TWI437039B - Liquid-crystalline polymer composition and molded article made of the same - Google Patents

Description

Liquid crystalline polymer composition and molded article thereof

The present invention relates to a liquid crystalline polymer composition and a molded article thereof.

A thermotropic liquid-crystalline polymer (hereinafter referred to as a liquid crystalline polymer or LCP) has good properties including heat resistance, mechanical properties such as rigidity, chemical resistance, and dimensional accuracy, not only It can be used for moldings and can also be used in a variety of products such as fibers and films.

In the field of information and telecommunications, sometimes very thin parts are required. In particular, personal computers and mobile phones employ highly integrated devices and the art is expected to use smaller, thinner and smaller components. Based on the excellent molding properties of LCPs compared to other thermoplastic resins, including good fluidity and low flash development, the consumption of LCPs has increased.

However, in the field of electronic components, such as connectors, lead-free solder alloys, such as Sn-Ag-Cu alloys, have recently been used to assemble products, and such alloys require high reflow temperatures. The high soldering temperature may cause warpage of the molded article produced by the LCPs.

In order to solve the problem of warpage formation of a molded article produced by LCPs, a liquid crystalline polymer supplemented with a layered filler has been proposed. For example, Japanese Patent No. JP-A-2001-106923 (corresponding to European Patent No. EP 1243620 A1) discloses a liquid crystalline polymer composition comprising, in addition to a liquid crystalline polymer, a layered filler such as talc, the layered filling The material satisfies the following formulas (1) and (2) and has an average particle diameter of 0.5 to 100 μm: Wherein "D" is the maximum particle size of the layered filler and the direction of the diameter D is defined as "x";"W" is the diameter of the particles in the direction y at right angles to the direction x; and H" is the thickness of the particle in the z direction perpendicular to the xy-plane.

For the talc, the Japanese patent JP-A-2001-106923 (corresponding to European Patent EP 1243620 A1) only discloses talc having a ratio of 1.0 to 1.3 D/W, that is, almost circular to square. These talc actually reduce the warpage of the articles made with the LCP composition, but their effectiveness is still insufficient.

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystalline polymer composition which can provide a molded article having low warpage.

The present invention provides a liquid crystalline polymer composition comprising: 100 parts by weight of a liquid crystalline polymer and 1 to 200 parts by weight of talc having an intermediate particle diameter of 5 to 100 μm and an aspect ratio of 3.0 to 5.0 (aspect ratio).

The liquid crystalline polymer of the present invention is not particularly limited and may be any polyester or polyamine which exhibits an anisotropic molten phase and is known to be skilled in the art as a thermotropic liquid crystalline polyester or a thermotropic liquid crystalline property. Polyester decylamine.

The anisotropic molten phase can be determined using a conventional polarized light system using a crossed polarizer. In more detail, samples placed on a Leitz's hot stage under a nitrogen atmosphere can be observed using a Leitz's polarizing microscope.

The liquid crystalline polymer of the present invention is composed of an aromatic oxycarbonyl repeating unit, an aromatic dicarbonyl repeating unit, an aromatic dioxy repeating unit, an aromatic amineoxy repeating unit, an aromatic aminocarbonyl repeating unit, and an aromatic diamine. A repeating unit, an aromatic oxydicarbonyl repeating unit, an aliphatic dioxy repeating unit, and the like.

The liquid crystalline polymer composed of the repeating units described above may include both an anisotropic molten phase and a non-administrative depending on the structural components of the polymer, the ratio thereof, and the sequence distribution thereof. The liquid crystalline polymer used in the present invention is limited to those exhibiting an anisotropic molten phase.

Examples of the monomer which provides an aromatic oxycarbonyl repeating unit are p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid, 3 -hydroxy-2-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, these are alkyl- , alkoxy- and halogen-substituted derivatives and their ester-forming derivatives such as their thiol, ester and acid halide derivatives.

Among them, p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferred because they can contribute to more easily controlling the properties and melting point of the resulting liquid crystalline polymer.

Examples of monomers which provide an aromatic dicarbonyl repeating unit are aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 2,7- Naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 4,4'-dicarboxybiphenyl, alkyl-, alkoxy- and halogen-substituted derivatives and their ester-forming derivatives Such as their esters and derivatives of acid halides.

Among them, terephthalic acid and 2,6-naphthalene dicarboxylic acid are preferred because they can facilitate the mechanical properties, heat resistance, moldability and the like of the obtained liquid crystalline polymer to be more easily controlled. Melting point.

Examples of the monomer which provides an aromatic dioxy repeating unit are aromatic diols such as hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxyl Naphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether These are alkyl-, alkoxy- and halogen-substituted derivatives and their ester-forming derivatives such as their mercapto derivatives.

Among them, preferred are hydroquinone and 4,4'-dihydroxybiphenyl because of good reactivity in the polymerization step and the obtained liquid crystalline polymer has excellent properties.

Examples of the monomer which provides an aromatic aminooxy repeating unit are aromatic hydroxylamines such as p-aminophenol, m-aminophenol, 4-amino-1-naphthol, 5-amino-1-naphthalene Phenol, 8-amino-2-naphthol, 4-amino-4-hydroxybiphenyl, which are formed by alkyl-, alkoxy- and halogen-substituted derivatives and their esters or decylamines Sex derivatives such as their mercapto derivatives.

Examples of the monomer which provides an aromatic aminocarbonyl repeating unit are aromatic aminocarboxylic acids such as p-aminobenzoic acid, m-aminobenzoic acid, 6-amino-2-naphthoic acid, and the like. - alkoxy- and halogen-substituted derivatives and their ester or guanamine-forming derivatives such as their thiol, ester and acid halide derivatives.

Examples of the monomer which provides an aromatic diamine group repeating unit are aromatic amine diamines such as p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diamino group. Naphthalenes, such alkyl-, alkoxy- and halogen-substituted derivatives and their guanamine-forming derivatives such as their fluorenyl derivatives.

Examples of monomers which provide an aromatic oxydicarbonyl repeating unit are hydroxyaromatic dicarboxylic acids such as 3-hydroxy-2,7-naphthalenedicarboxylic acid, 4-hydroxy-isodecanoic acid, 5-hydroxy-isodecanoic acid. These are alkyl-, alkoxy- and halogen-substituted derivatives and their ester-forming derivatives such as their thiol, ester, acid halide derivatives.

Examples of the monomer which provides an aliphatic dioxy repeating unit are aliphatic diols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and the mercapto derivatives thereof.

Further, the liquid crystalline polymer containing an aliphatic dioxy repeating unit may be obtained by reacting a polyester comprising an aliphatic dioxy repeating unit such as polyethylene terephthalate and polybutylene terephthalate Monomers such as aromatic oxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic hydroxylamines, aromatic aminocarboxylic acids, aromatic diamines, hydroxyaromatic dicarboxylic acids, and the like The thiol, ester and acid halide derivatives are obtained by reaction.

Further, the liquid crystalline polymer of the present invention may contain a thioester bond unless it would impair the object of the present invention. Examples of thioester-bondable monomers that can be provided are thiosulfanyl aromatic carboxylic acids, aromatic dithiols, and hydroxyaromatic thiols. These monomers are provided with an aromatic oxycarbonyl repeating unit, an aromatic dicarbonyl repeating unit, an aromatic dioxy repeating unit, an aromatic amineoxy repeating unit, an aromatic amine carbonyl repeating unit, and an aromatic diamine group. The proportion of the total monomer of the repeating unit, the aromatic oxydicarbonyl repeating unit and the aliphatic dioxy repeating unit is preferably equal to or less than 10 mol%.

The liquid crystalline polymer of the present invention preferably comprises a 4-oxybenzylidene repeating unit and/or a 6-oxy-2-naphthomethylthiol repeating unit, both of which are aromatic oxycarbonyl repeating units.

Among the liquid crystalline polymers containing a repeating unit of 4-oxybenzhydryl group and/or 6-oxy-2-naphthoquinone group, a copolymer composed of the following monomer components is preferred. :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/isodecanoic 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-hydroxyl -2-naphthoic acid/terephthalic acid/4,4'-dihydroxybiphenyl copolymer 8) 6-hydroxy-2-naphthoic acid/terephthalic acid/4,4'-dihydroxybiphenyl copolymer 9 ) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone copolymer 10) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / 4,4 '-dihydroxyl Benzene copolymer 11) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalene dicarboxylic acid / hydroquinone copolymer 12) 4- Benzoic acid/2,6-naphthalene dicarboxylic acid/hydroquinone copolymer 13) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/2,6-naphthalene dicarboxylic acid/hydroquinone copolymer 14)4 -hydroxybenzoic acid/terephthalic acid/2,6-naphthalene dicarboxylic acid/hydroquinone/4,4'-dihydroxybiphenyl copolymer 15) 4-hydroxybenzoic acid/terephthalic acid/4-amino group Phenol 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 Alcohol copolymer 20) 4-hydroxybenzoic acid/terephthalic acid/4,4'-dihydroxybiphenyl/ethylene glycol copolymer 21) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/p-benzene Dicarboxylic acid/ethylene glycol copolymer, and 22) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/4,4'-dihydroxybiphenyl/ethylene glycol copolymer.

Among the above, copolymers 1), 9) and 13) are particularly preferably used as the liquid crystalline polymer of the present invention in terms of good moldability and excellent mechanical properties.

The liquid crystalline polymer of the present invention may be obtained by blending two or more liquid crystalline polymers of the present invention to improve properties such as fluidity at the time of molding.

The liquid crystalline polymer of the present invention can be produced by the method described below.

The method for preparing the liquid crystalline polymer of the present invention is not limited and any known method can be employed. For example, a conventional polymerization method such as a melt acidolysis method and a slurry polymerization method can be used to prepare a polymer to impart an ester or a guanamine bond between the monomer components described above.

In the present invention, a melt acidolysis method is preferably used. In this method, a polymer monomer is heated to a molten solution to which a reactant is administered and then the solution is reacted to give a molten polymer. The final step of this process can be carried out under vacuum to facilitate the removal of volatile by-products such as acetic acid and water.

The slurry polymerization process is characterized in that the single systems are reacted in a heat exchange fluid to impart a solid polymer in the form of a suspension in the heat exchange liquid medium.

In any of the melt acidolysis or slurry polymerization processes, the polymerizable monomer component used in the preparation of the liquid crystalline polymer may be in a denatured form, that is, in the form of a C _2-5 decyl ester, which may be via a monomer The hydroxyl group and/or the amine group are obtained by thiolation. Among these C _2-5 fluorenyl groups, C _2-3 fluorenyl groups are preferred. The best is to use acetate to carry out the reaction.

The monomeric C _2-5 decyl ester may be prepared by previously thiolation of the monomer independently or may be added to the monomer during the preparation of the liquid crystalline polymer, such as acetic anhydride. Producer in the reaction system.

In any of the melt acid hydrolysis method or the slurry polymerization method, a catalyst may be used in the reaction if necessary.

Examples of the catalyst include organotin compounds such as dialkyltin oxide (e.g., dibutyltin oxide) and diaryltin oxide; antimony trioxide; titanium dioxide; organotitanium compounds such as titanium alkoxide and titanium alkoxide; carboxylic acid An alkali metal or alkaline earth metal salt such as potassium acetate; an alkali metal or alkaline earth metal salt of an inorganic acid such as potassium sulfate and Lewis acid (such as BF ₃ ); a gaseous acid catalyst such as a hydrogen halide (such as HCl) ).

The amount of the catalyst added to the reaction may preferably be from 10 to 1000 ppm, and more preferably from 20 to 200 ppm, based on the total monomers, when the catalyst is used.

The liquid crystalline polymer in a molten state is drawn from a polycondensation reaction vessel and processed into a pellet, flake or powder form.

Thereafter, the polymer may be subjected to a heating process under reduced pressure or in an inert gas atmosphere such as nitrogen and helium in a substantially solid state to increase the molecular weight and improve the heat resistance of the liquid crystalline polymer.

The temperature of the heating process in the solid state is not limited unless the liquid crystalline polymer is melted, and is preferably 260 to 350 ° C and more preferably 280 to 320 ° C.

The liquid crystalline polymer composition of the present invention can be added to the liquid crystalline polymer via a talc having an intermediate particle diameter of 5 to 100 μm and an aspect ratio of about 3.0 to 5.0, and using a kneading machine such as a Banbury mixer, a kneader, A single screw extruder, a twin screw extruder and the like melt-knead the mixture at a temperature close to the melting point of the polymer to the melting point plus 30 °C.

The melting point (Tm) of the liquid crystalline polymer of the present invention measured by a differential scanning calorimeter (DSC) according to the method described below is preferably 270 to 380 ° C, and more preferably 320 to 380 ° C.

A differential scanning calorimeter Exstar 6000 (Seiko Instruments Inc., Chiba, Japan) or a DSC device of the same type was used. The LCP sample to be tested was heated from room temperature at a rate of 20 ° C/min and its endothermic peak (Tm1) was recorded. Thereafter, the LCP sample was held at a temperature of 20 to 50 ° C above Tm1 for 10 minutes. The sample was then cooled to room temperature at a rate of 20 ° C/min. Then, the LCP sample was further heated at a rate of 20 ° C / minute and its exothermic peak was recorded. The endothermic peak measured in the last step was recorded as the melting point.

The liquid crystalline polymer of the present invention comprises talc having an intermediate particle diameter of 5 to 100 μm, preferably 5 to 75 μm, and more preferably 5 to 50 μm.

In the present invention, the intermediate particle diameter of the talc is measured by a laser diffraction measurement.

The aspect ratio of the talc used in the present invention is from 3.0 to 5.0, preferably from 3.0 to 4.5, and more preferably from 3.0 to 4.0.

In the present invention, the aspect ratio of the talc is determined according to the Coulter principle using a Multi Image Analyzer (Beckman Coulter, Inc.), and includes the following steps: i) when the talc particles pass through the pores, corresponding to the generated voltage Pulse illuminating the flash; ii) capturing a projected image of the particle; and iii) analyzing the projected image; wherein the aspect ratio of the talc particle is calculated by equation (A)/(B); wherein (A) is the projected image The maximum length between the two random points on the outer circumference and (B) is the minimum distance between the two straight lines that are in contact with the projected image and parallel to the line connecting the two points for measuring the maximum length (A).

In the present invention, the amount of talc is from 1 to 200 parts by weight, preferably from 5 to 150 parts by weight, and more preferably from 10 to 100 parts by weight, per 100 parts by weight of the liquid crystalline polymer.

The moisture content of the talc used in the present invention is less from the viewpoint of less formation of a so-called blister, which is a surface protrusion of a molded article, and a bad influence on properties of a molded article such as heat resistance. The best is equal to or less than 0.2% by weight.

The moisture content of the talc can be determined by using an infrared moisture meter (Kett Electric Laboratory) as described below.

<Method for measuring moisture content of talc>

A 10 gram talc sample was heated to 105 ° C and held at this temperature until the weight of the sample became fixed. The amount of weight loss measured at this time is defined as the moisture content of the talc.

When the moisture content of the talc exceeds 0.2% by weight, it may be dried at a temperature of, for example, 100 to 150 ° C before use to reduce the moisture content to be equal to or lower than 0.2% by weight.

The liquid crystalline polymer composition of the present invention may contain a fibrous filler other than talc, and the amount of the fibrous filler is preferably from 1 to 200 parts by weight per 100 parts by weight of the liquid crystalline polymer, more preferably 1 To 150 parts by weight and most preferably from 1 to 100 parts by weight.

The average fiber diameter of the fibrous filler is not limited and is preferably from 0.1 to 50 μm unless it is detrimental to the object of the present invention. Where the cross-section of the fibrous filler is not circular, the diameter of the fiber is defined as the maximum length between any two points on the outer circumference of the cross-section of the fibrous filler.

Examples of the fibrous filler include glass fiber, elliptical glass fiber, bismuth glass fiber, cerium oxide-alumina fiber, alumina fiber, carbon fiber, aramid fiber, potassium titanate fiber, aluminum borate fiber, bismuth Greystone (wollastonite) and their combination.

Among the fibrous fillers described above, glass fibers, elliptical glass fibers, scorpion glass fibers, and combinations thereof are preferred from the properties of the liquid crystalline polymer composition and the cost thereof.

Within the scope of the present specification and claims, the term "glass fiber" means a glass fiber having a circular cross section. The term "elliptical glass fiber" means a glass fiber having an elliptical cross section. The term "rhodium-shaped glass fiber" means a glass fiber whose cross-section is the shape observed when two small circular portions overlap each other. Such shapes include, for example, the longitudinal portion of the peanut shell. In the present invention, the term "circular" or "elliptical" shape means not only a geometric circular or elliptical shape but also a shape which is shown to be almost circular or elliptical. For example, a circular shape includes a square whose corner is rounded and the shape of the ellipse includes a rectangle whose corner is rounded.

The liquid crystalline polymer composition of the present invention may comprise one or more layered or granulated fillers in addition to talc unless the additional fillers impair the object of the present invention.

The amount of the layered or granular filler other than the talc is preferably from 1 to 200 parts by weight, more preferably from 1 to 150 parts by weight, and most preferably from 1 to 100, per 100 parts by weight of the liquid crystalline polymer. Parts by weight.

Examples of the layered or granular filler other than talc include mica, graphite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate, titanium oxide, and combinations thereof.

The total amount of the talc and the fibrous, layered or granular filler other than talc in the liquid crystalline polymer composition of the present invention is preferably from 1 to 200 parts by weight per 100 parts by weight of the liquid crystalline polymer. .

If necessary, the liquid crystalline polymer composition according to the present invention may further be mixed with an additive conventionally used for one or more LCP compositions, such as a molding lubricant such as a high carbon number aliphatic acid, a high carbon number aliphatic ester, and a high carbon number. Aliphatic guanamine, high carbon number aliphatic acid metal salt, polyoxyalkylene, fluorocarbon resin; colorants such as dyes and pigments; antioxidants; thermal stabilizers; UV absorbers; antistatic agents and surfactants.

Molding lubricants such as high carbon number aliphatic acids, high carbon number aliphatic esters, high carbon number aliphatic guanamines, high carbon number aliphatic acid metal salts and fluorocarbon type surfactants, which can be used in liquid crystalline polymers Or the pellets of the liquid crystalline polymer composition are added to the pellets prior to being subjected to the molding process so that the molding lubricant adheres to the outer surfaces of the pellets.

The term "high carbon number aliphatic acid" as used herein refers to those having from 10 to 25 carbon atoms.

One or more other resin components may be added to the liquid crystalline polymer of the present invention. Examples of such other resin components include thermoplastic resins such as polyamides, polyesters, polyphenylene sulfides, polyetherketones, polycarbonates, polyphenylene ethers and denatured derivatives thereof, polyfluorenes, polyether oximes, and Polyether sulfimine and thermosetting resins such as phenol resins, epoxy resins and polyimide resins. Liquid crystalline polymers containing other resin components may be included in the scope of the present invention.

The amount of such additional resins is not limited and may depend on the desired properties. Typically, the amount of such additional resin added to the liquid crystalline polymer composition may be from 1 to 200 parts by weight, preferably from 10 to 100 parts by weight, per 100 parts by weight of the liquid crystalline polymer.

The liquid crystalline polymer composition of the present invention can be added to the liquid crystalline polymer via other fibrous, layered and granular fillers, additives and other resin components, and talc, and from the melting point of the polymer to the melting point The temperature at 30 ° C is obtained by melt kneading the mixture using a kneading machine such as a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, and the like.

The obtained liquid crystalline polymer composition of the present invention exhibited extremely low warpage. For example, a test disk manufactured from the liquid crystalline polymer composition of the present invention exhibits a value equal to or less than 6.0 mm, preferably equal to or less than 5.5 mm, and more preferably equal to or less than 5.0 as measured as described below. Warp of millimeters.

<Method for measuring LCP warpage>

A test dish having a thickness of 1.0 mm and a diameter of 100 mm manufactured using an injection molding machine (Nissei Plastic Industrial Co., Ltd., UH-1000-110) was allowed to stand at a temperature of 23 ° C and a relative humidity of 50% for 24 hours. Then, the test dish was placed on the surface plate and the distance from the plane of the surface plate to the upper end of the edge of the test dish was measured using a height gauge (Mitutoyo Corporation, HDM-30). The measured distance is defined as the warpage of the test disc.

The liquid crystalline polymer composition according to the present invention can be molded into a molded article, a film, a sheet, and a non-woven fabric using a conventional melt molding method such as injection molding and compression molding.

In particular, the liquid crystalline polymer composition of the present invention can be suitably used to manufacture a molded article processed at a high soldering temperature, for example, a switch, a relay, a connector, a wafer, an optical reader, and an inverter converter ( The inverter trans) and the coil bobbin are because the liquid crystalline polymer composition of the present invention exhibits excellent fluidity upon molding and forms small warpage even at high temperatures.

[Examples]

The invention has been further described so far with reference to the following examples. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

In the examples and comparative examples, the following abbreviations are used: <liquid crystalline polymer> LCP 1: UENO LCP2500 (Ueno Fine Chemical Industry, Ltd., 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/ Terephthalic acid/hydroquinone copolymer, melting temperature 335 ° C) LCP 2: UENO LCP6700 (Ueno Fine Chemical Industry, Ltd., 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid/2,6-naphthalene Carboxylic acid / / hydroquinone copolymer, melting temperature 330 ° C)

<Talc> Talc 1: FUJI TALC INDUSTRIAL CO., HK-A (length to width ratio 3.6, intermediate particle diameter 24.0 μm, moisture content 0.13 wt%) Talc 2: FUJI TALC INDUSTRIAL CO., FG1-A (length ratio 3.6, intermediate particle diameter 26.1 μm, moisture content 0.07 wt%) Talc 3: FUJI TALC INDUSTRIAL CO., DS-34 (length to width ratio 2.6, intermediate particle diameter 19.8 μm, moisture Content 0.24% by weight)

<Fibrous filler> GF 1: Glass fiber, NSG Vetrotex KK, 10EC 3MM92C (intermediate fiber diameter 10 μm) GF 2: Elliptical glass fiber, Nitto Boseki Co., Ltd., CSG 3PA 831S (intermediate section short axis 7 μm , the middle section has a long axis of 28 microns)

Examples 1 to 5 and Comparative Examples 1 to 3 mixed LCP 1, talc, and fibrous filler (GF 1). The parts by weight of the talc and fibrous filler per 100 parts by weight of LCP 1 are shown in Table 2. The mixture was melt-kneaded using a twin-screw extruder (The Japan Steel Works, LTD., TEX-30 α) to give pellets of the liquid crystalline polymer composition.

Using the obtained liquid crystalline polymer composition pellets, injection molding was carried out under the conditions shown in Table 1 to obtain test discs. The warpage of the test disc was measured. Table 2 shows the results of the warpage measurement.

The liquid crystalline polymer composition of Example 1 containing talc but no fibrous filler had a warpage of less than 3 mm. This warpage value is extremely small.

The liquid crystalline polymer compositions of Example 2 and Comparative Example 1, the liquid crystalline polymer compositions of Example 3 and Comparative Example 2, and the liquid crystalline polymer compositions of Example 4 and Comparative Example 3 respectively contained The same amount of talc and fibrous filler. The difference between the examples and the comparative examples is the type of talc, and the talc contained in the former has a larger aspect ratio than that contained in the latter. Comparing the warpage of the LCP compositions of the examples and the comparative examples, the liquid crystalline polymer compositions of the above Examples 2 to 4 exhibited smaller warps than those of Comparative Examples 1 to 3, respectively. Curvature.

Examples 6 to 8 and Comparative Example 4 were mixed with LCP 2, talc, and fibrous filler. The parts by weight of the talc and fibrous filler per 100 parts by weight of LCP 2 are shown in Table 4. The mixture was melt-kneaded using a twin-screw extruder (The Japan Steel Works, LTD., TEX-30 α) to give a liquid crystal polymer composition pellet.

Using the obtained liquid crystalline polymer composition pellets, injection molding was carried out under the conditions shown in Table 1 to obtain test discs. The warpage of the test disc was measured.

Further, using the obtained liquid crystalline polymer composition pellets, injection molding was carried out under the conditions shown in Table 3 to obtain test strips having a length of 127 mm, a width of 12.7 mm, and a thickness of 3.2 mm. The load deformation temperature (DTUL) was measured using a test strip according to ASTM D 648 under a load of 1.82 MPa and using a heating rate of 2 ° C/min.

Table 4 shows the measurement results of warpage and DTUL.

The liquid crystal polymer compositions of Examples 6 to 8 containing talc having an aspect ratio of 3.6 had a warpage of less than 6.0 mm. On the other hand, the liquid crystal polymer composition of Comparative Example 4 containing talc having an aspect ratio of 2.6 had a warpage exceeding 6.0 mm.

Further, the liquid crystal polymer composition containing a large aspect ratio of talc and elliptical glass fiber (GF2) has a smaller warpage than those containing talc and GF1.

Further, the liquid crystalline polymer composition of Comparative Example 4 containing talc 3 having a moisture content of 0.24% by weight exhibited Example 6 to talc 1 and talc 2 having a moisture content of 0.2% by weight or less. 8 lower load deformation temperature (DTUL).

Claims (12)

A liquid crystalline polymer composition comprising: 100 parts by weight of a liquid crystalline polymer and 1 to 200 parts by weight of talc having an intermediate particle diameter of 5 to 100 μm and an aspect ratio of 3.0 or more and less than 4.0. The liquid crystalline polymer composition of claim 1, wherein the talc has an aspect ratio of 3.0 to 3.6. The liquid crystalline polymer composition of claim 1 or 2, wherein the liquid crystalline polymer composition is selected from the group consisting of 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/hydrogen A group of rhodium copolymers and 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/2,6-naphthalenedicarboxylic acid/hydroquinone copolymer. The liquid crystalline polymer composition of claim 1 or 2, wherein the talc has a moisture content of 0.2% by weight or less. The liquid crystalline polymer composition of claim 1 or 2 further comprising 1 to 200 parts by weight of a fibrous filler. The liquid crystalline polymer composition of claim 5, wherein the fibrous filler is selected from the group consisting of glass fiber, elliptical glass fiber, bismuth glass fiber, cerium oxide-alumina Fiber, alumina fiber, carbon fiber, aramid fiber, potassium titanate fiber, aluminum borate fiber, wollastonite, and combinations thereof. The liquid crystalline polymer composition of claim 6, wherein the fibrous filler is selected from the group consisting of glass fibers, elliptical glass fibers, scorpion glass fibers, and combinations thereof. A liquid crystalline polymer composition as claimed in claim 1 or 2, Further, 1 to 200 parts by weight of a layered or granular filler other than talc is contained. The liquid crystalline polymer composition of claim 8, wherein the layered or granular filler is selected from the group consisting of mica, graphite, calcium carbonate, dolomite, clay, glass flakes, Glass beads, barium sulfate, titanium oxide, and combinations thereof. The liquid crystalline polymer composition of claim 1 or 2, wherein the test disc having a thickness of 1.0 mm and a diameter of 100 mm is obtained by molding the liquid crystalline polymer composition at 23 ° C The warp value measured after the temperature and 50% relative humidity were allowed to stand for 24 hours was equal to or less than 6.0 mm. A molded article obtained by molding the liquid crystalline polymer composition according to any one of claims 1 to 10. The molded article of claim 11 is selected from the group consisting of a switch, a relay, a connector, a wafer, an optical reader, an inverter trans, and a coil reel. .