JP5030867B2 - Liquid crystal polymer composition - Google Patents

Description

  The present invention relates to a liquid crystal polymer composition having improved fluidity during molding.

  Liquid crystal polymers are excellent in mechanical properties such as heat resistance and rigidity, chemical resistance, dimensional accuracy, etc., and their use is expanding not only for molded products but also for various applications such as fibers and films. In particular, in the information / communication field such as personal computers and mobile phones, there are many cases where a thin-walled portion is formed due to high integration of components, miniaturization, thinning, low profile, and the like. Therefore, in such a field, the amount of the liquid crystal polymer used is greatly increased by taking advantage of the characteristics that the other resins do not have such as excellent moldability, that is, good fluidity and no burrs.

  However, the shape of electronic components used in the information / communication field is becoming thinner and more complex every day. Accordingly, liquid crystal polyesters are required to be further improved in fluidity during molding.

  Examples of the method for improving the fluidity at the time of molding the liquid crystal polymer include a method of blending a liquid crystal polymer having a specific molecular weight (see Patent Document 1), a 4-hydroxybenzoic acid having a specific flow temperature to the liquid crystal polymer. In a method of blending an oligomer (see Patent Document 2) and a method of producing a liquid crystal polymer by deacetic acid melt polymerization, the polymerization reaction solution is fed through a vertical stirring thin film evaporator, and the amount of acetic acid generated in the resulting liquid crystal polymer A number of methods are known, such as a method for obtaining a liquid crystal polymer with reduced fluidity and excellent fluidity (see Patent Document 3) and a method for adding a phosphoric acid compound during the production of a liquid crystal polymer (see Patent Document 4). ing.

  However, in the methods disclosed in Patent Document 1 and Patent Document 2, there is a problem that it is not easy to produce a liquid crystal polymer having a specific molecular weight or an oligomer of 4-hydroxybenzoic acid having a specific flow temperature, In the method disclosed in Patent Document 3, there is a problem in that it is necessary to use a special apparatus such as a vertical stirring thin film evaporator. In the method disclosed in Patent Document 4, the type of phosphoric acid compound and Depending on the amount used, there is a problem that the mechanical properties of the liquid crystal polymer are greatly impaired.

For these reasons, there is a need for a method for improving the fluidity of a liquid crystal polymer without impairing the mechanical properties of the liquid crystal polymer by using an inexpensive and easily available material without using a special apparatus.
JP-A-2-173156 JP-A-3-095260 JP 2000-309636 A Japanese Patent Laid-Open No. 06-032880

  An object of the present invention is to provide a liquid crystal polymer composition having improved fluidity without impairing mechanical properties.

The present invention relates to a liquid crystal polymer composition comprising 0.01 to 2.0 parts by weight of one or more aliphatic dicarboxylic acids represented by the following formula [1] with respect to 100 parts by weight of a liquid crystal polymer. I will provide a:
HOOC-R-COOH [1]
[Wherein R represents a divalent aliphatic hydrocarbon group having 8 to 30 carbon atoms which may have a branch and may have an unsaturated bond].

The present invention also includes blending 0.01 to 2.0 parts by weight of one or more aliphatic dicarboxylic acids represented by the following formula [1] with respect to 100 parts by weight of the liquid crystal polymer. A method for producing a liquid crystal polymer composition is provided:
HOOC-R-COOH [1]
[Wherein R represents a divalent aliphatic hydrocarbon group having 8 to 30 carbon atoms which may have a branch and may have an unsaturated bond].

  In the present invention, by blending 0.01 to 2.0 parts by weight of the aliphatic dicarboxylic acid represented by the above formula [1] with respect to 100 parts by weight of the liquid crystal polymer, the melt viscosity of the liquid crystal polymer composition is blended. This improves the fluidity during the molding of the liquid crystal polymer composition.

  The liquid crystal polymer used in the present invention is a polyester or polyester amide that forms an anisotropic melt phase, and is not particularly limited as long as it is called a thermotropic liquid crystal polyester or a thermotropic liquid crystal polyester amide by those skilled in the art.

  The property of the anisotropic molten phase can be confirmed by a normal deflection inspection method using an orthogonal deflector, that is, by observing a sample placed on a hot stage in a nitrogen atmosphere.

  As the repeating unit constituting the liquid crystal polymer used in the present invention, aromatic oxycarbonyl repeating unit, aromatic dicarbonyl repeating unit, aromatic dioxy repeating unit, aromatic aminooxy repeating unit, aromatic diamino repeating unit, aromatic amino Examples thereof include a carbonyl repeating unit, an aromatic oxydicarbonyl repeating unit, and an aliphatic dioxy repeating unit.

  The liquid crystal polymer composed of each of these repeating units may or may not form an anisotropic molten phase depending on the constituent components, the composition ratio in the polymer, and the sequence distribution, but the liquid crystal used in the present invention. Polymers are limited to those that form an anisotropic melt phase.

  Specific examples of the monomer that gives an aromatic oxycarbonyl repeating unit include, for example, 4-hydroxybenzoic acid, metahydroxybenzoic acid, orthohydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid. Acid, 3-hydroxy-2-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, their alkyl, alkoxy or Halogen-substituted products, and ester-forming derivatives such as acylated products, ester derivatives, and acid halides thereof can be mentioned. Among these, parahydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferable from the viewpoint of easy adjustment of characteristics and melting point of the liquid crystal polymer.

  Specific examples of the monomer giving the aromatic dicarbonyl repeating unit include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1, Examples thereof include aromatic dicarboxylic acids such as 4-naphthalenedicarboxylic acid and 4,4′-dicarboxybiphenyl, alkyl, alkoxy or halogen-substituted products thereof, and ester-forming derivatives such as ester derivatives and acid halides thereof. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable because the liquid crystal polymer from which terephthalic acid and 2,6-naphthalenedicarboxylic acid are obtained can easily adjust the mechanical properties, heat resistance, melting temperature, and moldability to appropriate levels.

  Specific examples of the monomer giving an aromatic dioxy repeating unit include, for example, hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4 Aromatic diols such as 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, alkyl, alkoxy or halogen substituents thereof, and Examples thereof include ester-forming derivatives such as acylated products. Among these, hydroquinone and 4,4'-dihydroxybiphenyl are preferable from the viewpoint of reactivity during polymerization, characteristics of the obtained liquid crystal polymer, and the like.

  Specific examples of the monomer that gives an aromatic aminooxy repeating unit include, for example, p-aminophenol, m-aminophenol, 4-amino-1-naphthol, 5-amino-1-naphthol, and 8-amino-2- Aromatic hydroxyamines such as naphthol and 4-amino-4′-hydroxybiphenyl, alkyl, alkoxy or halogen substituents thereof, and ester or amide-forming derivatives thereof such as acylated products thereof can be mentioned.

  Specific examples of the monomer that gives an aromatic diamino repeating unit include aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, alkyls thereof, Examples include amide-forming derivatives such as alkoxy or halogen-substituted products, and acylated products thereof.

  Specific examples of the monomer that gives an aromatic aminocarbonyl repeating unit include aromatic aminocarboxylic acids such as p-aminobenzoic acid, m-aminobenzoic acid, and 6-amino-2-naphthoic acid, their alkyls, Examples thereof include alkoxy or halogen-substituted products, and ester or amide-forming derivatives thereof such as acylated products, ester derivatives, and acid halides.

  Specific examples of monomers that give aromatic oxydicarbonyl repeating units include hydroxyaromatic dicarboxylic acids such as 3-hydroxy-2,7-naphthalenedicarboxylic acid, 4-hydroxyisophthalic acid, and 5-hydroxyisophthalic acid. And alkyl-substituted, alkoxy- or halogen-substituted products thereof, and ester-forming derivatives such as acylated products, ester derivatives, and acid halides thereof.

  Specific examples of the monomer giving the aliphatic dioxy repeating unit include aliphatic diols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and acylated products thereof. Polyesters containing aliphatic dioxy repeating units, such as polyethylene terephthalate and polybutylene terephthalate, are converted into the above aromatic oxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic hydroxyamines, aromatic diamines, aromatics. A liquid crystal polymer containing an aliphatic dioxy repeating unit can also be obtained by reacting with aminocarboxylic acids and their acylated products, ester derivatives, acid halides and the like. In addition, when using the polyester containing an aliphatic dioxy repeating unit for superposition | polymerization, this polyester shall not contain the aliphatic dicarbonyl unit derived from the aliphatic dicarboxylic acid represented by the said Formula [1].

  The liquid crystal polymer used in 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. These monomers are used in an aromatic oxycarbonyl repeating unit, an aromatic dicarbonyl repeating unit, an aromatic dioxy repeating unit, an aromatic aminooxy repeating unit, an aromatic diamino repeating unit, an aromatic aminocarbonyl repeating unit, The amount is preferably 10 mol% or less based on the total amount of monomers giving the aromatic oxydicarbonyl repeating unit and the aliphatic dioxy repeating unit.

  As mentioned above, although the repeating unit contained in the liquid crystal polymer used in this invention and the monomer which gives it were demonstrated, the liquid crystal polymer used in this invention is an aromatic oxycarbonyl repeating unit, 4-oxybenzoyl repeating unit, and / or Or it is more preferable to use what contains a 6-oxy-2- naphthoyl repeating unit.

Among the liquid crystal polymers containing 4-oxybenzoyl repeating units and / or 6-oxy-2-naphthoyl repeating units, preferred are, for example, copolymers composed of the following monomer constituent units.
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) 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone copolymer 7) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl Copolymer 8) 6-hydroxy-2-naphthoic acid / terephthalic acid / 4,4'-dihydroxybi Phenyl copolymer 9) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone copolymer 10) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / 4,4′-dihydroxy Biphenyl copolymer 11) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 12) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 13) 4 -Hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 14) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone / 4,4 '-Dihydroxybiphenyl copolymer 15) 4-hydroxybenzoic acid / tere Taric acid / 4-aminophenol copolymer 16) 6-hydroxy-2-naphthoic acid / terephthalic acid / 4-aminophenol copolymer 17) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / 4-aminophenol copolymer 18) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / 4-aminophenol copolymer 19) 4-hydroxybenzoic acid / terephthalic acid / ethylene glycol copolymer 20) 4-hydroxybenzoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl / ethylene glycol copolymer 21) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / ethylene glycol copolymer 22 ) 4-Hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / Telef Taric acid / 4,4′-dihydroxybiphenyl / ethylene glycol copolymer.

  Among these, it is particularly preferable to use the copolymers 1), 9), and 13) as liquid crystal polymers from the viewpoint of molding processability and mechanical properties.

  As the liquid crystal polymer in the present invention, a blend of two or more liquid crystal polymers may be used for the purpose of improving fluidity during molding.

Hereinafter, a method for producing a liquid crystal polymer used in the present invention will be described.
The production method of the liquid crystal polymer used in the present invention is not particularly limited, and a known polycondensation method for forming an ester bond or an amide bond composed of a combination of the above monomers, for example, a melt acidosis method, a slurry polymerization method, or the like is used. Can do.

  The melt acidosis method is a preferred method for use in the method for producing a liquid crystal polymer used in the present invention, and this method first heats a monomer to form a molten liquid of a reactant, and then performs a reaction. Subsequently, a molten polymer is obtained. Note that a vacuum may be applied to facilitate removal of volatiles (for example, acetic acid, water, etc.) by-produced in the final stage of the condensation.

  The slurry polymerization method is a method of reacting in the presence of a heat exchange fluid, and the 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 component used in producing the liquid crystal polymer is a modified form in which hydroxyl groups and / or amino groups are acylated, that is, as a lower acylated product. It can also be used for the reaction. 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 monomer in the reaction.

  The acylated product of the monomer may be prepared by separately acylating and synthesized in advance, or it may be generated in the reaction system by adding an acylating agent such as acetic anhydride to the monomer during the production of the liquid crystal polymer. it can.

In any case of the melt acidification method or the slurry polymerization method, a catalyst may be used as needed during the reaction.
Specific examples of the catalyst include organotin compounds such as dialkyltin oxide (eg, dibutyltin oxide) and diaryltin oxide; antimony trioxide; titanium dioxide; organotitanium compounds such as alkoxytitanium silicate and titanium alkoxide; Examples include alkaline earth metal salts (for example, potassium acetate); inorganic acid salts (for example, potassium sulfate); Lewis acid (for example, boron trifluoride); gaseous acid catalysts such as hydrogen halide (for example, hydrogen chloride).

  The ratio of the catalyst used is usually 10 to 1000 ppm, preferably 20 to 200 ppm, based on the monomer weight.

  The liquid crystal polymers obtained by the polycondensation reaction in this manner are each extracted from the polymerization reaction tank in a molten state, and then processed into pellets, flakes, or powders.

  The obtained liquid crystal polymer in the form of pellets, flakes, or powders is substantially a solid phase under reduced pressure or in 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 treatment temperature in the case of performing the heat treatment in the solid phase is not particularly limited as long as the liquid crystal polymer does not melt, but it is preferably 260 to 350 ° C, preferably 280 to 320 ° C.

  The liquid crystal polymer used in the present invention preferably has a crystal melting temperature (Tm) measured by a differential scanning calorimeter of 270 to 380 ° C., more preferably 280 to 340 ° C.

The crystal melting temperature (Tm) is measured by the method described below.
<Method for measuring crystal melting temperature>
After measuring the endothermic peak temperature (Tm1) observed when a liquid crystal polymer sample is measured at room temperature to 20 ° C./min, the sample is held at a temperature 20 to 50 ° C. higher than Tm1 for 10 minutes. Next, the sample was cooled to room temperature under a temperature drop condition of 20 ° C./min, and an endothermic peak was measured again when measured under a temperature rise condition of 20 ° C./min. Let melting temperature (Tm).

The liquid crystal polymer thus obtained is blended with one or more aliphatic dicarboxylic acids represented by the following formula [1] to obtain the liquid crystal polymer composition of the present invention.
HOOC-R-COOH [1]
[Wherein R represents a divalent aliphatic hydrocarbon group having 8 to 30 carbon atoms which may have a branch and may have an unsaturated bond].

  As the one or more aliphatic dicarboxylic acids used in the present invention, in consideration of volatility when blended in a liquid crystal polymer, the group R in the formula [1] has 16 to 30 carbon atoms, Those containing 75% by weight or more of an aliphatic dicarboxylic acid which is a divalent aliphatic hydrocarbon group which may have a branch and may have an unsaturated bond are more preferable, and those containing 80% by weight or more are further included. Those containing 85% by weight or more are most preferable.

  Examples of the aliphatic dicarboxylic acid used in the present invention include decanedioic acid (sebacic acid), 3-methylnonanedioic acid, 2-ethyloctanedioic acid, 2-methylnonanedioic acid, 2,6-dimethyloctanedioic acid, and 5-decene. Diacid, 4-decenedioic acid, 3-decenedioic acid, 2-decenedioic acid, 2,6-dimethyl-2-octenedioic acid, 3,7-dimethyl-2-octenedioic acid, 2,8-decadiene Diacid, 2,7-dimethyl-2,4-octadiene diacid, 2,6-dimethyl-2,6-octadiene diacid, 2,7-dimethyl-2,6-octadiene diacid, 3,6-dimethyl -2,6-octadiene diacid, 2,4,6,8-decatetraene diacid, undecanedioic acid, 2-undecenedioic acid, 2,9-undecadienedioic acid, dodecanedioic acid, 3-propylnonanedioic acid, 3-Isopropylno Diandioic acid, 2-butyloctanedioic acid, 3,3,6,6-tetramethyloctanedioic acid, 2-ethyl-2,6,6-trimethylheptanedioic acid, 2-dodecenedioic acid, 3-dodecenedioic acid Acid, 6-dodecenedioic acid, 4,8-dimethyl-3-decenedioic acid, 4,8-dodecadienedioic acid, 3,7-dimethyl-2,7-decadienedioic acid, 2,7,3,6- Tetramethyl-2,6-octadienedioic acid, 2,4,8,10-dodecatetraenedioic acid, tridecanedioic acid, 3,3,7,7-tetramethylnonanedioic acid, 2,4-tridecadienedioic acid 7-methyl-2,6,10-dodecatrienedioic acid, tetradecanedioic acid, 2,2,7,7-tetramethyldecanedioic acid, 4,9-dimethyldodeca-2,4,6,8,10 -Pentaene-1,12-diacid, pentadecanedioic acid, 3,7, 1-trimethyl-2,6,10-dodecatrienedioic acid, hexadecanedioic acid, 2,13-dimethyltetradecanedioic acid, 8-hexadecenedioic acid, heptadecanedioic acid, 3-methylhexadecanedioic acid, 2-methylhexadecanediate Acid, 3-heptyldecanedioic acid, octadecanedioic acid, 9-octadecenedioic acid, nonadecanedioic acid, 5,8,11,14-nonadecatetraenedioic acid, 4,9,13-trimethylhexadeca-2 4,6,8,12-pentaenedioic acid, icosanedioic acid, 2-ethyloctadecanedioic acid, 8-ethyloctadecanedioic acid, 8,9-diethylhexadecanedioic acid, 8,12-icosadienedioic acid, heneicosanedioic acid , Docosanedioic acid, 3,3,16,16-tetramethyloctadecanedioic acid, 11-docosenedioic acid, 8,12-dimethyl-8,12- Cosadiendioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, 13-hexacosenedioic acid, heptacosanedioic acid, octacosanedioic acid, 10,12,14,16,18-octacosapentaenedioic acid, nonacosanedioic acid , Triacontanedioic acid, 10,12,14,16,18,20-triacontahexaenedioic acid, 11,13,15,17,19,21-dotriacontahexaenedioic acid and mixtures thereof It is done.

  Specific examples of industrially available aliphatic dicarboxylic acids used in the present invention include SL-12, SL-20, UL-20, MMA-10R, SB-12, and IPU- manufactured by Okamura Oil Co., Ltd. 22, IPS-22, SB-20, UB-20, ULB-20, SLB-20 and the like.

  The amount of the aliphatic dicarboxylic acid used in the present invention is 0.01 to 2.0 parts by weight with respect to 100 parts by weight of the liquid crystal polymer, more preferably 0.01 to 1.0 parts by weight, and 0.01 to 0.8 part by weight is particularly preferred.

When the amount of the aliphatic dicarboxylic acid used is less than 0.01 parts by weight, there is a problem that the effect of improving the fluidity when molding the liquid crystal polymer is not sufficiently exhibited.
Also, when the amount of aliphatic dicarboxylic acid used is more than 2.0 parts by weight, white smoke is generated due to the effect of volatilization of aliphatic dicarboxylic acid when the liquid crystal polymer composition is processed at a high temperature. In addition to the above problems, there are problems that the mechanical properties deteriorate.

  In the present invention, the method for blending the aliphatic dicarboxylic acid into the liquid crystal polymer is not particularly limited, but for example, using a Banbury mixer, kneader, uniaxial or biaxial extruder, etc., near the crystal melting temperature of the liquid crystal polymer or the crystal melting temperature +30. Liquid crystal polymer composition by applying a predetermined amount of aliphatic dicarboxylic acid to the surface of pellet, flake, or powder liquid crystal polymer using a method such as melt kneading at 0 ° C. to form a liquid crystal polymer composition or using a tumbler The method of making it a thing is mentioned.

  The liquid crystal polymer composition in the present invention may contain a filler in addition to the aliphatic dicarboxylic acid for the purpose of improving mechanical properties. The shape of the filler is not particularly limited as long as the object of the present invention is not impaired, but it is preferable to use one or more fillers selected from fibrous, plate-like, or powdery fillers.

  Specific examples of fillers include fibrous fillers such as glass fiber, milled glass, silica alumina fiber, alumina fiber, carbon fiber, aramid fiber, potassium titanate whisker, aluminum borate whisker, and wollastonite. Can be mentioned. In these, glass fiber is preferable at the point which the balance of a physical property and cost is excellent. Examples of the plate or powder filler include talc, mica, graphite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate, and titanium oxide.

  The amount of the filler used in the liquid crystal polymer composition of the present invention is preferably 0.1 to 200 parts by weight, and preferably 0.1 to 150 parts by weight, with respect to 100 parts by weight of the liquid crystal polymer. More preferred is 0.1 to 100 parts by weight.

  In addition to the aliphatic dicarboxylic acid and the filler, the liquid crystal polymer composition of the present invention further includes a mold release improver; a colorant such as a dye or a pigment; an antioxidant; a heat stabilizer. One type or a combination of two or more types such as an ultraviolet absorber, an antistatic agent and a surfactant may be added.

  The mold release improving material may be attached in advance to the surface of the liquid crystal polymer in the form of pellets, flakes or powders at the time of molding.

  In addition, the liquid crystal polymer used in the present invention includes other resin components such as polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene ether, and modified products thereof, polysulfone, and the like within a range not impairing the object of the present invention. Thermoplastic resins such as polyethersulfone and polyetherimide, and thermosetting resins such as phenol resin, epoxy resin, and polyimide resin may be added alone or in combination of two or more.

  The blending amount of other resin components is not particularly limited, and may be determined as appropriate according to the use and purpose of the resin. Typically, the resin component is blended in an amount of 1 to 200 parts by weight, particularly 10 to 100 parts by weight, based on 100 parts by weight of the liquid crystal polymer of the present invention.

  These fillers, additives and other resins are melt-kneaded using a Banbury mixer, kneader, uniaxial or biaxial extruder, etc. near the crystal melting temperature of the liquid crystal polymer or at the crystal melting temperature + 30 ° C. What is necessary is just to mix | blend with.

  As described above, according to the present invention, it is possible to produce a liquid crystal polymer composition having greatly improved fluidity during molding.

  Since the liquid crystal polymer composition obtained by the present invention is excellent in fluidity at the time of molding, it is particularly suitably used as a molding material for electric parts, electronic parts, mechanical parts having complicated shapes and thin parts. .

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to a following example at all.

[Examples 1 to 6, Comparative Example 1 and Comparative Example 2]
In Examples and Comparative Examples, as a liquid crystal polymer, UENO LCP 2500 (manufactured by Ueno Pharmaceutical Co., Ltd., 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone copolymer, crystal melting temperature 330 ° C.) It was used.

  As the aliphatic dicarboxylic acid, SL-20, SL-12, and UL-20 manufactured by Okamura Oil Co., Ltd. were used. The structures of these aliphatic dicarboxylic acids are shown below.

[Aliphatic dicarboxylic acid]
○ SL-20

○ SL-12

○ UL-20

[Example of liquid crystal polymer composition preparation]
For 100 parts by weight of the liquid crystal polymer, the types and amounts of the aliphatic dicarboxylic acids listed in Table 1 were used using a twin screw extruder PCM-30 (manufactured by Ikegai Co., Ltd.), cylinder temperature, 330-320-320-310 ° C. Then, the mixture was melt-kneaded under the condition of a screw rotation speed of 150 rpm to prepare pellets of the liquid crystal polymer composition.
About the pellet of the liquid crystal polymer composition obtained by each Example and the comparative example, melt viscosity, tensile strength, bending strength, and deflection temperature under load (DTUL) were measured.
The measurement results are shown in Table 1.

<Measuring method of melt viscosity>
Using a 0.7 mmφ × 10 mm capillary with a melt viscosity measuring device (Capillograph 1A manufactured by Toyo Seiki Co., Ltd.), the viscosity at a crystal melting temperature of the liquid crystal polymer composition sample + 30 ° C. and a shear rate of 10 ³ s ⁻¹ Is measured as the melt viscosity.

<Tensile strength measurement method>
An ASTM No. 4 dumbbell test piece was molded using an injection molding machine (UH1000-110 manufactured by Nissei Plastic Industry Co., Ltd.), and measured according to ASTM D638.

<Bending strength measurement method>
A strip-shaped test piece having a length of 127 mm, a width of 3.2 mm, and a thickness of 12.7 mm is formed using an injection molding machine (UH1000-110 manufactured by Nissei Plastic Industry Co., Ltd.), and this is used to comply with ASTM D790. Measured.

<Method of measuring deflection temperature under load (DTUL)>
A strip-shaped test piece having a length of 127 mm, a width of 3.2 mm, and a thickness of 12.7 mm is molded using an injection molding machine (UH1000-110 manufactured by Nissei Plastic Industry Co., Ltd.), and this is used to comply with ASTM D648. And a load of 1.82 MPa and a temperature elevation rate of 2 ° C./min.

＊溶融粘度が低すぎたために測定できなかった。

* Could not be measured because the melt viscosity was too low.

  From Table 1, in Examples 1-6 which mix | blended 0.01-2.0 weight part aliphatic dicarboxylic acid with respect to 100 weight part of liquid crystal polymers, all are tensile strength, bending strength, and deflection temperature under load. Compared with Comparative Example 1 in which no aliphatic dicarboxylic acid is blended without significantly impairing mechanical properties such as (DTUL), the melt viscosity is significantly reduced, and the fluidity during molding is improved. I understood.

  In Comparative Example 2 in which the amount of the aliphatic dicarboxylic acid exceeding 2.0 parts by weight with respect to 100 parts by weight of the liquid crystal polymer was blended, the mechanical properties tended to decrease, and the tensile strength value was greatly decreased. .

  Further, when the liquid crystal polymer and the aliphatic dicarboxylic acid were melted and kneaded in order to prepare the liquid crystal polymer composition of Comparative Example 2, operational problems such as generation of white smoke also occurred.

Claims (5)

A liquid crystal polymer composition comprising 0.01 to 2.0 parts by weight of an aliphatic dicarboxylic acid represented by the following formula [1] with respect to 100 parts by weight of a liquid crystal polymer:
HOOC-R-COOH [1]
[Wherein R represents a divalent aliphatic hydrocarbon group having 8 to 30 carbon atoms which may have a branch and may have an unsaturated bond].   The aliphatic dicarboxylic acid represented by the formula [1] is a divalent aliphatic hydrocarbon group in which the group R has 16 to 30 carbon atoms and may have a branch or an unsaturated bond. The liquid crystal polymer composition according to claim 1, comprising 75% by weight or more of the aliphatic dicarboxylic acid.   Furthermore, the liquid crystal polymer composition of Claim 1 or 2 containing 0.1-200 weight part of 1 or more types selected from a fibrous, plate-shaped, or powdery filler with respect to 100 weight part of liquid crystal polymers. object.   One or more fibrous materials in which the filler is selected from the group consisting of glass fiber, milled glass, silica alumina fiber, alumina fiber, carbon fiber, aramid fiber, potassium titanate whisker, aluminum borate whisker, and wollastonite. And at least one plate-like or powdery filler selected from the group consisting of talc, mica, graphite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate, and titanium oxide. The liquid crystal polymer composition according to claim 3. A liquid crystal polymer composition comprising 0.01 to 2.0 parts by weight of one or more aliphatic dicarboxylic acids represented by the following formula [1] with respect to 100 parts by weight of a liquid crystal polymer Production method:
HOOC-R-COOH [1]
[Wherein R represents a divalent aliphatic hydrocarbon group having 8 to 30 carbon atoms which may have a branch and may have an unsaturated bond].