JP7174640B2 - liquid crystal polymer - Google Patents

Description

The present invention relates to a liquid crystal polymer capable of forming articles such as molded articles with improved weld strength.

Liquid crystal polymers are excellent in mechanical properties such as heat resistance and rigidity, chemical resistance, dimensional accuracy, etc. Therefore, their use is expanding not only for molded products but also for various applications such as fibers and films. Especially in the field of information and communication such as personal computers and mobile phones, parts are becoming more highly integrated, smaller, thinner, and lower in height. is formed in many cases, and the amount of liquid crystal polymer used has increased significantly, taking advantage of the excellent moldability of liquid crystal polymer, that is, good fluidity and no burrs, which are not found in other polymers. there is

However, liquid crystal polymer has the property that the molecules are easily oriented even with a small amount of shearing force, and the anisotropy of mechanical strength is large in the flow direction (MD) and the direction perpendicular to it (TD) during molding, and the molded product In the case of having a weld part in the inner part, there is a problem that the strength of the weld part is weak.

Various methods have been conventionally proposed to solve such problems.

For example, Patent Document 1 describes a method for improving the anisotropy and weld strength of a liquid crystal polymer by copolymerizing a trifunctional naphthalene hydroxycarboxylic acid with another polymerizable monomer. However, when such polyfunctional monomers are used, excessive functional groups are present, resulting in a branched structure in the molecular chain of the polymer, which may result in insufficient physical properties of the molded article.

Also proposed is a method of improving the weld strength by blending a liquid crystal polymer with a filler such as diatomaceous earth (Patent Document 2) or titania-supported calcium carbonate (Patent Document 3). However, there has been a demand for a method of suppressing the blending of these fillers and improving the weld strength by improving the polymer itself.

Japanese Patent Application Laid-Open No. 2002-371127 JP 2008-111034 A JP 2010-241950 A

An object of the present invention is to provide a liquid crystal polymer capable of forming articles such as molded articles with improved weld strength.

In view of the above problems, the present inventors have made intensive studies and found that it is possible to form a molded product or the like with improved weld strength by copolymerizing a diol component having a specific structure with another polymerizable monomer. The inventors have found that a liquid crystal polymer can be obtained, and have completed the present invention.

That is, the present invention provides a structural unit derived from one or more polymerizable compounds (A) selected from the group consisting of diol compounds represented by formula (1 ) and reactive derivatives thereof, and a polymerizable monomer ( A liquid crystal polymer containing structural units derived from B), wherein the total amount of structural units derived from the polymerizable compound (A) is 0.01 to 0.01 with respect to 100 mol% of all structural units constituting the liquid crystal polymer. 7 mol %, with respect to the liquid crystal polymer.

According to the liquid crystal polymer of the present invention, articles such as molded articles having improved weld strength can be formed.

The diol compound represented by formula (1 ) is referred to herein as bis(4-hydroxybenzoic acid) 1,4:3,6-dianhydrosorbitol. Also, the diol compound represented by formula (1 ) may be simply referred to as a diol compound.

In the present specification and claims, the term "weld part" means a part where molten liquid crystal polymer or liquid crystal polymer composition flowing from two or more directions joins in the mold during molding of liquid crystal polymer or liquid crystal polymer composition. means

The liquid crystalline polymers of the present invention are preferably polyesters or polyesteramides that form anisotropic melt phases. These are commonly referred to in the art as thermotropic liquid crystalline polyesters or thermotropic liquid crystalline polyester amides, but are not particularly limited.

In the present specification, the term "reactive derivative" of a polymerizable compound refers to a derivative of a compound having reactivity capable of introducing a target structural unit. Examples of suitable reactive derivatives of diol compounds that can be used in the present invention include ester-forming derivatives such as acylated diol compounds, ester derivatives, and acid halides. As the polymerizable compound (A) selected from the group consisting of diol compounds and reactive derivatives thereof, only one compound may be used, or two or more compounds may be used in combination.

The diol compound used in the present invention may have a substituent as long as it does not impair the effects of the present invention. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen. As the alkyl group or alkoxy group as a substituent, those having up to 6 carbon atoms are preferably used.

As used herein, an "aromatic" compound (eg, aromatic hydroxycarboxylic acid) is intended to mean a compound containing an aromatic group with up to 4 condensed rings. In addition, "aliphatic" compounds (eg, aromatic diols) are intended to indicate compounds containing saturated or unsaturated carbon chains of 2 to 12 carbon atoms, which may be branched.

The total amount of one or more polymerizable compounds (A) selected from the group consisting of diol compounds and reactive derivatives thereof used to obtain the liquid crystal polymer of the present invention is the polymerizable compound (A ) corresponds to the total amount of structural units derived from The total amount of the polymerizable compound (A) used, that is, the total amount of structural units derived from the polymerizable compound (A) contained in the liquid crystal polymer, is the total amount of the polymerizable compound and polymerizable monomers used, that is, the liquid crystal polymer 0.01 to 7 mol%, preferably 0.05 to 5 mol%, more preferably 0.07 to 4 mol%, more preferably 100 mol% of all structural units constituting is 0.1 to 3 mol %. When the total amount of the structural units derived from the polymerizable compound (A) exceeds 7 mol % with respect to 100 mol % of all structural units constituting the liquid crystal polymer, heat resistance and mechanical properties are deteriorated. When the total amount of structural units derived from the polymerizable compound (A) is less than 0.01 mol% with respect to 100 mol% of all structural units constituting the liquid crystal polymer, mechanical properties including weld strength are improved. No effect.

The polymerizable monomer (B) used to obtain the liquid crystal polymer of the present invention includes monomers used in conventional liquid crystal polymers, such as aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, and polymerizable compounds (A). aromatic diols different from (i.e., aromatic diols excluding the diol compound represented by formula (1 ) ), aromatic aminocarboxylic acids, aromatic hydroxylamines, aromatic diamines, aliphatic diols and aliphatic dicarboxylic acids. be done. 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 polymerizable monomer (B) used to obtain the liquid crystal polymer of the present invention may be an oligomer in which one or more than two of the above compounds are bonded to each other. In addition, regarding the amount of the polymerizable monomer (B) in the present specification and claims, even when the polymerizable monomer is an oligomer, the monomer units constituting the oligomer shall be calculated based on

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

Specific examples of aromatic dicarboxylic acids 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, alkyl-, alkoxy- or halogen-substituted products thereof, ester derivatives thereof, and ester-forming derivatives such as acid halides.

Among these, one or more selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid is preferably used.

Specific examples of aromatic diols include hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, Ester-forming derivatives such as 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenol ether, and 2,2'-dihydroxybinaphthyl, alkyl, alkoxy or halogen substituted products thereof and acylated products thereof can be mentioned.

Among these, one or more selected from the group consisting of hydroquinone, 4,4′-dihydroxybiphenyl, and 2,6-dihydroxynaphthalene is preferably used. ,4'-dihydroxybiphenyl is preferred.

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

Specific examples of aromatic hydroxylamines 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 such as acylated products thereof. Among these, 4-aminophenol is preferably used because it is easy to balance the heat resistance and mechanical strength of the resulting liquid crystal polymer.

Specific examples of aromatic diamines include 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, alkyl-, alkoxy- or halogen-substituted products thereof, and their Amide-forming derivatives such as acylated products are included.

Specific examples of aliphatic diols include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and acylates thereof. In addition, a polymer containing an aliphatic diol such as polyethylene terephthalate or polybutylene terephthalate is reacted with the above aromatic oxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol and their acylated products, ester derivatives, acid halides, etc. You may let

Specific examples of aliphatic dicarboxylic acids 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 their excellent reactivity during polymerization.

Polymerizable monomer (B) consisting of aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic aminocarboxylic acid, aromatic hydroxyamine, aromatic diamine, aliphatic diol and aliphatic dicarboxylic acid A combined use of two or more compounds selected from the group is one of 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, a combination of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, aromatic dicarboxylic acid and aromatic diol as the polymerizable monomer (B) is particularly preferably used.

Specific examples of the polymerizable monomer (B) used in the liquid crystal polymer of the present invention include, for example, 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'-dihydroxybiphenyl 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-naphthoic 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/terephthalic acid/4-aminophenol copolymer Coalescence 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/4,4'-dihydroxybiphenyl/ethylene glycol copolymer 23) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/ethylene glycol copolymer 24) 4-hydroxy Benzoic 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, the liquid crystal polymer composed of the monomer units of 11) or 15) is preferable.

The above liquid crystal polymers may be used alone, or two or more of them may be blended to form the liquid crystal polymer of the present invention.

The method for producing the liquid crystal polymer of the present invention is described below.

The liquid crystal polymer of the present invention is a liquid crystal polymer obtained by polymerizing one or more polymerizable compounds (A) selected from the group consisting of the above diol compounds and reactive derivatives thereof and polymerizable monomers (B). is. The method for producing the liquid crystal polymer of the present invention is not particularly limited. The liquid crystal polymer of the present invention can be obtained by subjecting it to known polycondensation methods for forming bonds, such as melt acidolysis and slurry polymerization.

The melt acidolysis method is the preferred method for making the liquid crystalline polymers of the present invention. This method first heats the polymerizable compound and/or the polymerizable monomer to form a molten solution of the reactants and then continues the polycondensation reaction to obtain the molten polymer. A vacuum may be applied to facilitate removal of volatiles (eg, acetic acid, water, etc.) that are by-produced in the final stages of condensation.

A slurry polymerization method is a method of reacting a polymerizable compound and/or a polymerizable monomer in the presence of a heat exchange fluid, and a solid product is obtained in a state of being suspended in the heat exchange medium.

In both the melt acidolysis method and the slurry polymerization method, both the polymerizable compound (A) and the polymerizable monomer (B) used in producing the liquid crystal polymer have hydroxyl groups and / Alternatively, it can be subjected to the reaction as a modified form in which the amino group is acylated, that is, as 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 the polymerizable compound and/or the acetylated product of the polymerizable monomer for the reaction.

The lower acylated product of the polymerizable compound and/or the polymerizable monomer may be previously synthesized by acylation separately, or may be added to the polymerizable compound and/or the polymerizable monomer during the production of the liquid crystal polymer. It can also be produced in the reaction system by adding an acylating agent such as acetic acid.

In either case of the melt acidolysis method or the slurry polymerization method, the polymerization reaction is preferably 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 catalysts include organotin compounds such as dialkyltin oxide (e.g., dibutyltin oxide) and diaryltin oxide; titanium dioxide; antimony trioxide; organotitanium compounds such as alkoxytitanium silicates and titanium alkoxides; Earth metal salts (eg, potassium acetate); gaseous acid catalysts such as Lewis acids (eg, boron trifluoride) and hydrogen halides (eg, hydrogen chloride).

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

The liquid crystal polymer of the present invention obtained by the polycondensation reaction in this manner is generally extracted from the polymerization reactor in a molten state and then processed into pellets, flakes, or powder.

Pellet-shaped, flake-shaped, or powder-shaped liquid crystal polymers are placed in a substantially solid state under reduced pressure, vacuum, or in an inert gas atmosphere such as nitrogen or helium for the purpose of increasing the 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 to obtain a liquid crystal polymer. It may be used as a composition.

Inorganic or organic fillers that may be blended in the liquid crystal polymer of the present invention may be fibrous, plate-like, or granular, such as glass fiber, milled glass, silica-alumina fiber, alumina fiber, carbon fiber, and aramid. Fibers, potassium titanate whiskers, aluminum borate whiskers, wollastonite, talc, mica, graphite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate, and titanium oxide. Among these, glass fiber is preferable because it has an excellent balance between physical properties and cost. These fillers may be used in combination of two or more.

The total amount of inorganic or organic fillers 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, per 100 parts by weight of the liquid crystal polymer. When the total amount of the inorganic or organic filler exceeds 200 parts by mass with respect to 100 parts by mass of the liquid crystal polymer, the molding processability of the liquid crystal polymer composition tends to decrease, and the cylinder of the molding machine and the mold may be damaged. Wear tends to increase.

In the liquid crystal polymer of the present invention, other additives such as higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty acid metal salts (here, the higher fatty acid is usually carbon release improvers such as polysiloxanes and fluorine resins; coloring agents such as dyes and pigments; antioxidants; heat stabilizers; ultraviolet absorbers; antistatic agents; etc. may be added. These additives may be blended alone, or may be blended 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, per 100 parts by weight of the liquid crystal polymer. If the total amount of the other additives exceeds 10 parts by mass with respect to 100 parts by mass of the liquid crystal polymer, the liquid crystal polymer composition tends to deteriorate in moldability and thermal stability.

Further, when molding the liquid crystal polymer or the liquid crystal polymer composition of the present invention, among the above other additives, additives having an external lubricant effect such as higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, fluorocarbon surfactants, etc. may be attached in advance to the surface of the liquid crystal polymer pellets.

The liquid crystal polymer of the present invention may contain other resin components. Other resin components include, for example, polyamides, polyesters, polyolefins, polyacetals, polyphenylene ethers, modified products thereof, thermoplastic resins such as polysulfones, polyethersulfones, polyetherimides and polyamideimides, phenolic resins, epoxy resins, A thermosetting resin such as a polyimide resin can be used. Other resin components can be blended alone or in combination of two or more. The blending amount of the other resin component is not particularly limited, and may be appropriately determined according to the application and purpose of the liquid crystal polymer. In one typical example, the total amount of other resin components is usually 0.1 to 100 parts by weight, particularly 0.1 to 80 parts by weight, per 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, still more preferably 10 Pa s when measured using a capillary rheometer at a shear rate of 1000 s ^-1 . ~50 Pa·s. It should be noted that the lower the melt viscosity, the better the fluidity during molding.

The liquid crystal polymer composition of the present invention is produced by adding inorganic or organic fillers, other additives, other resin components, etc. can be obtained by melt-kneading in a temperature range from the vicinity of the crystal melting temperature of the liquid crystal polymer to the crystal melting temperature plus 100°C.

The thus obtained liquid crystal polymer or liquid crystal polymer composition of the present invention is processed into articles such as molded articles, films or fibers by known processing methods such as injection molding, compression molding, extrusion molding and blow molding.

The liquid crystal polymer or liquid crystal polymer composition of the present invention has improved weld strength and preferably excellent mechanical properties, and is particularly useful as electric/electronic parts, mechanical parts, automobile parts, and the like.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these.

Each characteristic value in the examples was measured by the following method.

<Crystal melting temperature>
Using a differential scanning calorimeter (Exstar 6000 manufactured by Seiko Instruments Inc.), the endothermic peak temperature (Tm1) observed when the sample was measured from room temperature at a temperature increase of 20 ° C./min. It was held at a temperature higher by 20-50°C for 10 minutes. Next, the sample was cooled to room temperature under a temperature decrease condition of 20°C/min, and the endothermic peak was observed when the temperature was increased again at 20°C/min. ).

<Melt viscosity>
Melt viscosities were measured at 350° C. under conditions of a shear rate of 1000 sec ⁻¹ with a melt viscosity measuring device (Capilograph 1D manufactured by Toyo Seiki Co., Ltd.) using a capillary of 0.7 mmφ×10 mm.

<Weld strength, elastic modulus>
Cylindrical test piece having a weld part, injection molded at a cylinder temperature of +20 to 40 ° C and a mold temperature of 70 ° C using an injection molding machine (NEX15-1E manufactured by Nissei Plastic Industry Co., Ltd.) with a mold clamping pressure of 15 tons. (thickness 0.8 mm, outer diameter 10 mm, height 5 mm). Each test piece was subjected to a compression test using INSTRON5567 (a universal testing machine manufactured by Instron Japan Company Limited) to measure the strength and elastic modulus when the weld portion was broken.

<Tensile strength>
Using an injection molding machine (MINIMAT M26/15 manufactured by Sumitomo Heavy Industries, Ltd.) with a mold clamping pressure of 15 tons, injection molding is performed at a cylinder temperature of +20 to 40 ° C. and a mold temperature of 80 ° C., and a dumbbell-shaped tensile test piece is produced. made. Tensile strength was measured using INSTRON5567 (universal testing machine manufactured by Instron Japan Co., Ltd.) at a span-to-span distance of 25.4 mm and a tensile speed of 5 mm/min.

<Bending strength, bending elastic modulus>
Using an injection molding machine with a mold clamping pressure of 15 tons (MINIMAT M26/15 manufactured by Sumitomo Heavy Industries, Ltd.), injection molding was performed at a cylinder temperature of crystal melting temperature +20 to 40 ° C. and a mold temperature of 80 ° C., and a strip bending test was performed. A piece (65 mm long x 12.7 mm wide x 2.0 mm thick) was made. For the bending test, a three-point bending test was performed using INSTRON5567 (a universal testing machine manufactured by Instron Japan Co., Ltd.) at a span-to-span distance of 40.0 mm and a compression rate of 1.3 mm/min.

<Izod impact strength>
Using the same test piece as the test piece used for the bending strength measurement, the measurement was performed according to ASTM D256.

In the examples, the following abbreviations refer to the following compounds.
POB: 4-hydroxybenzoic acid BON6: 6-hydroxy-2-naphthoic acid HQ: hydroquinone BP: 4,4'-dihydroxybiphenyl TPA: terephthalic acid NDA: 2,6-naphthalenedicarboxylic acid
IS-POB2: bis(4-hydroxybenzoic acid) 1,4:3,6-dianhydrosorbitol

Comparative example 1
The following compounds were placed in a reaction vessel equipped with a stirring blade and a distillation tube, heated to 40 to 140°C over 50 minutes under a nitrogen gas atmosphere, maintained at 140°C for 30 minutes, and then heated to 345°C. The temperature was raised over a period of time, and after reacting at 345°C for 10 minutes, the pressure was reduced at 345°C. After reducing the pressure to 5 torr over 80 minutes, polycondensation was completed when a predetermined stirring torque was reached. The amount of acetic acid distilled off during the polymerization was almost the same as the theoretical value. The content was taken out from the reaction vessel, and pellets of the liquid crystal polymer were obtained with a pulverizer.
POB: 314.2 g (35 mol%)
BON6: 61.2 g (5 mol%)
HQ: 121.7 g (17 mol%)
BP: 157.3 g (13 mol%)
TPA: 323.9 g (30 mol% )
Acetic anhydride: 683.5 g (103 mol parts per 100 mol parts of hydroxy groups of all monomers)
The obtained pellets were molded and evaluated for each characteristic value. The results are shown in Tables 1 and 2 together with the crystalline melting temperature and melt viscosity of the liquid crystal polymer obtained.

Example 1
The following compounds were placed in a reaction vessel equipped with a stirring blade and a distillation tube, heated to 40 to 140°C over 50 minutes under a nitrogen gas atmosphere, maintained at 140°C for 30 minutes, and then heated to 345°C. The temperature was raised over a period of time, and after reacting at 345°C for 10 minutes, the pressure was reduced at 345°C. After reducing the pressure to 10 torr over 60 minutes, polycondensation was completed when a predetermined stirring torque was reached. The amount of acetic acid distilled off during the polymerization was almost the same as the theoretical value. The content was taken out from the reaction vessel, and pellets of the liquid crystal polymer were obtained with a pulverizer.
POB: 628.4 g (70 mol%)
BON6: 24.5 g (2 mol%)
HQ: 93 g (13 mol%)
NDA: 196.7 g (14 mol%)
IS-POB2: 25.1 g (1 mol%)
Acetic anhydride: 696.8 g (105 mol parts per 100 mol parts of hydroxy groups of all monomers)
The obtained pellets were molded and evaluated for each characteristic value. The results are shown in Tables 3 and 4 together with the crystalline melting temperature and melt viscosity of the liquid crystal polymer obtained.

Example 2
The following compounds were placed in a reaction vessel equipped with a stirring blade and a distillation tube, polycondensed and molded in the same manner as in Example 1 , and each characteristic value was evaluated. The results are shown in Tables 3 and 4 together with the crystalline melting temperature and melt viscosity of the liquid crystal polymer obtained.
POB: 628.4 g (70 mol%)
BON6: 24.5 g (2 mol%)
HQ: 85.9 g (12 mol%)
NDA: 196.7 g (14 mol%)
IS-POB2: 50.2 g (2 mol%)
Acetic anhydride: 696.8 g (105 mol parts per 100 mol parts of hydroxy groups of all monomers)

Comparative example 2
The following compounds were placed in a reaction vessel equipped with a stirring blade and a distillation tube, polycondensed and molded in the same manner as in Example 1 , and each characteristic value was evaluated. The results are shown in Tables 3 and 4 together with the crystalline melting temperature and melt viscosity of the liquid crystal polymer obtained.
POB: 628.4 g (70 mol%)
BON6: 24.5 g (2 mol%)
HQ: 100.1 g (14 mol%)
NDA: 196.7 g (14 mol%)
Acetic anhydride: 696.8 g (105 mol parts per 100 mol parts of hydroxy groups of all monomers)

で表されるジオール化合物およびその反応性誘導体からなる群から選択される１種以上の重合性化合物（Ａ）に由来する構成単位と、重合性単量体（Ｂ）に由来する構成単位とを含む液晶ポリマーであって、重合性化合物（Ａ）に由来する構成単位の合計量が、液晶ポリマーを構成する全構成単位１００モル％に対して０．０１～７モル％である、液晶ポリマー。
〔２〕重合性単量体（Ｂ）は、芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸、重合性化合物（Ａ）とは異なる芳香族ジオール、芳香族アミノカルボン酸、芳香族ヒドロキシアミン、芳香族ジアミン、脂肪族ジオールおよび脂肪族ジカルボン酸からなる群から選択される１種以上である、〔１〕に記載の液晶ポリマー。
〔３〕重合性単量体（Ｂ）は芳香族ヒドロキシカルボン酸を含む、〔１〕または〔２〕に記載の液晶ポリマー。
〔４〕重合性単量体（Ｂ）は、芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸および重合性化合物（Ａ）とは異なる芳香族ジオールを含む、〔１〕～〔３〕のいずれかに記載の液晶ポリマー。
〔５〕芳香族ヒドロキシカルボン酸は、４－ヒドロキシ安息香酸および／または６－ヒドロキシ－２－ナフトエ酸である、〔２〕～〔４〕のいずれかに記載の液晶ポリマー。
〔６〕芳香族ジカルボン酸は、テレフタル酸、イソフタル酸および２，６－ナフタレンジカルボン酸からなる群から選択される１種以上である、〔２〕～〔５〕のいずれかに記載の液晶ポリマー。
〔７〕前記の重合性化合物（Ａ）とは異なる芳香族ジオールは、ハイドロキノン、４,４'－ジヒドロキシビフェニルおよび２，６－ジヒドロキシナフタレンからなる群から選択される１種以上である、〔２〕～〔６〕のいずれかに記載の液晶ポリマー。
〔８〕〔１〕～〔７〕のいずれかに記載の液晶ポリマーと無機または有機充填材とを含む液晶ポリマー組成物。
〔９〕〔１〕～〔７〕のいずれかに記載の液晶ポリマーまたは請求項８に記載の液晶ポリマー組成物を加工してなる、成形品、フィルムまたは繊維からなる物品。 As shown in Tables 1 to 4, the liquid crystal polymer of the present invention containing the specific diol compound (Examples 1 to 2 ) is superior in weld strength, etc., to the liquid crystal polymer not containing the diol compound (Comparative Example 2 ). It is understood that the mechanical properties are excellent.
Preferred embodiments of the invention include the following.
[1] Formula (1)

A structural unit derived from one or more polymerizable compounds (A) selected from the group consisting of a diol compound and a reactive derivative thereof represented by and a structural unit derived from a polymerizable monomer (B) wherein the total amount of structural units derived from the polymerizable compound (A) is 0.01 to 7 mol% with respect to 100 mol% of all structural units constituting the liquid crystal polymer.
[2] The polymerizable monomer (B) is an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, an aromatic diol different from the polymerizable compound (A), an aromatic aminocarboxylic acid, an aromatic hydroxylamine, an aromatic The liquid crystal polymer according to [1], which is at least one selected from the group consisting of diamines, aliphatic diols and aliphatic dicarboxylic acids.
[3] The liquid crystal polymer according to [1] or [2], wherein the polymerizable monomer (B) contains an aromatic hydroxycarboxylic acid.
[4] Any one of [1] to [3], wherein the polymerizable monomer (B) contains an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid and an aromatic diol different from the polymerizable compound (A) The liquid crystalline polymer described.
[5] The liquid crystal polymer according to any one of [2] to [4], wherein the aromatic hydroxycarboxylic acid is 4-hydroxybenzoic acid and/or 6-hydroxy-2-naphthoic acid.
[6] The liquid crystal polymer according to any one of [2] to [5], wherein the aromatic dicarboxylic acid is one or more selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid. .
[7] The aromatic diol different from the polymerizable compound (A) is one or more selected from the group consisting of hydroquinone, 4,4'-dihydroxybiphenyl and 2,6-dihydroxynaphthalene [2 ] to [6].
[8] A liquid crystal polymer composition comprising the liquid crystal polymer according to any one of [1] to [7] and an inorganic or organic filler.
[9] An article comprising a molded article, film or fiber obtained by processing the liquid crystal polymer according to any one of [1] to [7] or the liquid crystal polymer composition according to [8].

Claims (9)

formula (1)

From structural units derived from one or more polymerizable compounds (A) selected from the group consisting of diol compounds and reactive derivatives thereof represented by and structural units derived from the polymerizable monomer (B) The liquid crystal polymer composed , wherein the total amount of structural units derived from the polymerizable compound (A) is 0.01 to 7 mol% with respect to 100 mol% of all structural units constituting the liquid crystal polymer ,
The polymerizable monomer (B) includes an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, an aromatic diol different from the polymerizable compound (A), an aromatic aminocarboxylic acid, an aromatic hydroxylamine, an aromatic diamine, an aliphatic one or more selected from the group consisting of group diols and aliphatic dicarboxylic acids,
Here, the aromatic diol different from the polymerizable compound (A) is one or more selected from the group consisting of hydroquinone, 4,4'-dihydroxybiphenyl and 2,6-dihydroxynaphthalene.
liquid crystal polymer. 2. The liquid crystal polymer according to claim 1 , wherein the total amount of structural units derived from the polymerizable compound (A) is less than 3 mol % with respect to 100 mol % of all structural units constituting the liquid crystal polymer. 3. The liquid crystal polymer according to claim 1, wherein the polymerizable monomer (B) contains an aromatic hydroxycarboxylic acid. 4. The liquid crystal polymer according to any one of claims 1 to 3, wherein the polymerizable monomer (B) contains an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid and an aromatic diol different from the polymerizable compound (A). A liquid-crystalline polymer according to any one of claims 1 to 4, wherein the aromatic hydroxycarboxylic acid is 4-hydroxybenzoic acid and/or 6-hydroxy-2-naphthoic acid. 6. The liquid crystal polymer according to any one of claims 1 to 5, wherein the aromatic dicarboxylic acid is one or more selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid. 7. The aromatic diol different from the polymerizable compound (A) is one or more selected from the group consisting of hydroquinone and 4,4'-dihydroxybiphenyl according to any one of claims 1 to 6. liquid crystal polymer. A liquid crystal polymer composition comprising the liquid crystal polymer according to any one of claims 1 to 7 and an inorganic or organic filler. An article comprising a molded article, film or fiber obtained by processing the liquid crystal polymer according to any one of claims 1 to 7 or the liquid crystal polymer composition according to claim 8.