TW201932534A - Liquid crystal polyester composition, molded article and method for producing liquid crystal polyester composition - Google Patents

Abstract

A liquid crystal polyester composition including a liquid crystal polyester, and an olefin copolymer having a repeating unit derived from an [alpha]-olefin and a repeating unit derived from a glycidyl ester of an [alpha], [beta]-unsaturated acid, when the total content of the liquid crystal polyester and the olefin copolymer is 100% by mass, the content of the liquid crystal polyester is more than 80% by mass and not more than 95% by mass, and the content of the olefin copolymer is 5% by mass or more and less than 20% by mass, and the dispersion diameter of the olefin copolymer measured by the following measuring method is less than 0.8 [mu]m: [Measuring method] In the scanning electron microscopic image of the liquid crystal polyester composition, the circle equivalent diameters of 100 olefin copolymers are measured and the average value of the obtained values is calculated.

Description

Liquid crystal polyester composition, molded body, and method for producing liquid crystal polyester composition

The present invention relates to a liquid crystal polyester composition, a molded body, and a method for producing a liquid crystal polyester composition.

The present application claims priority based on Japanese Patent Application No. 2017-242144, filed on Dec.

Liquid crystal polyesters are known to have high fluidity and heat resistance and can be molded into molded articles having high dimensional accuracy. In general, the liquid crystal polyester is less used alone, and can be used in the form of a liquid crystal polyester composition containing a filler in order to satisfy characteristics (for example, bending strength) required for various uses. The forming system obtained from such a liquid crystal polyester composition is known to be lightweight and high in strength.

In recent years, in order to utilize the characteristics of the liquid crystal polyester as described above, liquid crystal polyester is being used in place of a material for forming a high-strength outer panel member for automobiles, in place of the current metal material. By using liquid crystal polyester as a material for forming an outer panel member for an automobile, it is possible to obtain an automobile outer panel member which is lighter than the prior art.

However, the above-mentioned molding system obtained from the liquid crystal polyester composition has a problem that "the punching strength is lower than that of the molded body obtained from the liquid crystal polyester monomer".

In order to solve the above problem, it is considered to use a liquid crystal polyester composition containing a rubber-like modified material. Patent Document 1 and Patent Document 2 describe a liquid crystalline resin composition containing a ruthenium-modified material.

Patent Document 1 discloses a liquid crystal resin composition in which at least one or more inorganic fillers selected from a fibrous filler such as glass fiber and a non-fibrous filler such as talc are selected from the group consisting of an olefin-based copolymer and The at least one copolymer of the styrene-based copolymer is formulated to the liquid crystalline resin so that the liquid crystalline resin is 65 to 93% by mass, the inorganic filler is 5 to 20% by mass, and the copolymer is 2 to 10% by mass. in.

Patent Document 2 discloses a liquid crystalline resin composition in which at least one of a plate-like filler such as mica, talc, and glass-flake, and at least one selected from the group consisting of an olefin-based copolymer and a styrene-based copolymer is copolymerized. The amount of the liquid crystalline resin is 64 to 78% by mass, the plate-like filler is 20 to 30% by mass, and the copolymer is 2 to 6% by mass.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5680788

[Patent Document 2] JP-A-2015-021110

However, when the liquid crystalline resin composition disclosed in Patent Document 1 and Patent Document 2 is to be used as a material for forming a large molded body such as an automobile outer panel member, it is necessary to further improve fluidity.

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a liquid crystal polyester composition, a molded body, and a method for producing a liquid crystal polyester composition which can be formed into a molded article having high punching strength and which has high fluidity.

In order to solve the above problems, the present invention includes the following aspects.

[1] A liquid crystal polyester composition comprising: a liquid crystal polyester; and an olefin-based copolymer containing a repeating unit derived from an α-olefin and a repeating unit derived from a glycidyl ester of an α,β-unsaturated acid; When the total content of the liquid crystal polyester and the olefin-based copolymer is 100% by mass, the content of the liquid crystal polyester is more than 80% by mass and 95% by mass or less, and the olefin-based copolymer is used. a content of 5% by mass or more and less than 20% by mass; the dispersion diameter of the olefin-based copolymer measured by the following measurement method is less than 0.8 μm;

[test methods]

In the scanning electron microscope image of the liquid crystal polyester composition, the equivalent circle diameter of 100 olefin copolymers was measured, and the average value of the obtained measured values was calculated.

[2] The liquid crystal polyester composition according to [1], wherein the liquid crystal polyester has a repeat represented by the following formula (1) with respect to the total amount of all the repeating units constituting the liquid crystal polyester. Unit 30% or more of 80% or less; (1)-O-Ar ¹ -CO-

(Ar ¹ represents a phenyl group, a naphthyl group or a biphenyl group. The hydrogen atom in the group represented by Ar ¹ may be independently substituted by a halogen atom, an alkyl group or an aryl group).

[3] A molded body formed from the liquid crystal polyester composition according to [1] or [2].

[4] A method for producing a liquid crystal polyester composition, comprising: a liquid crystal polyester, and a repeating unit comprising a repeating unit derived from an α-olefin and a glycidyl ester derived from an α,β-unsaturated acid; The olefin-based copolymer is melt-kneaded; wherein the melt-kneading is performed at a processing temperature in a temperature region of 10 ° C or more and 20 ° C or less with respect to a flow initiation temperature of the liquid crystal polyester. The speed is 3000s ^-1 or more and 10000s ^-1 or less.

According to an aspect of the present invention, it is possible to provide a liquid crystal polyester composition which can be formed into a molded article having high punching strength and has high fluidity, a molded article thereof, and a method for producing a liquid crystal polyester composition.

<Liquid crystal polyester composition>

The liquid crystal polyester composition of this embodiment contains a liquid crystal polyester and an olefin type copolymer.

In addition, in the present specification, a case where a mixture containing a liquid crystal polyester and an olefin-based copolymer is formed into a pellet shape is referred to as a "liquid crystal polyester composition".

The liquid crystal polyester composition of the present embodiment can be used as a material for forming a molded body to be described later.

[Liquid Crystal Polyester]

The liquid crystal polyester of the present embodiment is a liquid crystal polyester which exhibits liquid crystallinity in a molten state, and is preferably melted at a temperature of 250 ° C or more and 450 ° C or less. Further, the liquid crystal polyester of the present embodiment may be a liquid crystal polyester decylamine, a liquid crystal polyester ether, a liquid crystal polyester carbonate, or a polyester quinone. The liquid crystal polyester of the present embodiment is preferably a wholly aromatic liquid crystal polyester obtained by using only an aromatic compound as a raw material monomer.

Typical examples of the liquid crystal polyester of the present embodiment include an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and a group selected from the group consisting of an aromatic diol, an aromatic hydroxylamine, and an aromatic diamine. At least one compound is polymerized (polycondensed); a plurality of aromatic hydroxycarboxylic acids are polymerized; an aromatic dicarboxylic acid is selected from an aromatic diol, an aromatic hydroxylamine, and an aromatic A compound obtained by polymerizing at least one compound of a group consisting of diamines; and a polyester obtained by polymerizing a polyester such as polyethylene terephthalate with an aromatic hydroxycarboxylic acid. Among them, the aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, the aromatic diol, the aromatic hydroxyamine, and the aromatic diamine may be independently used as a part or all of the derivative capable of being polymerized. .

Examples of the polymerizable derivative of a compound having a carboxyl group such as an aromatic hydroxycarboxylic acid or an aromatic dicarboxylic acid include those in which a carboxyl group is converted into an alkoxycarbonyl group or an aryloxycarbonyl group (that is, Ester), a compound obtained by converting a carboxyl group into a haloformyl group (that is, an acid halide) and a carboxyl group to be converted into a fluorenyloxy group (that is, an acid anhydride). Such as aromatic hydroxycarboxylic acids, aromatic diols and aromatic hydroxy groups Examples of the polymerizable derivative of the amine-like compound having a hydroxyl group include those obtained by deuteration of a hydroxy group and conversion to a decyloxy group (that is, a hydrazine compound of a hydroxyl group). Examples of the polymerizable derivative of the compound having an amine group such as an aromatic hydroxylamine and an aromatic diamine include, for example, an amine group which is deuterated and converted into a mercapto group (that is, an amine). Base telluride).

The liquid crystal polyester of the present embodiment preferably has a repeating unit represented by the following formula (1) (hereinafter also referred to as "repeating unit (1)"), and more preferably has a repeating unit (1) and a following formula ( 2) The repeating unit (hereinafter also referred to as "repeating unit (2)") and the repeating unit shown in the following formula (3) (hereinafter also referred to as "repeating unit (3)").

(1)-O-Ar ¹ -CO-

(2)-CO-Ar ² -CO-

(3)-X-Ar ³ -Y-

(Ar ¹ represents a phenyl group, an anthranyl group or a phenyl group. Ar ² and Ar ³ each independently represent a phenyl group, a naphthyl group, a biphenyl group or a group represented by the following formula (4). X and Y each independently represent an oxygen atom or an imido group (-NH-). The hydrogen atom in the aforementioned group represented by Ar ¹ , Ar ² or Ar ³ may independently pass through a halogen atom, an alkyl group or an aryl group, respectively. Replace.)

(4)-Ar ⁴ -Z-Ar ⁵ -

(Ar ⁴ and Ar ⁵ each independently represent a phenyl or anthracenyl group. Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group or an alkylene group. Hydrogen in the aforementioned group represented by Ar ⁴ or Ar ⁵ The atoms may be independently substituted by a halogen atom, an alkyl group or an aryl group.)

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group and tertiary group. Butyl, n-hexyl, 2-ethylhexyl, n-octyl and n-decyl.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a 1-naphthyl group, and a 2-naphthyl group. When the hydrogen atom is substituted by such a group, the number thereof is preferably two or less each of the groups represented by each of Ar ¹ , Ar ² or Ar ³ , and more preferably one.

The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, an isopropylidene group, a n-butylene group, and a 2-ethylhexylene group.

The repeating unit (1) is derived from a repeating unit of a predetermined aromatic hydroxycarboxylic acid. The repeating unit (1) is preferably those in which Ar ¹ is a p-phenylene group (for example, a repeating unit derived from p-hydroxybenzoic acid), and Ar ¹ is a 2,6-anthranyl group (for example, from 6). - a repeating unit of -hydroxy-2-naphthoic acid).

Further, "derived from" in the present specification means that the chemical structure of a functional group which is favorably polymerized by a raw material monomer for polymerization is changed without causing other structural changes.

The repeating unit (2) is derived from a repeating unit of a given aromatic dicarboxylic acid. The repeating unit (2) is preferably a group in which Ar ² is a pendant phenyl group (for example, a repeating unit derived from terephthalic acid), and Ar ² is an exophenyl group (for example, derived from isophthalic acid). a repeating unit), wherein Ar ² is a 2,6-anthranyl group (for example, a repeating unit derived from 2,6-naphthalenedicarboxylic acid), and Ar ² is a diphenylether-4,4'-diyl group. (For example: a repeating unit derived from diphenyl ether-4,4'-dicarboxylic acid).

The repeating unit (3) is derived from a repeating unit of a predetermined aromatic diol, an aromatic hydroxylamine or an aromatic diamine. The repeating unit (3) is preferably such that Ar ³ is a pendant phenyl group (for example, a repeating unit derived from hydroquinone, p-aminophenol or p-phenylenediamine), and Ar ³ is 4, 4'-extended. Biphenyl group (for example: a repeating unit derived from 4,4'-dihydroxybiphenyl, 4-amino-4'-hydroxybiphenyl or 4,4'-diaminobiphenyl).

The material equivalent of each repeating unit is determined by dividing the total amount of all the repeating units constituting the liquid crystal polyester (that is, dividing the mass of each repeating unit constituting the liquid crystal polyester by the formula of each repeating unit) And the content of the repeating unit (1) in the liquid crystal polyester is preferably 30 mol% or more, more preferably 30 mol% or more and 80 mol% or less. Preferably, 40 mol% or more and 70 mol% or less are more preferably, and 45 mol% or more and 65 mol% or less are particularly preferable.

The content of the repeating unit (2) in the liquid crystal polyester is preferably 35 mol% or less, more preferably 10 mol% or more and 35 mol% or less, based on the total amount of all repeating units constituting the liquid crystal polyester. More preferably, 15 mol% or more and 30 mol% or less are more preferably, and 17.5 mol% or more and 27.5 mol% or less are particularly preferable.

The content of the repeating unit (3) in the liquid crystal polyester is preferably 35 mol% or less, more preferably 10 mol% or more and 35 mol% or less, based on the total amount of all the repeating units constituting the liquid crystal polyester. More preferably, 15 mol% or more and 30 mol% or less are more preferably, and 17.5 mol% or more and 27.5 mol% or less are particularly preferable.

In one aspect, in the liquid crystal polyester of the present embodiment, the content of the repeating unit (1) is 30 to 80 mol%, preferably 40 to the total measurement of all the repeating units constituting the liquid crystal polyester. 70 mol%, more preferably 45 to 65 mol%; the content of the repeating unit (2) is 10 to 35 mol%, preferably 15 to 30 mol%, more preferably 17.5 to 27.5 mol%; The content of the repeating unit (3) is 10 to 35 mol%, preferably 15 to 30 mol%, more preferably 17.5 to 27.5 mol%.

However, the total content of the repeating unit (1), the repeating unit (2), and the repeating unit (3) does not exceed 100 mol.

The more the content of the repeating unit (1) is, the easier it is to improve the melt fluidity, the heat resistance, and the strength/rigidity. However, if the amount is too large, the melting temperature and the melt viscosity are likely to be high, and the temperature required for molding tends to be high. In other words, when the content of the repeating unit (1) is within the above range, the melt fluidity and heat resistance are easily improved, and the strength/rigidity as the molded body is easily increased, and the melting temperature and the melt viscosity are not improved. Too high, the temperature required for forming will not become too high.

The ratio of the content of the repeating unit (2) to the content of the repeating unit (3) is represented by [the content of the repeating unit (2)] / [the content of the repeating unit (3)] (mol/mole), preferably. It is from 0.9/1 to 1/0.9, more preferably from 0.95/1 to 1/0.95, still more preferably from 0.98/1 to 1/0.98.

Further, the liquid crystal polyester of the present embodiment may independently have two or more types of repeating units (1) to (3). Further, the aforementioned liquid crystal polyester may further have a repeating unit other than the repeating units (1) to (3). The content of the repeating unit other than the repeating units (1) to (3) is preferably 0 mol% or more and 10 mol% or less, based on the total amount of all the repeating units constituting the liquid crystal polyester. More than % and less than 5 mol% is more preferred.

In the liquid crystal polyester of the present embodiment, since the melt viscosity is likely to be low, it is preferred that the X and Y are each an oxygen atom as a repeating unit (3), that is, having a predetermined aromatic diol. The repeating unit is a repeating unit (3); more preferably, it is a repeating unit (3) having only X and Y as oxygen atoms, respectively.

In the liquid crystal polyester of the present embodiment, it is preferred that the corresponding raw material monomers constituting the repeating unit of the liquid crystal polyester are melt-polymerized, and the obtained polymer (hereinafter also referred to as "prepolymer") is solidified. It is produced by phase polymerization. Thereby, a high molecular weight liquid crystal polyester having high heat resistance and high strength/rigidity can be produced with good operability. The melt polymerization can be carried out in the presence of a catalyst, and examples of the catalyst include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and cerium (III) oxide; A nitrogen-containing heterocyclic compound such as 4-(dimethylamino)pyridine or 1-methylimidazole is preferably a nitrogen-containing heterocyclic compound.

The liquid crystal polyester of the present embodiment preferably has a flow initiation temperature of 270 ° C or higher, more preferably 270 ° C or more and 400 ° C or less, and still more preferably 280 ° C or more and 380 ° C or less.

The higher the flow initiation temperature of the liquid crystal polyester of the present embodiment, the higher the heat resistance and strength/rigidity of the liquid crystal polyester tend to be. On the other hand, when the flow initiation temperature of the liquid crystal polyester exceeds 400 ° C, the melting temperature and the melt viscosity of the liquid crystal polyester tend to become high. Therefore, the temperature required for the formation of the liquid crystal polyester tends to become high. That is, when the flow initiation temperature of the liquid crystal polyester is within the above range, the heat resistance and strength/rigidity of the liquid crystal polyester are improved, and the melting temperature and melt viscosity of the liquid crystal polyester do not become too high, and the liquid crystal The temperature required for the formation of the polyester does not become too high.

In the present specification, the flow initiation temperature of the liquid crystal polyester is also referred to as a fluid temperature or a flow temperature, and is a temperature which is a reference of the molecular weight of the liquid crystal polyester (refer to: Komori Naoko, "Liquid Crystal Polymer-Synthesis/Forming/ Application - ", CMC Corporation, June 5, 1987, p. 95). Flow initiation temperature: The liquid crystal polyester was heated and melted at a rate of 4 ° C/min under a load of 9.8 MPa (100 kg/cm ² ) using a capillary rheometer, and was 1 mm in inner diameter and 10 mm in length. When the nozzle was extruded, it showed a temperature of 4800 Pa ‧ (48,000 poise).

[Olefin Copolymer]

The olefin-based copolymer of the present embodiment is dispersed in a liquid crystal polyester and has a function as a ruthenium absorbing material (also referred to as a ruthenium-modified material). The absorbing absorbent absorbs the rinsing from the outside of the formed body.

In one aspect, in the liquid crystal polyester composition of the present invention, the liquid crystal polyester forms a continuous phase, and the olefin-based copolymer forms a dispersed phase.

In the other aspect, the olefin-based copolymer in the liquid crystal polyester composition of the present invention is dispersed, and the content of the olefin-based copolymer per unit mass in the plurality of samples randomly taken from the liquid crystal polyester composition described above. For the same.

The olefin-based copolymer of the present embodiment comprises (a) a repeating unit derived from an α-olefin (hereinafter referred to as a repeating unit (a)), and (b) a shrinkage derived from an α,β-unsaturated acid. A repeating unit of glyceride (hereinafter referred to as repeating unit (b)).

The content of the repeating unit (a) is preferably 50% by mass or more and 99% by mass or less based on the total mass of the olefin-based copolymer.

The content of the repeating unit (b) is preferably 0.1% by mass or more and 30% by mass or less based on the total mass of the olefin-based copolymer, and more preferably 0.5% by mass or more and 20% by mass or less, and 2% by mass or less. The above and 4% by mass or less are more preferably.

Further, in terms of the content of the repeating unit (a) and the content of the repeating unit (b), the total content of the repeating unit (a) and the repeating unit (b) is 100 mass with respect to the total mass of the olefin-based copolymer. % is combined in the following ways.

In one aspect, the total content of the repeating unit (a) and the repeating unit (b) is preferably 80% by mass or more and 100% by mass or less based on the total mass of the olefin-based copolymer, and is preferably 90% by mass or more. 100% by mass or less is more preferable.

The olefin-based copolymer preferably further comprises (c) a repeating unit derived from an ethylene-based unsaturated ester (hereinafter referred to as a repeating unit (c)).

The "ethylene-based unsaturated ester" referred to herein is a compound represented by the chemical formula R ₁ -CO-OR _{2 , and} in the compound, R ₁ and R ₂ are each independently a vinyl group or a vinyl derivative. And a methyl group or an ethyl group, and at least one of R ₁ and R ₂ is a derivative of the above vinyl group or the above vinyl group.

Here, the "vinyl derivative" is one in which one or more hydrogen atoms bonded by two carbons in a vinyl group are independently substituted with a methyl group or an ethyl group.

In the case where the above repeating unit (c) is contained, the content of the repeating unit (c) is preferably more than 0% by mass and not more than 50% by mass based on the total mass of the olefin-based copolymer.

Further, in terms of the content of the repeating unit (a), the content of the repeating unit (b), and the content of the repeating unit (c), the units (a) to (c) are repeated with respect to the total mass of the olefin-based copolymer. The total content is 100% by mass or less.

In one aspect, the total content of the repeating units (a) to (c) is preferably 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass based on the total mass of the olefin-based copolymer. % below is better.

The olefin-based copolymer may further contain repeating units other than the repeating units (a) to (c).

In one aspect, the olefin-based copolymer of the present embodiment comprises: a repeating unit derived from an α-olefin (repeating unit (a)), and a repeating unit derived from a glycidyl ester of an α,β-unsaturated acid (Repeating unit (b)), and optionally a repeating unit derived from an ethylenically unsaturated ester (repeating unit (c)).

In another aspect, the olefin-based copolymer of the present embodiment comprises: a repeating unit derived from an α-olefin (repeating unit (a)), and a repeat of a glycidyl ester derived from an α,β-unsaturated acid The unit (repeating unit (b)), and optionally the repeating unit derived from the ethylenically unsaturated ester (repeating unit (c)), and the repeating units other than the above repeating units (a) to (c).

The compound which can provide the repeating unit (a) is not particularly limited, and examples thereof include an α-olefin having 2 to 13 carbon atoms, and examples thereof include an α-olefin such as ethylene, propylene or butene.

Examples of the compound capable of imparting the repeating unit (b) include glycidyl esters of α,β-unsaturated acids having 2 to 13 carbon atoms, such as glycidol of α,β-unsaturated acids represented by the following formula (B1). Ester and the like.

(R is a hydrocarbon group having 2 to 13 carbon atoms having an ethylenically unsaturated bond.)

In other words, R in the above formula (B1) represents an alkenyl group having a carbon number of 2 to 13 having a double bond at the α-position and the β-position of the adjacent carbonyl group.

More specifically, examples of the compound capable of imparting the repeating unit (b) include glycidyl acrylate and glycidyl methacrylate.

The compound capable of imparting the repeating unit (c) may, for example, be a vinyl carboxylate such as vinyl acetate or vinyl propionate, or methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate or methacrylic acid B. An ethylenically unsaturated ester such as an α,β-unsaturated carboxylic acid alkyl ester such as an ester or a butyl methacrylate. Among them, the compound capable of imparting the repeating unit (c) is preferably vinyl acetate, methyl acrylate or ethyl acrylate.

The olefin-based copolymer of the liquid crystal polyester composition of the present embodiment may, for example, be a repeating unit derived from ethylene in a repeating unit (a), and a repeating unit (b) derived from glycidyl methacrylate. a copolymer formed by repeating units; a repeating unit derived from ethylene in repeating unit (a), a repeating unit (b) derived from a repeating unit of glycidyl methacrylate, and a repeating unit (c) source a copolymer derived from a repeating unit of methyl acrylate; a repeating unit derived from ethylene in repeating unit (a), a repeating unit (b) derived from a repeating unit of glycidyl methacrylate, and a repeat The unit (c) is a copolymer derived from a repeating unit of ethyl acrylate; The repeating unit derived from ethylene (a) is a repeating unit derived from ethylene, the repeating unit (b) is derived from a repeating unit of glycidyl methacrylate, and the repeating unit (c) is derived from a repeating unit of vinyl acetate. The resulting copolymer and the like.

[plate filler]

The term "plate-like filler" as used in the present invention means an aspect ratio of 5 to 200.

The liquid crystal polyester composition of the present embodiment is preferably a plate-like filler. The plate-like filler of the present embodiment is not particularly limited, and examples thereof include talc, mica, graphite, apatite, glass flakes, barium sulfate or calcium carbonate. Mica can be muscovite, it can be phlogopite, it can also be fluorophlogopite, or it can be four mica.

The platy filler of the present embodiment is preferably talc or mica, preferably mica. Thereby, the punching strength of the molded body obtained by using the liquid crystal polyester composition is improved.

The particle diameter of the plate-like filler of the present embodiment is not particularly limited. For example, the volume average particle diameter of the plate-like filler is preferably 15 μm or more and 40 μm or less, more preferably 20 μm or more and 35 μm or less, still more preferably 20 μm or more and 30 μm or less, and even more preferably 22 μm or more and 30 μm or less. . When the volume average particle diameter of the platy filler is 15 μm or more, the impact resistance of the molded body formed of the liquid crystal polyester composition tends to be improved. Further, when the volume average particle diameter of the platy filler is 40 μm or less, the deformation of the molded body tends to be further suppressed.

The volume average particle diameter of the platy filler can be measured by a laser diffraction method.

Moreover, it is known that the volume average particle diameter of the plate-like filler does not substantially change by melt-kneading which will be described later. Therefore, the volume average particle diameter of the platy filler can also be determined by measuring the volume average particle diameter of the platy filler before the melt-kneading of the liquid crystal polyester composition.

[Liquid crystal polyester composition]

When the total content of the liquid crystal polyester and the olefin-based copolymer is 100% by mass, the content of the liquid crystal polyester in the liquid crystal polyester composition of the present embodiment is more than 80% by mass and not more than 95% by mass. When the content of the liquid crystal polyester exceeds 80% by mass, the fluidity and heat resistance of the liquid crystal polyester composition are improved. In addition, when the content of the liquid crystal polyester exceeds 80% by mass, the impact strength of the molded body obtained from the liquid crystal polyester composition is improved. On the other hand, when the content of the liquid crystal polyester is 95% by mass or less, the liquid crystal polyester composition is easily formed.

When the total content of the liquid crystal polyester and the olefin-based copolymer is 100% by mass, the content of the liquid crystal polyester in the liquid crystal polyester composition of the present embodiment is preferably 83% by mass or more, and preferably 85% by mass or more. For better.

In addition, when the total content of the liquid crystal polyester and the olefin-based copolymer is 100% by mass, the content of the liquid crystal polyester is preferably 95% by mass or less, and more preferably 90% by mass or less.

The above upper limit value and lower limit value can be arbitrarily combined.

In the case where the total content of the liquid crystal polyester and the olefin-based copolymer is 100% by mass, the content of the liquid crystal polyester is preferably 83% by mass or more and 95% by mass or less, and 85% by mass or less. The above and 90% by mass or less are more preferable.

In the other aspect, the content of the liquid crystal polyester is more than 80% by mass and 95% by mass or less, preferably 83% by mass or more and 95% by mass or less, more preferably the total mass of the liquid crystal polyester composition. It is 85 mass% or more and 90 mass% or less.

When the total content of the liquid crystal polyester and the olefin-based copolymer is 100% by mass, the content of the olefin-based copolymer in the liquid crystal polyester composition of the present embodiment is 5% by mass or more and less than 20% by mass. When the content of the olefin-based copolymer is 5% by mass or more, the liquid crystal polyester composition is obtained. The punching strength of the body will increase. On the other hand, when the content of the olefin-based copolymer is less than 20% by mass, the fluidity of the liquid crystal polyester composition is sufficiently improved.

When the total content of the liquid crystal polyester and the olefin-based copolymer is 100% by mass, the content of the olefin-based copolymer in the liquid crystal polyester composition of the present embodiment is preferably 5% by mass or more, and preferably 6% by mass. The above is more preferable, and 8 mass% or more is more preferable. In addition, when the total content of the liquid crystal polyester and the olefin-based copolymer is 100% by mass, the content of the olefin-based copolymer is preferably 18% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. For even better.

The above upper limit value and lower limit value can be arbitrarily combined.

When the total content of the liquid crystal polyester and the olefin-based copolymer is 100% by mass, the content of the olefin-based copolymer is preferably 5% by mass or more and 18% by mass or less, and preferably 6% by mass. The above is more preferably 15% by mass or less, and more preferably 8% by mass or more and 10% by mass or less.

In the other aspect, the content of the olefin-based copolymer is 5% by mass or more and less than 20% by mass, preferably 5% by mass or more and 18% by mass or less, based on the total mass of the liquid crystal polyester composition. It is preferably 6% by mass or more and 15% by mass or less, and more preferably 8% by mass or more and 10% by mass or less.

The liquid crystal polyester composition of the present embodiment may further contain a plate-like filler. When the total content of the liquid crystal polyester, the olefin copolymer, and the platy filler is 100% by mass, the content of the platy filler is preferably 15% by mass or more and 30% by mass. %the following. When the content of the platy filler is 15% by mass or more, the anisotropy of the liquid crystal polyester is suppressed, and the liquid crystal polyester composition is easily formed. On the other hand, when the content of the platy filler is 30% by mass or less, the content of the liquid crystal polyester is relatively large, and the pulverization strength of the molded body obtained from the liquid crystal polyester composition is improved.

When the total content of the liquid crystal polyester, the olefin copolymer, and the platy filler is 100% by mass, the content of the plate-like filler in the liquid crystal polyester composition is preferably 20% by mass or more, and 23% by mass or more. For better. In addition, when the total content of the liquid crystal polyester, the olefin copolymer, and the platy filler is 100% by mass, the content of the plate-like filler is preferably 28% by mass or less, and preferably 25% by mass or less.

The above upper limit value and lower limit value can be arbitrarily combined.

In a case where the total content of the liquid crystal polyester, the olefin copolymer, and the platy filler is 100% by mass, the content of the platy filler is preferably 20% by mass or more and 28% by mass or less. 23% by mass or more and 25% by mass or less are more preferably.

In the other aspect, the content of the plate-like filler is 15% by mass or more and 30% by mass or less, preferably 20% by mass or more and 28% by mass or less, more preferably the total mass of the liquid crystal polyester composition. It is 23% by mass or more and 25% by mass or less.

The term "plate-like filler" as used in the present invention means an aspect ratio of 5 to 200.

In the liquid crystal polyester composition of the present embodiment, one of the indexes of the dispersion state of the olefin-based copolymer is defined as "the dispersion diameter of the olefin-based copolymer".

First, the liquid crystal polyester and the olefin copolymer are melt-kneaded at a predetermined shear rate at a processing temperature of 10 ° C to 20 ° C or higher with respect to the flow initiation temperature of the liquid crystal polyester to prepare a pellet. Liquid crystal polyester composition. Then, a cross-sectional sample processing apparatus ("Cross section polisher SM-09010", manufactured by JEOL Ltd.) was used, and a cross-sectional processing of the particulate liquid crystal polyester composition was carried out under conditions of an acceleration voltage of 4.5 kV for 20 hours. Then, a cross-sectional image of the particulate liquid crystal polyester composition was imaged under the conditions of an acceleration voltage of 10 kV using a scanning electron microscope ("S-4800" manufactured by Hitachi High-Technologies Co., Ltd.). The cross-sectional image is taken with the attached The YAG type reflected electron detector was carried out under conditions of a magnification of 5000 times. Then, the image analysis software ("WinROOF" Ver. 3.54, manufactured by Sangu Trading Co., Ltd.) was used, and the dispersion diameter of the olefin-based copolymer was determined by the following analysis method.

The dispersion diameter of the olefin-based copolymer in the liquid crystal polyester composition of the present embodiment tends to be smaller as the shear rate increases. In addition, the dispersion diameter of the olefin-based copolymer in the liquid crystal polyester composition of the present embodiment tends to increase as the shear rate becomes slower.

[Analytical method]

Using the cross-sectional image of the obtained small piece, a median process of a filter size of 5 × 5 was carried out, and then a region containing the liquid crystal polyester and a region of the olefin-based copolymer were binarized. After the processed image was used to remove the noise and the region cut off from the end of the image, the equivalent circle diameter of 100 or more (for example, 100) olefin-based copolymers in the olefin-based copolymer region was measured. The average value of the obtained measured values was calculated as the dispersion diameter of the olefin-based copolymer.

Further, the "equivalent circle diameter" is a diameter of a perfect circle corresponding to the area of the measurement target (olefin-based copolymer) observed on the processed image.

The dispersion diameter of the olefin-based copolymer in the liquid crystal polyester composition of the present embodiment measured by the above measurement method is less than 0.8 μm. Further, the dispersion diameter of the olefin-based copolymer is, for example, 0.01 μm or more.

In the liquid crystal polyester composition of the present embodiment, the dispersion diameter of the olefin-based copolymer is preferably 0.6 μm or less, more preferably 0.5 μm or less. Further, in the liquid crystal polyester composition of the present embodiment, the dispersion diameter of the olefin-based copolymer is preferably 0.05 μm or more, and more preferably 0.2 μm or more.

The above upper limit value and lower limit value can be arbitrarily combined.

In one aspect, the olefin-based copolymer has a dispersion diameter of 0.01 μm or more and less than 0.8 μm, preferably 0.05 μm or more and 0.6 μm or less, more preferably 0.2 μm or more and 0.5 μm or less.

In the molded article obtained from the liquid crystal polyester composition of the present embodiment, it is considered that a spheroidal olefin-based copolymer is present in the liquid crystal polyester. When the dispersion diameter of the olefin-based copolymer is less than 0.8 μm, it is presumed that the olefin-based copolymer is dispersed in the liquid crystal polyester, and a large amount of the olefin-based copolymer having a small particle diameter is present in the liquid crystal polyester. It is noted that in such a molded body, the distance between the particles of the olefin-based copolymer becomes small. As a result, it is considered that the propagation of the crack of the above-mentioned formed body is suppressed, and the punching strength is increased.

Further, according to the liquid crystal polyester composition of the present embodiment, since the effect of improving the punching strength of the molded body is high, the content of the olefin-based copolymer belonging to the absorbing absorbent can be reduced. As a result, the liquid crystal polyester composition of the present embodiment is more improved in fluidity than the conventional liquid crystal polyester composition, and the conventional liquid crystal polyester composition is used in order to obtain a molded body having the same punching strength. Those containing an olefin-based copolymer.

In the present specification, the fluidity of the liquid crystal polyester composition is measured by measuring the flow direction (also referred to as flow length) of the resin in the molded body obtained from the liquid crystal polyester composition by using a mold for measuring the flow length. Evaluate. In this evaluation, it can be said that the longer the length of the flow length, the higher the fluidity of the liquid crystal polyester composition.

In the liquid crystal polyester composition of the present embodiment, when the flow length is measured by the method described in <Flow Length of Liquid Crystal Polyester Composition>, the flow length is preferably 800 mm or more. Further, it is more preferable to have a flow length of 810 mm or more and 900 mm or less.

[Other ingredients]

The liquid crystal polyester composition may further contain at least one other component such as a filler other than the plate-like filler, an additive, a resin other than the liquid crystal polyester, or the like.

In one aspect, the liquid crystal polyester composition of the present embodiment may further comprise: a liquid crystal polyester, a repeat containing a repeating unit derived from an α-olefin, and a glycidyl ester derived from an α,β-unsaturated acid. The olefin-based copolymer of the unit and, if necessary, selected from the group consisting of a plate-like filler and other components (at least one component selected from the group consisting of fillers other than the above-mentioned plate-like filler, additives, and resins other than the liquid crystal polyester) Forming at least one component of the group.

The content of the other components is preferably 0.01 to 30% by mass based on the total mass of the liquid crystal polyester composition.

The filler may be a fibrous filler, or may be a spherical or other granular filler other than a fibrous shape or a plate shape. Further, the filler may be an inorganic filler or an organic filler. Examples of the fibrous inorganic filler include glass fibers; carbon fibers such as polyacrylonitrile (PAN)-based carbon fibers and pitch-based carbon fibers; ceramic fibers such as cerium oxide fibers, alumina fibers, and alumina cerium oxide fibers; and stainless steel. Metal fibers such as fibers. Further, whiskers such as potassium titanate whisker, barium titanate whisker, ash stone whisker, aluminum borate whisker, tantalum nitride whisker, and strontium carbide whisker may be mentioned. Examples of the fibrous organic filler include polyester fibers and aramid fibers. Examples of the particulate inorganic filler include cerium oxide, aluminum oxide, titanium oxide, glass beads, glass balloons, boron nitride, cerium carbide, and calcium carbonate. The content of the filler other than the platy filler is preferably from 0 to 100 parts by mass based on 100 parts by mass of the liquid crystal polyester.

Examples of the additives include antioxidants, heat stabilizers, ultraviolet absorbers, antistatic agents, surfactants, flame retardants, and color formers. The content of the additive is preferably from 0 to 5 parts by mass based on 100 parts by mass of the liquid crystal polyester.

Examples of the resin other than the liquid crystal polyester include, for example, polypropylene, polyamine, polyester other than liquid crystal polyester, polyfluorene, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene ether, polyether oxime A thermoplastic resin other than a liquid crystal polyester such as an imide; and a thermosetting resin such as a phenol resin, an epoxy resin, a polyimide resin, or a cyanate resin. The content of the resin other than the liquid crystal polyester is preferably from 0 to 20 parts by mass based on 100 parts by mass of the liquid crystal polyester.

<Method for Producing Liquid Crystal Polyester Composition>

The liquid crystal polyester composition of the present embodiment is preferably melt-kneaded by using the liquid crystal polyester, the olefin-based copolymer, and optionally the plate-like filler and other components in an extruder, and extruded into pellets. And modulation. In the present invention, such a step is referred to as a "melt kneading step."

The extruder used in the melt-kneading step preferably uses a cylinder having at least one screw disposed in the cylinder and a supply port provided at at least one of the cylinders, and more preferably has a use. A vent portion provided at at least one of the cylinder blocks.

In the melt-kneading step of the present embodiment, the melt-kneading conditions can be set by a preliminary experiment so that the dispersion diameter of the olefin-based copolymer in the liquid crystal polyester composition is less than 0.8 μm.

Further, in another method, a processing temperature in a temperature range of 10 ° C or more and 20 ° C or less which is set in relation to a flow initiation temperature of the liquid crystal polyester is used, and 3000 s ^-1 or more and 10000 s ^- A method of melt-kneading at a shear rate of ¹ or less. When the shear rate is 3,000 s ^-1 or more, the olefin-based copolymer can be favorably dispersed in the liquid crystal polyester in the obtained liquid crystal polyester composition.

Here, "good dispersion" means that a plurality of olefin-based copolymers having a dispersion diameter of less than 0.8 μm as measured by the above-described measurement method are present in the liquid crystal polyester. On the other hand, when the shear rate is 10000 s ^-1 or less, heat generated during melt kneading is suppressed, and deterioration of the liquid crystal polyester due to heat can be suppressed.

The shearing speed is preferably 3,000 s ^-1 or more, more preferably 5,000 s ^-1 or more. Further, the shear rate is preferably 10000 s ^-1 or less.

The above upper limit value and lower limit value can be arbitrarily combined.

On one face, the above is preferably a shear rate of 3000s ^-1 or more 10000s ^-1 or less, more preferably less 10000s ^-1 5000s ^-1 or more.

In the extruder used in the melt-kneading step of the present embodiment, it is preferable to use a cylinder having at least one screw disposed in the cylinder and a supply port provided in at least one of the cylinders. It is preferred to use a venting portion that is provided at least in one of the cylinder blocks.

<Formed body>

The molded article of the present embodiment can be obtained from a liquid crystal polyester resin composition by a known molding method.

In the molding method of the liquid crystal polyester composition of the present embodiment, a melt molding method is preferred, and examples thereof include extrusion molding, a T-die method, and an inflation molding method. Method, compression molding method, blow molding method, vacuum forming method, and press forming. Among them, an injection molding method is preferred.

According to this embodiment, the liquid crystal polyester composition has high fluidity and the obtained molded body has high punching strength. Therefore, the molded article of the present embodiment can be applied to various uses in which a general liquid crystal polyester resin can be applied.

In one aspect, the molded article of the present embodiment preferably has a thickness of 7 mm or less, and more preferably has a thickness of 5 mm or less.

For example, in the automotive field, the injection molded body for automotive interior materials, such as an injection molded body for a ceiling material, an injection molded body for a wheel cover, an injection molded body for a trunk, and an instrument panel surface material. The injection molded body, the injection molded body for the steering wheel sheath, the injection molded body for the armrest, the injection molded body for the headrest, the injection molded body for the seat belt sheath, the injection molded body for the shift lever boots, and the armrest In the case of the injection box, the injection molded body, the injection molded body for the horn pad, the injection molded body for the knob, the injection molded body for the airbag cover, and various trims are used for injection molding. For injection molding of a body, various pillars, an injection molded body for a door lock bezel, an injection molded body for a glove box, an injection molded body for a defroster nozzle, and a scuff plate. The injection molded body, the injection molded body for the steering wheel, the injection molded body for the steering column cover, and the like.

Examples of the injection molded body for an automobile exterior material include an injection molded body for a bumper, an injection molded body for a spoiler, an injection molded body for a fender, and an injection molded body for a side trim.

Other injection molded articles for automobile parts include an injection molded body for an automobile headlight, an injection molded body for a glass run channel, an injection molded body for a weather strip, and a drain hose. For injection moldings, injection moldings for window injection pipes, injection moldings, tube injection moldings, rack and pinion boots, injection moldings, and gaskets (for injection moldings) The gasket is used for injection molding or the like.

In addition, examples thereof include a sensor, an LED lamp, a connector, a socket, a resistor, a relay case, a switch, a coil bobbin, a capacitor, a variable capacitor case, and an optical pickup. (optical pickup), oscillator, various terminal blocks, transformers, plugs, printed circuit boards, tuners, speakers, microphones, earphones, small motors, head bases, power modules, semiconductors, liquid crystal displays, floppy disk drives FDD carriage, FDD chassis, Motor brush holder, parabola antenna, computer related parts, microwave oven parts, audio/audio machine parts, lighting parts, air conditioning parts, office computer related parts, telephone/FAX related parts and copiers Parts, etc.

In the present specification, the punching strength of the molded body is measured in accordance with ASTM D256.

In the case of the molded article of the present embodiment, the above-described <Izod impact strength> of the molded article is measured by the method described in the following description. The Cao Te impact strength is 800 J/m or more, preferably 1400 J/m or more and 1900 J/m or less, more preferably 1600 J/m or more and 1900 J/m or less, and still more preferably 1700 J/m or more and 1900 J/m or less.

According to the present embodiment, it is possible to provide a liquid crystal polyester composition which can be formed into a molded body having a high punching strength and which has high fluidity, and a molded body thereof.

In one aspect, the liquid crystal polyester composition of one embodiment of the present invention comprises a liquid crystal polyester composition of a liquid crystal polyester and an olefin copolymer; wherein the liquid crystal polyester has the above repeating unit (1), The liquid crystal polyester of the above repeating unit (2) and the above repeating unit (3), preferably the liquid crystal polyester has: a repeating unit derived from p-hydroxybenzoic acid, derived from 4,4'-dihydroxybiphenyl a repeating unit, a repeating unit derived from terephthalic acid, a repeating unit derived from isophthalic acid, and a repeating unit derived from 4,4′-dihydroxybiphenyl; the aforementioned olefin-based copolymer comprises: a repeating unit derived from an α-olefin (the aforementioned repeating unit (a)), and a repeating unit derived from a glycidyl ester of an α,β-unsaturated acid (the aforementioned repeating unit (b)); When the total content of the olefin-based copolymer is 100% by mass, The content of the liquid crystal polyester is more than 80% by mass and 95% by mass or less, preferably 83% by mass or more and 95% by mass or less, more preferably 85% by mass or more and 90% by mass or less, and further, the olefin copolymerization. The content of the substance is 5% by mass or more and less than 20% by mass, preferably 5% by mass or more and 18% by mass or less, more preferably 6% by mass or more and 15% by mass or less, still more preferably 8% by mass or more. 10% by mass or less; the dispersion diameter of the olefin-based copolymer measured by the above measurement method is less than 0.8 μm, preferably 0.4 μm or more and 0.6 μm or less.

In another aspect, the liquid crystal polyester composition is characterized in that the content of the liquid crystal polyester is more than 80% by mass and not more than 95% by mass, based on the total mass of the liquid crystal polyester composition. It is 83% by mass or more and 95% by mass or less, more preferably 85% by mass or more and 90% by mass or less, and the content of the olefin-based copolymer is 5% by mass or more and less than 20% by mass, preferably 5% by mass. % or more and 18 mass% or less, more preferably 6% by mass or more and 15% by mass or less, more preferably 8% by mass or more and 10% by mass or less; however, the total content of the liquid crystal polyester and the olefin-based copolymer is not More than 100% by mass.

Further, a liquid crystal polyester composition in which the flow length is 800 mm when the flow length is measured by the method described in <Flow Length of Liquid Crystal Polyester Composition> described later. In the above, the liquid crystal polyester composition is formed into a molded body from the liquid crystal polyester composition, and is described by the <Essert impact strength of the molded body described later>. The Ectotech impact strength of the molded article measured by the method is preferably 800 J/m or more, and may be 1400 J/m or more and 1900 J/m or less, or 1600 J/m or more and 1900 J/m or less. It can be 1700 J/m or more and 1900 J/m or less.

In the other aspect, the liquid crystal polyester composition has the aforementioned load deformation temperature when the load deformation temperature is measured by the method described in <Loading Deformation Temperature of Liquid Crystal Polyester Composition> described later. It is a characteristic of 227 ° C or more and 233 ° C or less.

The molding system according to an embodiment of the present invention is a molded article formed of the liquid crystal polyester composition, and the liquid crystal polyester composition is measured by a method described in <Essert Impact Strength of a molded article described later>. In the case of the Austen's impact strength, it is preferably a composition capable of imparting an impact strength of 800 J/m or more, and more preferably a composition capable of imparting an impact strength of 1400 J/m or more and 1900 J/m or less. Further, it is more preferably a composition capable of imparting an Ectotech impact strength of 1600 J/m or more and 1900 J/m or less, and particularly preferably a composition capable of imparting an Essant impact strength of 1700 J/m or more and 1900 J/m or less; When the tensile strength and the tensile growth rate are measured by the method described in the following section, the tensile strength and the tensile growth rate of the molded article, it is preferable to provide a composition having a tensile strength of 104 MPa or more and 138 MPa or less. It is preferable to provide a composition having a tensile growth rate of 6.2% or more and 7.2% or less; when the bending strength and the bending elastic modulus are measured by the method described in <Bending strength and bending elastic modulus of the molded body> described later , preferably capable of I 73MPa or more and the flexural strength of the compositions of 76MPa or less, preferably 3200MPa or more and can impart the following compositions of the number of 3400MPa flexural modulus.

(Example)

The invention is illustrated by the following examples, but the invention is not limited thereto. Each measurement system was carried out as follows.

<Production Example 1 [Production of Liquid Crystal Polyester]

In a reactor equipped with a stirring device, a torque meter, a nitrogen inlet tube, a thermometer and a reflux cooler, 994.5 g (7.2 mol) of p-hydroxybenzoic acid, 299.0 g (1.8 mol) of terephthalic acid, and isophthalic acid were fed. 99.7 g (0.6 mol) of dicarboxylic acid, 446.9 g (2.4 mol) of 4,4'-dihydroxybiphenyl and 1347.6 g (13.2 mol) of acetic anhydride. After the gas in the reactor was substituted with nitrogen, 1 was added. 0.18 g of methylimidazole was stirred under a nitrogen gas stream while heating from room temperature to 150 ° C for 30 minutes, and refluxed at 150 ° C for 30 minutes. Then, 2.4 g of 1-methylimidazole was added to distill off by-produced acetic acid and unreacted acetic anhydride, and the temperature was raised from 150 ° C to 320 ° C in 2 hours and 50 minutes. The contents were taken out of the reactor at a point where the torque rise was seen and cooled to room temperature. The obtained solid matter was pulverized by a pulverizer, and the temperature was raised from room temperature to 250 ° C in a nitrogen gas atmosphere for 1 hour, and the temperature was raised from 250 ° C to 295 ° C for 5 hours, and was 295 ° C. After maintaining solid phase polymerization for 3 hours, it was cooled to obtain a powdery liquid crystal polyester. The liquid crystal polyester had a flow initiation temperature of 327 °C. And the apparent melt viscosity is 5.9 Pa‧s.

<Flow initiation temperature of liquid crystal polyester>

First, about 2 g of the liquid crystal polyester was filled into a cylinder to which a die having a nozzle having an inner diameter of 1 mm and a length of 10 mm was attached, using a flow tester ("CFT-500 type" of Shimadzu Corporation). Then, the temperature was raised at a rate of 4 ° C/min under a load of 9.8 MPa (100 kg/cm ² ), and the liquid crystal polyester was melted and extruded from a nozzle, and the viscosity was measured to be 4800 Pa·s (48,000 poise). The temperature (flow initiation temperature) was set to the flow initiation temperature of the liquid crystal polyester.

<Apparent Melt Viscosity of Olefin Copolymer>

After the olefin-based copolymer was placed in a furnace of a capillary rheometer ("Capilograph 1B", manufactured by Toyo Seiki Seisakusho Co., Ltd.), the temperature was set to be 10 ° C higher than the flow initiation temperature of the liquid crystal polyester, The melt viscosity at a shear rate of 10000 s ^-1 was measured while maintaining the above temperature.

<Flow length of liquid crystal polyester composition>

The liquid crystal polyester composition which can be used for the flow length measurement mold having a thickness of 1 mm and a width of 10 mm in the present embodiment was molded by an injection molding machine ("UH1000" manufactured by Nissei Resin Co., Ltd.) under the following conditions. The length of the resin in the flow direction was measured for the molded body taken out. This test was carried out for 10 molded bodies, and the average value of the obtained measured values was defined as the flow length of the liquid crystal polyester composition. The results are shown in Table 2.

[condition]

Cylinder temperature: (nozzle side) 340 ° C; 350 ° C; 340 ° C; 330 ° C; 80 ° C (hopper side)

Mold temperature: 80 ° C

Measurement value: 25mm

Injection speed: 100mm / sec

VP switching: pressure switching at 100MPa

Packing pressure: 100MPa

<Load deformation temperature of liquid crystal polyester composition>

The liquid crystal polyester composition was molded into a shape of 127 mm × 12.7 mm × 6.4 mm by a molding temperature of 340 ° C, a mold temperature of 130 ° C, and an injection speed of 50% using an injection molding machine ("PNX40-5A" manufactured by Nissei Resin Co., Ltd.). Test piece. The load deformation temperature of the obtained test piece was measured twice at a temperature increase rate of 4 ° C / min under a load of 1.82 MPa in accordance with ASTM D648. The load deformation temperature of the liquid crystal polyester composition is an average value of the obtained measured values. The results are shown in Table 2.

<Dispersion diameter of olefin-based copolymer>

A granular liquid crystal polyester composition was produced by the production method described later.

Then, a cross-sectional sample processing apparatus ("Cross section polisher SM-09010" manufactured by JEOL Ltd.) was used, and the cross-sectional processing of the granular liquid crystal polyester composition was carried out under the conditions of an acceleration voltage of 4.5 kV for 20 hours.

Then, a cross-sectional image of the particulate liquid crystal polyester composition was imaged under the conditions of an acceleration voltage of 10 kV using a scanning electron microscope ("S-4800" manufactured by Hitachi High-Technologies Co., Ltd.). The photographing of the cross-sectional image was carried out under the conditions of an observation magnification of 5000 times using the attached YAG-type reflection electron detector.

Then, the image analysis software ("WinROOF" Ver. 3.54, manufactured by Sangu Trading Co., Ltd.) was used, and the dispersion diameter of the olefin-based copolymer was determined by the following analysis method.

[Analytical method]

Using the cross-sectional image of the obtained small piece, a median process of a filter size of 5 × 5 was carried out, and then a region containing the liquid crystal polyester and a region of the olefin-based copolymer were binarized. After the processed image was used to remove the noise and the region cut off from the end of the image, the equivalent circle diameter of 100 or more (for example, 100) olefin-based copolymers in the olefin-based copolymer region was measured. The average value of the obtained measured values was calculated as the dispersion diameter of the olefin-based copolymer.

<Stretching strength and tensile growth rate of the molded body>

The liquid crystal polyester composition was molded into a ASTM No. 4 test piece having a thickness of 2.5 mm at a molding temperature of 340 ° C, a mold temperature of 130 ° C, and an injection speed of 50% using an injection molding machine ("PNX40-5A" manufactured by Nissei Resin Co., Ltd.). . Tensile strength and tensile growth rate of the obtained test piece according to ASTM D638 Determined 5 times. The tensile strength and the tensile growth rate of the molded body were the average values of the obtained measured values. The results are shown in Table 2.

<Bending strength and flexural modulus of the molded body>

The liquid crystal polyester composition was molded into a shape of 127 mm × 12.7 mm × 6.4 mm by a molding temperature of 340 ° C, a mold temperature of 130 ° C, and an injection speed of 50% using an injection molding machine ("PNX40-5A" manufactured by Nissei Resin Co., Ltd.). Test piece. The bending strength and flexural modulus of the obtained test piece were measured three times in accordance with ASTM D790. The bending strength and the flexural modulus of the molded body were the average values of the obtained measured values. The results are shown in Table 2.

<Anchor impact strength of the molded body>

The liquid crystal polyester composition was molded into a shape of 127 mm × 12.7 mm × 6.4 mm by a molding temperature of 340 ° C, a mold temperature of 130 ° C, and an injection speed of 50% using an injection molding machine ("PNX40-5A" manufactured by Nissei Resin Co., Ltd.). Test piece. The Essert impact strength of the obtained test piece was measured 10 times in accordance with ASTM D256. At this time, the test was performed without giving a notch to the molded body. The Essert impact strength of the formed body is the average value of the obtained measured values. The results are shown in Table 2.

<Manufacture of Liquid Crystal Polyester Composition>

[Examples 1-1 to 1-3, Comparative Example 1-1, and Reference Example 1-1]

Using a two-axis extruder ("PCM-30HS" manufactured by Chiba Iron Works Co., Ltd.), the liquid crystal polyester and the olefin copolymer were subjected to a shear rate at a cylinder temperature of 340 ° C in the ratio shown in Table 1. Various changes were made and melt-kneaded to obtain a particulate liquid crystal polyester composition. In addition, all the ratios shown in Table 1 are ratio (% by mass) based on 100% by mass of the total of the liquid crystal polyester and the olefin-based copolymer.

[Reference Example 1-1]

Using a two-axis extruder ("PCM-30HS" manufactured by Chiba Iron Works Co., Ltd.), the liquid crystal polyester was melt-kneaded at a cylinder temperature of 340 ° C and a shear rate of 1000 s ^-1 according to the ratio shown in Table 1. A granular liquid crystal polyester composition.

All of the particulate liquid crystal polyester composition was subjected to hot air drying at 130 ° C for 4 hours.

Moreover, the following materials were used for the olefin-based copolymer used for the liquid crystal polyester composition. In addition, the "ethylene ratio" means the content of the repeating unit derived from the α-olefin (ethylene) with respect to the total mass of the olefin-based copolymer, and the "glycidyl methacrylate ratio" means the olefin-based copolymer. The total mass is derived from the content of the repeating unit of the glycidyl ester of α,β-unsaturated acid (glycidyl methacrylate), and the “methyl acrylate ratio” means the total mass relative to the olefin copolymer. In other words, the content of the repeating unit derived from the ethylenically unsaturated ester (methyl acrylate).

(olefin copolymer)

Olefin-based copolymer: ethylene ratio: 70.2% by mass, glycidyl methacrylate ratio: 2.9% by mass, methyl acrylate ratio: 26.9% by mass, apparent melt viscosity: 11.7 Pa‧s

The obtained liquid crystal polyester composition was subjected to comprehensive determination using the following criteria.

A...The flow length is 800mm or more, and the strength of Ai Cao Teic is 800J/m or more.

B...other than the above

As shown in Table 2, the liquid crystal polyester compositions to which Examples 1-1 to 1-3 of the present invention were applied had high fluidity and the obtained molded body had high punching strength.

Specifically, in the liquid crystal polyester compositions of Examples 1-1 to 1-3, the dispersion diameter of the olefin-based copolymer was less than 0.8 μm, and Comparative Example 1-1 was 0.8 μm.

The liquid crystal polyester compositions of Examples 1-1 to 1-3 were all highly fluid, and the obtained molded body had high punching strength.

From the above results, it was confirmed that the present invention is useful.

[Industrial availability]

According to the present invention, it is possible to provide a liquid crystal polyester composition which can be formed into a molded article having high punching strength and has high fluidity, a molded article thereof, and a method for producing a liquid crystal polyester composition, which is extremely useful industrially.

Claims (4)

A liquid crystal polyester composition comprising: a liquid crystal polyester; and an olefin-based copolymer containing a repeating unit derived from an α-olefin and a repeating unit derived from a glycidyl ester of an α,β-unsaturated acid; When the total content of the liquid crystal polyester and the olefin-based copolymer is 100% by mass, the content of the liquid crystal polyester is more than 80% by mass and 95% by mass or less, and the content of the olefin-based copolymer is 5% by mass. % or more and less than 20% by mass, the dispersion diameter of the olefin-based copolymer measured by the following measurement method is less than 0.8 μm; [Measurement method] In the scanning electron microscope image of the liquid crystal polyester composition, measurement The equivalent circle diameter of 100 of the aforementioned olefin-based copolymers was calculated, and the average value of the obtained measured values was calculated. The liquid crystal polyester composition according to the first aspect of the invention, wherein the liquid crystal polyester has a repeat represented by the following formula (1) with respect to the total amount of all the repeating units constituting the liquid crystal polyester. Unit 30 mol% or more and 80 mol% or less; (1)-O-Ar ¹ -CO-Ar ¹ represents a phenyl group, a naphthyl group or a biphenyl group; the hydrogen atom in the group represented by Ar ¹ may be Each is independently substituted with a halogen atom, an alkyl group or an aryl group. A molded body formed by the liquid crystal polyester composition described in claim 1 or 2. A method for producing a liquid crystal polyester composition, comprising: a liquid crystal polyester, and an olefin system comprising a repeating unit derived from an α-olefin and a repeating unit derived from a glycidyl ester of an α,β-unsaturated acid; The copolymer is subjected to melt-kneading; wherein the melt-kneading is performed at a processing temperature in a temperature region of 10 ° C or more and 20 ° C or less with respect to a flow initiation temperature of the liquid crystal polyester, at a shear rate of 3000 s ^{- 1} or more is performed at 10000 s ^-1 or less.