JP2017043705A - Liquid crystal polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal polymer composition having excellent weighing stability at the time of molding, and excellent fluidity.SOLUTION: The present invention provides a liquid crystal polymer that is a copolymer composed of a polymerizable monomer (A) selected from the group consisting of bisphenol A represented by formula (I) and a reactive derivative thereof, and another polymerizable monomer (B).SELECTED DRAWING: None

Description

  The present invention relates to a liquid crystal polymer excellent in fluidity and metering stability during molding.

  Thermotropic liquid crystal polymer (hereinafter abbreviated as liquid crystal polymer or LCP) is excellent in mechanical properties such as heat resistance and rigidity, chemical resistance, dimensional accuracy, etc. Its use is expanding in various applications.

  Especially in the information / communication field such as personal computers and mobile phones, there is a case where a very thin part is formed due to the rapid progress of high integration, miniaturization, thinning, and low profile of parts. Many. Therefore, the amount of LCP is greatly increased by taking advantage of its excellent moldability, that is, good fluidity and no characteristics of other resins such as no burrs.

  On the other hand, although the liquid crystal polymer has low viscosity and excellent fluidity, there is a problem in measurement stability at the time of molding as an opposite action. In particular, when the molded product becomes large or the amount of molding resin (measured value) increases once due to multiple molding, short shots and overpacks are repeated alternately due to unstable measurement, There were many cases where molding problems such as the resin not completely filling the mold due to the flow (reverse flow of resin) occurred. In the case of forming a part having a thin portion as described above, the solution of such molding problems has been a major issue.

  In order to improve the measurement stability at the time of molding, a method of blending glass fibers and glass beads with a liquid crystal polymer (Patent Document 1) and a method of incorporating a specific higher fatty acid metal salt into a liquid crystal polymer (Patent Document 2) are proposed. Has been.

  However, the measurement stability improvement effect by these methods is not sufficient, and because the use of specific glass beads and higher fatty acid metal salts is required, the use of the liquid crystal polymer composition is limited. The versatility was poor.

  Accordingly, there has been a demand for the development of a liquid crystal polymer having an effect of improving measurement stability in the resin itself and having good fluidity.

Japanese Patent No. 5727229 Japanese Patent Laying-Open No. 2015-63641

  An object of the present invention is to provide a liquid crystal polymer composition having excellent metering stability during molding and good fluidity.

  As a result of intensive studies on improving the measurement stability of the liquid crystal polymer, the present inventors have found that the measurement stability is remarkably improved by using a repeating unit derived from bisphenol A as a constituent component of the liquid crystal polymer. It came to complete.

That is, the present invention comprises a polymerizable monomer (A) selected from the group consisting of bisphenol A represented by formula (I) and reactive derivatives thereof, and another polymerizable monomer (B). And a liquid crystal polymer obtained by polymerizing the above polymerizable monomer (A) and another polymerizable monomer (B).

  The liquid crystal polymer composition of the present invention is excellent in metering stability and fluidity at the time of molding, and is suitably used as a molding material for molded products such as injection molded products, films and fibers.

  The liquid crystal polymer of the present invention is a polyester or polyester amide that forms an anisotropic molten phase, and is not particularly limited as long as it is called a thermotropic liquid crystal polyester or a thermotropic liquid crystal polyester amide in the technical field.

  In the present specification, the “reactive derivative” of a polymerizable monomer shall mean a derivative of a monomer having reactivity capable of introducing a target structural unit. Suitable reactive derivatives of bisphenol A that can be used in the present invention include bisphenol A alkyl-, alkoxy- or halogen-substituted products, acylated products, ester derivatives such as ester derivatives, acid halides, and acylated products of these substituted products. And ester-forming derivatives such as ester derivatives and acid halides. As the alkyl group or alkoxy group as a substituent, those having up to 6 carbon atoms are preferably used. As the polymerizable monomer (A) selected from the group consisting of bisphenol A represented by the formula (I) and its reactive derivative, only one type of compound may be used, or two or more types of compounds are combined. May be used.

  In the present specification, “aromatic” means a compound containing an aromatic group having up to 4 condensed rings. The term “aliphatic” refers to a compound containing a saturated or unsaturated carbon chain having 2 to 12 carbon atoms, which may have a branch.

  The total amount of the polymerizable monomer (A) selected from the group consisting of bisphenol A represented by the formula (I) and its reactive derivative used in the liquid crystal polymer of the present invention is the other polymerizable monomer. It is preferable that it is 0.01-10 mol part with respect to 100 mol part of total amounts of (B), It is more preferable that it is 0.05-5 mol part, It is 0.1-3 mol part Is more preferable. When the total amount of the polymerizable monomer (A) exceeds 10 mol parts with respect to 100 mol parts of the total amount of the other polymerizable monomers (B), the fluidity tends to be remarkably lowered. When the total amount of the polymerizable monomer (A) is less than 0.01 mol part with respect to 100 mol parts of the total amount of the other polymerizable monomers (B), the measurement stability improvement effect cannot be obtained. Tend.

  Examples of the other polymerizable monomer (B) used in the liquid crystal polymer of the present invention include monomers used in conventional liquid crystal polymers, such as aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic amino acids. Carboxylic acids, aromatic hydroxyamines, aromatic diamines, aliphatic diols and aliphatic dicarboxylic acids. These compounds may be used alone or in combination of two or more, but it is desirable to use at least one monomer having a hydroxy group or an amino group.

  The other polymerizable monomer (B) used in the liquid crystal polymer of the present invention may be an oligomer formed by bonding one or more of the above compounds. In addition, about the quantity of the other polymerizable monomer (B) in this specification and a claim, even if it is a case where a polymerizable monomer is an oligomer, the monomer which comprises the said oligomer It shall be calculated based on the unit.

  Specific examples of the aromatic hydroxycarboxylic acid include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 6-hydroxy-1-naphthoic acid, and 7-hydroxy. 2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 7-hydroxy-1-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxy Examples thereof include phenyl-3-benzoic acid and alkyl, alkoxy or halogen substituents thereof, and ester-forming derivatives thereof such as acylated products, ester derivatives, and acid halides. Among these, 4-hydroxybenzoic acid or 6-hydroxy-2-naphthoic acid or a combination thereof is more preferable in that the heat resistance and mechanical strength and melting point of the obtained liquid crystal polymer can be easily adjusted.

  Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, 3 , 4′-dicarboxybiphenyl and 4,4′-dicarboxyterphenyl, their alkyl, alkoxy or halogen substituents and their ester-forming derivatives such as their ester derivatives, acid halides.

  Among these, terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferably used, and terephthalic acid is particularly preferable because the heat resistance of the obtained liquid crystal polymer can be effectively enhanced.

  Specific examples of the aromatic diol include hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, Examples include ester-forming derivatives such as 4,4′-dihydroxybiphenyl, 4,4′-dihydroxybiphenol ether, and 2,2′-dihydroxybinaphthyl, alkyl, alkoxy or halogen substituents thereof, and acylated products thereof.

  Among these, hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, and 2,6-dihydroxynaphthalene are preferably used. In particular, hydroquinone, 4,4′-dihydroxybiphenyl or 2 is excellent in reactivity at the time of polymerization. 1,6-dihydroxynaphthalene is preferred.

  Specific examples of the aromatic aminocarboxylic acid include 4-aminobenzoic acid, 3-aminobenzoic acid, 6-amino-2-naphthoic acid, their alkyl, alkoxy or halogen-substituted products, and acylated products and ester derivatives thereof. And ester-forming derivatives such as acid halides.

  Specific examples of the aromatic hydroxyamine include 4-aminophenol, N-methyl-4-aminophenol, 3-aminophenol, 3-methyl-4-aminophenol, 4-amino-1-naphthol, 4-amino- 4'-hydroxybiphenyl, 4-amino-4'-hydroxybiphenyl ether, 4-amino-4'-hydroxybiphenylmethane, 4-amino-4'-hydroxybiphenyl sulfide and 2,2'-diaminobinaphthyl, their alkyl , Alkoxy- or halogen-substituted products, and ester-forming derivatives thereof such as acylated products thereof. Among these, 4-aminophenol is preferably used because it easily balances the heat resistance and mechanical strength of the obtained liquid crystal polymer.

  Specific examples of the aromatic diamine include 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, alkyl, alkoxy or halogen substituted products thereof, and their Examples include amide-forming derivatives such as acylated products.

  Specific examples of the aliphatic diol include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and acylated products thereof. Also, polymers containing aliphatic diols such as polyethylene terephthalate and polybutylene terephthalate react with the above aromatic oxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols and their acylated products, ester derivatives, acid halides, etc. You may let them.

  Specific examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. Among these, oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid are preferably used because of excellent reactivity during polymerization.

  The liquid crystal polymer of the present invention may contain a thioester bond as long as the object of the present invention is not impaired. Examples of the monomer that gives such a bond include mercapto aromatic carboxylic acid, aromatic dithiol, and hydroxy aromatic thiol. It is preferable that the usage-amount of these monomers is 10 mol% or less with respect to the total amount of another polymerizable monomer (B).

  As other polymerizable monomer (B), aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic aminocarboxylic acid, aromatic hydroxyamine, aromatic diamine, aliphatic diol and aliphatic dicarboxylic acid The combined use of two or more compounds selected from the group consisting of is one of the preferred embodiments of the present invention.

  Among these polymerizable monomers, a combination containing an aromatic hydroxycarboxylic acid is more preferably used, and a combination containing an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid and an aromatic diol is more preferably used.

  Among these, the other polymerizable monomer (B) is a combination of 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, aromatic A combination of dicarboxylic acid and aromatic diol is particularly preferably used.

Specific examples of the other polymerizable monomer (B) used in the liquid crystal polymer of the present invention include, for example, those comprising the following combinations:
1) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid copolymer 2) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer 3) 4-hydroxybenzoic acid / terephthalic acid / Isophthalic acid / 4,4'-dihydroxybiphenyl copolymer 4) 4-hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4,4'-dihydroxybiphenyl / hydroquinone copolymer 5) 4-hydroxybenzoic acid / terephthalic acid / Hydroquinone copolymer 6) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / hydroquinone copolymer 7) 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone copolymer 8) 4- Hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / 4,4′-dihydride Roxybiphenyl copolymer 9) 6-hydroxy-2-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer 10) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone Copolymer 11) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone / 4,4′-dihydroxybiphenyl copolymer 12) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / 4,4'-dihydroxybiphenyl copolymer 13) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 14) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / Hydroquinone copolymer 15) 4-hydroxybenzoic acid / 6-hydroxy-2- Futheic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 16) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone / 4,4′-dihydroxybiphenyl copolymer 17) 4- Hydroxybenzoic acid / terephthalic acid / 4-aminophenol copolymer 18) 6-hydroxy-2-naphthoic acid / terephthalic acid / 4-aminophenol copolymer 19) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid Acid / terephthalic acid / 4-aminophenol copolymer 20) 4-hydroxybenzoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl / 4-aminophenol copolymer 21) 4-hydroxybenzoic acid / terephthalic acid / ethylene Glycol copolymer 22) 4-hydroxybenzoic acid / terephthalic acid / , 4'-dihydroxybiphenyl / ethylene glycol copolymer 23) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / ethylene glycol copolymer 24) 4-hydroxybenzoic acid / 6-hydroxy-2 -Naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / ethylene glycol copolymer 25) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / 4,4'-dihydroxybiphenyl copolymer.

  Among these, liquid crystal polymers composed of the monomer structural units 1), 10), 11) and 15) are preferred.

  Said liquid crystal polymer may be used independently, and 2 or more types may be blended and used. In the case of blending, it is preferable to use a blend of the liquid crystal polymer composed of the monomer constituent unit of 1) and any one of the liquid crystal polymers composed of the monomer constituent units of 10), 11) and 15).

  Hereinafter, the manufacturing method of the liquid crystal polymer of this invention is demonstrated.

  The liquid crystal polymer of the present invention comprises a polymerizable monomer (A) selected from the group consisting of bisphenol A represented by the above formula (I) and a reactive derivative thereof, and another polymerizable monomer (B). Is a liquid crystal polymer. The method for producing the liquid crystal polymer of the present invention is not particularly limited, and the polymerizable monomer (A) selected from the group consisting of bisphenol A represented by the formula (I) and reactive derivatives thereof, and other polymerizable properties The liquid crystal polymer of the present invention can be obtained by subjecting the monomer (B) to a known polycondensation method for forming an ester bond or an amide bond, such as a melt acididation method or a slurry polymerization method.

  The melt acidolysis method is a preferred method for producing the liquid crystal polymer of the present invention. In this method, the polymerizable monomer is first heated to form a molten solution of the reactants, and then the polycondensation reaction is continued to obtain a molten polymer. A vacuum may be applied to facilitate removal of volatiles (for example, acetic acid, water, etc.) by-produced in the final stage of condensation.

  The slurry polymerization method is a method in which a polymerizable monomer is reacted in the presence of a heat exchange fluid, and a solid product is obtained in a state suspended in a heat exchange medium.

  In both cases of the melt acidification method and the slurry polymerization method, the polymerizable monomer (A) and the other polymerizable monomer (B) used in producing the liquid crystal polymer are both at room temperature. Further, it can be subjected to the reaction as a modified form obtained by acylating a hydroxyl group and / or an amino group, that is, a lower acylated product.

  The lower acyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. Particularly preferred is a method using an acetylated product of the polymerizable monomer in the reaction.

  The lower acylated product of the polymerizable monomer may be separately acylated and synthesized beforehand, or an acylating agent such as acetic anhydride may be added to the polymerizable monomer during the production of the liquid crystal polymer. It can also be generated with

  In either case of the melt acidification method or the slurry polymerization method, the polymerization reaction is carried out at a temperature of 150 to 400 ° C., preferably 250 to 370 ° C. under normal pressure and / or reduced pressure. May be used.

  Specific examples of the catalyst include organotin compounds such as dialkyltin oxide (for example, dibutyltin oxide) and diaryltin oxide; titanium dioxide; antimony trioxide; organotitanium compounds such as alkoxytitanium silicate and titanium alkoxide; alkali and alkali of carboxylic acid Examples include earth metal salts (for example, potassium acetate); gaseous acids catalysts such as Lewis acids (for example, boron trifluoride) and hydrogen halides (for example, hydrogen chloride).

  When a catalyst is used, the amount of the catalyst is preferably 1 to 1000 ppm, more preferably 2 to 100 ppm, based on the total amount of the other polymerizable monomer (B).

  The liquid crystal polymer of the present invention obtained by the polycondensation reaction in this manner is usually processed into a pellet, flake, or powder after being extracted from the polymerization reaction tank in a molten state.

  A liquid crystal polymer in the form of pellets, flakes, or powders is substantially a solid phase under reduced pressure, vacuum, or an inert gas atmosphere such as nitrogen or helium for the purpose of increasing molecular weight and improving heat resistance. You may heat-process in a state.

  The liquid crystal polymer of the present invention obtained as described above is blended with one or more selected from inorganic or organic fillers, other additives described below, and other resin components, and the liquid crystal polymer It is good also as a composition.

  The inorganic or organic filler that may be blended in the liquid crystal polymer of the present invention may be in the form of fibers, plates, or granules, such as glass fibers, milled glass, silica alumina fibers, alumina fibers, carbon fibers, aramids. Examples include fibers, potassium titanate whiskers, aluminum borate whiskers, wollastonite, talc, mica, graphite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate, and titanium oxide. In these, glass fiber is preferable at the point which the balance of a physical property and cost is excellent. Two or more of these fillers may be used in combination.

  The total amount of the inorganic or organic filler in the liquid crystal polymer composition of the present invention is preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the liquid crystal polymer. When the total amount of the inorganic or organic filler exceeds 200 parts by weight with respect to 100 parts by weight of the liquid crystal polymer, the molding processability of the liquid crystal polymer composition tends to decrease, or the cylinder or mold of the molding machine Wear tends to increase.

  In the liquid crystal polymer of the present invention, other additives such as higher fatty acid, higher fatty acid ester, higher fatty acid amide, higher fatty acid metal salt (here, higher fatty acid means the number of carbon atoms) within the range not impairing the effect of the present invention. 10-25), release agents such as polysiloxanes and fluororesins; coloring agents such as dyes and pigments; antioxidants; thermal stabilizers; ultraviolet absorbers; antistatic agents; You may mix | blend. These additives may be blended alone or in combination of two or more.

  The total amount of other additives in the liquid crystal polymer composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the liquid crystal polymer. When the total amount of other additives exceeds 10 parts by weight with respect to 100 parts by weight of the liquid crystal polymer, the molding processability of the liquid crystal polymer composition tends to decrease and the thermal stability tends to deteriorate.

  Further, in molding the liquid crystal polymer or liquid crystal polymer composition of the present invention, among the other additives, an additive having an external lubricant effect such as higher fatty acid, higher fatty acid ester, higher fatty acid metal salt, fluorocarbon surfactant, etc. May be previously attached to the pellet surface of the liquid crystal polymer.

  The liquid crystal polymer of the present invention may contain other resin components. Examples of other resin components include polyamide, polyester, polyacetal, polyphenylene ether, and modified products thereof, and thermoplastic resins such as polysulfone, polyethersulfone, polyetherimide, and polyamideimide, phenol resin, epoxy resin, and polyimide resin. And other thermosetting resins. Other resin components can be blended alone or in combination of two or more. The blending amount of the other resin components is not particularly limited, and may be appropriately determined according to the use and purpose of the liquid crystal polymer. In one typical example, the total amount of the other resin components is usually 0.1 to 100 parts by weight, particularly 0.1 to 80 parts by weight with respect to 100 parts by weight of the liquid crystal polymer.

The melt viscosity of the liquid crystal polymer of the present invention is preferably 1 to 300 Pa · s, more preferably 5 to 100 Pa · s, and still more preferably 10 when measured using a capillary rheometer under conditions of a shear rate of 1000 s ^−1. ~ 50 Pa · s.
The lower the melt viscosity, the better the fluidity during molding.

In the liquid crystal polymer of the present invention, the stirring torque value at the end of the polymerization is preferably 0.1 to 3.0 N · m, more preferably 0.2 to 2.0 N · m, still more preferably 0.3 to 1. .5 N · m.
The higher the stirring torque value, the higher the viscosity of the resin, which means that back flow (reverse flow of the resin) hardly occurs during molding, that is, excellent measurement stability during molding. Due to the excellent measurement stability during molding, burrs and molding defects are less likely to occur in the molded product.
The liquid crystal polymer of the present invention has a stirring torque value of preferably 1.05 times or more, more preferably 1.1 times or more, and even more preferably 1.15, as compared with the case where bisphenol A is not used as a monomer component. It is more than double.

Further, the smaller the index represented by “melt viscosity / stirring torque value” is, the more the increase in melt viscosity with respect to the increase of the stirring torque value is suppressed by using bisphenol A as a monomer component. It means that the measurement stability is improved without impairing the balance.
The liquid crystal polymer of the present invention has a “melt viscosity / stirring torque value” of preferably 95% or less, more preferably 90% or less, and even more preferably 85%, compared with the case where bisphenol A is not used as a monomer component. It is as follows.

  In the liquid crystal polymer composition of the present invention, an inorganic or organic filler, other additives and other resin components are added to the liquid crystal polymer, and this is added using a Banbury mixer, a kneader, a single or twin screw extruder, and the like. It can be obtained by melt-kneading in the temperature range from near the crystal melting temperature of the liquid crystal polymer to the crystal melting temperature plus 100 ° C.

  The liquid crystal polymer or liquid crystal polymer composition of the present invention thus obtained has the characteristics of excellent measurement stability and fluidity, and is obtained by a known processing method such as injection molding, compression molding, extrusion molding or blow molding. Processed into molded products such as injection molded products, films and fibers.

  Such products include components selected from the group consisting of connectors, switches, relays, capacitors, coils, transformers, camera modules, antennas and chip antennas.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
In addition, the characteristic value in an Example was measured with the following method.

<Melt viscosity>
The melt viscosity was measured under the condition of a shear rate of 1000 s ⁻¹ using a 0.7 mmφ × 10 mm capillary with a melt viscosity measuring apparatus (Capillograph 1D manufactured by Toyo Seiki Co., Ltd.).

<Agitation torque value>
Using a stirring motor with a torque meter (three-one motor BL600 manufactured by Shinto Kagaku Co., Ltd.), the stirring torque value at the end of the polymerization reaction was measured.

<Crystal melting temperature>
Using a differential scanning calorimeter (ExstAr6000 manufactured by Seiko Instruments Inc.), after measuring the endothermic peak temperature (Tm1) observed when the sample was measured at room temperature to 20 ° C./min, from Tm1 The temperature was kept at 20-50 ° C. for 10 minutes. Next, the sample was cooled to room temperature under a temperature decrease condition of 20 ° C./min, and an endothermic peak was measured again when measured under a temperature increase condition of 20 ° C./min. ).

<Tensile strength>
Using an injection molding machine with a clamping pressure of 15 t (MINIMAT M26 / 15 manufactured by Sumitomo Heavy Industries, Ltd.), injection molding was performed at a cylinder temperature of melting point + 20-40 ° C. and a mold temperature of 70 ° C., and dumbbell-shaped tensile test pieces ( 63.5 mm long × 3.5 mm wide × 2.0 mm thick). Using an INSTRON 5567 (universal testing machine manufactured by Instron Japan Company Limited), the distance between spans was 25.4 mm and the tensile speed was 5 mm / min.

<Bending strength, flexural modulus>
A strip-shaped bending test piece (length 65 mm × width 12.7 mm × thickness 2.0 mm) was produced under the same conditions as the molded piece used for measurement of tensile strength. For the bending test, a three-point bending test was performed at an interspan distance of 40.0 mm and a compression speed of 1.3 mm / min using an INSTRON 5567 (universal testing machine manufactured by Instron Japan Ltd.).

Example 1
The following compounds were charged into a 2 L reaction vessel equipped with a stirring blade and a distillation tube, heated between 40-170 ° C. over 1 hour in a nitrogen gas atmosphere, maintained at 170 ° C. for 30 minutes, and then up to 350 ° C. The temperature was raised over 7.5 hours, and the mixture was further reacted at 350 ° C. for 10 minutes, and then reduced in pressure at 350 ° C. Subsequently, the pressure was reduced to 10 mmHg over 1.5 hours, and the mixture was further stirred for 60 minutes to complete the polycondensation. The amount of acetic acid distilled off during the polymerization was almost the same as the theoretical value. The contents were taken out from the reaction vessel, and liquid crystal polymer pellets were obtained by a pulverizer.
4-hydroxybenzoic acid: 384.9 g (42 mol parts)
6-hydroxy-2-naphthoic acid: 192.5 g (16 mole parts)
Hydroquinone: 144.5 g (20.5 mol parts)
Terephthalic acid: 223.4 g (21 mole parts)
Bisphenol A: 7.4 g (0.5 mole part)
Acetic anhydride: 685.0 g (103 mole parts)

  The obtained pellets were molded and evaluated for tensile strength, bending strength and bending elastic modulus. The results are shown in Table 1 together with the melt viscosity and crystal melting temperature of the obtained resin.

Example 2
Liquid crystal polymer pellets were obtained in the same manner as in Example 1 except that the following compounds were charged in a reaction vessel.
4-hydroxybenzoic acid: 384.9 g (42 mol parts)
6-hydroxy-2-naphthoic acid: 192.5 g (16 mole parts)
Hydroquinone: 140.9 g (20 mol parts)
Terephthalic acid: 223.4 g (21 mole parts)
Bisphenol A: 14.8 g (1 mol part)
Acetic anhydride: 685.0 g (103 mole parts)

  The obtained pellets were molded and evaluated for tensile strength, bending strength and bending elastic modulus. The results are shown in Table 1 together with the melt viscosity and crystal melting temperature of the obtained resin.

Example 3
Liquid crystal polymer pellets were obtained in the same manner as in Example 1 except that the following compounds were charged in a reaction vessel.
4-hydroxybenzoic acid: 384.9 g (42 mol parts)
6-hydroxy-2-naphthoic acid: 192.5 g (16 mole parts)
Hydroquinone: 133.7 g (19 mol parts)
Terephthalic acid: 223.4 g (21 mole parts)
Bisphenol A: 29.6 g (2 mol parts)
Acetic anhydride: 685.0 g (103 mole parts)

  The obtained pellets were molded and evaluated for tensile strength, bending strength and bending elastic modulus. The results are shown in Table 1 together with the melt viscosity and crystal melting temperature of the obtained resin.

Comparative Example 1
Liquid crystal polymer pellets were obtained in the same manner as in Example 1 except that the following compounds were charged in a reaction vessel.
4-hydroxybenzoic acid: 384.9 g (42 mol parts)
6-hydroxy-2-naphthoic acid: 192.5 g (16 mole parts)
Hydroquinone: 148.1 g (21 mole parts)
Terephthalic acid: 223.4 g (21 mole parts)
Acetic anhydride: 685.0 g (103 mole parts)

  The obtained pellets were molded and evaluated for tensile strength, bending strength and bending elastic modulus. The results are shown in Table 1 together with the melt viscosity and crystal melting temperature of the obtained resin.

  As shown in Table 1, all of the liquid crystal polymers of Examples 1 to 3 and Comparative Example 1 had a crystal melting temperature of about 330 ° C. and the melt viscosity did not change greatly, but bisphenol A was used as a monomer component. The liquid crystal polymers of Examples 1 to 3 have a higher stirring torque and a lower value of [melt viscosity / stirring torque] than the liquid crystal polymer of Comparative Example 1 in which bisphenol A was not used as a monomer component. It can be seen that the measurement stability at the time of molding is excellent and at the same time it has high fluidity. It can also be seen that it has sufficient tensile strength, flexural strength and flexural modulus for use in molded products such as injection molded products, films and fibers.

Example 4
The following compounds were charged into a 2 L reaction vessel equipped with a stirring blade and a distillation tube, heated between 40-170 ° C. over 1 hour in a nitrogen gas atmosphere, maintained at 170 ° C. for 30 minutes, and then up to 350 ° C. The temperature was raised over 7 hours, and the reaction was further continued at 350 ° C. for 10 minutes, followed by reducing the pressure at 350 ° C. Subsequently, the pressure was reduced to 10 mmHg over 1 hour, and the mixture was further stirred for 30 minutes to complete the polycondensation. The amount of acetic acid distilled off during the polymerization was almost the same as the theoretical value. The contents were taken out from the reaction vessel, and liquid crystal polymer pellets were obtained by a pulverizer.
4-hydroxybenzoic acid: 366.6 g (40 mol parts)
6-hydroxy-2-naphthoic acid: 481.3 g (40 mole parts)
Hydroquinone: 68.4 g (9.7 mol parts)
Terephthalic acid: 106.4 g (10 mol parts)
Bisphenol A: 4.4 g (0.3 mol part)
Acetic anhydride: 685.0 g (103 mole parts)

  The obtained pellets were molded and evaluated for tensile strength, bending strength and bending elastic modulus. The results are shown in Table 2 together with the melt viscosity and crystal melting temperature of the obtained resin.

Example 5
Liquid crystal polymer pellets were obtained in the same manner as in Example 4 except that the following compounds were charged in a reaction vessel.
4-hydroxybenzoic acid: 366.6 g (40 mol parts)
6-hydroxy-2-naphthoic acid: 481.3 g (40 mole parts)
Hydroquinone: 67.0 g (9.5 mol parts)
Terephthalic acid: 106.4 g (10 mol parts)
Bisphenol A: 7.4 g (0.5 mole part)
Acetic anhydride: 685.0 g (103 mole parts)

  The obtained pellets were molded and evaluated for tensile strength, bending strength and bending elastic modulus. The results are shown in Table 2 together with the melt viscosity and crystal melting temperature of the obtained resin.

Example 6
Liquid crystal polymer pellets were obtained in the same manner as in Example 4 except that the following compounds were charged in a reaction vessel.
4-hydroxybenzoic acid: 366.6 g (40 mol parts)
6-hydroxy-2-naphthoic acid: 481.3 g (40 mole parts)
Hydroquinone: 63.5 g (9.0 mol parts)
Terephthalic acid: 106.4 g (10 mol parts)
Bisphenol A: 14.8 g (1.0 mol part)
Acetic anhydride: 685.0 g (103 mole parts)

  The obtained pellets were molded and evaluated for tensile strength, bending strength and bending elastic modulus. The results are shown in Table 2 together with the melt viscosity and crystal melting temperature of the obtained resin.

Example 7
Liquid crystal polymer pellets were obtained in the same manner as in Example 4 except that the following compounds were charged in a reaction vessel.
4-hydroxybenzoic acid: 366.6 g (40 mol parts)
6-hydroxy-2-naphthoic acid: 481.3 g (40 mole parts)
Hydroquinone: 56.4 g (8.0 mol parts)
Terephthalic acid: 106.4 g (10 mol parts)
Bisphenol A: 29.6 g (2.0 mole parts)
Acetic anhydride: 685.0 g (103 mole parts)

  The obtained pellets were molded and evaluated for tensile strength, bending strength and bending elastic modulus. The results are shown in Table 2 together with the melt viscosity and crystal melting temperature of the obtained resin.

Comparative Example 2
Liquid crystal polymer pellets were obtained in the same manner as in Example 4 except that the following compounds were charged in a reaction vessel.
4-hydroxybenzoic acid: 366.6 g (40 mol parts)
6-hydroxy-2-naphthoic acid: 481.3 g (40 mole parts)
Hydroquinone: 70.5 g (10 mole parts)
Terephthalic acid: 106.4 g (10 mol parts)
Acetic anhydride: 685.0 g (103 mole parts)

  The obtained pellets were molded and evaluated for tensile strength, bending strength and bending elastic modulus. The results are shown in Table 2 together with the melt viscosity and crystal melting temperature of the obtained resin.

  As shown in Table 2, all of the liquid crystal polymers of Examples 4 to 7 and Comparative Example 2 had a crystal melting temperature of about 210 ° C. and the melt viscosity did not change greatly, but bisphenol A was used as a monomer component. The liquid crystal polymers of Examples 4 to 7 have higher stirring torque and lower [melt viscosity / stirring torque] values than the liquid crystal polymer of Comparative Example 2 in which bisphenol A was not used as a monomer component. It can be seen that the measurement stability at the time of molding is excellent and at the same time it has high fluidity. It can also be seen that it has sufficient tensile strength, flexural strength and flexural modulus for use in molded products such as injection molded products, films and fibers.

Example 8
The following compounds were charged into a 2 L reaction vessel equipped with a stirring blade and a distillation pipe, heated between 40-170 ° C. in a nitrogen gas atmosphere over 1 hour, maintained at 170 ° C. for 30 minutes, and then up to 330 ° C. The temperature was raised over 7.5 hours, and the mixture was further reacted at 330 ° C. for 10 minutes, and then reduced in pressure at 330 ° C. Subsequently, the pressure was reduced to 10 mmHg over 1.5 hours, and the mixture was further stirred for 10 minutes to complete the polycondensation. The amount of acetic acid distilled off during the polymerization was almost the same as the theoretical value. The contents were taken out from the reaction vessel, and liquid crystal polymer pellets were obtained by a pulverizer.
4-hydroxybenzoic acid: 655.3 g (73 mol parts)
6-hydroxy-2-naphthoic acid: 330.3 g (27 mol parts)
Bisphenol A: 4.5 g (0.3 mol part)
Acetic anhydride: 679 g (101 mol parts)

  The obtained pellets were molded and evaluated for tensile strength, bending strength and bending elastic modulus. The results are shown in Table 3 together with the melt viscosity and crystal melting temperature of the obtained resin.

Example 9
Liquid crystal polymer pellets were obtained in the same manner as in Example 8 except that the following compounds were charged in a reaction vessel.
4-hydroxybenzoic acid: 655.3 g (73 mol parts)
6-hydroxy-2-naphthoic acid: 330.3 g (27 mol parts)
Bisphenol A: 7.4 g (0.5 mole part)
Acetic anhydride: 681 g (101 mol parts)

  The obtained pellets were molded and evaluated for tensile strength, bending strength and bending elastic modulus. The results are shown in Table 3 together with the melt viscosity and crystal melting temperature of the obtained resin.

Comparative Example 3
Liquid crystal polymer pellets were obtained in the same manner as in Example 8 except that the following compounds were charged in a reaction vessel.
4-hydroxybenzoic acid: 655.3 g (73 mol parts)
6-hydroxy-2-naphthoic acid: 330.3 g (27 mol parts)
Acetic anhydride: 675 g (101 mol parts)

  The obtained pellets were molded and evaluated for tensile strength, bending strength and bending elastic modulus. The results are shown in Table 3 together with the melt viscosity and crystal melting temperature of the obtained resin.

  As shown in Table 3, all of the liquid crystal polymers of Examples 8 and 9 and Comparative Example 3 had a crystal melting temperature of about 280 ° C. and the melt viscosity did not change greatly, but bisphenol A was used as a monomer component. The liquid crystal polymers of Examples 8 and 9 have higher stirring torque and lower [melt viscosity / stirring torque] values than the liquid crystal polymer of Comparative Example 3 in which bisphenol A was not used as a monomer component. It can be seen that the measurement stability at the time of molding is excellent and at the same time it has high fluidity. It can also be seen that it has sufficient tensile strength, flexural strength and flexural modulus for use in molded products such as injection molded products, films and fibers.

Claims (12)

A copolymer composed of a polymerizable monomer (A) selected from the group consisting of bisphenol A represented by the formula (I) and a reactive derivative thereof, and another polymerizable monomer (B) A liquid crystal polymer.

  The liquid crystal polymer according to claim 1, wherein the total amount of the polymerizable monomer (A) is 0.01 to 10 mol parts relative to 100 mol parts of the total amount of the other polymerizable monomers (B). .   The other polymerizable monomer (B) is selected from the group consisting of aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic aminocarboxylic acid, aromatic hydroxyamine, aromatic diamine and aliphatic diol. The liquid crystal polymer according to claim 1, wherein the liquid crystal polymer is one or more compounds.   The liquid crystal polymer according to any one of claims 1 to 3, wherein the other polymerizable monomer (B) contains an aromatic hydroxycarboxylic acid.   The liquid crystal polymer according to claim 1, wherein the other polymerizable monomer (B) contains an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and an aromatic diol.   The liquid crystal polymer according to any one of claims 3 to 5, wherein the aromatic hydroxycarboxylic acid is 4-hydroxybenzoic acid and / or 6-hydroxy-2-naphthoic acid.   The liquid crystal polymer according to any one of claims 1 to 6, wherein the other polymerizable monomer (B) is 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.   The liquid crystal according to any one of claims 1 to 6, wherein the other polymerizable monomer (B) is 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, aromatic dicarboxylic acid and aromatic diol. polymer.   The liquid crystal polymer according to claim 3, 5 or 8, wherein the aromatic dicarboxylic acid is one or more compounds selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid.   The liquid crystal polymer according to claim 3, 5 or 8, wherein the aromatic diol is one or more compounds selected from the group consisting of hydroquinone, resorcin, 4,4'-dihydroxybiphenyl and 2,6-dihydroxynaphthalene. .   A liquid crystal polymer composition comprising the liquid crystal polymer according to claim 1 and an inorganic or organic filler.   A molded article selected from the group consisting of an injection molded article, a film and a fiber, comprising the liquid crystal polymer according to claim 1 or the liquid crystal polymer composition according to claim 11.