TW201932533A - Liquid crystal polyester composition and molded article - Google Patents

Abstract

A liquid crystal polyester composition including a liquid crystal polyester, 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 and a plate filler, when the total content of the liquid crystal polyester, the olefin copolymer and the plate filler is 100% by mass, the content of the liquid crystal polyester is more than 50% by mass and not more than 80% by mass, the content of the olefin copolymer is 5% by mass or more and less than 20% by mass, the content of the plate filler is 15% by mass or more and 30% by mass or less, and the ratio (V2/V1) of the apparent melt viscosity (V2) of the olefin copolymer to the apparent melt viscosity (V1) of the liquid crystal polyester is more than 0.1 and not more than 3.0.

Description

Liquid crystal polyester composition and formed body

The present invention relates to a liquid crystal polyester composition and a molded body.

The present application claims priority based on Japanese Patent Application No. 2017-242143, filed on Jan.

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 inorganic filler selected from a fibrous filler such as glass fiber and a non-fibrous filler such as talc, and an olefin-based copolymer and styrene are selected. The at least one copolymer of the copolymer is blended into 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.

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 which can be formed into a molded body having high punching strength and which has high fluidity, and a molded body.

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, 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; In the case where the total content of the liquid crystal polyester, the olefin-based copolymer, and the platy filler is 100% by mass, the content of the liquid crystal polyester is more than 50% by mass and 80% by mass. % or less, the content of the olefin-based copolymer is 5% by mass or more and less than 20% by mass, and the content of the platy filler is 15% by mass or more and 30% by mass or less; and the apparent fused viscosity of the olefin-based copolymer ( The ratio (V2/V1) of V2) to the apparent melt viscosity (V1) of the liquid crystal polyester is more than 0.1 and 3.0 or less.

The apparent apparent viscosity (V1) (Pa s) is the liquid crystal polyester of the above-mentioned liquid crystal polyester at a shear rate of 10000 s ^-1 at a measurement temperature higher than the flow initiation temperature of the liquid crystal polyester by 10 ° C. Melt viscosity; the aforementioned apparent melt viscosity (V2) (Pa‧s) is the above-mentioned olefin at a shear rate of 10000 s ^-1 at a measurement temperature higher by 10 ° C than the flow initiation temperature of the liquid crystal polyester. The melt viscosity of the copolymer.

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

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 body having a high punching strength and which has high fluidity, and a molded body thereof.

<Liquid crystal polyester composition>

The liquid crystal polyester composition of the present embodiment contains a liquid crystal polyester, an olefin-based copolymer, and a plate-like filler.

In the present specification, a mixture containing a liquid crystal polyester, an olefin-based copolymer, and a plate-like filler is referred to as a "liquid crystal polyester composition". Further, the case where the mixture is formed into a pellet shape is also 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 and an aromatic dicarboxylic acid include, for example, conversion of a carboxyl group to an alkoxycarbonyl group or an aromatic group. An oxycarbonyl group (i.e., an ester), a carboxyl group converted to a halocarbenyl group (i.e., an acid halide), and a carboxyl group converted to a fluorenyloxy group (i.e., an acid anhydride). Examples of the polymerizable derivative of a compound having a hydroxyl group like an aromatic hydroxycarboxylic acid, an aromatic diol, and an aromatic hydroxyamine include those obtained by deuteration of a hydroxy group and conversion to an oxiranyl group ( That is, a hydrazine 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) 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 than or equal to the ear and 30 mol% or less is 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 aforementioned 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 50% by mass or less 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, and the repeating unit (b) is derived from glycidyl methacrylate. The repeating unit and the repeating unit (c) are derived from a copolymer of a repeating unit of vinyl acetate or the like.

[plate filler]

The term "plate-like filler" as used in the present invention means an aspect ratio of 5 to 200. The plate-like filler of the present embodiment is not particularly limited, and examples thereof include talc, mica, graphite, ash, and glass. 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 from 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 the following conditions using a laser diffraction method.

[Measurement conditions]

Measuring device: laser diffraction/scattering particle size distribution measuring device (manufactured by HORIBA Co., Ltd., LA-950V2)

Particle refractive index: 1.53 to 0.1i

Dispersing medium: water

Dispersion medium refractive index: 1.33

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, the olefin copolymer, and the platy filler is 100% by mass, the content of the liquid crystal polyester in the liquid crystal polyester composition of the present embodiment is more than 50% by mass. And 80% by mass or less. When the content of the liquid crystal polyester exceeds 50% 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 50% 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 80% by mass or less, the liquid crystal polyester composition is easily formed.

When the total content of the liquid crystal polyester, the olefin copolymer, and the platy filler is 100% by mass, the content of the liquid crystal polyester in the liquid crystal polyester composition of the present embodiment is preferably 55 mass% or more. 60% by mass or more is more preferable, and 65% by mass or more is more preferable.

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 liquid crystal polyester is preferably 78% by mass or less, more preferably 75% by mass or less, and 70%. The mass % below is better.

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 liquid crystal polyester is preferably 55 mass% or more and 78 mass% or less. 60% by mass or more and 75% by mass or less are more preferably, and 65% by mass or more and 70% by mass or less are more preferably.

In the other aspect, the content of the liquid crystal polyester is more than 50% by mass and 80% by mass or less, preferably 55% by mass or more and 78% by mass or less, more preferably the total mass of the liquid crystal polyester composition. It is 60% by mass or more and 75% by mass or less, and more preferably 65% by mass or more and 70% by mass or less.

When the total content of the content of the liquid crystal polyester, the olefin-based copolymer, and the platy filler 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. quality%. When the content of the olefin-based copolymer is 5% by mass or more, 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 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, the olefin-based copolymer, and the platy filler is 100% by mass, the content of the olefin-based copolymer in the liquid crystal polyester composition of the present embodiment is preferably 6% by mass or more. More than 8 mass% is more preferable. In addition, when the total content of the liquid crystal polyester, the olefin-based copolymer, and the platy filler is 100% by mass, the content of the olefin-based copolymer is preferably 15% by mass or less, more preferably 10% 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, the olefin copolymer, and the platy filler is 100% by mass, the content of the olefin copolymer is preferably 6% by mass or more and 15% by mass or less. More preferably, it is 8 mass% or more and 10 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 6% by mass or more and 15% by mass or less, based on the total mass of the liquid crystal polyester composition. It is preferably 8 mass% or more and 10 mass% or less.

When the total content of the liquid crystal polyester, the olefin-based copolymer, and the platy filler is 100% by mass, the content of the plate-like filler in the liquid crystal polyester composition of the present embodiment is 15% by mass or more and 30% by mass or less. . When the content of the platy filler is less than 15% by mass, the liquid crystal polyester remarkably exhibits anisotropy, and the liquid crystal polyester composition becomes difficult to form. On the other hand, when the content of the platy filler is more than 30% by mass, the content of the liquid crystal polyester is relatively small, and the pulverization strength of the molded body obtained from the liquid crystal polyester composition is lowered.

That is, when the content of the platy filler is within the above range, the liquid crystal polyester is suppressed from remarkably exhibiting anisotropy, and the liquid crystal polyester composition can be easily formed. Further, the content of the liquid crystal polyester does not become relatively small, and the impact strength of the molded body obtained from the liquid crystal polyester composition is easily 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 platy filler in the liquid crystal polyester composition of the present embodiment is 20 The mass% or more is more preferably 23% by mass or more. In addition, when the total content of the liquid crystal polyester, the olefin-based copolymer, and the platy filler is 100% by mass, the content of the plate-like filler is preferably 28% by mass or less, more 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.

Wherein, the liquid crystal polyester is kept in the furnace of the capillary rheometer (the temperature of which is set to be 10 ° C higher than the flow initiation temperature of the liquid crystal polyester of the liquid crystal polyester composition produced) for 5 minutes. The melt viscosity at a shear rate of 10000 s ^-1 in the above temperature state is defined as "the apparent melt viscosity (V1) of the liquid crystal polyester".

Further, the olefin-based copolymer is kept in a furnace of a capillary rheometer (the temperature of which is set to be 10 ° C higher than the flow initiation temperature of the liquid crystal polyester of the liquid crystal polyester composition to be produced) for 10 minutes. The melt viscosity at a shear rate of 10000 s ^-1 in the above temperature state is defined as "the apparent melt viscosity (V2) of the olefin-based copolymer".

In the liquid crystal polyester composition of the present embodiment, the ratio (V2/V1) of the apparent melt viscosity (V2) of the above olefin-based copolymer to the apparent melt viscosity (V1) of the liquid crystal polyester is more than 0.1. And 3.0 or less.

When the melt viscosity ratio (V2/V1) is more than 0.1 and 3.0 or less, the punching strength of the molded body obtained from the liquid crystal polyester composition is improved. When the melt viscosity ratio (V2/V1) is closer to 1, the punching strength of the molded body is more likely to increase. Specifically, the above melting The viscosity ratio (V2/V1) is preferably 0.3 or more, more preferably 0.5 or more, and still more preferably 0.8 or more. Further, the melt viscosity ratio (V2/V1) is preferably 2.8 or less, more preferably 2.5 or less, and still more preferably 2.0 or less.

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

In the first aspect, the melt viscosity ratio (V2/V1) is preferably 0.3 or more and 2.8 or less, more preferably 0.5 or more and 2.5 or less, and still more preferably 0.8 or more and 2.0 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 melt viscosity ratio (V2/V1) is more than 0.1 and 3.0 or less, it is presumed that the olefin-based copolymer is easily dispersed in the liquid crystal polyester. When the olefin-based copolymer is easily dispersed in the liquid crystal polyester, it is presumed that a large amount of the olefin-based copolymer having a small particle diameter is present in the liquid crystal polyester. It is noted that the distance between the particles of the olefin-based copolymer in such a molded body 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 improved.

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 using a mold for measuring the flow length, and the length of the flow direction of the resin (also referred to as flow) is measured for the molded body obtained from the liquid crystal polyester composition of the present embodiment. Length) can be evaluated. 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> described later, the flow length is long. A characteristic of a degree of 800 mm or more is preferable, and a characteristic having a flow length of 825 mm or more and less than 980 mm is more preferable.

[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, the plate-like filler, and optionally at least one other 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.

The content of the above other components is preferably from 0.1 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 0.1 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 0.1 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 0.1 to 20 parts by mass based on 100 parts by mass of the liquid crystal polyester.

The liquid crystal polyester composition of the present embodiment is preferably obtained by melt-kneading the liquid crystal polyester, the olefin-based copolymer, the plate-like filler, and other components as necessary, using an extruder, and extruding into pellets. modulation. Preferably, the extruder uses a supply port having a cylinder, at least one screw disposed in the cylinder, and at least one of the cylinders, and more preferably at least one of the cylinders One of the vents.

<Formed body>

The molded article of the present embodiment can be obtained from a liquid crystal polyester 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.

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 The injection box is used for injection molding, The injection molded body for the horn pad, the injection molded body for the knob, the injection molded body for the airbag cover, the injection molded body for various trims, and the injection molded body for various pillars. In the case of a door lock bezel, an injection molded body, an injection molded body for a glove box, an injection molded body for a defroster nozzle, an injection molded body for a scuff plate, and a steering wheel for injection molding. The body, the steering column cover, the injection molded body, 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 copier related parts.

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 900 J/m or more and 1200 J/m or less, more preferably 1000 J/m or more and 1200 J/m or less, and still more preferably 1000 J/m or more and 1200 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 high punching strength and which has high fluidity, and a molded body thereof.

In one aspect, a liquid crystal polyester composition according to an embodiment of the present invention is a liquid crystal polyester composition comprising a liquid crystal polyester, an olefin copolymer, and a plate filler; wherein the liquid crystal polyester has the aforementioned repetition The liquid crystal polyester of the unit (1), the repeating unit (2), and the repeating unit (3), preferably having a repeating unit derived from p-hydroxybenzoic acid, derived from 4,4'-dihydroxyl linkage a repeating unit of benzene, a repeating unit derived from terephthalic acid, a repeating unit derived from isophthalic acid, and a liquid crystal polyester derived from a repeating unit of 4,4′-dihydroxybiphenyl; the aforementioned olefin The copolymer comprises: a repeating unit derived from an α-olefin (the aforementioned repeating unit (a)), a repeating unit derived from a glycidyl ester of an α,β-unsaturated acid (the aforementioned repeating unit (b)), and a repeating unit derived from an ethylenically unsaturated ester (the aforementioned repeating unit (c)) and a repeating unit other than the above repeating units (a) to (c), as required; and the aforementioned total mass of the olefin-based copolymer The total content of the repeating units (a) to (c) is 80% by mass or more and 100% by mass or less. Best is 90 mass% and 100 mass% or less; The content of the repeating unit (b) is preferably 0.5% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 4% by mass or less based on the total mass of the olefin-based copolymer; Mica (volume average particle diameter 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 total content of the liquid crystal polyester, the olefin-based copolymer, and the platy filler is 100% by mass, the content of the liquid crystal polyester is more than 50% by mass and 80% by mass or less, preferably 55% by mass or more. 78% by mass or less, more preferably 60% by mass or more and 75% by mass or less, still more preferably 65% by mass or more and 70% by mass or less, and the content of the olefin-based copolymer is 5% by mass or more and less than 20% by mass. It is 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, and the content of the plate-like filler is 15% by mass or more and 30% by mass or less, preferably 20% by mass or less. More than 28% by mass, more preferably 23% by mass or more and 25% by mass The ratio (V2/V1) of the apparent melt viscosity (V2) of the olefin-based copolymer to the apparent melt viscosity (V1) of the liquid crystal polyester is more than 0.1 and 3.0 or less, preferably 0.3 or more and 2.8 or less. More preferably, it is 0.5 or more and 2.5 or less, and more preferably 0.8 or more and 2.0 or less.

In another aspect, the liquid crystal polyester composition is characterized in that the content of the liquid crystal polyester is more than 50% by mass and not more than 80% by mass, based on the total mass of the liquid crystal polyester composition. 55% by mass or more and 78% by mass or less, more preferably 60% by mass or more and 75% by mass or less, still more preferably 65% by mass or more and 70% by mass or less; and the content of the olefin-based copolymer is 5% by mass or more It is less than 20% by mass, 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, and the content of the platy filler is 15% by mass or more and 30% by mass or less. It is preferably 20% by mass or more and 28% by mass or less, more preferably 23% by mass or more and 25% by mass or less; However, the total content of the liquid crystal polyester, the olefin-based copolymer, and the platy filler is not more than 100% by mass.

In addition, the liquid crystal polyester composition is a liquid crystal polyester composition, and the flow length is measured by a method described in <Flow Length of Liquid Crystal Polyester Composition> described later. It is preferable that it is 800 mm or more, and may be 825 mm or more and less than 980 mm. When the liquid crystal polyester composition is formed into a molded body from the liquid crystal polyester composition, the <Essert impact strength> of the molded body described later is used. The Ectotech impact strength of the molded article measured by the method described above is preferably 800 J/m or more, and may be 900 J/m or more and 1200 J/m or less, and may be 1000 J/m or more and 1200 J/m or less. It can also be 1000 J/m or more and 1200 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 231 ° C or more and 236 ° 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 900 J/m or more and 1200 J/m or less. Further, it is more preferably a composition capable of imparting an Ecant impact strength of 1000 J/m or more and 1200 J/m or less; and measuring the tensile strength by the method described in <Tensile strength and tensile growth rate of the molded body> described later. And a tensile growth rate, and a composition capable of imparting tensile strength of 112 MPa or more and 124 MPa or less is preferable. It is preferably a composition capable of imparting a tensile growth rate of 8.1% or more and 9.7% or less; and measuring the bending strength and the bending elastic modulus in the method described in <Bending strength and bending elastic modulus of the molded body> described later. In the case of a composition capable of imparting a bending strength of 112 MPa or more and 127 MPa or less, a composition capable of imparting a bending elastic modulus of 8300 MPa or more and 9500 MPa or less is preferable.

(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 (V1), apparent melt viscosity (V2), melt viscosity ratio (V2/V1)>

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

The melt viscosity ratio (V2/V1) was calculated from the apparent melt viscosity (V1) of the obtained liquid crystal polyester and the apparent melt viscosity (V2) of the olefin copolymer.

<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.

<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.). . The tensile strength and tensile growth rate of the obtained test piece were measured 5 times in accordance with ASTM D638. 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 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.). A test piece of 127 mm × 12.7 mm × 6.4 mmt. The Essert impact strength of the 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 to 4, Comparative Example 1 and Comparative Example 2]

Using a two-axis extruder (PCM-30HS manufactured by Chiba Iron Works Co., Ltd., screw rotation: same direction, L/D = 44), the liquid crystal polyester, olefin copolymer, and platy filler obtained in Production Example 1 were used. The mixture was melt-kneaded and pelletized at 340 ° C in the ratio shown in Table 1. A particulate liquid crystal polyester composition was obtained. 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, the olefin-based copolymer, and the platy filler.

[Reference example]

Using a two-axis extruder ("PCM-30" manufactured by Chiba Iron Works Co., Ltd.), the liquid crystal polyester and the plate-like filler were melt-kneaded at a cylinder temperature of 340 ° C according to the ratio shown in Table 1, to obtain a granular shape. Liquid crystal polyester composition.

All of the particulate liquid crystal polyester composition was dried by hot air at 120 ° C for 6 hours.

Further, the following materials were used for the olefin-based copolymer and the plate-like filler used in 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 copolymer (1):

Ethylene ratio: 70.0% by mass, glycidyl methacrylate ratio: 3.0% by mass, methyl acrylate ratio: 27.0% by mass, apparent melt viscosity (V2) 16.2 Pa‧ s

Olefin copolymer (2):

Ethylene ratio: 70.2% by mass, glycidyl methacrylate ratio: 2.9% by mass, methyl acrylate ratio: 26.9% by mass, apparent melt viscosity (V2) 11.7 Pa‧s

Olefin copolymer (3):

Ethylene ratio: 70.5 mass%, glycidyl methacrylate ratio: 3.2 mass%, methyl acrylate ratio: 26.3 mass%, apparent melt viscosity (V2) 3.1 Pa‧s

Olefin copolymer (4):

Ethylene ratio: 71.2% by mass, glycidyl methacrylate ratio: 3.2% by mass, methyl acrylate ratio: 25.6% by mass, apparent melt viscosity (V2) 0.4 Pa‧s

(plate filler)

A-31S: Mica, manufactured by YAMAGUCHI MICA AG, with an average particle size of 30μm (length to width ratio of 75)

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 to 4 of the present invention were applied had high fluidity and the obtained molded body had high punching strength.

Although the liquid crystal polyester composition of Examples 1 to 4 and the liquid crystal polyester composition of the reference example were both highly fluid and the obtained molded body had high punching strength, the liquid crystal polyester compositions of Examples 1 to 4 were used. In terms of the tensile growth rate, the liquid crystal polyester composition of the reference example has a higher tensile growth rate.

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, and a molded body thereof, and is extremely useful industrially.

Claims (2)

A liquid crystal polyester composition comprising: a liquid crystal polyester, 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, and a plate When the total content of the liquid crystal polyester, the olefin-based copolymer, and the platy filler is 100% by mass, the content of the liquid crystal polyester is more than 50% by mass and 80% by mass or less. The content of the olefin-based copolymer is 5% by mass or more and less than 20% by mass, and the content of the platy filler is 15% by mass or more and 30% by mass or less; and the apparent entangled viscosity (V2) of the olefin-based copolymer is relatively The ratio (V2/V1) of the apparent melt viscosity (V1) of the liquid crystal polyester is more than 0.1 and 3.0 or less. A molded body formed by the liquid crystal polyester composition described in claim 1 of the patent application.