived from (structural unit (IV)) 18. 4 mol%, the structural unit (structural unit (V)) derived from isophthalic acid l.
- structural unit (I) is 75 mol% of the total of the structural units (1), (II) and (III), and the structural unit (IV) is the total of the structural units (IV) and (V). And the sum of the structural units (II) and (III) and the sum of (IV) and (V) were equimolar.
- Example 1 was the same composition as in Example 1 except that the charged amount of acetic anhydride was changed to 1286 g (1.12 equivalents of the total phenolic hydroxyl group), and the acetylation conditions were 155 ° C for 2 hours. Polymerization was performed under the same conditions as described above.
- the reaction was continued for 2 minutes at a final polymerization temperature of 360 ° C and a reduced pressure of 133 Pa, and the polycondensation was completed when the torque reached 20 kgcm.
- the inside of the reaction vessel was pressurized to O.lMPa, the polymer was discharged into a strand through a die having one circular discharge port with a diameter of 10 mm, and pelletized by a cutter.
- the liquid crystal ⁇ (A- 6) is p- structural units derived from hydroxybenzoic acid (structural unit (I)) 60 mol 0/0, 4, 4, over-dihydroxy bi Hue - from Le structural unit (structural unit (II)) 14% by mole, the structural unit derived from hydroquinone (structural unit (III)) 6 mole 0/0, structural units derived from terephthalic acid (structural unit (IV)) 18. 4 .
- structural units derived from isophthalic acid structural unit (V)) l 6 mole 0/0 power et becomes, 4, 4, over-dihydroxy bi Hue - from Le and two aromatic diols hydroquinone
- the structural units had a ratio of 70:30 (structural unit ( ⁇ ): structural unit (III)).
- the structural unit (I) is 75 mol% of the total of the structural units (1), (II) and (III)
- structural unit (IV) is the total of the structural units (IV) and (V).
- the sum of the structural units (II) and (III) and the sum of (IV) and (V) were equimolar.
- the melting point of the liquid crystalline ⁇ is AS in 349 ° C is 1. 4 X 10- 3 jZg'K, using Koka type flow tester, the temperature 359 ° C, measured at a shear rate of 1000 / s Melt viscosity is 21 Pa's I
- Example 1 was the same as Example 1 except that the amount of acetic anhydride charged was changed to 1205 g (1.05 equivalent of the total phenolic hydroxyl group), and the conditions of acetylation were performed at 155 ° C for 3 hours. Polymerization was performed under the same conditions as described above.
- the reaction was continued for 2 minutes at a final polymerization temperature of 360 ° C and a reduced pressure of 133 Pa, and the polycondensation was completed when the torque reached 20 kgcm.
- the inside of the reaction vessel was pressurized to O.lMPa, the polymer was discharged into a strand through a die having one circular discharge port with a diameter of 10 mm, and pelletized by a cutter.
- the liquid crystal ⁇ (A- 7) is p- structural units derived from hydroxybenzoic acid (structural unit (I)) 60 mol 0/0, 4, 4, over-dihydroxy bi Hue - from Le structural unit (structural unit (II)) 14% by mole, the structural unit derived from hydroquinone (structural unit (III)) 6 mole 0/0, structural units derived from terephthalic acid (structural unit (IV)) 18. 4 .
- structural units derived from isophthalic acid structural unit (V)) l 6 mole 0/0 power et becomes, 4, 4, over-dihydroxy bi Hue - from Le and two aromatic diols hydroquinone
- the structural units had a ratio of 70:30 (structural unit ( ⁇ ): structural unit (III)).
- the structural unit (I) is 75 mol% of the total of the structural units (1), (II) and (III)
- structural unit (IV) is the total of the structural units (IV) and (V).
- the sum of the structural units (II) and (III) and the sum of (IV) and (V) were equimolar.
- the melting point of the liquid crystalline ⁇ is AS in 349 ° C is 1. 4 X 10- 3 jZg'K, using Koka type flow tester, the temperature 359 ° C, measured at a shear rate of 1000 / s The melt viscosity was 21 Pa's.o
- Example 1 was the same composition as Example 1 except that the charged amount of acetic anhydride was changed to 1263 g (1.10 equivalents of the total phenolic hydroxyl group), and the conditions were changed to 140 ° C for 3 hours. Polymerization was performed under the same conditions as described above.
- the reaction was continued for 3 minutes at a final polymerization temperature of 360 ° C and a reduced pressure of 133 Pa, and the polycondensation was completed when the torque reached 20 kgcm.
- the inside of the reaction vessel is pressurized to O.lMPa, and the polymer is discharged into a strand through a die having one circular discharge port with a diameter of 10 mm. Pelletized.
- the liquid crystal ⁇ (A- 8) is p- structural units derived from hydroxybenzoic acid (structural unit (I)) 60 mol 0/0, 4, 4, over-dihydroxy bi Hue - from Le structural unit (structural unit (II)) 14% by mole, the structural unit derived from hydroquinone (structural unit (III)) 6 mole 0/0, structural units derived from terephthalic acid (structural unit (IV)) 18. 4 .
- structural units derived from isophthalic acid structural unit (V)) l 6 mole 0/0 power et becomes, 4, 4, over-dihydroxy bi Hue - from Le and two aromatic diols hydroquinone
- the structural units had a ratio of 70:30 (structural unit ( ⁇ ): structural unit (III)).
- the structural unit (I) is 75 mol% of the total of the structural units (1), (II) and (III)
- structural unit (IV) is the total of the structural units (IV) and (V).
- the sum of the structural units (II) and (III) and the sum of (IV) and (V) were equimolar.
- the melting point of the liquid crystalline ⁇ is AS in 348 ° C are 1. 5 X 10- 3 jZg'K, using Koka type flow tester, the temperature 349 ° C, measured at a shear rate of 1000 / s The melt viscosity was 22 Pa's.o
- Example 1 was the same composition as in Example 1 except that the charged amount of acetic anhydride was changed to 1183 g (1.03 equivalents of the total phenolic hydroxyl group), and the acetyl chloride conditions were 145 ° C for 2 hours. Polymerization was performed under the same conditions as described above.
- the reaction was continued for 121 minutes at a final polymerization temperature of 360 ° C. and a reduced pressure of 133 Pa. When the torque reached 20 kgcm, the polycondensation was completed.
- the inside of the reaction vessel was pressurized to O.lMPa, the polymer was discharged into a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.
- the liquid crystal ⁇ (A- 9) is p- structural units derived from hydroxybenzoic acid (structural unit (I)) 60 mol 0/0, 4, 4, over-dihydroxy bi Hue - from Le structural unit (structural unit (II)) 14% by mole, the structural unit derived from hydroquinone (structural unit (III)) 6 mole 0/0, structural units derived from terephthalic acid (structural unit (IV)) 18. 4 .
- Structural unit (I) is the sum of structural units (1), (II) and (III)
- the structural unit (IV) is 92 mol% with respect to the total of the structural units (IV) and (V), and the total of the structural units (II) and (III) and (IV) and ( The sum of V) was equimolar.
- the melting point of the liquid crystalline ⁇ is AS in 345 ° C is 1. 4 X 10- 3 jZg'K, using Koka type flow tester, the temperature 355 ° C, measured at a shear rate looo / s The melt viscosity was 23 Pa's.o
- the pressure was reduced to 133 Pa in 1.0 hour, and the reaction was continued for another 12 minutes.
- the torque reached 20 kgcm, the polycondensation was completed.
- the inside of the reaction vessel was pressurized to O.lMPa, the polymer was discharged into a strand through a die having one circular discharge port with a diameter of 10 mm, and pelletized with a cutter.
- the liquid crystal ⁇ (A- 10) is p- hydroxy structural unit derived from benzoic acid (structural unit (1)) 60 mol 0/0, 4, 4, over-dihydroxy bi Hue - from Le Structural unit (structural unit (II)) 20 mol%, structural unit derived from terephthalic acid (structural unit (IV)) 15 mol%, structural unit derived from isophthalic acid (structural unit (V)) 5 mol% , melting point is AS in 342 ° C is 2.
- IX 10- 3 j / g'K using Koka type flow tester, the temperature 352 ° C, melt viscosity measured at a shear rate of 1000 / s 25 Pa's met was.
- the structural unit (I) is 75 mol% based on the total of the structural units (1), (II) and (III), and the structural unit (IV) is the total of the structural units (IV) and (V). And the sum of structural units (II) and (III) and the sum of (IV) and (V) were the same.
- Comparative Example 6 except that the charged amount of acetic anhydride was changed to 1183 g (1.03 equivalent of the total phenolic hydroxyl group), and that the composition was the same as that of Example 1 and that the acetylation conditions were performed at 145 ° C for 2 hours. Polymerization was performed under the same conditions as described above. The reaction was continued for 145 minutes at a final polymerization temperature of 360 ° C. and a reduced pressure of 133 Pa. Since the torque did not reach 20 kgcm, the polycondensation was terminated.
- Polymerization was carried out under the same composition as in Example 2 except that the conditions were changed to 155 ° C. for 2 hours.
- the reaction was continued for 8 minutes at a final polymerization temperature of 350 ° C and a reduced pressure of 133 Pa, and the polycondensation was completed when the torque reached 20 kgcm.
- the inside of the reaction vessel was pressurized to O.lMPa, the polymer was discharged into a strand through a die having one circular discharge port with a diameter of 10 mm, and pelletized by a cutter.
- the liquid crystal ⁇ (A- 12) is p- hydroxy structural unit derived from benzoic acid (structural unit (1)) 54 mol 0/0, 4, 4, over-dihydroxy bi Hue - from Le structural unit (structural unit (II)) 16.
- structural unit (III) derived from hydroquinone 6.9 mol%
- structural units derived from terephthalic Le acid structural units derived from terephthalic Le acid
- structural unit derived from 2,6-naphthalenedicarboxylic acid structural unit (V) ') 3.8 mol%, consisting of 4, 4' dihydroxybiphenyl and hydroquinone It had structural units derived from the aromatic diol in a ratio of 70:30 (structural unit (V) ′).
- the structural unit (I) is 70 mol% with respect to the total of the structural units (1), ( ⁇ ) and (III), and the structural unit (IV) is the same as the structural unit (IV) and (V) ′. It was 83 mol% of the total, and the total of structural units (II) and (III) and the total of (IV) and (V) were equimolar.
- the melting point of the liquid crystalline ⁇ is AS in 335 ° C 1.
- a 2 X 10- 3 jZg'K using Koka type flow tester, the temperature 345 ° C, measured at a shear rate of 1000 / s
- the melt viscosity was 22 Pa's.o
- Polymerization was carried out under the same conditions as in Example 4 except that the conditions were set to 170 ° C. for 1.5 hours under the same composition.
- the reaction was continued for 4 minutes at a final polymerization temperature of 330 ° C and a reduced pressure of 133 Pa, and the polycondensation was completed when the torque reached 20 kgcm.
- the inside of the reaction vessel is pressurized to O.lMPa, and the polymer is discharged into a strand through a die having one circular discharge port with a diameter of 10 mm. Pelletized.
- the liquid crystal ⁇ (A- 13) is derived from p- hydroxybenzoic acid, a structural unit derived from (structural unit (1)) 53.8 mole 0/0, 4, 4 'over dihydroxy Biff enyl structural unit (structural unit (II)) 15 mol 0/0, the structural unit derived from hydroquinone (structural unit (III)) 8.
- structural unit (IV) 1 mole 0/0
- structural unit (IV) structural unit 15 mol%
- structural units derived from isophthalic acid structural unit (V)
- the structural unit (I) is 70 mol% with respect to the total of the structural units (1), (II) and (III)
- structural unit (IV) is the same as the structural unit (IV) and (V).
- the polymerization was carried out under the same conditions as in Example 4 except that the composition was the same as that of Example 4, and the acetyl sulfide conditions were 145 ° C. for 2 hours.
- reaction was continued for 141 minutes at a final polymerization temperature of 330 ° C and a reduced pressure of 133 Pa, and the polycondensation was completed when the torque reached 20 kgcm.
- the inside of the reaction vessel was pressurized to O.lMPa, the polymer was discharged into a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.
- the liquid crystal ⁇ (A- 14) is derived from p- hydroxybenzoic acid, a structural unit derived from (structural unit (1)) 53.8 mole 0/0, 4, 4 'over dihydroxy Biff enyl structural unit (structural unit (II)) 15 mol 0/0, the structural unit derived from hydroquinone (structural unit (III)) 8.
- structural unit (IV) 1 mole 0/0, the structural unit derived from terephthalic Le acid (structural unit (IV) ) 15 mol%, structural units derived from isophthalic acid (structural unit (V)) consists 8.1 mole 0/0, 4, 4, over-dihydroxy bi Hue - two aromatic Le and Hyde port quinone It had structural units derived from diol in a ratio of 65:35 (structural unit (II): structural unit (III)).
- the structural unit (I) is the sum of the structural units (1), (II) and (III).
- the total amount of structural units (IV) is 65 mol% based on the total of structural units (IV) and (V), and the total of structural units (II) and (III) is ) And (V) were equimolar.o
- the melting point of the liquid crystalline ⁇ is delta S at 308 ° C was 0. 9 X 10- 3 jZg'K, using Koka type flow tester, the temperature 318 ° C, at a shear rate of 1000 / s
- the measured melt viscosity was 19 Pa's.o
- DHB Structural unit derived from 4,4, dihydroxybiphenyl
- DHN Structural unit derived from 2,6-dihydroxynaphthalene
- the liquid crystalline resins of Examples have the terminal control shown in Comparative Examples. Compared to the liquid crystalline resin which does not have a low gaseous property, it can be seen that the molded product does not have blistering and that it does not corrode the metal and does not cause clouding on the glass surface.
- the liquid crystalline resin (A-1) obtained in Example 1 was converted to a liquid crystalline resin by using a film forming apparatus having a T-die connected to a twin-screw extruder having a vent mechanism via a die plate.
- a film was formed at a melting point of + 20 ° C.
- the T die has a structure in which the horizontal width is gradually increased while gradually decreasing the vertical width to the position 2 mm immediately before the manifold lip, which is divided into the upper right and lower left channels of the die. From the upper right corner, the vertical width at the right end is always smaller than the vertical width at the left end. At 2 mm just before the lip, the both margins are narrowed to 0.1 mm in thickness. At a position 2 mm immediately before the lip, the two resin flows led from the two manifolds overlap vertically, are led to a lip with an opening of 0.2 mm width, and are discharged.
- a 0.1 mm thick copper foil was thermocompression-bonded to the obtained film at a melting point of liquid crystalline resin of 5 ° C, and heat-treated in an oven at 250 ° C for 200 hours. Discoloration and corrosion of copper foil were visually judged. Discoloration and corrosion were not observed.
- the liquid crystalline resin (A-12) obtained in Comparative Example 8 was formed into a film in the same apparatus as in Example 6.
- the polymerization temperature was maintained at 330 ° C., and the mixture was heated with stirring for 1 hour. Thereafter, the pressure was reduced to 133 Pa in 1.0 hour, and the reaction was continued for another 60 minutes. When the torque reached 20 kgcm, the polycondensation was completed.
- the inside of the reaction vessel was pressurized to O.lMPa, and the polymer was discharged into a strand through a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.
- the liquid crystal ⁇ (A-15) is a structural unit (structural unit (1)) derived from p- hydroxybenzoic acid 53.85 mol 0/0, 4, 4, over-dihydroxy bi Hue - Le a structural unit derived from (a structural unit ( ⁇ )) 16. 15 mole 0/0, the structural unit derived from hydroquinone (structural unit (III)) 6. 92 mole 0/0, the structural unit (structural unit derived from terephthalic acid (IV)) 15 mol%, becomes a structural unit (structural unit (V)) 8.
- structural unit (II) structural unit (III)
- the structural unit (I) is 70 mol% of the total of the structural units (1), (II) and (III)
- structural unit (IV) is the total of the structural units (IV) and (V).
- the sum of structural units (II) and (III) and the sum of (IV) and (V) were the same.
- the fiber was wound 10 m by a winder, the weight was measured, and the fineness was calculated. This operation was performed 50 times, and the average value is shown in Table 2. Regarding the variation in fineness, the larger of the absolute value of the difference between the average value and the maximum value and the absolute value of the difference between the average value and the minimum value was defined as the fineness unevenness.
- Fineness unevenness (%) I (maximum or minimum)-average
- Fiber strength was measured for every 50 fibers using Orientec Tensilon UCT-100 according to JIS L1013. The average value of the fiber strength is shown in Table 2.
- Fiber strength unevenness (%)
- Both ends of the fiber were constrained with a tension of O.OlN / cm 2 in an actual microscope equipped with a temperature control mechanism. The temperature was raised while measuring the outer diameter of the fiber with a micrometer. Calculate the change in the fiber outer diameter at 200 ° C with respect to the outer diameter at 30 ° C, and use it as the coefficient of thermal expansion in the thickness direction of the fiber.
- Fibers were measured by differential calorimetry. Measured under heating condition of 20 ° CZ from room temperature The heat of fusion (AHml) CiZg) at the endothermic peak (Tml) observed at that time was measured. Subsequently, after holding at a temperature of Tml + 20 ° C for 5 minutes, once cooling to room temperature under the temperature-lowering condition of 20 ° CZ, and endothermic peak observed when measuring again at the temperature-raising condition of 20 ° CZ The heat of fusion ( ⁇ Hm2) ⁇ / g) at (Tm2) was measured.
- the liquid crystal ⁇ (A- 16) is structural units 74.42 mol% from p- hydroxybenzoic acid, 4, 4, over-dihydroxy bi Hue - structural units derived from Le 6.98 mole 0/0 , structural units derived from terephthalic acid 6.98 mol 0/0, consists structural units 11.62 mol 0/0 from polyethylene terephthalate, the AS with the melting point 314 ° C 1.
- 36 X 10- 3 jZg'K Using a Koka flow tester, the melt viscosity was 15 Pa's, measured at a temperature of 324 ° C and a shear rate of 100000s.
- a fiber was obtained in the same manner as in Example 7, except that the spinning temperature and the draft ratio were as shown in Table 2.
- the fiber was subjected to solid-state polymerization by heat treatment in a nitrogen gas atmosphere at 250 ° C. for 2 hours, 260 ° C. for 2 hours, and 270 ° C. for 6 hours. Table 2 shows the evaluation results.
- liquid crystalline resin fiber having a fineness of 21 dtex or less was obtained stably by melt spinning, and the obtained liquid crystalline resin fiber had extremely uneven fineness. It turns out that there are few.
- liquid crystalline resin fibers produced by melt spinning without solid-phase polymerization have extremely high strength, and have low strength unevenness and high reliability. Understand. Further, the liquid crystalline resin fiber of the present invention has a remarkably improved dimensional change in the fiber cross-sectional direction, which indicates that it is very useful. Industrial applicability
- the liquid crystalline resin of the present invention generates an extremely small amount of gas and does not easily cause blistering on the surface when a molded article is formed using the resin. Further, when the molded article is used in combination with a transparent part made of glass or plastic, the transparent part does not become cloudy. Further, when the molded article is used in contact with metal parts, the metal parts do not corrode. Therefore, the liquid crystalline resin of the present invention is most suitable for electric and electronic applications.
- the film of the present invention has very low copper corrosiveness, and therefore is suitable for a copper-clad circuit board material and the like.
- the fiber of the present invention can be obtained at a low cost by a melt spinning without solid-phase polymerization, which has a very high strength, a high strength fiber with little unevenness in strength and a high reliability. More books The liquid crystalline resin fiber of the present invention is extremely useful because the dimensional change in the fiber cross-sectional direction is significantly improved.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP04822182.4A EP1760104B1 (en) | 2004-06-22 | 2004-11-25 | Liquid-crystalline resin, process for producing the same, composition of liquid-crystalline resin, and molded article |
US11/628,329 US7914699B2 (en) | 2004-06-22 | 2004-11-25 | Liquid crystal resin, method for making the same, liquid crystal resin composition, and molded article |
CN2004800434217A CN1972981B (zh) | 2004-06-22 | 2004-11-25 | 液晶性树脂、其制造方法、液晶性树脂组合物和成型品 |
KR1020067026915A KR101109947B1 (ko) | 2004-06-22 | 2004-11-25 | 액정성 수지, 그의 제조 방법, 액정성 수지 조성물 및성형품 |
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US (1) | US7914699B2 (ja) |
EP (1) | EP1760104B1 (ja) |
KR (1) | KR101109947B1 (ja) |
CN (1) | CN1972981B (ja) |
MY (1) | MY162506A (ja) |
TW (1) | TWI373514B (ja) |
WO (1) | WO2005123804A1 (ja) |
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JP2008240229A (ja) * | 2007-02-28 | 2008-10-09 | Toray Ind Inc | 液晶ポリエステル繊維 |
JP2010084301A (ja) * | 2008-10-02 | 2010-04-15 | Toray Ind Inc | 液晶ポリエステル繊維 |
CN103122493B (zh) * | 2007-02-28 | 2015-06-24 | 东丽株式会社 | 液晶聚酯纤维及其制造方法 |
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JP4577271B2 (ja) * | 2006-05-25 | 2010-11-10 | 三菱エンジニアリングプラスチックス株式会社 | 光記録媒体基板の製造方法 |
TW201030087A (en) * | 2008-10-30 | 2010-08-16 | Solvay Advanced Polymers Llc | Power LED device with a reflector made of aromatic polyester and/or wholly aromatic polyester |
KR101663317B1 (ko) * | 2010-01-12 | 2016-10-06 | 심천 워트 어드밴스드 머티리얼즈 주식회사 | 전방향족 액정 폴리에스테르 수지의 제조방법과 그 방법에 의해 제조된 전방향족 액정 폴리에스테르 수지, 및 상기 전방향족 액정 폴리에스테르 수지의 컴파운드 |
WO2011115043A1 (ja) * | 2010-03-16 | 2011-09-22 | Jx日鉱日石エネルギー株式会社 | 全芳香族サーモトロピック液晶ポリエステル樹脂組成物、成形体及びledリフレクター |
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JP5062381B2 (ja) * | 2010-12-27 | 2012-10-31 | 東レ株式会社 | 全芳香族液晶ポリエステルおよびその製造方法 |
US9109159B2 (en) | 2010-12-27 | 2015-08-18 | Toray Industries, Inc. | Liquid crystalline polyester and production method of the same |
JP2012153855A (ja) * | 2011-01-28 | 2012-08-16 | Sumitomo Chemical Co Ltd | 熱処理された液晶ポリエステル含浸基材の製造方法 |
EP2692913B2 (en) * | 2011-03-29 | 2022-03-02 | Toray Industries, Inc. | Liquid crystal polyester fibers and method for producing same |
KR101763948B1 (ko) * | 2011-05-06 | 2017-08-01 | 심천 워트 어드밴스드 머티리얼즈 주식회사 | 반사체 및 이를 구비하는 발광장치 |
JP5909508B2 (ja) * | 2012-01-31 | 2016-04-26 | Jxエネルギー株式会社 | 液晶ポリエステルアミド、液晶ポリエステルアミド樹脂組成物及び成形体 |
TWI576378B (zh) * | 2012-02-29 | 2017-04-01 | Toray Industries | 液晶聚酯樹脂組成物 |
CN102643415B (zh) * | 2012-04-19 | 2014-04-02 | 深圳君泽电子有限公司 | 液晶聚合物、其制备方法以及液晶聚合物复合材料 |
JP6625050B2 (ja) | 2013-06-07 | 2019-12-25 | ティコナ・エルエルシー | 高強度サーモトロピック液晶ポリマー |
CN105593266B (zh) * | 2013-07-31 | 2017-12-12 | 东丽株式会社 | 液晶聚酯的制造方法和液晶聚酯 |
DE112016000328T5 (de) * | 2015-01-13 | 2017-10-19 | Ube Exsymo Co., Ltd. | Flexible Verbundplatte und mehrschichtige Leiterplatte |
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- 2004-11-25 WO PCT/JP2004/017445 patent/WO2005123804A1/ja active Application Filing
- 2004-11-25 KR KR1020067026915A patent/KR101109947B1/ko active IP Right Grant
- 2004-11-25 EP EP04822182.4A patent/EP1760104B1/en active Active
- 2004-11-25 US US11/628,329 patent/US7914699B2/en active Active
- 2004-11-25 TW TW093136275A patent/TWI373514B/zh active
- 2004-11-25 CN CN2004800434217A patent/CN1972981B/zh not_active Expired - Fee Related
- 2004-11-29 MY MYPI20044923A patent/MY162506A/en unknown
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Also Published As
Publication number | Publication date |
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KR101109947B1 (ko) | 2012-02-15 |
US20070243376A1 (en) | 2007-10-18 |
CN1972981B (zh) | 2010-05-12 |
KR20070034509A (ko) | 2007-03-28 |
EP1760104B1 (en) | 2019-01-02 |
MY162506A (en) | 2017-06-15 |
CN1972981A (zh) | 2007-05-30 |
EP1760104A1 (en) | 2007-03-07 |
TWI373514B (en) | 2012-10-01 |
US7914699B2 (en) | 2011-03-29 |
TW200600567A (en) | 2006-01-01 |
EP1760104A4 (en) | 2007-04-04 |
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