JP7266633B2 - liquid crystal polymer composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a liquid crystal polymer composition having excellent flexibility, extensibility and fluidity during molding.

Thermotropic liquid crystal polymer (hereinafter abbreviated as liquid crystal polymer or LCP) is excellent in heat resistance, high strength, chemical resistance, dimensional accuracy, low water absorption, etc., so its use is expanding in various applications. .

Especially in the electrical and electronic fields such as personal computers, mobile phones, smart phones, and automobiles, parts are becoming more highly integrated, smaller, thinner, and lower in height. transformation is required. Therefore, the amount of liquid crystal polymer used has increased significantly, taking advantage of its excellent moldability, that is, good fluidity in thin walls and no burrs, which are not found in other resins.

However, liquid crystal polymers have the drawback of being inferior in flexibility and extensibility due to their rigid molecular structure. Connector parts, which are one of the important parts in the electrical and electronic fields, are required to have flexibility and extensibility because fitting is necessary for connection between parts. From the viewpoint of material evaluation, the tensile product, which is the product of tensile strength and tensile elongation at break, is one standard, and a liquid crystal polymer having both strength and elongation and a large tensile product is desired.

Patent Document 1 describes a liquid crystal polyesteramide resin composition having excellent toughness. However, since the resin composition described in Patent Document 1 has a high molding temperature and a high melt viscosity, there is a problem that molding processability is insufficient.

Patent Literature 2 proposes, as a liquid crystal polymer composition having excellent tensile properties, a liquid crystal polymer containing an epoxy group-containing ethylene copolymer and a surface-untreated glass fiber. However, the liquid crystal polymer composition described in Patent Document 2 has a problem that the melt viscosity increases due to the inclusion of surface-untreated glass fibers, and the improvement in tensile elongation is insufficient.

JP 2015-108037 A JP-A-8-134334

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal polymer composition having improved flexibility and elongation without impairing fluidity and mechanical strength.

The inventors of the present invention have made intensive studies on improving the flexibility and elongation of liquid crystal polymers. The inventors have found that flexibility and extensibility are improved without impairing them, leading to the completion of the present invention.

That is, the present invention contains 100 parts by weight of a liquid crystal polymer, 1 to 30 parts by weight of an epoxy group-containing ethylene copolymer, 1 to 30 parts by weight of a plate-like filler, and 0.01 to 20 parts by weight of a melamine compound. provides a liquid crystal polymer composition, which is melamine cyanurate.

The liquid crystal polymer composition of the present invention is excellent in flexibility and elongation without impairing fluidity and mechanical strength, so it is used for molding parts that require fitting for connection or parts that require miniaturization and thinning. It can be suitably used as a resin.

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

The nature of the anisotropic melt phase can be confirmed by conventional polarimetry using crossed polarizers. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing a sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times. The liquid crystal polymer in the present invention is optically anisotropic, ie, it transmits light when examined between crossed polarizers. If the sample is optically anisotropic, polarized light is transmitted even at rest.

Examples of polymerizable monomers constituting the liquid crystal polymer of the present invention include aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic aminocarboxylic acids, aromatic hydroxylamines, aromatic diamines, and aliphatic diols. and aliphatic dicarboxylic acids. As for the polymerizable monomers constituting the liquid crystal polymer, only one of these compounds may be used, or two or more of these compounds may be combined. It is desirable to include mers.

The polymerizable monomer that constitutes the liquid crystal polymer may be an oligomer formed by bonding one or more of the above compounds, that is, an oligomer composed of one or more of the above compounds.

Specific examples of aromatic hydroxycarboxylic acids include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid, 7-hydroxy -2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid and their Examples include alkyl, alkoxy or halogen-substituted products, and ester-forming derivatives such as acylated products, ester derivatives, and acid halides thereof. Among these, one or more compounds selected from the group consisting of 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid from the viewpoint of facilitating adjustment of the heat resistance, mechanical strength, and melting point of the resulting liquid crystal polymer. is preferred.

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 compounds selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferred from the viewpoint of effectively increasing the heat resistance of the obtained liquid crystal polymer, and terephthalic acid and 2,6-naphthalenedicarboxylic acid are more preferred.

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'-dihydroxybiphenyl ether and 2,2'-dihydroxybinaphthyl, their alkyl, alkoxy or halogen substituted products and their acylated products are included. Among these, one or more compounds selected from the group consisting of hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl and 2,6-dihydroxynaphthalene are preferable from the viewpoint of excellent reactivity during polymerization. More preferred are one or more compounds selected from the group consisting of ,4'-dihydroxybiphenyl and 2,6-dihydroxynaphthalene.

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 preferable from the viewpoint of easily balancing 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, dodecanedioic acid, tetradecanedioic acid, fumaric acid, and maleic acid. , 1,4-cyclohexanedicarboxylic acid and hexahydroterephthalic acid. Among these, oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid and 1,4-cyclohexanedicarboxylic acid are preferred from the viewpoint of excellent reactivity during polymerization.

In the present invention, the liquid crystal polymer includes dihydroxyterephthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, trimellitic acid, 1,3,5-benzenetricarboxylic acid, and pyromellitic acid, as long as the objects of the present invention are not impaired. Alternatively, those alkyl-, alkoxy- or halogen-substituted products, and ester-forming derivatives such as acylated products, ester derivatives and acid halides thereof may be included as polymerizable monomers. The amount of these polymerizable monomers to be used is preferably 10 mol % or less based on the total amount of other polymerizable monomers.

In the present invention, the liquid crystal polymer may contain thioester bonds as long as the object of the present invention is not impaired. Polymerizable monomers that provide such bonds include mercaptoaromatic carboxylic acids, and aromatic dithiols and hydroxyaromatic thiols. The content of these polymerizable monomers is preferably 10 mol % or less based on the total amount of other polymerizable monomers.

Depending on the composition and composition ratio of the monomers, and the sequence distribution of each repeating unit in the polymer, polymers that combine these repeating units form an anisotropic melt phase and those that do not form an anisotropic melt phase. However, the liquid crystal polymer used in the present invention is limited to those that form an anisotropic melt phase. A person skilled in the art can appropriately select and adjust the composition and composition ratio of the monomers and the sequence distribution of each repeating unit in the polymer so as to obtain a liquid crystal polymer that forms an anisotropic melt phase.

Specific examples of combinations of polymerizable monomers constituting the liquid crystal polymer used in the liquid crystal polymer composition of the present invention include the following.
1) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid,
2) 4-hydroxybenzoic acid/terephthalic acid/4,4'-dihydroxybiphenyl,
3) 4-hydroxybenzoic acid/terephthalic acid/isophthalic acid/4,4'-dihydroxybiphenyl,
4) 4-hydroxybenzoic acid/terephthalic acid/isophthalic acid/4,4'-dihydroxybiphenyl/hydroquinone,
5) 4-hydroxybenzoic acid/terephthalic acid/hydroquinone,
6) 6-hydroxy-2-naphthoic acid/terephthalic acid/hydroquinone,
7) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/4,4'-dihydroxybiphenyl,
8) 6-hydroxy-2-naphthoic acid/terephthalic acid/4,4'-dihydroxybiphenyl,
9) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/hydroquinone,
10) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/hydroquinone/4,4'-dihydroxybiphenyl,
11) 4-hydroxybenzoic acid/2,6-naphthalenedicarboxylic acid/4,4'-dihydroxybiphenyl,
12) 4-hydroxybenzoic acid/terephthalic acid/2,6-naphthalenedicarboxylic acid/hydroquinone,
13) 4-hydroxybenzoic acid/2,6-naphthalenedicarboxylic acid/hydroquinone,
14) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/2,6-naphthalenedicarboxylic acid/hydroquinone,
15) 4-hydroxybenzoic acid/terephthalic acid/2,6-naphthalenedicarboxylic acid/hydroquinone/4,4'-dihydroxybiphenyl,
16) 4-hydroxybenzoic acid/terephthalic acid/4-aminophenol,
17) 6-hydroxy-2-naphthoic acid/terephthalic acid/4-aminophenol,
18) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/4-aminophenol,
19) 4-hydroxybenzoic acid/terephthalic acid/4,4'-dihydroxybiphenyl/4-aminophenol,
20) 4-hydroxybenzoic acid/terephthalic acid/ethylene glycol,
21) 4-hydroxybenzoic acid/terephthalic acid/4,4'-dihydroxybiphenyl/ethylene glycol,
22) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/ethylene glycol,
23) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/4,4'-dihydroxybiphenyl/ethylene glycol,
24) 4-hydroxybenzoic acid/terephthalic acid/2,6-naphthalenedicarboxylic acid/4,4'-dihydroxybiphenyl.

The above liquid crystal polymers may be used alone or as a mixture of two or more liquid crystal polymers.

As the liquid crystal polymer used in the liquid crystal polymer composition of the present invention, a liquid crystal polyester resin containing repeating units represented by the formula (I) and/or the formula (II) is preferable in terms of excellent fluidity and mechanical properties. used for

Further, the liquid crystal polymer used in the liquid crystal polymer composition of the present invention is a wholly aromatic polymer composed of repeating units represented by the formulas (I) and (II) in terms of excellent fluidity and mechanical properties. A liquid crystalline polyester resin is preferably used.

The crystal melting temperature of the liquid crystal polymer used in the liquid crystal polymer composition of the present invention is not particularly limited. can be set relatively low, preferably 350° C. or lower, more preferably 340° C. or lower, and even more preferably 330° C. or lower. A liquid crystal polymer having a crystal melting temperature of 170° C. or higher is preferable, a liquid crystal polymer having a crystal melting temperature of 180° C. or higher is more preferable, and a liquid crystal melting temperature of 190° C. or higher is even more preferable.

A method for producing the liquid crystal polymer used in the present invention will be described below.

The method for producing the liquid crystal polymer used in the present invention is not particularly limited, and a polymerizable monomer is subjected to a known polycondensation method for forming an ester bond or an amide bond, such as a melt acidolysis method, a slurry polymerization method, or the like to obtain a liquid crystal polymer. A polymer can be obtained.

The melt acidolysis method is the preferred method for producing the liquid crystalline polymer used in the liquid crystalline polymer composition of the present invention. This method first heats the polymerizable monomers 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.

Slurry polymerization is a process in which polymerizable monomers are reacted in the presence of a heat exchange fluid, resulting in a solid product suspended in the heat exchange medium.

In both the melt acidolysis method and the slurry polymerization method, the polymerizable monomer used in producing the liquid crystal polymer is, at room temperature, a modified form in which the hydroxyl group and/or amino group is acylated, that is, a low-grade It can also be subjected to the reaction as an acylated product.

The lower acyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. In a preferred embodiment of the present invention, the acetylated product of the polymerizable monomer is subjected to the reaction.

The lower acylated product of the polymerizable monomer may be one synthesized in advance by acylation separately, or an acylating agent such as acetic anhydride may be added to the polymerizable monomer during the production of the liquid crystal polymer in the reaction system. can also be generated with

In either the melt acidolysis method or the slurry polymerization method, the polycondensation 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. A catalyst 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, based on the total amount of polymerizable monomers.

The liquid crystalline polymer 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 temperature of the heat treatment performed in the solid state is not particularly limited as long as the liquid crystal polymer is not melted, but it is preferably 260 to 350°C, preferably 280 to 320°C.

The liquid crystal polymer composition of the present invention contains, in addition to 100 parts by weight of the liquid crystal polymer obtained as described above, 1 to 30 parts by weight of an epoxy group-containing ethylene copolymer and 1 to 30 parts by weight of a plate-like filler. contains.

The content of the epoxy group-containing ethylene copolymer is preferably 5 to 25 parts by weight, more preferably 5 to 15 parts by weight, per 100 parts by weight of the liquid crystal polymer. When the content of the epoxy group-containing ethylene copolymer exceeds 30 parts by weight based on 100 parts by weight of the liquid crystal polymer, the fluidity of the liquid crystal polymer composition is lowered. If the content of the epoxy group-containing ethylene copolymer is less than 1 part by weight, the effect of improving the flexibility and elongation of the liquid crystal polymer composition cannot be exhibited.

Examples of epoxy group-containing ethylene copolymers include copolymers consisting of ethylene units and glycidyl methacrylate units, copolymers consisting of ethylene units, glycidyl methacrylate units and methyl acrylate units, and ethylene units, glycidyl methacrylate units and ethyl acrylate units. A copolymer consisting of ethylene units, glycidyl methacrylate units and vinyl acetate units, and a copolymer consisting of ethylene units and glycidyl ether units. Among them, a copolymer composed of an ethylene unit, a glycidyl methacrylate unit and a methyl acrylate unit is preferable in that the mechanical strength of the liquid crystal polymer composition can be maintained.

Epoxy group-containing ethylene copolymers are usually composed of a compound giving ethylene units, a compound giving unsaturated carboxylic acid glycidyl ester units or unsaturated glycidyl ether units, and optionally a compound giving ethylenically unsaturated ester units. , in the presence of a radical generator, under conditions of 500 to 4000 atmospheres and 100 to 300°C, in the presence or absence of a suitable solvent or chain transfer agent.

In the present invention, the plate-shaped filler means a disk-shaped, rectangular plate-shaped, strip-shaped, or irregular plate-shaped filler that has a three-dimensional shape that spreads in two directions and does not spread in the other one direction. specifically, talc, mica, graphite, dolomite, clay, glass flakes, kaolin, vermiculite, calcium silicate, aluminum silicate, feldspar powder, acid clay, roseite clay, sericite, sillimanite, bentonite, slate powder, silicates such as silane, calcium carbonate, chalk, barium carbonate, magnesium carbonate, barite powder, precipitated calcium sulfate, calcined gypsum, sulfates such as barium sulfate, hydroxides such as hydrated alumina, A group consisting of alumina, antimony oxide, magnesia, titanium oxide, zinc white, silica, silica sand, quartz, white carbon, oxides such as diatomaceous earth, sulfides such as molybdenum disulfide, plate-like wollastonite, and metal powders One or more selected from the above can be mentioned. Among these plate-like fillers, one or more selected from the group consisting of talc, mica, graphite, dolomite, clay and glass flakes in that they are excellent in improving the flexibility of the liquid crystal polymer composition and the fluidity during molding. is preferred, and talc is particularly preferred.

The plate-like filler has no particular limitation on the average particle diameter, but the median diameter measured by laser diffraction/scattering particle size distribution measurement is preferably 50 μm or less from the viewpoint of fluidity. Moreover, the average particle size of the plate-like filler is usually 0.5 μm or more.

The content of the plate-like filler is preferably 5 to 25 parts by weight, more preferably 5 to 15 parts by weight, based on 100 parts by weight of the liquid crystal polymer. If the content of the plate-like filler exceeds 30 parts by weight with respect to 100 parts by weight of the liquid crystal polymer, the effect of improving the flexibility of the liquid crystal polymer composition is reduced. If the content of the plate-like filler is less than 1 part by weight, the effect of improving the flexibility of the liquid crystal polymer composition and the fluidity during molding cannot be exhibited.

The tensile product of the liquid crystal polymer composition of the present invention is preferably 800 MPa·% or more, more preferably 900 MPa·% or more, still more preferably 1000 MPa·% or more.

The tensile product is the product of tensile strength and tensile elongation at break (MPa %), and is used as a measure of the breaking energy of a polymer compound. The higher the tensile product value, the better the balance between strength and elongation. Indicates material.

In this specification, the tensile strength and tensile elongation at break are measured using ASTM No. 4 dumbbells with a thickness of 3.2 mm, using a contact-type extensometer with a gauge length of 25 mm, a test speed of 5 mm / min, and a chuck distance of 64 mm. , measured according to ASTM D638.

The tensile modulus of the liquid crystal polymer composition of the present invention is preferably 10 GPa or less, more preferably 9 GPa or less, and still more preferably 8 GPa or less. In this specification, the tensile modulus is measured according to ASTM D638 using an ASTM No. 4 dumbbell with a thickness of 3.2 mm, a test speed of 5 mm / min, and a distance between chucks of 64 mm. It shows that it is superior to

The bending elastic modulus of the liquid crystal polymer composition of the present invention is preferably 7 GPa or less, more preferably 6.5 GPa or less, and still more preferably 6 GPa or less.

In this specification, the flexural modulus is measured using a strip-shaped bending test piece (length 127 mm × width 12.7 mm × thickness 3.2 mm) under the conditions of a test speed of 1.3 mm / min and a span distance of 50 mm. Measured according to ASTM D790, lower values indicate better flexibility.

The liquid crystal polymer composition of the present invention preferably further contains 0.01 to 20 parts by weight of a melamine compound from the viewpoint of improving fluidity during molding.

Melamine compounds used in the present invention include one or more selected from the group consisting of melamine cyanurate, melamine acrylate, melamine hydrochloride, melamine sulfonate, melamine borate, and melamine pyrophosphate. be done. Among these, melamine cyanurate is preferable because of its excellent fluidity and mechanical strength.

If the content of the melamine compound exceeds 20 parts by weight with respect to 100 parts by weight of the liquid crystal polymer, the effect of improving the elongation of the liquid crystal polymer composition tends to decrease. When the content of the melamine compound is less than 0.01 parts by weight, the effect of improving the flame retardancy of the liquid crystal polymer composition and the fluidity during molding cannot be exhibited.

In the present invention, the liquid crystal polymer composition may contain 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 means a carbon atom number 10 to 25), release improvers such as polysiloxane and fluororesin, colorants such as carbon black, dyes and pigments, antioxidants, heat stabilizers, ultraviolet absorbers, antistatic agents, interfaces It may contain active agents and the like. In the present invention, the liquid crystal polymer composition may contain one of these additives, or may contain two or more of them in combination. Among these, carbon black is preferred. When the liquid crystal polymer composition of the present invention contains carbon black, its content is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less based on 100 parts by weight of the liquid crystal polymer. is. When the liquid crystal polymer composition of the present invention contains 20 parts by weight or less of carbon black, the function as a coloring agent is obtained and the effect of improving the tensile product tends to be easily obtained.

The liquid crystal polymer composition of the present invention may contain fillers other than plate fillers, such as spherical fillers (balloons, glass beads, etc.) and fibrous fillers (glass fibers, etc.). When a filler other than the plate-like filler is contained, it is preferably less than 1 part by weight, more preferably less than 0.5 part by weight, and even more preferably less than 0.1 part by weight with respect to 100 parts by weight of the liquid crystal polymer. It is particularly preferred to be free of material.

The total amount of other additives in the liquid crystal polymer composition 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. If the total amount of the other additives exceeds 10 parts by weight with respect to 100 parts by weight of the liquid crystal polymer, the liquid crystal polymer composition tends to deteriorate in moldability and thermal stability. If the total amount of other additives is less than 0.1 parts by weight, the function of the additives cannot be realized.

When molding 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 added in advance. , may be attached to the surface of the liquid crystal polymer pellets.

Other resin components may be added to the liquid crystal polymer composition of the present invention. Other resin components include, for example, polyamides, polyesters, polyacetals, polyphenylene ethers, modified products thereof, thermoplastic resins such as polysulfone, polyethersulfone, polyetherimide, and polyamideimide, phenolic resins, epoxy resins, and polyimide resins. and thermosetting resins such as Other resin components can be contained singly or in combination of two or more. When the liquid crystal polymer composition contains other resin components, the content of the other resin components is not particularly limited, but in one typical example, the total amount of the other resin components is 100 parts by weight of the liquid crystal polymer. is usually 0.1 to 100 parts by weight, especially 0.1 to 80 parts by weight.

The above-described epoxy group-containing ethylene copolymer, plate-like filler, melamine compound, other additives, and other resin components are added to the liquid crystal polymer and processed by a Banbury mixer, kneader, single-screw or twin-screw extruder, or the like. A liquid crystal polymer composition can be obtained by melt-kneading at a temperature in the vicinity of the crystal melting temperature of the liquid crystal polymer or up to +20°C.

The liquid crystal polymer composition of the present invention thus obtained is processed into molded articles such as injection molded articles, films, sheets and non-woven fabrics by known molding methods using injection molding machines, extruders and the like. These molded articles are composed of the liquid crystal polymer of the present invention, that is, obtained by molding the liquid crystal polymer composition of the present invention.

Since the liquid crystal polymer composition of the present invention is excellent in flexibility and elongation, it can be suitably used as a molding resin that requires miniaturization and thinning. It is suitably used for connectors, tubes, clips, etc., and is particularly suitable for binding bands.

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

<Liquid crystal polymer>
First, synthesis examples of liquid crystal polymers used in Examples and Comparative Examples are described.

Abbreviations in Synthesis Examples represent the following compounds.
[Polymerizable Monomer Used for Synthesis of Liquid Crystal Polymer]
POB: 4-hydroxybenzoic acid BON6: 6-hydroxy-2-naphthoic acid

The crystalline melting temperatures of the liquid crystal polymers obtained in Synthesis Examples were measured by the following method.
<Crystal melting temperature>
Using Exstar 6000 manufactured by Seiko Instruments Inc. as a differential scanning calorimeter, the endothermic peak temperature (Tm1) observed when measuring the sample under the temperature rising condition of 20 ° C./min from room temperature was measured, and then 50 from Tm1. C. higher temperature 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. ).

[Synthesis example (LCP)]
POB: 655.4 g (73 mol %) and BON6: 476.0 g (27 mol %) were charged into a 2 L reaction vessel equipped with a stirring device with a torque meter and a distillation tube, and further the hydroxyl group amount of all monomers was determined. Acetic anhydride was added in an amount of 1.01 mol per (mol), and deacetic acid polymerization was carried out under the following conditions.

In a nitrogen gas atmosphere, the temperature was raised from room temperature to 145° C. over 1 hour and maintained at the same temperature for 30 minutes. Next, the temperature was raised to 330° C. over 7 hours while acetic acid, which was produced as a by-product, was distilled off, and then the pressure was reduced to 10 mmHg over 80 minutes. When a predetermined torque was exhibited, the polymerization reaction was terminated, the contents were taken out from the reaction vessel, and pellets of the liquid crystalline polyester resin were obtained with a pulverizer. The amount of acetic acid distilled off during polymerization was almost the same as the theoretical value. The crystalline melting temperature (Tm) of the pellets obtained was 278°C.

[Examples 1-5 and Comparative Examples 1-5] (Examples 1-2 are reference examples)
To 100 parts by weight of the liquid crystal polymer obtained in Synthesis Example, an ethylene copolymer, a plate-like filler and a melamine compound were blended in the weight ratios shown in Table 1, and extruded by a twin-screw extruder (JSW, TEX Co., Ltd.). -30) was melt-kneaded and pelletized to prepare a liquid crystal polymer composition.

The following ethylene copolymer, plate-like filler and melamine compound were used.

<Ethylene-based copolymer-1>
Sumitomo Chemical Co., Ltd. Bond Fast BF-2C (ethylene-glycidyl methacrylate copolymer)

<Ethylene-based copolymer-2>
Sumitomo Chemical Co., Ltd. Bond Fast BF-7M (ethylene-glycidyl methacrylate-methyl acrylate copolymer)

<Plate-shaped filler>
Fuji Talc Kogyo Co., Ltd. RH415 (platy talc, average particle size 14 μm)

<Melamine compound>
Melamine cyanurate MC-6000 manufactured by Nissan Chemical Co., Ltd.

<Glass fiber>
EFH150-01 manufactured by Central Glass Fiber Co., Ltd. (surface untreated glass fiber, average fiber length 150 μm, average fiber diameter 11 μm)

<Carbon black>
#950B manufactured by Mitsubishi Chemical Corporation

The melt viscosity, deflection temperature under load, tensile strength, tensile modulus, tensile elongation at break, flexural strength, flexural modulus and Izod impact strength of the resulting liquid crystal polymer composition pellets were measured by the following methods. Table 1 shows the results.

<Melt viscosity>
The value was measured at a shear rate of 1000 sec ⁻¹ at 320° C. using a 1.0 mmφ×10 mm capillary with a melt viscosity measuring device (Toyo Seiki Co., Ltd., Capilograph 1D).

<Deflection temperature under load>
Using an injection molding machine (UH1000-110 manufactured by Nissei Plastic Industry Co., Ltd.), injection molding was performed at a cylinder temperature of crystal melting temperature +20 to 40 ° C. and a mold temperature of 70 ° C., and a strip-shaped test piece (length 127 mm x width 12.7 mm×thickness 3.2 mm). Using this, in accordance with ASTM D648, a load of 1.82 MPa and a temperature increase rate of 2° C./min were used to measure the temperature at which the deflection amount (0.254 mm) was reached.

<Tensile strength, tensile modulus and tensile elongation at break>
Injection molding is performed using an injection molding machine (UH1000-110 manufactured by Nissei Plastic Industry Co., Ltd.) at a cylinder temperature of crystal melting temperature +20 to 40 ° C. and a mold temperature of 70 ° C., and an ASTM No. 4 dumbbell test piece with a thickness of 3.2 mm is made. made. Using INSTRON 5567 (Instron Japan Co., Ltd. universal testing machine), using a contact type extensometer with a gauge line distance of 25 mm, a test speed of 5 mm / min, a distance between chucks of 64 mm, ASTM D638 compliant. measured by

<Bending strength, bending elastic modulus>
A strip-shaped bending test piece (length 127 mm×width 12.7 mm×thickness 3.2 mm) was prepared under the same conditions as the molded piece used for measurement of deflection temperature under load. In the bending test, a three-point bending test was performed using INSTRON 5567 (universal testing machine manufactured by Instron Japan Company Limited) under the conditions of a test speed of 1.3 mm/min and a span distance of 50 mm, and was measured according to ASTM D790. .

<Izod impact strength>
Using the same test piece as the test piece used for the load deflection temperature measurement, the center of the test piece was cut perpendicular to the length direction and notched. A strip-shaped specimen with a length of 63.5 mm, a width of 12.7 mm and a thickness of 3.2 mm was obtained and measured according to ASTM D256.

As shown in Table 1, the liquid crystal polymer compositions of Examples 1 to 5 containing the epoxy group-containing ethylene copolymer and the plate-like filler were the liquid crystals of Comparative Examples 1, 2, 4 and 5. It is understood that flexibility is improved by lowering the elastic modulus and elongation is improved compared to polymer compositions without impairing fluidity and mechanical strength.

The liquid crystal polymer composition of Comparative Example 3 had excellent flexibility, but had high melt viscosity and poor fluidity.

In addition, it is understood that the liquid crystal polymer compositions of Examples 1 to 5 have a larger tensile product than the liquid crystal polymer compositions of Comparative Examples 1 to 5, and are materials having a good balance between strength and elongation.

〔９〕液晶ポリマーが、式（Ｉ）および式（ＩＩ）で表される繰返し単位から構成される全芳香族液晶ポリエステル樹脂である、〔１〕～〔８〕のいずれかに記載の液晶ポリマー組成物。
［化２］

〔１０〕厚み３．２ｍｍのＡＳＴＭ４号ダンベルを使用し、ＡＳＴＭ Ｄ６３８に準拠して測定した引張強度（ＭＰａ）と引張破断伸び（％）の積である抗張積が８００ＭＰａ・％以上である、〔１〕～〔９〕のいずれかに記載の液晶ポリマー組成物。
〔１１〕厚み３．２ｍｍのＡＳＴＭ４号ダンベルを使用し、ＡＳＴＭ Ｄ６３８に準拠して測定した引張弾性率が１０．０ＧＰａ以下であり、かつ、短冊状曲げ試験片（長さ１２７ｍｍ×幅１２．７ｍｍ×厚さ３．２ｍｍ）を使用し、ＡＳＴＭ Ｄ７９０に準拠して測定した曲げ弾性率が７．０ＧＰａ以下である、〔１〕～〔１０〕のいずれかに記載の液晶ポリマー組成物。
〔１２〕〔１〕～〔１１〕のいずれかに記載の液晶ポリマー組成物から構成される成形品。
〔１３〕成形品が結束バンドである、〔１２〕に記載の成形品。 The present application is a divisional application whose original application is Japanese Patent Application No. 2017-107023, and includes all the contents described in the specification of the original application, including at least the following preferred embodiments.
[1] A liquid crystal polymer composition containing 100 parts by weight of a liquid crystal polymer, 1 to 30 parts by weight of an epoxy group-containing ethylene copolymer, and 1 to 30 parts by weight of a plate-like filler.
[2] The epoxy group-containing ethylene copolymer is a copolymer consisting of ethylene units and glycidyl methacrylate units, a copolymer consisting of ethylene units, glycidyl methacrylate units and methyl acrylate units, an ethylene unit, glycidyl methacrylate units and acrylic acid. It is one or more selected from the group consisting of copolymers consisting of ethyl units, copolymers consisting of ethylene units, glycidyl methacrylate units and vinyl acetate units, and copolymers consisting of ethylene units and unsaturated glycidyl ether units. , the liquid crystal polymer composition according to [1].
[3] The liquid crystal polymer composition of [1] or [2], wherein the plate-like filler is one or more selected from the group consisting of talc, mica, graphite, dolomite, clay and glass flakes.
[4] The liquid crystal polymer composition according to any one of [1] to [3], wherein the plate-like filler is talc.
[5] The liquid crystal polymer composition according to any one of [1] to [4], further containing 0.01 to 20 parts by weight of a melamine compound.
[6] The melamine compound according to [5], wherein the melamine compound is one or more selected from the group consisting of melamine cyanurate, melamine acrylate, melamine hydrochloride, melamine sulfonate, melamine borate, and melamine pyrophosphate. A liquid crystal polymer composition.
[7] The liquid crystal polymer composition of [5] or [6], wherein the melamine compound is melamine cyanurate.
[8] The liquid crystal polymer composition according to any one of [1] to [7], wherein the liquid crystal polymer is a liquid crystal polyester resin containing repeating units represented by formula (I) and/or formula (II).
[Chemical 1]

[9] The liquid crystal polymer according to any one of [1] to [8], wherein the liquid crystal polymer is a wholly aromatic liquid crystal polyester resin composed of repeating units represented by formula (I) and formula (II). Composition.
[Chemical 2]

[10] Using an ASTM No. 4 dumbbell with a thickness of 3.2 mm, the tensile product, which is the product of the tensile strength (MPa) and the tensile elongation at break (%) measured according to ASTM D638, is 800 MPa % or more. [1] The liquid crystal polymer composition according to any one of [9].
[11] Using an ASTM No. 4 dumbbell with a thickness of 3.2 mm, a tensile modulus measured according to ASTM D638 is 10.0 GPa or less, and a strip-shaped bending test piece (length 127 mm × width 12.7 mm × thickness 3.2 mm), and the flexural modulus measured according to ASTM D790 is 7.0 GPa or less, the liquid crystal polymer composition according to any one of [1] to [10].
[12] A molded article composed of the liquid crystal polymer composition according to any one of [1] to [11].
[13] The molded article according to [12], which is a binding band.

Claims (9)

100 parts by weight of a liquid crystal polymer, 9.5 to 30 parts by weight of an epoxy group-containing ethylene copolymer, 1 to 30 parts by weight of a plate-like filler, and 0.01 to 20 parts by weight of a melamine compound,
The liquid crystal polymer is a liquid crystal polyester resin containing repeating units represented by formula (I) and formula (II),

A tensile product, which is the product of tensile strength (MPa) and tensile elongation at break (%) measured according to ASTM D638 using an ASTM No. 4 dumbbell with a thickness of 3.2 mm, is 800 MPa % or more,
The plate-like filler is one or more selected from the group consisting of talc, mica, graphite, dolomite, clay and glass flakes,
The plate-like filler has an average particle size of 0.5 μm or more and 50 μm or less, where the average particle size is a median diameter measured by a laser diffraction/scattering particle size distribution measurement method.
the melamine compound is melamine cyanurate,
A liquid crystal polymer composition. The epoxy group-containing ethylene copolymer is a copolymer consisting of ethylene units and glycidyl methacrylate units, a copolymer consisting of ethylene units, glycidyl methacrylate units and methyl acrylate units, and an ethylene unit, glycidyl methacrylate units and ethyl acrylate units. A copolymer consisting of ethylene units, glycidyl methacrylate units and vinyl acetate units, and a copolymer consisting of ethylene units and glycidyl ether units. The liquid crystalline polymer composition described. 3. The liquid crystal polymer composition according to claim 1, wherein the plate-like filler is talc. 4. The liquid crystal polymer composition according to any one of claims 1 to 3, wherein the content of the plate-like filler is 1 to 25 parts by weight. 5. The liquid crystal polymer composition according to any one of claims 1 to 4, further comprising carbon black in an amount of 20 parts by weight or less. 6. The liquid crystal polymer composition according to any one of claims 1 to 5, wherein the liquid crystal polymer is a wholly aromatic liquid crystal polyester resin composed of repeating units represented by formulas (I) and (II).

Using an ASTM No. 4 dumbbell with a thickness of 3.2 mm, a tensile modulus measured in accordance with ASTM D638 is 10.0 GPa or less, and a strip-shaped bending test piece (length 127 mm × width 12.7 mm × thickness 3.2 mm) and has a flexural modulus of 7.0 GPa or less measured according to ASTM D790. A molded article composed of the liquid crystal polymer composition according to any one of claims 1 to 7. 9. The molded article according to claim 8, wherein the molded article is a zip tie.