JP2009256415A - Nano whisker and resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nano whisker useful as an organic filler since high dimension stability effect and heat-resistance enhancement effect are given, toughness of a film is not reduced and low dielectric effect is obtained at a high frequency area when it is formulated to a thermoplastic resin, and a thermoplastic resin composition formulated with it. <P>SOLUTION: The nano whisker, i.e., a polymer of an aromatic hydroxycarboxylic acid having the whole length of at least 10 nm and less than 900 nm, and the thermoplastic resin composition obtained by formulating it to the thermoplastic resin are provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to nanowhiskers and resin compositions thereof.

  In recent years, high performance of resin materials has been demanded, and highly functional resins containing various fillers have been proposed. Among them, organic fillers are attracting attention from the environmental aspect.

  Among organic fillers made of organic polymers, whiskers made of aromatic polyester have a high crystal elastic modulus of 35 GPa and are known to be very useful as organic fillers for composite materials because of their reinforcing effects (for example, (See Patent Documents 1 to 4).

  Patent Documents 1 and 2 describe a method for producing whisker-like poly (p-oxybenzoyl) crystals, whisker-like poly (2-oxy-6-naphthoyl) crystals, and a sheet-like shape produced by dispersing the solution in a thermoplastic resin. Although the composition is disclosed, the size of the whisker is as large as 8 to 200 μm.

  Patent Document 3 discloses polyester fiber coagulation obtained by polymerizing 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4′-hydroxy-4-biphenylcarboxylic acid, compounds having these substituents, and acetyl compounds. Although the aggregate is described, the size of the fiber aggregate is as large as 2 to 4 μm in length.

  Patent Document 4 describes fibril-like crystals obtained by polymerizing 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, hydroxynaphthoic acid, biphenyldicarboxylic acid, and the like. Is as large as 1 to 200 μm in length.

Such a large whisker has poor compatibility with the resin and has poor dispersibility, so that the reinforcing effect that should be obtained when well dispersed cannot be obtained sufficiently.
JP 61-136156 A JP-A 61-285217 JP 2007-177004 A JP 2007-254645 A

  The present invention is a liquid crystal polyester whisker that is very familiar with the resin because it is a nano-order size whisker, and gives a high dimensional stability effect and heat resistance improvement effect by the good dispersion of the whisker in the resin, It is an object of the present invention to provide a thermoplastic resin composition in which the toughness of a molded product, a film, a fiber, or the like is not lowered, can be reduced in weight, and has a high dielectric effect in a high frequency range.

  As a result of intensive studies to solve the above problems, the present inventors have found that when an aromatic hydroxycarboxylic acid is polymerized in a specific solvent system and in a temperature range, nano-order size whiskers can be generated, and the present invention has been achieved. did.

That is, the present invention is (1) a polymer of aromatic hydroxycarboxylic acid, a nanowhisker having a total length of 10 nm or more and less than 900 nm,
(2) The nanowhisker according to (1) above, wherein the thickness of the needle-like part is 1 nm or more and less than 100 nm,
(3) A thermoplastic resin composition in which the nanowhisker described in the above (1) or (2) is blended with a thermoplastic resin is provided.

  The nanowhisker of the present invention is a polymer of an aromatic hydroxycarboxylic acid.

  The aromatic hydroxycarboxylic acid herein has at least one aromatic ring, a hydroxyl group bonded to the aromatic ring, and at least one carboxylic acid group in the molecule. For example, 4-hydroxybenzoic acid, 3 -Hydroxybenzoic acid, 2-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, 4-hydroxy -4'-biphenylcarboxylic acid and the like. These may be used alone or in combination. Among these, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-hydroxy-4′-biphenylcarboxylic acid or a mixture thereof is preferable, and 4-hydroxybenzoic acid, 6-hydroxy-2 is more preferable. -Naphthoic acid or a mixture thereof, most preferably 4-hydroxybenzoic acid.

  The nanowhiskers of the present invention can be copolymerized with an aromatic diol that can be polymerized with an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, or the like as long as the properties are not affected.

  The polymer referred to in the present invention is a polymer in which a hydroxyl group and a carboxylic acid group of an aromatic hydroxycarboxylic acid are linked by generating an ester bond between molecules, and the number of molecules to be linked is at least 2 or more, More preferably, it is 3 or more, more preferably 5 or more.

  The nanowhisker referred to in the present invention has a total length of 10 nm or more and less than 900 nm. More preferably, the total length is 20 nm or more and 700 nm or less, and further preferably 50 nm or more and 500 nm or less.

  The whisker here refers to a needle-like structure, and may have a structure grown in a bowl shape from the crystal surface to the outside or a structure having only a needle, but its total length is 10 nm or more and less than 900 nm. The total length here refers to the length when the distance between the longest tips of whiskers is projected onto a plane, and can be measured by taking a photograph with a transmission electron microscope or a scanning electron microscope, for example.

  In the nanowhisker of the present invention, the thickness of the needle-like portion is preferably 1 nm or more and less than 100 nm, more preferably 3 nm or more and 80 nm or less, and further preferably 5 nm or more and 50 nm or less.

  The length (L) / diameter (D) of the needle-like part is preferably 1 to 100, more preferably 5 to 80, and still more preferably 20 to 50.

  The method for producing nanowhiskers of the present invention includes, for example, acetylating an aromatic hydroxycarboxylic acid and a phenolic hydroxyl group of a copolymer component that does not affect other properties using acetic anhydride, and the resulting aromatic hydroxycarboxylic acid. It can be obtained by polymerizing at 135-250 ° C. under slightly reduced pressure in a solvent in which nano whiskers that are acid polymers are slightly soluble.

  As a method for acetylating the phenolic hydroxyl group of the aromatic diol, acetic anhydride, a polymerization solvent and these monomers are allowed to coexist, for example, reflux heating is performed at a temperature of 120 to 160 ° C. for 0.5 to 5 hours, and then 160 to A method of polymerizing while distilling off the acetic acid produced by heating to about 250 ° C., or a monomer and acetylating the monomer and acetic anhydride by heating at a temperature of 120 to 160 ° C. for 0.5 to 5 hours. Then, the method of heating to about 160-250 degreeC and distilling off the acetic acid produced | generated by reaction, and adding a polymerization solvent after that, etc. are mentioned. Alternatively, by using a monomer acetylated in advance using a separate reactor, the acetic acid produced by reaction by heating to about 160 ° C. to 250 ° C. may be distilled off, and then polymerization may be performed by adding a polymerization solvent.

  The amount of acetic anhydride used for acetylation is preferably 1.02 to 1.15 times excess, more preferably 1.05 to 1.10 times excess relative to the equivalent amount of the phenolic hydroxyl group.

  The polymerization solvent to be used is liquid at room temperature from the viewpoint of handling properties, and preferably has a boiling point of 200 ° C. or higher, more preferably 250 ° C. or higher.

  The nanowhisker of the present invention is preferably slightly soluble. The slightly soluble as used herein refers to a state in which precipitation starts when the average degree of polymerization of the aromatic hydroxycarboxylic acid forming nanowhiskers becomes 3 or more at the polymerization temperature. By selecting such a solvent and polymerizing at 160 ° C. to 250 ° C., unprecedented fine crystals are precipitated, and nanowhiskers are obtained. As polymerization temperature, More preferably, it is 180-240 degreeC, More preferably, it is 200-230 degreeC.

  The average degree of polymerization can be measured, for example, by high pressure liquid chromatography using a pentafluorophenol solvent.

  In the case of producing the nanowhisker of the present invention, the slightly reduced pressure refers to 10 to 600 torr, more preferably 30 to 500 torr, and still more preferably 50 to 350 torr. A fine pressure reduction is preferable because nanowhisker formation easily proceeds.

  When manufacturing the nanowhisker of this invention, the polymerization solvent to be used may be the solvent (A) used mainly shown below, or the mixed solvent which mixed the solvent (B).

  The solvent (A) mainly used is specifically an aromatic compound such as diisopropylnaphthalene, diethylnaphthalene, ethyl-isopropylnaphthalene, cyclohexylbiphenyl, diethylbiphenyl, triethylbiphenyl, diphenyl ether, or paraffin having a boiling point of 200 ° C. or higher under normal pressure. Aliphatic compounds such as hydrocarbons. In particular, paraffinic hydrocarbons having a boiling point of 200 ° C. or higher, triethylbiphenyl, diphenyl ether and the like are preferable, and diphenyl ether is particularly preferable.

  Examples of the solvent (B) include halogen-substituted phenols, which are good solvents for nanowhiskers, and specifically include pentafluorophenol, 2,4-difluorophenol, orthochlorophenol, parachlorophenol, and metachloro. Examples include phenol, dichlorophenol, trichlorophenol, pentachlorophenol, 4-chloro-1-naphthol, and parachlorophenol is preferred.

  The mixing ratio of (A) and (B) is preferably 99/1 to 50/50, and more preferably 98/2 to 70/30.

  Nanowhiskers are self-deposited from the polymerization solvent. However, as a method for positively precipitating nanowhiskers, precipitation can be promoted by providing a magnetic current in the polymerization system or applying ultrasonic waves or laser.

  When the nanowhisker of the present invention is produced, the concentration of the aromatic hydroxycarboxylic acid and the aromatic diol and / or aromatic dicarboxylic acid copolymerized to such an extent that there is no problem in properties is 0.01 to 60 wt. % Is preferable, more preferably 0.1 to 40% by weight, and still more preferably 1 to 20% by weight.

  The thermoplastic resin composition of the present invention is a thermoplastic resin composition in which a nano whisker having a total length of 10 nm or more and less than 900 nm is blended with a thermoplastic resin. Furthermore, the thermoplastic resin composition of the present invention is preferably a thermoplastic resin composition in which nanowhiskers having a needle-like thickness of 1 nm or more and less than 100 nm are blended with a thermoplastic resin.

  Preferred specific examples of the thermoplastic resin in the present invention include polyesters, liquid crystal polyesters, polyamides, polyarylene sulfides, polyoxymethylenes, polyolefin polymers, non-crystalline resins such as polystyrene, polycarbonates, polyarylates, polyarylene oxides and the like. Examples thereof include crystalline resins. Among these, polyester, liquid crystal polyester, polyamide, polyarylene sulfide, polypropylene, polyethylene, and polycarbonate are preferable, and polyester, liquid crystal polyester, and polyamide are most preferable. Two or more of these thermoplastic resins may be used.

  The polyester is a polyester having an aromatic ring in a polymer chain unit, and is obtained by a condensation reaction mainly comprising an aromatic dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof). A polymer or copolymer is preferred. Examples of the dicarboxylic acid herein include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, Anthracene dicarboxylic acid, 4,4′-biphenyl carboxylic acid, 4,4′-diphenyl ether carboxylic acid, 1,2-bis (p-carboxyphenoxy) ethane, or an ester-forming derivative thereof may be used. In addition, if it is 30 mol% or less, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid and dimer acid, alicyclic rings such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid It may be substituted with a group carboxylic acid. The diol component includes aliphatic diols having 2 to 10 carbon atoms, that is, ethylene glycol, propylene glycol, butylene glycol, 1,5-pentane glycol, decamethylene glycol, 3-methyl-1,3-propenediol, neopentyl. Examples include, but are not limited to, glycol, cyclohexanedimethanol, cyclohexanediol, and the like. Specific examples of preferred polyesters include polyethylene terephthalate, polybutylene terephthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4′-dicarboxylate, polyethylene-2,6-naphthalate, poly-1,4- Cyclohexane dimethylene terephthalate, etc. and polyethylene terephthalate / isophthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / sebacate, polybutylene terephthalate / decane dicarboxylate, poly-1,4-cyclohexanedimethylene terephthalate / isophthalate, etc. Polymerized polyester is exemplified. Among these, preferred polyesters include polybutylene terephthalate, polyethylene terephthalate, and poly-1,4-cyclohexanedimethylene terephthalate. Furthermore, polybutylene terephthalate is more preferable. The logarithmic viscosity of polybutylene terephthalate is preferably 0.9 to 1.3, more preferably 0.92 to 1.25. In addition, the logarithmic viscosity of polybutylene terephthalate can be obtained by dividing the logarithm of the relative viscosity obtained by using a 0.5% orthochlorophenol solution at 25 ° C. by the concentration.

  The liquid crystalline polyester is a polyester capable of forming an anisotropic melt phase, and is selected from, for example, aromatic oxycarbonyl units, aromatic and / or aliphatic dioxy units, aromatic and / or aliphatic dicarbonyl units, and the like. It is a liquid crystalline polyester which consists of a structural unit and forms an anisotropic melt phase.

  Examples of the aromatic oxycarbonyl unit include a structural unit generated from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and the like, and examples of the aromatic and / or aliphatic dioxy unit include 4,4′- Dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2, Structural units formed from 2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, aromatic and / or aliphatic di Examples of the carbonyl unit include te Phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 1,2-bis (2-chloro) Phenoxy) ethane-4,4′-dicarboxylic acid and 4,4′-diphenyl ether dicarboxylic acid, adipic acid, sebacic acid and the like.

  Specific examples of the liquid crystalline polyester include a liquid crystalline polyester composed of a structural unit generated from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, a structural unit generated from p-hydroxybenzoic acid, and 6-hydroxy-2. A structural unit produced from naphthoic acid, a liquid crystalline polyester comprising a structural unit produced from an aromatic dihydroxy compound, an aromatic dicarboxylic acid and / or an aliphatic dicarboxylic acid, a structural unit produced from p-hydroxybenzoic acid, 4, 4 A liquid crystalline polyester comprising a structural unit produced from a structural unit produced from '-dihydroxybiphenyl, an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid and / or an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, p-hydroxybenzoic acid Structural units generated from acids, 4,4 ' Liquid crystalline polyester comprising structural units generated from dihydroxybiphenyl, structural units generated from hydroquinone, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid and / or structural units generated from aliphatic dicarboxylic acids such as adipic acid and sebacic acid , A structural unit produced from p-hydroxybenzoic acid, a structural unit produced from ethylene glycol, a liquid crystalline polyester comprising a structural unit produced from terephthalic acid and / or isophthalic acid, a structural unit produced from p-hydroxybenzoic acid, ethylene A liquid crystalline polyester comprising a structural unit produced from glycol, a structural unit produced from 4,4′-dihydroxybiphenyl, a structural unit produced from an aliphatic dicarboxylic such as terephthalic acid and / or adipic acid, sebacic acid, Structural units generated from loxybenzoic acid, structural units generated from ethylene glycol, structural units generated from aromatic dihydroxy compounds, structures generated from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid Examples thereof include liquid crystalline polyester composed of units.

  Particularly preferred are liquid crystalline polyesters composed of the following structural units (I), (II), (III), (IV) and (V).

  The structural unit (I) is a structural unit generated from p-hydroxybenzoic acid, the structural unit (II) is a structural unit generated from 4,4′-dihydroxybiphenyl, and the structural unit (III) is generated from hydroquinone. The structural unit, the structural unit (IV) represents a structural unit produced from terephthalic acid, and the structural unit (V) represents a structural unit produced from isophthalic acid.

  The structural unit (I) is 65 to 80 mol%, more preferably 68 to 75 mol%, based on the total of the structural units (I), (II) and (III). Moreover, structural unit (II) is 60 to 75 mol% with respect to the sum total of structural units (II) and (III), More preferably, it is 65 to 73 mol%. The structural unit (IV) is 60 to 92 mol%, preferably 60 to 70 mol%, more preferably 62 to 68 mol%, based on the total of the structural units (IV) and (V). .

  In particular, when the structural unit (IV) is 62 to 68 mol% with respect to the total of the structural units (IV) and (V), the moldability, which is a characteristic of the present invention, is preferably expressed in a balanced manner.

  The sum of structural units (II) and (III) and (IV) and (V) is substantially equimolar, but an excess of carboxylic acid component or hydroxyl component is added to control the end groups of the polymer. May be. That is, “substantially equimolar” means that the unit constituting the polymer main chain excluding the terminal is equimolar, but the unit constituting the terminal is not necessarily equimolar.

  In the thermoplastic resin composition of the present invention, the method for producing the liquid crystalline polyester preferably used can be produced according to a known polycondensation method of polyester.

For example, in the production of liquid crystalline polyester, the following production method is preferably exemplified.
(1) A method for producing a liquid crystalline polyester from p-acetoxybenzoic acid and 4,4′-diacetoxybiphenyl, diacetoxybenzene, terephthalic acid and isophthalic acid by a deacetic acid condensation polymerization reaction.
(2) p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone and terephthalic acid, isophthalic acid is reacted with acetic anhydride to acylate the phenolic hydroxyl group, and then the liquid crystalline polyester is subjected to deacetic acid polycondensation reaction. How to manufacture.
(3) A method for producing a liquid crystalline polyester from a phenyl ester of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, and diphenyl ester of isophthalic acid by a dephenol polycondensation reaction.
(4) A predetermined amount of diphenyl carbonate is reacted with p-hydroxybenzoic acid and aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid to form diphenyl ester, and then aromatics such as 4,4′-dihydroxybiphenyl and hydroquinone. A method for producing a liquid crystalline polyester by adding a group dihydroxy compound and dephenol polycondensation reaction.

  Among them, p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid are reacted with acetic anhydride to acylate the phenolic hydroxyl group, and then the liquid crystalline polyester is obtained by deacetic acid polycondensation reaction. The manufacturing method is preferred.

  Furthermore, the total amount of 4,4'-dihydroxybiphenyl and hydroquinone and the total amount of terephthalic acid and isophthalic acid are substantially equimolar. The amount of acetic anhydride used is preferably 1.15 equivalents or less, more preferably 1.10 equivalents or less of the total of the phenolic hydroxyl groups of p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl and hydroquinone. Preferably, the lower limit is 1.0 equivalent or more.

  When producing the liquid crystalline polyester of the present invention by a deacetic acid polycondensation reaction, a melt polymerization method in which the polycondensation reaction is completed by reacting under reduced pressure at a temperature at which the liquid crystalline polyester melts is preferable. For example, in a reaction vessel equipped with a predetermined amount of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid, acetic anhydride, a stirring blade, a distillation pipe, and a discharge port at the bottom. There is a method in which the reaction is completed after charging and heating under stirring in a nitrogen gas atmosphere to acetylate the hydroxyl group, raising the temperature to the melting temperature of the liquid crystalline polyester, and performing polycondensation under reduced pressure. The conditions for the acetylation are usually 130 to 300 ° C., preferably 135 to 200 ° C., usually 1 to 6 hours, preferably 140 to 180 ° C. for 2 to 4 hours. The polycondensation temperature is a melting temperature of the liquid crystalline polyester, for example, in the range of 250 to 350 ° C., and preferably a melting point of the liquid crystalline polyester + 10 ° C. or higher. The degree of vacuum during polycondensation is usually 0.1 mmHg (13.3 Pa) to 20 mmHg (2660 Pa), preferably 10 mmHg (1330 Pa) or less, more preferably 5 mmHg (665 Pa) or less. In addition, although acetylation and polycondensation may be performed continuously in the same reaction vessel, acetylation and polycondensation may be performed in different reaction vessels.

The obtained polymer is pressurized in the reaction vessel to, for example, approximately 1.0 kg / cm ² (0.1 MPa) at a temperature at which it melts, and discharged in a strand form from the discharge port provided in the lower portion of the reaction vessel. Can do. The melt polymerization method is an advantageous method for producing a uniform polymer, and an excellent polymer with less gas generation can be obtained, which is preferable.

  When producing the liquid crystalline polyester of the present invention, the polycondensation reaction can be completed by a solid phase polymerization method. For example, the polymer or oligomer of the liquid crystalline polyester of the present invention is pulverized by a pulverizer and the melting point of the liquid crystalline polyester is −5 ° C. to the melting point −50 ° C. (for example, 200 to 300 ° C.) under a nitrogen stream or under reduced pressure. A method of heating in the range for 1 to 50 hours, polycondensing to a desired degree of polymerization, and completing the reaction can be mentioned. Solid phase polymerization is an advantageous method for producing polymers with a high degree of polymerization.

  The polycondensation reaction of the liquid crystalline polyester proceeds even without a catalyst, but metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and magnesium metal can also be used.

  The liquid crystalline polyester preferably used in the thermoplastic resin composition of the present invention preferably has a number average molecular weight of 3,000 to 25,000, more preferably 5,000 to 20,000, more preferably It is in the range of 8,000 to 18,000.

  The number average molecular weight can be measured by GPC-LS (gel permeation chromatography-light scattering) method using a solvent in which liquid crystalline polyester is soluble.

  The melt viscosity of the liquid crystalline polyester in the thermoplastic resin composition of the present invention is preferably 1 to 200 Pa · s, more preferably 10 to 200 Pa · s, and particularly preferably 10 to 100 Pa · s.

  The melt viscosity is a value measured by a Koka flow tester under the condition of melting point of liquid crystalline polyester + 10 ° C. and shear rate of 1,000 / s.

  In the present invention, the melting point (Tm) refers to the endothermic peak temperature (Tm1) observed when the polymer having been polymerized is measured under a temperature rising condition from room temperature to 20 ° C./min in differential calorimetry. , After being held at a temperature of Tm1 + 20 ° C. for 5 minutes, once cooled to room temperature under a temperature decrease condition of 20 ° C./min, and then endothermic peak temperature (Tm2) observed when measured again under a temperature increase condition of 20 ° C./min Point to.

  In the thermoplastic resin composition of the present invention, polyamide can be preferably used as the thermoplastic resin.

  The polyamide is obtained from ω-amino acid or ω-lactam, or from diamine or m-xylenediamine and dicarboxylic acid such as adipic acid, sebacic acid, dodecanedioic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, etc. These are homopolymers, copolymers, and mixed polymers. Preferred polyamides include homopolyamides such as nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, and adipic acid / terephthalic acid / hexamethylenediamine, adipic acid / 1,4-cyclohexanedicarboxylic acid / hexamethylenediamine, adipine Examples thereof include copolymer polyamides such as acid / 1,3-cyclohexanedicarboxylic acid / hexamethylenediamine, terephthalic acid / isophthalic acid / hexamethylenediamine / bis (paraaminocyclohexyl) methane.

  In the thermoplastic resin composition of the present invention, polyarylene sulfide can be preferably used as the thermoplastic resin.

  The polyarylene sulfide is obtained by bonding an aromatic ring and sulfur. Preferred polyarylene sulfides include polyparaphenylene sulfide, which may be partially branched.

  In the thermoplastic resin composition of the present invention, polyoxymethylene can be preferably used as the thermoplastic resin.

  Examples of the polyoxymethylene include a polyoxymethylene homopolymer and a copolymer in which most of the main chain is composed of oxymethylene chains.

  In the thermoplastic resin composition of the present invention, a polyolefin polymer can be preferably used as the thermoplastic resin.

  Examples of the polyolefin polymer include homopolymers or copolymers mainly composed of repeating units formed from α-olefins such as ethylene and propylene. For example, homopolymers of propylene, homopolymers of ethylene, and ethylene. Block or random copolymer obtained by copolymerizing other α-olefin (for example, propylene, butene-1, etc.), specifically, copolymer of ethylene and α-olefin having 3 or more carbon atoms (for example, ethylene / propylene copolymer) , Ethylene / butene-1 copolymer, etc.), a copolymer comprising ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated diene (for example, ethylene / propylene / 1,4-hexadiene copolymer, ethylene / propylene / Dicyclopentadiene copolymer, ethylene / propylene / ethylene Isopropylidene norbornene copolymer) and the like, which can be used singly or two or more. Preferred polyolefin polymers include polypropylene homopolymers, polyethylene homopolymers, copolymers of ethylene having an ethylene content of 50 mol% or more and α-olefins having 3 or more carbon atoms (for example, ethylene / propylene copolymers, ethylene / butene- 1 copolymer, etc.), propylene / ethylene copolymer having an ethylene content of 30 mol% or less, elastomer having an ethylene content of 50 wt% or less, an α-olefin having 3 or more carbon atoms and a non-conjugated diene, and polypropylene A composition comprising a homopolymer, a composition comprising an elastomeric copolymer comprising 50% by weight or less of ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated diene, and a polyethylene homopolymer, and a propylene content of 30% by mole or less. A propylene / ethylene copolymer is mentioned.

  Further, the polyolefin polymer is more preferably modified with an unsaturated carboxylic acid or a derivative thereof. Examples of the unsaturated carboxylic acid to be modified include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, 5-norbornene-2,3-dicarboxylic acid, tetrahydrophthalic acid, and dimer acid. Examples of the derivatives include anhydrides, esters, amides, imides and salts of the above acids.

  In the thermoplastic resin composition of the present invention, preferably, polystyrene can be used as the thermoplastic resin.

  In addition to polystyrene homopolymers, the polystyrene includes HIPS (high impact polystyrene), AS (acrylonitrile / styrene copolymer), ABS (acrylonitrile / butadiene / styrene copolymer), MBS (methyl methacrylate / butadiene / styrene). Copolymer) and the like.

  In the thermoplastic resin composition of the present invention, polycarbonate or polyarylate can be preferably used as the thermoplastic resin.

  Examples of the polycarbonate or polyarylate include hydrocarbon derivatives having bis (4-hydroxyphenyl), bis (3,5-dialkyl-4-hydroxyphenyl) or bis (3,5-dihalo-4-hydroxyphenyl) substitution. Those based are preferred, polycarbonates or polyarylates based on 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) being particularly preferred. Moreover, these may contain a small amount of copolymerization components.

  In the thermoplastic resin composition of the present invention, polyarylene oxide can be preferably used as the thermoplastic resin.

  Examples of the polyarylene oxide include poly (2,6-dimethyl-1,4-phenylene) ether, 2,6-dimethylphenol / 2,4,6-trimethylphenol copolymer, 2,6-dimethylphenol / 2. 3,6-triethylphenol copolymer and the like. These can be used after being graft-reacted with an unsaturated carboxylic acid or a derivative thereof and modified. Examples of the unsaturated carboxylic acid to be modified include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, 5-norbornene-2,3-dicarboxylic acid, tetrahydrophthalic acid, and dimer acid. Examples of the derivatives include anhydrides, esters, amides, imides and salts of the above acids. Moreover, styrene resin, such as a polystyrene and an impact-resistant polystyrene, can be added to polyarylene oxide.

  The thermoplastic resin composition of the present invention is a thermoplastic resin composition in which a nano whisker having a total length of 10 nm or more and less than 900 nm is blended with a thermoplastic resin.

  The amount of nanowhiskers to the thermoplastic resin is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, and still more preferably 100 parts by weight of the thermoplastic resin. 1 to 20 parts by weight.

  When nano whisker is blended with 0.1 to 50 parts by weight of nano whisker with respect to 100 parts by weight of thermoplastic resin, aggregation and dispersion failure do not occur, and the effect of improving dimensional stability and dielectric properties is remarkably obtained. preferable.

  A filler can be arbitrarily used in the thermoplastic resin composition of the present invention.

  As the filler, for example, a filler such as a fiber, a plate, a powder, or a granule can be used. Specifically, glass fibers, PAN and pitch carbon fibers, stainless fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers and liquid crystalline polyester fibers, gypsum fibers, ceramic fibers, Fibrous and whisker-like fillers such as asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker , Mica, talc, kaolin, silica, glass beads, glass flakes, clay, molybdenum disulfide, wollastonite, titanium oxide, zinc oxide, calcium polyphosphate and graphite, and the like. The above-mentioned filler used in the present invention can be used by treating the surface thereof with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.) or other surface treatment agents. .

  Among these fillers, glass fiber is particularly preferably used from the viewpoint of balance between availability and mechanical strength. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing resin, and can be selected from, for example, long fiber type or short fiber type chopped strands and milled fibers. Two or more of these can be used in combination. As the glass fiber used in the present invention, a weakly alkaline glass fiber is excellent in terms of mechanical strength and can be preferably used. In particular, glass fibers having a silicon oxide content of 50 to 80% by weight are preferably used, and more preferably 65 to 77% by weight. The glass fiber is preferably treated with an epoxy-based, urethane-based, acrylic-based coating or sizing agent, and epoxy-based is particularly preferable. Further, it is preferably treated with a silane-based or titanate-based coupling agent or other surface treatment agent, and an epoxysilane or aminosilane-based coupling agent is particularly preferable.

  The glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

  The blending amount of the filler is usually 30 to 100 parts by weight, preferably 40 to 60 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

  The thermoplastic resin composition of the present invention includes an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and substituted products thereof), an ultraviolet absorber (for example, resorcinol, salicylate), phosphorous acid Colorants including salts, anti-coloring agents such as hypophosphite, lubricants and mold release agents (such as montanic acid and its metal salts, its esters, their half esters, stearyl alcohol, stearamide and polyethylene wax), dyes and pigments Carbon black, crystal nucleating agent, plasticizer, flame retardant (bromine flame retardant, phosphorus flame retardant, red phosphorus, silicone flame retardant, etc.), flame retardant aid, antistatic agent, etc. The conventional additive and a polymer other than the thermoplastic resin can be blended to further impart predetermined characteristics.

  As a method of blending nanowhiskers, optional fillers, and additives into the thermoplastic resin, dry blending, solution blending methods, addition during polymerization of the thermoplastic resin, melt kneading, and the like can be used, and melt kneading is preferred.

  A known method can be used for melt kneading. For example, using a Banbury mixer, rubber roll machine, kneader, single-screw or twin-screw extruder, etc., the resin composition can be melt-kneaded at a temperature not lower than the melting point of the thermoplastic resin and not higher than + 50 ° C. to obtain a resin composition. Among these, a twin screw extruder is preferable.

  As a kneading method, 1) a batch kneading method with a thermoplastic resin, nano whisker, an optional filler, and other additives, 2) a thermoplastic resin composition containing nano whisker in a high concentration in the thermoplastic resin. (Master Pellet), then add a thermoplastic resin, optional fillers and other additives to the specified concentration (Master Pellet Method), 3) With a thermoplastic resin and optional ingredients Any method may be used, such as a partial addition method in which a part of a certain other additive is once kneaded and then the remaining nanowhiskers, a filler as an optional component, and other additives are added.

  The thermoplastic resin composition of the present invention thus obtained has high dimensional stability and heat resistance due to good dispersion of nano-order size whiskers, and has a low dielectric constant in a high frequency range.

  The thermoplastic resin composition of the present invention is a molded article or sheet having excellent surface appearance (color tone), mechanical properties, heat resistance, and flame retardancy by a molding method such as normal injection molding, extrusion molding or press molding. It can be processed into pipes, films, fibers and the like.

  The thermoplastic resin composition thus obtained includes, for example, an air flow meter, an air pump, a thermostat housing, an engine mount, an ignition hobbin, an ignition case, a clutch bobbin, a sensor housing, an idle speed control valve, a vacuum switching valve, and an ECU housing. , Vacuum pump case, inhibitor switch, rotation sensor, acceleration sensor, distributor cap, coil base, actuator case for ABS, radiator tank top and bottom, cooling fan, fan shroud, engine cover, cylinder head cover, oil cap, oil pan , Oil filter, fuel cap, fuel strainer, distributor Cap, vapor canister housing, air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes such as underhood parts for automobiles, torque control levers, Safety belt parts, register blades, washer levers, window regulator handles, knobs for window regulator handles, passing light levers, sun visor brackets, various motor housings and other automotive interior parts, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers , Hood louver, wheel cover, wheel cap, grill apron cover frame, lamp reflector, run Automotive exterior parts such as bezels and door handles, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors and other automotive connectors, relay cases, coil bobbins, optical pickup chassis, motor cases, laptop housings and internal parts, CRT Display housings and internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile PCs, handheld mobiles, recording media (CD, DVD, PD, FDD, etc.) drive housings and internal parts, copy Examples thereof include electrical and electronic parts such as machine housings and internal parts, facsimile housings and internal parts, and parabolic antennas. Furthermore, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video camera parts, video equipment parts such as projectors, laser discs (registered trademark), compact discs (CD), CD-ROMs , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts , Etc., home and office electrical appliance parts. Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, Optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders , Electrical and electronic parts such as transformer members, coil bobbins, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels, Hot walls, adjusters, plastic bundles, ceiling fishing gear, staircases, doors, floors and other building materials, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other marine products, vegetation nets, vegetation mats, weedproof bags, protection Grass net, curing sheet, slope protection sheet, fly ash holding sheet, drain sheet, water retention sheet, sludge / sludge dehydration bag, concrete formwork and other civil engineering related parts, gears, screws, springs, bearings, levers, key stems, cams , Ratchet, roller, water supply parts, toy parts, fans, tegus, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches and other mechanical parts, multi-films, tunnel films, bird protection sheets, vegetation protection Non-woven fabric, seedling pots, vegetation piles, seed string tape, germination sheets, house lining sheets, farmhouse fasteners, slow-release fertilizers, root-proof sheets, garden nets Insect-proof nets, infant tree nets, printed laminates, fertilizer bags, sample bags, sandbags, animal damage prevention nets, incentive strings, windproof nets and other agricultural materials, paper diapers, sanitary products packaging materials, cotton swabs, towels, toilet seat wipes, etc. Medical supplies such as medical supplies, non-woven fabric for medical use (stitching reinforcing material, anti-adhesion film, prosthetic repair material), wound dressing material, wound tape bandage, sticking material base fabric, surgical suture, fracture reinforcing material, medical film, etc. , Calendars, stationery, clothing, food packaging films, trays, blisters, knives, forks, spoons, tubes, plastic cans, pouches, containers, tanks, baskets, etc., hot-fill containers, microwave ovens Containers for cooking Cosmetic containers, wraps, foam buffers, paper lami, shampoo bottles, beverage bottles, cups, candy packaging, shrink labels, lids Materials, envelopes with windows, fruit baskets, hand cut tape, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, containers and packaging such as wrapping films for electrical and electronic parts, natural fibers Various clothing such as composites, polo shirts, T-shirts, inners, uniforms, sweaters, socks, ties, curtains, chairs, carpets, tablecloths, futons, wallpaper, furoshiki and other interior goods, carrier tapes, prints, thermal Film for stencil printing, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather, nonwoven fabric, hot melt binder, magnetic material, zinc sulfide, electrode material powder, etc. Binders, optical elements, conductive embossed tape, C tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, draining net, body towel, hand towel, tea pack, drainage filter, clear file, coating agent, adhesive, bag, chair, table, Useful as a cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter, wire harness connector, SMJ connector, PCB connector, door grommet connector, etc. It is particularly useful as a connector for various automobiles.

  Hereinafter, the present invention will be described in more detail by way of examples.

  The characteristics in the examples were measured by the following methods.

(1) Total length of nanowhiskers and diameter of needle-like part 50 samples of the obtained nanowhiskers were observed using a scanning electron microscope (JSM-5300 manufactured by JEOL), and samples were observed by Pt / Pd ion sputtering. Images were taken, the longest distance between the needle tips was measured, and the total length was calculated as a number average value. Similarly, the diameter of 50 needle-like parts was measured, and the diameter was calculated as a number average value.

(2) Dispersion state in thermoplastic resin An arbitrary cross section of the thermoplastic resin composition is cut with a diamond knife and observed with a transmission electron microscope (JEMOL JEM-3100F), and three in a 50 μm square cross section are observed. The number of aggregates in which the above whiskers were aggregated was evaluated.

(3) Dimensional stability A square-shaped product (80 mm x 80 mm x 2 mm thick) was formed, and the center part was cut perpendicularly to the flow direction into a prismatic shape with a width of 1 mm x length of 10 mm x thickness of 2 mm. Was measured under the conditions of 30 ° C. → 5 ° C./min→100° C. using TMA (Seiko Denshi Kogyo SSC-5020) to obtain the linear expansion coefficient.

(4) Heat resistance In accordance with JIS K 7207, a test piece having a thickness of 3 mm, a length of 110 mm and a width of 12.6 mm was injection-molded, annealed at 120 ° C. for 4 hours, and then subjected to a bending stress of 18.5 kgf / cm ² . The deflection temperature under load (HDT) was measured.

(5) Dielectric characteristics The dielectric constant was evaluated at a temperature of 25 ° C. and a frequency of 10 GHz using a perturbation type cavity resonance method dielectric property measurement system for ultra-thin sheets (manufactured by Keycom) with a closed sample hole.

(6) Toughness A film having a thickness of 0.2 mm and a thickness of 200 mm was obtained by press molding at a melting point of the thermoplastic resin + 10 ° C. The film was subjected to a 180 ° bending test, and the number of times until breakage was evaluated.

Nano Whisker (A)
Example 1
In a 0.5 L reaction vessel equipped with a stirring blade and a distillation tube, 13.8 g (0.1 mol) of 4-hydroxybenzoic acid and 11.2 g of acetic anhydride (1.10 times equivalent to phenolic hydroxyl group), 76.2 g of diphenyl ether and 2 g of parachlorophenol (total solvent amount corresponding to 15% by weight as the concentration of 4-hydroxybenzoic acid) were weighed.

  The acetylation reaction was carried out at 140 ° C. for 2 hours under a nitrogen stream, and then the temperature was raised to 180 ° C. over 1 hour, the pressure was reduced to 650 torr and stirring was continued for 1 hour, and acetic acid was distilled off while diphenyl ether was returned. . Thereafter, the temperature was raised to 200 ° C. in 0.5 hours, the pressure was reduced to 500 torr, the heating and stirring was continued for 1 hour, the stirring was stopped, and ultrasonic waves were applied for 10 minutes.

  After cooling the solution, the solution was filtered using a membrane filter, washed with acetone, and then vacuum dried to collect nanowhiskers. The recovered nanowhiskers were subjected to solid phase polymerization under high vacuum at 200 ° C. for 2 hours at 220 ° C. for 2 hours and at 250 ° C. for 3 hours to obtain nanowhiskers (A-1).

  The average degree of polymerization measured by high pressure liquid chromatography with a pentafluorophenol solvent was 41.

Example 2
In a 0.5 L reaction vessel equipped with a stirring blade and a distilling tube, 13.8 g (0.1 mol) of 4-hydroxybenzoic acid and 11.2 g of acetic anhydride (1.10 times equivalent to phenolic hydroxyl group) were added. Weighed. The acetylation reaction was carried out at 140 ° C. for 2 hours under a nitrogen stream, and then the temperature was raised to 200 ° C. over 1 hour, the pressure was reduced to 500 torr, and stirring was continued for 1 hour to distill off acetic acid.

  Add 76.2 g of diphenyl ether and 2 g of parachlorophenol (total solvent amount equivalent to 15% by weight as the concentration of 4-hydroxybenzoic acid), adjust the internal temperature to 180 ° C., reduce the pressure to 650 torr and stir for 1 hour. Then, acetic acid was further distilled off while diphenyl ether was distilled off. Thereafter, the temperature was raised to 200 ° C. in 0.5 hours, the pressure was reduced to 500 torr, and the stirring was stopped after 1 hour of heating and stirring.

  After cooling the solution, the solution was filtered using a membrane filter, washed with acetone, and then vacuum dried to collect nanowhiskers. The recovered nanowhiskers were subjected to solid state polymerization under high vacuum at 200 ° C. for 2 hours at 220 ° C. for 2 hours and at 250 ° C. for 3 hours to obtain nanowhiskers (A-2).

  The average degree of polymerization measured by high pressure liquid chromatography with a pentafluorophenol solvent was 37.

Example 3
In a 0.5 L reaction vessel equipped with a stirring blade and a distillation tube, 13.8 g (0.1 mol) of 4-hydroxybenzoic acid and 11.2 g of acetic anhydride (1.10 times equivalent to phenolic hydroxyl group) and 78.2 g of diphenyl ether (total amount of solvent corresponding to 15% by weight as the concentration of 4-hydroxybenzoic acid) was weighed. The acetylation reaction was carried out at 140 ° C. for 2 hours under a nitrogen stream, and then the temperature was raised to 180 ° C. over 1 hour, the pressure was reduced to 650 torr, and stirring was continued for 1 hour to distill off acetic acid. Thereafter, the temperature was raised to 200 ° C. in 0.5 hours, the pressure was reduced to 500 torr, the stirring was continued for 1 hour, and then the stirring was stopped.

  After the solution was cooled, it was filtered using a membrane filter, washed with acetone, and then vacuum dried to collect nanowhiskers (A-3). The recovered nanowhiskers were subjected to solid state polymerization under high vacuum at 200 ° C. for 2 hours at 220 ° C. for 2 hours and at 250 ° C. for 3 hours to obtain nanowhiskers (A-3).

  The average degree of polymerization measured by high pressure liquid chromatography with a pentafluorophenol solvent was 38.

Example 4
In a 0.5 L reaction vessel equipped with a stirring blade and a distillation tube, 11.1 g (0.067 mol) of 4-hydroxybenzoic acid, 3.72 g (0.0167 mol) of 4,4′-dihydroxybiphenyl, terephthalic acid 3.32 g (0.0167 mol) and 11.2 g of acetic anhydride (1.10 times equivalent to phenolic hydroxyl group), 76.2 g of diphenyl ether and 2 g of parachlorophenol (15% by weight as the concentration of 4-hydroxybenzoic acid) A considerable amount of total solvent) was weighed.

  The acetylation reaction was carried out at 140 ° C. for 2 hours under a nitrogen stream, and then the temperature was raised to 180 ° C. over 1 hour, the pressure was reduced to 650 torr and stirring was continued for 1 hour, and acetic acid was distilled off while diphenyl ether was returned. . Thereafter, the temperature was raised to 200 ° C. in 0.5 hours, the pressure was reduced to 500 torr, the heating and stirring was continued for 1 hour, the stirring was stopped, and ultrasonic waves were applied for 10 minutes.

  After cooling the solution, the solution was filtered using a membrane filter, washed with acetone, and then vacuum dried to collect nanowhiskers. The recovered nanowhiskers were subjected to solid state polymerization under high vacuum at 200 ° C. for 2 hours at 220 ° C. for 2 hours and at 250 ° C. for 3 hours to obtain nanowhiskers (A-4).

  The average degree of polymerization measured by high pressure liquid chromatography with a pentafluorophenol solvent was 38.

Comparative Example 1
Fibrillar crystals (D-5) synthesized according to Example 1 of Japanese Patent Application Laid-Open No. 2007-254645 (total length: 9.5 μm, needle-shaped portion diameter: 1.8 μm)

Examples 5-12, Comparative Examples 2-6
The thermoplastic resin (B) and filler (C) used in Examples 5 to 12 and Comparative Examples 2 to 6 are described below.

Thermoplastic resin (B)
B-1: Polycarbonate (PC): Iupilon S-3000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.

B-2: Liquid crystalline resin (LCP)
p-Hydroxybenzoic acid 870 g (6.300 mol), 4,4'-dihydroxybiphenyl 327 g (1.890 mol), hydroquinone 89 g (0.810 mol), terephthalic acid 292 g (1.755 mol), isophthalic acid 157 g (0.945 mol) and 1367 g of acetic anhydride (1.03 equivalents of total phenolic hydroxyl groups) were added and reacted at 145 ° C. for 2 hours with stirring in a nitrogen gas atmosphere, and then heated to 320 ° C. over 4 hours. did. Thereafter, the polymerization temperature was maintained at 320 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction was continued for 90 minutes, and the polycondensation was completed when the torque reached 12 kg · cm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer was discharged to a strand-like material via a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  In this liquid crystalline polyester (B-2), the p-oxybenzoate unit was 70 mol% based on the total of the p-oxybenzoate unit, the 4,4′-dioxybiphenyl unit and the 1,4-dioxybenzene unit. , 4′-dioxybiphenyl units are 70 mol% based on the total of 4,4′-dioxybiphenyl units and 1,4-dioxybenzene units, and terephthalate units are based on the total of terephthalate units and isophthalate units. It consists of 65 mol%, Tm (melting point of liquid crystalline polyester) is 314 ° C., liquid crystal starting temperature is 295 ° C., number average molecular weight is 12,000, and Koka type flow tester (orifice 0.5φ × 10 mm) is used. The melt viscosity measured at a temperature of 324 ° C. and a shear rate of 1000 / s was 20 Pa · s.

  The melting point (Tm) is determined by differential calorimetry. After observing the endothermic peak temperature (Tm1) observed when the polymer is measured at room temperature to 20 ° C./minute, the temperature is maintained at Tm1 + 20 ° C. for 5 minutes. Then, after cooling to room temperature under a temperature drop condition of 20 ° C./minute, the endothermic peak temperature (Tm 2) observed when measured again under a temperature rise condition of 20 ° C./minute was used.

  The liquid crystal starting temperature was measured with a shear stress heating device (CSS-450) at a shear rate of 1,000 (1 / second), a heating rate of 5.0 ° C./min, and an objective lens of 60 times. The starting temperature was taken as the measurement.

  The molecular weight was measured by GPC-LS (gel permeation chromatography-light scattering) method using pentafluorophenol which is a solvent in which liquid crystalline polyester is soluble, and the number average molecular weight was determined.

Filler (C)
C-1 E glass chopped strand (ECS-03T747GH) manufactured by Nippon Electric Glass.

  It describes below about the thermoplastic resin composition described in Examples 5-12 and Comparative Examples 2-6.

  A side feeder is installed in C3 part of cylinder C1 (former feeder side heater) to C6 (die side heater) in TEM35B type twin screw extruder (meshing type same direction) manufactured by Toshiba Machine, and a vacuum vent is provided in C5 part. installed.

  Using a screw arrangement in which kneading blocks are incorporated in C2 part and C4 part, 100 parts by weight of thermoplastic resin (B-1 or B-2) is introduced from the hopper, and nano whisker (A- 1-4) and fibrillar crystals (D-1), and in some cases, filler (C-1) is charged from the side, the cylinder temperature is set to the melting point of the thermoplastic resin + 10 ° C., and melt-kneaded to form pellets. .

  The obtained pellets were dried with hot air and then subjected to a FANUC α30C injection molding machine (manufactured by FANUC) to obtain a molded product, which was evaluated as described above. The results are shown in Table 1.

  As is clear from Table 2, the nanowhisker of the present invention is very familiar with the thermoplastic resin, and has a high effect of improving dimensional stability, heat resistance, and dielectric properties because it is well dispersed.

  Moreover, it turns out that the film excellent in toughness is obtained also when the thermoplastic resin composition which mix | blended the nanowhisker of this invention is used as a film.

Claims (6)

A nanowhisker which is a polymer of aromatic hydroxycarboxylic acid and has a total length of 10 nm or more and less than 900 nm. The nanowhisker according to claim 1, wherein a thickness of the needle-like portion is 1 nm or more and less than 100 nm. The thermoplastic resin composition which mix | blended the nano whisker of Claim 1 or 2 with the thermoplastic resin. A molded article comprising the thermoplastic resin composition according to claim 3. A film comprising the thermoplastic resin composition according to claim 3. A fiber comprising the thermoplastic resin composition according to claim 3.