TW200831584A - Liquid-crystalline polymer composition and molded article made of the same - Google Patents

Abstract

The present invention provides a liquid-crystalline polymer composition, comprising: 100 parts by weight of a liquid-crystalline polymer and 1-200 parts by weight of talc which has a median particle diameter of 5-100 μm and an aspect ratio of 3.0-5.0. The liquid-crystalline polymer composition of the present invention can provide a molded article with less development of warpage.

Description

200831584 </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; [Prior Art] Thermotropic 1 iquid-crystalline polymer (hereinafter referred to as liquid crystalline polymer or LCP) has good properties including heat resistance, mechanical properties such as rigidity, and chemical resistance. And dimensional accuracy, not only for moldings but also for 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 0 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. High solder avoidance temperatures may cause the curvature of the molded articles 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, 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 of 5 319 703 200831584 The layered filler satisfies the following formula (1) and has an average particle diameter of 0.5 to 1 μm: ϋ (2) D/W &lt; 5 (1) 3 &lt; W/H &lt; 200 (2) where D is the maximum particle size of the layered filler and the formula of the diameter D is defined as "X"; "W" is the diameter of the particles in a square y at right angles to the direction ;; and Η" is the thickness of the particle in 2 squares perpendicular to the xy-plane. ask

For talc, the Japanese patent jp-A-2〇〇1 -1〇6923 (corresponding to European patent EP124362G A1) only reveals talc having a ratio of up to 13 D/w, that is, almost round to square. . Such talc actually reduces the warpage of the article made of the LCP composition, but its utility is twofold. SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystalline polymer which can provide a molded article having low warpage. Composition. The present invention provides a liquid crystalline polymer composition comprising: 1 part of a liquid crystalline polymer and 1 part by weight of talc having a particle diameter of 5 to 100 μm and 30 Å. Aspect ratio of up to 5 。. [Embodiment] The liquid crystalline polymer of the present invention is not particularly limited and may be any polyester or polyamine which exhibits a respective molten phase and is known as a thermotropic liquid crystalline polyester or Thermally oriented liquid crystalline polyester decylamine. 319703 6 200831584 偏振 ❹ 四 四 四 四 四 四 四 偏振 偏振 偏振 正交 正交 正交 正交 正交 正交 正交 正交 正交 正交 正交 正交 正交 正交 正交 正交In more detail, samples placed on the Leitz, s mouth under nitrogen 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 dicarbyl repeating unit, an aromatic dioxy repeating unit, an aromatic amineoxy group, an aromatic amine group repeating unit, and an aromatic group. The group consists of a family diamine repeating unit, an aromatic oxy group repeat unit, a m-based heavy fresh position, and the like. The liquid crystalline polymer composed of the above repeating unit may include both an anisotropic molten phase and a non-stained person depending on the structural components of the polymer, the ratio thereof, and the sequence distribution thereof. The liquid crystal 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-carbamic acid, ortho-benzoic acid, 6-transyl-2-naphthoic acid, 5 Iyl 2 naphthic acid, 3-hydroxy-2-naphthoic acid, 4,-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4, monohydroxyphenyl-3-benzoic acid, their transalkanes Derivatives of thio-, alkoxy- and dentate-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 the monomer which provides an aromatic dicarbonyl repeating unit are aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2, naphthalene dicarboxylic acid, anthracene, 6-naphthalene dicarboxylic acid, 2, 7- Naphthalene dicarboxylic acid, hydrazine, 4 - naphthalene dicarboxylic acid, 4, 4 ' dicarboxybiphenyl, derivatives of 319703 200831584 and derivatives of their ester forming compounds.元元基-, :fc methoxy- and dentate-substituted derivatives such as their esters and acid halides among them, preferably terephthalic acid and 2,6-cai dicarboxylic acid, = for them to facilitate easier control of the mechanical properties, heat resistance, moldability and melting point of the resulting liquid crystalline polymer.

Examples of monomers which provide an aromatic dioxy repeating unit are aromatic diols such as hydroquinone, isophthalic acid, 2,6-di-perylene, 2,7-di-naphthalene, and u- Hydroxy f naphthalene, 1,4 dihydroxy naphthalene, 4,4, dihydroxybiphenyl, 3,3, dihydroxyl % benzene, 3,4-hydroxyl biphenyl, 4, 4, dihydroxyl Phenyl ethers, such calcinyl-, alkoxy- and argin-substituted derivatives and their _ forming derivatives such as their stilbene derivatives. Among them, preferred are hydroquinone and 4,4,-dihydroxybiphenyl because of good reactivity in the polymerization step and the liquid crystalline polymer obtained has excellent properties. An example of a monomer which provides an aromatic amineoxy repeating unit is an aromatic hydroxylamine φ such as p-aminophenol, m-aminophenol, 4-amino-quinone-naphthol, 5-aminol group Naphthol, 8-amino-2-naphthol, 4-amino-4-hydroxybiphenyl, alkyl-, alkoxy- and halogen-substituted derivatives and their esters or decylamines Formative derivatives such as their fluorenyl 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 sulfhydryl groups, g- and acid halide derivatives ~. : A 8 319703 200831584 Examples of monomers which provide an aromatic diamine repeating unit are aromatic amine diamines such as p-phenylenediamine, m-phenylenediamine, anthracene, 5-diaminonaphthalene, anthracene, 8-Diaminone, their thiol-, alkoxy- and halogen-substituted derivatives and their enamine-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. And derivatives thereof which are substituted with alkyl-, alkoxy- and halogen-- and their ester-forming derivatives such as those of sulfhydryl, ester and acid halide. Examples of monomers which provide a dioxy-free repeating unit are aliphatic diols such as ethylene glycol, hydrazine, 4-butanediol, hydrazine, 6-hexanediol and their fluorenyl derivatives. Further, the liquid crystalline polymer containing an aliphatic dioxy repeating unit may be via a polyester comprising an aliphatic dioxy repeating unit such as polyethylene terephthalate and::butylene terephthalate, And the above monomers such as an aromatic oxy-carboxylic acid, an aromatic carboxylic acid, an aromatic diol, an aromatic hydroxylamine, an aromatic aminocarboxylic acid, an aromatic diamine, a trans-aromatic diweiric acid, And obtained by reacting their acid groups, vinegar and acid halide derivatives. 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 the thioacetate-bonded monomer which can be provided are a thiosulfanyl aromatic carboxylic acid, an aromatic dithiol and a silk aromatic thiol. These monomers are relative to an aromatic oxygen radical repeating unit, an aromatic di(tetra) repeating unit, an aromatic j-based repeating unit, an aromatic county-based repeating unit, an aromatic amine-based carboxy group, and an early H-group repeating unit. , Aromatic Oxygen County Repeat Unit 319703 9 200831584 The ratio is preferably equal to or less than 10 mol% of the total monomer of the aliphatic dioxy repeat unit. The liquid crystalline polymer of the present invention preferably comprises a 4-fold unit and/or a 6-oxy-2-naphthoquinone-based repeating mono-indenyloxy group repeating unit. (4) Among the liquid crystalline polymers which are aromatic in a repeating unit containing a 4-oxybenzhydryl group and/or a 6-oxocarbyl group, preferably a copolymer composed of the following components Object:

1) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid copolymer 2) 4-Sisbenzoic acid/terephthalic acid/4,4, di-based biphenyl copolymer 3) 4-Pheptylbenzene Formic acid/terephthalic acid/isodecanoic acid/4, 4, a di-biphenyl copolymer 4) 4-benzoic 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 / hydrazine copolymer 7) 4-aminobenzene Formic acid / 6 - hydroxy - 2 - naphthoic acid / terephthalic acid ^ 1 - base biphenyl copolymer 8) 6-hydroxy-2-naphthoic acid / terephthalic acid / 4, 4, dihydroxybiphenyl Copolymer 9) 4-P-benzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/hydroquinone copolymer^ 10) 4-Phenylbenzoic acid/2,6-naphthalene dicarboxylic acid/4 , 4,-Dihydroxybiphenyl copolymer 10 319703 200831584 11) 4-hydroxybenzoic acid / terephthalic acid / 2, 6 - naphthalene dicarboxylic acid / hydroquinone copolymer 12) 4-hydroxybenzoic acid / 2,6-naphthalene dicarboxylic acid/argon argon copolymer 13) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/2,6-naphthalene dicarboxylic acid/hydroquinone copolymer 14) 4-hydroxybenzene Formic acid/terephthalic acid/2, 6-naphthalene Dicarboxylic acid/hydroquinone/4,4'-dihydroxybiphenyl copolymer 15) 4-hydroxybenzoic acid/terephthalic acid/4-aminophenol copolymer _ 16) 6-hydroxy-2_naphthalene Tannic acid/terephthalic acid/4-aminophenol copolymer 17) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/4-amine based copolymer 18) 4- Hydroxybenzoic acid/terephthalic acid/4,4'-dihydroxybiphenyl/4-amino-based copolymer 19) 4-hydroxybenzoic acid/terephthalic acid/ethylene glycol copolymer 20) 4-hydroxybenzoic acid/terephthalic acid/4,4'-dihydroxybiphenyl/ethylene glycol φ copolymer 21) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/p-benzene Diterpene 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 present invention relates to a crystalline polymer which may be via two or more inventive liquids 11 319703 200831584

The A crystalline polymer is blended to improve flow properties such as during 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 may be used to prepare a polymer; an ester or a guanamine bond between the above monomer components. Preferably, the melt acidolysis method is used in the present invention. 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 to facilitate the removal of volatile by-products such as acetic acid and water. The sputum polymerization method is characterized in that the single systems are in a fluid exchange

The polymer is reacted in the form of a suspension in the heat exchange liquid medium. 'U In any of the melt acidolysis or slurry polymerization methods, the polymerized monomer component used in the preparation of the liquid helium polymer may be in a denatured form, that is, in the form of a C2-5 mercapto vinegar, which may be The mesogenic and/or amine groups of the body are obtained by saccharification. Among these C2-5 bases, C2-3 is preferred. The best is to use acetate to carry out the reaction. The monomeric CH acid-based vinegar may be prepared by separately encapsulating the monomer by itself or may be added to the reaction system by adding an emulsification agent such as acetic anhydride to the monomer at the time of preparing the liquid crystalline polymer. Producer. Among any of the melt acidolysis or slurry polymerization methods, a catalyst may be used in the reaction.. 319703 12 200831584 Examples of catalysts include organotin compounds such as dialkyltin oxides (eg, oxidation) Butyltin) and diaryltin oxide; antimony trioxide; titanium dioxide; having an organic titanium compound such as titanium alkoxide and titanium alkoxide; an alkali metal salt or an alkaline earth metal salt of a carboxylic acid such as potassium acetate; Alkali metal or alkaline earth metal salts such as potassium sulfate and Lewis acid (WB{?3); gaseous acid catalysts such as hydrogen halides (such as HCl). When the catalyst is used, the amount of the catalyst added to the reaction is preferably

The liquid crystalline polymer in a molten state of 10 to 1000 ppm based on the total monomer, and more preferably in the molten state of 200 ppm, is drawn from the polycondensation reaction vessel and processed to give small particles and flakes. Or in powder form. The polymer may be subjected to a heating process under reduced pressure or in an inert gas atmosphere such as nitrogen gas and helium gas 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 35 (rc and more preferably 280 to 32 (TC). The liquid crystalline polymer composition of the present invention The talc having an aspect ratio of 5 to micrometers and an aspect ratio of about 3. to 5. G may be added to the liquid crystalline polymer and a kneading machine such as a Banbury mixer, a kneader, a single screw extrusion may be used. Machine, twin-screw extruder and the like, the mixture is melt-kneaded at a temperature close to the melting point of the compound to the melting point plus 3 ° C. The difference is measured using a differential scanning calorimeter (DSC) according to the method described below. The melting point (Tn) of the liquid crystalline polymer of the invention is preferably from 27 to 38 ,, 319703 13 200831584 and more preferably from 320 to 380 ° C. Using a differential scanning calorimeter Exstar 6000 (Seiko

Instruments Inc., Chiba, Japan) or the same type of DSC device. The LCP sample to be tested was heated from room temperature at a rate of 20 ° C / minute and its endothermic peak (Tml) was recorded. Thereafter, the LCP sample was maintained at a temperature of 20 to 50 C above Tmi for 1 Torr. The sample was then cooled to room temperature at a rate of 20 ° C / minute. Then, the Lcp sample was further heated at a rate of 20X/min and its exothermic peak was recorded. The endothermic peak measured in the last step was recorded as 10 melting points. The liquid crystalline polymer of the present invention comprises talc having an intermediate particle diameter of 5 to 1 μm, preferably 5 to 75 μm, and more preferably 5 to 5 μm. In the present invention, the intermediate particle diameter of the talc is measured by a laser diffraction measurement method. The aspect ratio of the talc used in the present invention is from 3·〇 to 4.5, and more preferably from 3.〇 to 4. . • In the present invention, the aspect ratio of the talc is Multi Inmge

Analyzer (Beckman Coulter, Inc. Coulter ^ m ^, J'' includes the following steps: · When the talc particles pass through the pores, 'corresponds to the generated voltage pulse to illuminate the flash lamp; ii) takes a projected image of the particle; And 111 斫 斫 the projected image; different; where (A) and (B) are the maximum Ί 319 319 与 其中 其中 ' 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 14 200831584 The projected image is in contact with and parallel to the minimum distance between the two straight lines connecting the two points of the two points used to determine the maximum length (4). The amount of talc is from 1 to 200 parts by weight, preferably from 5 to 15 parts by weight, and more preferably from 10 to 100 parts by weight, based on the 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 so-called smear (which is a surface protrusion of the molded article) and adverse effects on the properties of the 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 g sample of talc was heated to 105 t: and maintained 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 talc. • When the moisture content of the f talc exceeds 0.2% by weight, it may be dried at a temperature of, for example, 100 to 15 Torr 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 1 to 2 Torr per 1 part by weight of the liquid crystal material. Parts, more preferably i to 15 parts by weight and most preferably 1 to 100 parts by weight. The average fiber diameter of the fibrous filler is not limited and is preferably from 1 to 50 μm unless it is impaired by the present invention. In the case of the fiber 319703 15 200831584 v, the cross section of the male 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 Mori fibrous fillers include glass fiber, elliptical glass fiber, blue glass fiber, oxygen-oxidized fiber, oxygen storage fiber, stone fiber, aramid fiber, potassium titanate fiber, aluminum borate Fiber, stone: Wollastonite and their combination. Among the fibrous fillers described above, from the properties of the liquid materials and the cost thereof, preferred are site materials, and fiber-forming, germinated glass fibers and their t-glass fibers, rounded. Shaped glass ^ In the scope of the present specification and the scope of the patent, the term "glass fiber, glass fiber having a circular cross section. The term "expanded glass fiber" means glass having an enlarged circular cross section: Fiber!, 'meaning that its cross-section is to reduce the small part of the two rounds to each other to reduce the shape of the glass fiber. These shapes include, for example, the longitudinal portion of #. In the present invention, the term "circular," or "expanded," means not only a geometric circular or elliptical shape, but also a circular or _ shape. For example, a square of ==:= and the shape of the ellipse includes a rectangular opening whose corners are rounded: the eutectic polymer composition may contain two in addition to talc and the filling section of the object of the present invention' unless the addition The filler may be damaged, and the amount of the layered or granular filler other than the talc is preferably 1 part by weight of the liquid crystalline polymer, more preferably 1 319703 16 200831584

A to 150 parts by weight and most preferably i to 1 part by weight. Examples of layered or granular fillers other than talc include a combination of cloud sulfur, titanium oxide, and the like. The total amount of the talc and the fibrous, layered or granular filler other than the talc in the liquid Ba polymer composition of the present invention is preferably from 1 to 200 parts by weight per 1 (10) parts by weight of the liquid crystalline polymer. % necessary, the liquid crystalline polymer composition according to the present invention may be used as an additive which is conventionally used in the genus or the genus Lcp group, such as a mold 2 lubricant such as a high carbon (qua) acid, a high carbon aliphatic vinegar. , high carbon family t, surface carbon number aliphatic acid metal salt, oxy-oxygen, fluorocarbon resin; coloring and pigment; antioxidant; thermal stabilizer; uv absorber; anti-resistance; Quangong lubricants such as high-carbon months acid, high-carbon months, Gao Shihu, April, no amine, 冋 slave (four), acid metal salt and fluorocarbon type interface activity 2: can be in liquid crystal The pellets of the polymer or liquid crystalline polymer composition are added to the pellets prior to the molding process such that the molding lubricant 4 is attached to the outer surfaces of the pellets. The term "high carbon number aliphatic acid, as used herein, refers to those having 10 to 25 carbon atoms. 2 One or more of the other liquid crystal polymers may be added to the invention. Examples of such other resin components include thermoplastic resins such as amines, polyfluorenes, polyphenylene sulfides, polyetherketones, polycarbonates, polybenzazoles, and their modified derivatives, polyhard, polyclimatous winds, And poly(tetra)imine are packaged in 319703 17 200831584 200831584, resins such as phenol resins, epoxy resins and polyimide resins. 3 Liquid crystalline polymers of other resin components may be included in the scope of the present invention. (4) The amount of addition of trees (four) is not affected by the dragon, and may be determined according to the desired properties. Typically, the amount of the liquid crystal polymer added to the liquid crystalline polymer composition is from 1 to a part by weight, preferably from 10 to 100 parts by weight per 100 parts by weight of the liquid crystalline polymer. The clear liquid crystalline polymer composition can be added to the liquid crystalline polymer by adding other fibrous, layered and granular fillers, additives and other resin components and talc, and from the melting point close to the polymer to the The temperature at which the melting point is added to 30 C is obtained by kneading and kneading the mixture using a kneading machine such as a Banbury mixer, a kneader, a single-screw extrusion, a twin-screw extruder, and the like. The obtained liquid crystalline polymer composition of the present invention exhibited extremely low warpage. For example, the test disk manufactured by the liquid crystal polymer composition of the present invention has a test disk of equal to or less than 6 〇m. The warp is equal to or less than 5.0 mm. <Method for measuring LCP distortion> An injection molding machine (Nissei Plastic Industrial,

Ltd., UH-100 0-1 10) manufactured with ι·〇 mm thickness and IQ. Mm. Straight I plate inspection disc is allowed to stand at 2 3 C temperature and 50% relative humidity for 24 hours. Then, the test disc was placed on the surface plate and the distance from the hiring plane of the surface plate of 319703 18 200831584 to the upper end of the edge of the test disc was measured using an altimeter (heimeter gage; Mitutoyo Gorpomtion, 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 connection, a wafer, an optical reader, and an inverter converter ( The inverter and the coil bobbin are because the liquid crystalline polymer composition of the present invention exhibits excellent fluidity at the time of molding and forms a small Wei Qu even at a high temperature [ [Examples] The following examples are intended to illustrate the invention. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Φ In the examples and comparative examples, the following abbreviations are used: Hybrid polymer > LCP 1 : UENO LCP2500 (Ueno Fine Chemical Industry, Ltd 4- 4-benzoic acid / 6 monohydroxy 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-naphthalenedicarboxylic acid / hydrogen waking copolymer, melting temperature 33 ( TC), <Talc>,, - 319703 19 20 0831584 talc l (Talc 1) ·· FUJI TALC INDUSTRIAL CO·,Μ-A (aspect ratio 3.6, intermediate particle diameter 24·0 μm, moisture content 0.13 wt%) Talc 2: FUJI TALC INDUSTRIAL C0·, FG1-A (length to width ratio 3.6, intermediate particle diameter 26·1 μm, moisture content 〇·07 weight °/〇) talc 3 (Talc 3) : FUJI TALC INDUSTRIAL CO·, DS-34 (long觅 ratio 2·β, intermediate particle diameter 19·8 μm, moisture content 〇·24% by weight) <Fibrous filler> GF 1 : Glass fiber, NSG Vetr〇tex κ·κ·, 1〇EC 3 Li 92C ( Intermediate fiber diameter 10 μm) GF 2 · Elliptical glass fiber, Niu〇B〇seki c〇., [μ·, CSG = is (intermediate section short axis 7 μm, intermediate section long axis 28 μm) Example 1 to 5 And Comparative Examples 1 to 3, LCP 1, talc, and fibrous filler (GF 1) were mixed. The parts by weight of the talc and the fibrous filler per 100 parts of the wound LCP 1 are shown in Table 2. The liquid crystalline polymer composition was granulated by melt-kneading the mixture using a twin-screw extruder (The steei w〇rks, 'TEX 30 α). Uot; &quot; jin% liquid daily polymer composition small particles in the table 丄t not tilt, out into a $ and inspection pieces. The surface curvature of the test disc is measured. The warpage measurement results are shown. 319703 20 200831584 Table 1 · Manufacture of the bell test 3: Molding conditions of the test disc used Molding machine Nissei nastic Industrial Co. , Ltd., UH-1000 Cartridge temperature 350-350-350-310-280 Mold temperature 70 ( °C) ~ -- Injection speed 60 0 house meter / second holding pressure 300 gram / square centimeter injection time ^ ' Cooling time 9 seconds a screw speed 150 rpm screw back pressure 5 gram / square centimeter table 2 · Liquid crystal Measurement of warpage of polymer composition talc fibrous filler surface roughness (millimeter) Type by weight parts by weight Example 1 Talc 1 66. 7 0 2. 96 Example 2 Talc 1 80 20 1. 62 Example 3 Talc 1 50 16· 7 3. 46 Example 4 Talc 1 33· 3 33· 3 4· 99 Example 5 Talc 2 50 16· 7 2. 15 Comparative Example t Talc 3 80 20 3. 84 Comparative Example 2 Talc 3 50 16· 7 4· 67 Comparative Example 3 Talc 3 33. 3 33. 3 5. 61 The liquid crystalline polymer composition of Example 1 containing talc but no fibrous filler has a warpage of less than 3 mm. . This warpage value is extremely small. 21 319703 200831584 The liquid crystalline polymer composition of Example 2 and Comparative Example 1, the liquid crystalline polymer composition of Example 3 and Comparative Example 2, and the liquid crystalline polymer composition of Example 4 and Comparative Example 3 The talc and fibrous fillers of the same bismuth are respectively contained. 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 Weiqu composition 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 cutters than those of Comparative Examples 1 to 3. Lightly curved value. Examples 6 to 8 and Comparative Example 4 LCP 2, talc, and fibrous filler were mixed. The parts by weight of the talc and fibrous filler per part by weight of LCP 2 are shown in Table 4. The mixture was melt-kneaded using a twin-screw extruder (The japan Steel w〇rks, Ltd, TEX 30 α) to give liquid crystal polymer composition pellets. The test discs were obtained by injection molding using the known liquid enthalpy polymer composition pellets under the conditions shown in Table 1. 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 a test strip having a length of 127 mm and a shoulder width of i2.7 mm. The test strip is measured for the deformation temperature under load (] TUL) according to the heating rate of ASTM D 641 ^ 2 (4) and the heating rate of 2 minutes. , . Table 4 shows the measurement results of the fun and DTUL. 319703 22 200831584 1 Table 3: Molding conditions for the manufacture of test strips for DTUL measurement Molding machine Nissei Plastic Industrial Co.5 Ltd” UH-1000 5 Barrel temperature 370-370-370-340-31 0 (〇C ) Mold Temperature 70 (°C) Injection speed 35 mm / sec. Pressure of 500 gram / cm ^2 injection time 5 seconds ' Cooling time 8 seconds Screw speed 150 rpm Screw back pressure 5 gram / cm ^ 2 Table 4 = Liquid crystalline polymer The warpage of the composition and the result of DTUL measurement The talc fibrous filler is lightly curved (mm) DTUL (°〇 type by weight part type by weight Example 6 talc 1 33.3 GF1 33.3 5· 80 300 Example 7 If ^ 2 —GF1 13·3 —5· 84 304 Example 8 Talc 1 3^3 GF2 33.3 4.55 302 Comparative Example 4 Talc 3 —GF2 ~ Fly 35 ~2%~ Contains an aspect ratio of 3·6; Xijie l ^. ^ nh 月石之贝 yoke examples 6 to 8 liquid crystalline polymer = the surface curvature of the object is less than 6.0 mm. On the other hand, it contains the aspect ratio u Rr = than the car body of the liquid crystal polymer composition of Example 4 The volume exceeds 6.0. The amount: the head. One::==:=f 319703 23 200831584 4 Furthermore, the moisture content is 0. 24% by weight of talc 3 Comparative Example 4 of the liquid crystalline polymer composition exhibits an embodiment having a content of ice equal to or less than 0.2% by weight of talc 1 and talc 2 of Examples 6 to 8 Low load deformation temperature (DTUL).

〇 24 319703

Claims (1)

200831584, the scope of application for patents: 2· 3. 4· 5· A liquid crystalline polymer composition comprising: 丨〇 () parts by weight of a liquid crystalline polymer and 1 to 200 parts by weight of talc, the talc having 5 to ι The diameter of the intermediate particles of the rice and the aspect ratio of 3.0 to 5.0. The liquid crystal polymer composition of the ninth aspect of the invention, wherein the talc has a moisture content of equal to or less than 0.2% by weight. The liquid crystalline polymer composition of claim i or 2, further comprising 1 to 2 parts by weight of the fibrous filler. The liquid crystalline polymer composition of claim 3, wherein the fibrous filler is selected from the group consisting of glass fibers, elliptical/glass-bound fibers, bismuth-shaped glass fibers, and cerium oxide mono-oxidation. Aluminum fiber, alumina fiber, carbon fiber, aramid fiber, potassium titanate fiber, 'sauer fiber, 7 ash ^ (WGllastc) nite) and a combination thereof. For example, the liquid crystalline polymer composition of the third aspect is applied, wherein the fibrous filler is selected from the group consisting of glass fibers, elliptical glass fibers, scorpion glass fibers, and the like. combination. ★ The liquid crystalline polymer group of the patents 1-5 to 1-5, the progress includes 1 to 200 parts by weight of the filler or granular filler other than talc. The liquid crystalline polymer composition of Patent No. 6 is claimed, wherein § "large or granular filler is selected from the group consisting of mica, stone =, carbon_, dolomite, clay, glass flakes. , glass beryllate, titanium oxide, and combinations thereof. Liquid crystal polymer group 319703 25 200831584 u as in the scope of application of the patent scope to item 7: • The crystal polymer composition The test disc having a diameter of 邗ι〇0 pens was obtained by molding, and the warpage value measured after the test disc was placed at a relative humidity of 50% for 24 hours was equal to or less than 6 mm. 9. The molded article 'is obtained by molding the liquid crystalline polymer composition of any one of the claims 1 to 8. H) · The molded article of claim 9 It is selected from the group consisting of switches, relays, connectors, wafers, optical readers, inverter translators, and coil reels. 26 319703 200831584 VII. Designation of representative drawings: None (1) The representative representative of the case is: () Representative of the symbol elements of FIG briefly described: eight, when the case if the formula, please disclosed invention features most indicative of the formula: the formula of the case not represented. 319703