JP2019094497A - Liquid-crystal polyester resin composition and molded body - Google Patents

Abstract

To provide a liquid-crystal polyester resin composition with a high retention rate of mechanical strength during regrinding.SOLUTION: Provided is a liquid-crystal polyester resin composition that contains 100 pts.mass of a liquid-crystal polyester resin, and 5 pts.mass or more and 100 pts.mass or less of a glass component, wherein the glass component contains glass fibers in which the lengths thereof are greater than 50 μm, and glass fine powder in which the lengths thereof are 4 μm or more and 50 μm or less, the number-average fiber length of the glass fibers is 200 μm or more and 400 μm or less, and the fine powder is contained at a proportion that is 20% or more and 95% or less with respect to the total amount of the glass component.SELECTED DRAWING: None

Description

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

  The liquid crystal polyester resin is extremely excellent in melt flowability, and depending on the structure, has heat deformation resistance of 300 ° C. or more. Liquid crystal polyester resins are used for molded articles in applications such as electronic parts, OA parts, AV parts, heat-resistant dishes and the like, taking advantage of such characteristics.

  In the field of electronic components, miniaturization and refinement are in progress, and the thickness of a molded body obtained using a liquid crystal polyester resin is also extremely thin. As the thickness of the molded body becomes thinner, problems such as a decrease in the strength of the molded body and control of the anisotropy of the liquid crystal polyester resin have become problems. In order to solve these problems, the liquid-crystal polyester resin composition which mix | blended the fibrous filler with liquid-crystal polyester resin is used (for example, patent documents 1-3).

Japanese Patent Application Laid-Open No. 6-240115 JP, 2009-191088, A International Publication No. 2012/090410

  By the way, from the viewpoint of environmental protection to reduce waste materials and the viewpoint of cost reduction, the molded articles such as runners and sprues generated at the time of injection molding are crushed, and the crushed molded articles are reused as raw materials for manufacturing molded articles. A recycling method has begun to be studied in which a part of the ground compact is mixed with a raw material not used for producing a compact and reused as a raw material for producing a compact.

  Hereinafter, in the present specification, it is called "regrind" that the molded body is crushed and regenerated as a raw material used for producing the molded body, and the obtained pulverized material is called "regrind material". On the other hand, the raw material which is not used for manufacture of a molded object is called a "virgin material."

Regrind materials are generally known to have lower physical properties than virgin materials. Regrind materials have more heat history than virgin materials. Therefore, it is considered that the deterioration of the resin due to heat reduces the mechanical strength of the molded product using the regrind material. Moreover, regrind material is manufactured by grinding. Therefore, it is believed that the physical failure of the filler reduces the mechanical strength of the regrind-formed compact.
Therefore, in order to effectively use the regrind material, the mechanical strength of the molded product using the regrind material is unlikely to be reduced relative to the mechanical strength of the molded product using the virgin material, and the usable range for the molded product Liquid crystalline polyester resin compositions (virgin materials) that can be maintained by

  The resin compositions described in Patent Documents 1 to 3 do not necessarily have high retention rates of mechanical strength at the time of regrind.

  In the present specification, "mechanical strength" refers to tensile strength and Izod impact strength. Moreover, "the maintenance rate of mechanical strength" is the value which calculated the physical-property value of the mechanical strength of the molded object using the regrind material with respect to the physical property value of the mechanical strength of the molded object using a virgin material.

  This invention is made in view of such a situation, Comprising: It aims at providing the liquid crystalline polyester resin composition and molded object with a high maintenance factor of mechanical strength at the time of regrind.

  In order to solve the above-mentioned subject, one mode of the present invention contains 100 mass parts of liquid crystalline polyester resin, and 5 mass parts or more and 100 mass parts or less of glass component, and a glass component has a length of 50 μm or more glass fiber And glass fine powder having a length of 4 μm to 50 μm, the number average fiber length of glass fiber is 200 μm to 400 μm, and the content ratio of the fine powder is 20% or more with respect to the total number of glass components Provided is a liquid crystal polyester resin composition that is 95% or less.

  In one aspect of the present invention, the fine powder comprises a first fine powder made of glass having a length of 4 μm or more and 40 μm or less and a second fine powder of 40 μm or more and 50 μm or less, and the first fine powder is the total number of glass components. On the other hand, it may be 40% or more and 90% or less.

  In one aspect of the present invention, the fine powder content may be 70% to 90% of the total number of the glass components.

  In one aspect of the present invention, the fine powder may have a diameter of 9 μm to 12 μm, and the fine powder may have an aspect ratio of 0.3 to 5.6.

In one aspect of the present invention, the liquid crystal polyester resin may contain repeating units represented by the following formulas (1) to (3).
(1) ^-O-Ar 1 -CO-
(2) ^-CO-Ar 2 -CO-
(3) ^-X-Ar 3 -Y-
[Ar ¹ represents a phenylene group, a naphthylene group or a biphenylylene group.
Ar ² and Ar ³ each independently represent a phenylene group, a naphthylene group, a biphenylylene group or a group represented by the following formula (4).
X and Y each independently represent an oxygen atom or an imino group (-NH-).
At least one hydrogen atom in the group represented by Ar ¹ , Ar ² or Ar ³ is independently substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms It may be ]
^{(4) -Ar 4 -Z-Ar} 5 -
[Ar ⁴ and Ar ⁵ each independently represent a phenylene group or a naphthylene group. Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group or an alkylidene group having 1 to 10 carbon atoms.
One or more hydrogen atoms in the group represented by Ar ⁴ or Ar ⁵ may be independently substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Good. ]

In one embodiment of the present invention, Ar ¹ is a 1,4-phenylene group, Ar ² is a 1,4-phenylene group and a 1,3-phenylene group, Ar ³ is a biphenylylene group, and X and Y are Each may be an oxygen atom.

  In one aspect of the present invention, the molar ratio (3) / (1) of the repeating unit represented by the formula (1) to the repeating unit represented by the formula (3) is 0.2 or more and 1.0 or less The molar ratio (2) / (3) of the repeating unit represented by the formula (3) to the repeating unit represented by the formula (2) may be 0.9 or more and 1.1 or less.

In one aspect of the present invention, the molar ratio y / x of the repeating unit represented by the formula (2) may be more than 0 and 1 or less.
[X represents a molar content of a repeating unit in which Ar ² is a 1,4-phenylene group. y represents the molar content of repeating units in which Ar ² is a 1,3-phenylene group. ]

In one aspect of the present invention, the liquid crystal polyester resin may include the first liquid crystal polyester resin and the second liquid crystal polyester resin, and α / β may be 0.1 or more and 0.6 or less.
[Α represents a molar ratio y / x of the first liquid crystal polyester resin. β represents a molar ratio y / x of the second liquid crystal polyester resin. ]

  One aspect of the present invention provides a molded article using the above liquid crystal polyester resin composition as a forming material.

  According to one aspect of the present invention, a liquid crystal polyester resin composition and a molded article having a high maintenance rate of mechanical strength at the time of regrind are provided.

<Liquid crystal polyester resin composition>
The liquid crystal polyester resin composition of the present embodiment contains a liquid crystal polyester resin and a glass component.

[Liquid crystal polyester resin]
Typical examples of the liquid crystal polyester resin used in the present embodiment include at least one compound selected from the group consisting of aromatic diols, aromatic hydroxyamines and aromatic diamines, aromatic hydroxycarboxylic acids, and aromatics. Polymer formed by condensation polymerization of an aromatic dicarboxylic acid (polycondensation); a polymer formed by polymerization of plural types of aromatic hydroxycarboxylic acids; selected from the group consisting of aromatic diols, aromatic hydroxyamines and aromatic diamines And polymers obtained by polymerizing at least one compound of the present invention and an aromatic dicarboxylic acid; and polymers obtained by polymerizing a polyester such as polyethylene terephthalate and an aromatic hydroxycarboxylic acid.

  Among them, it is obtained by condensation polymerization (polycondensation) of at least one compound selected from the group consisting of aromatic diols, aromatic hydroxyamines and aromatic diamines, aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids. Polymers are preferred.

  Here, the aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, the aromatic diol, the aromatic hydroxyamine and the aromatic diamine are, independently of one another, substituted for part or all of the polymerizable ester-forming derivatives thereof. May be

  Examples of polymerizable derivatives of compounds having a carboxy group, such as aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids, include esters, acid halides, and acid anhydrides. Examples of the above-mentioned ester include compounds obtained by converting a carboxy group into an alkoxycarbonyl group or an aryloxycarbonyl group. Examples of the above-mentioned acid halides include compounds obtained by converting a carboxy group into a haloformyl group. Examples of the above-mentioned acid anhydride include compounds obtained by converting a carboxy group into an acyloxycarbonyl group.

  Examples of polymerizable derivatives of compounds having an amino group, such as aromatic hydroxyamines and aromatic diamines, include compounds (acylated products) obtained by acylating an amino group to convert it into an acylamino group.

  Among the examples of the polymerizable derivatives exemplified above, as a raw material monomer of the liquid crystal polyester resin, an acylated product obtained by acylating an aromatic hydroxycarboxylic acid and an aromatic diol is preferable.

  It is preferable that the liquid-crystal polyester resin used for this embodiment has a repeating unit (Hereinafter, it may be mentioned "repeating unit (1).") Represented by following formula (1). In addition, the liquid crystal polyester resin is represented by a repeating unit (1), a repeating unit represented by the following formula (2) (hereinafter sometimes referred to as "repeating unit (2)"), and a formula (3) below. It is more preferable to have a repeating unit (hereinafter sometimes referred to as "repeating unit (3)").

(1) ^-O-Ar 1 -CO-
(2) ^-CO-Ar 2 -CO-
(3) ^-X-Ar 3 -Y-

[In Formula (1)-Formula (3), Ar ¹ represents a phenylene group, a naphthylene group, or a biphenylylene group.
Ar ² and Ar ³ each independently represent a phenylene group, a naphthylene group, a biphenylylene group or a group represented by the following formula (4). X and Y each independently represent an oxygen atom or an imino group (-NH-).
One or more hydrogen atoms in the group represented by Ar ¹ , Ar ² or Ar ³ are each independently substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms It may be done. ]

^{(4) -Ar 4 -Z-Ar} 5 -

[In Formula (4), Ar ⁴ and Ar ⁵ independently represent a phenylene group or a naphthylene group. Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group or an alkylidene group having 1 to 10 carbon atoms.
At least one hydrogen atom in the group represented by Ar ⁴ or Ar ⁵ is independently substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. It is also good. ]

  As said halogen atom which can be substituted with a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are mentioned.

  As an example of the said C1-C10 alkyl group which can be substituted with a hydrogen atom, a methyl group, an ethyl group, 1-propyl group, isopropyl group, 1-butyl group, isobutyl group, sec-butyl group, tert-butyl group Groups, 1-hexyl group, 2-ethylhexyl group, 1-octyl group, 1-decyl group and the like.

  Examples of the aryl group having 6 to 20 carbon atoms which can be substituted with a hydrogen atom include monocyclic aromatic groups such as phenyl group, orthotolyl group, metatolyl group, paratolyl group and the like, 1-naphthyl group, 2--2-naphthyl group A fused aromatic group such as a naphthyl group etc. may be mentioned.

In the group represented by Ar ¹ , Ar ² , Ar ³ , Ar ⁴ or Ar ⁵ , when one or more hydrogen atoms are substituted with the above-mentioned substituents, the number of the substituents is Ar ¹ It is preferable that the number of each of the groups represented by each of Ar ² , Ar ³ , Ar ^{4 and} Ar ⁵ be one or two independently. The number of the substituents is more preferably one for each group represented by Ar ¹ , Ar ² , Ar ³ , Ar ⁴ or Ar ⁵ .

  A methylene group, an ethylidene group, isopropylidene group, 1-butylidene group, 2-ethylhexylidene group etc. are mentioned as an example of the said C1-C10 alkylidene group.

  The repeating unit (1) is a repeating unit derived from a predetermined aromatic hydroxycarboxylic acid.

  In the present specification, “derived from” means that the chemical structure changes due to the polymerization of the raw material monomer and no other structural change occurs.

  Examples of the aromatic hydroxycarboxylic acid include 4-hydroxybenzoic acid, metahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-3-naphthoic acid, 1-hydroxy-5-naphthoic acid, and the like. -Hydroxy-4'-carboxydiphenyl ether or a part of hydrogen atoms in the aromatic ring of these aromatic hydroxycarboxylic acids is substituted by a substituent selected from the group consisting of an alkyl group, an aryl group and a halogen atom Aromatic hydroxycarboxylic acids are mentioned.

  The aromatic hydroxycarboxylic acid may be used alone or in combination of two or more in the production of a liquid crystalline polyester resin.

As the repeating unit (1), a unit in which Ar ¹ is a 1,4-phenylene group (a repeating unit derived from 4-hydroxybenzoic acid), and a unit (6-hydroxy in which Ar ¹ is a 2,6-naphthylene group A repeating unit derived from -2-naphthoic acid is preferable, and a unit which is a 1,4-phenylene group is more preferable.

  The repeating unit (2) is a repeating unit derived from a predetermined aromatic dicarboxylic acid.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, biphenyl-4,4'-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenylthioether-4,4. '-Dicarboxylic acid or an aromatic dicarboxylic acid obtained by substituting a part of hydrogen atoms in the aromatic ring of these aromatic dicarboxylic acids with a substituent selected from the group consisting of an alkyl group, an aryl group and a halogen atom It can be mentioned.

  The aromatic dicarboxylic acid may be used alone or in combination of two or more kinds in the production of a liquid crystal polyester resin.

As the repeating unit (2), a unit in which Ar ² is a 1,4-phenylene group (for example, a repeating unit derived from terephthalic acid), a unit in which Ar ² is a 1,3-phenylene group (for example, isophthalic acid) Repeating unit), a unit wherein Ar ² is a 2,6-naphthylene group (eg, a repeating unit derived from 2,6-naphthalenedicarboxylic acid), and Ar ² is a diphenyl ether-4,4'-diyl group A unit (e.g., a repeating unit derived from diphenyl ether-4,4'-dicarboxylic acid) is preferable, and a unit which is a 1,4-phenylene group and a unit which is a 1,3-phenylene group are more preferable.

  The repeating unit (3) is a repeating unit derived from a predetermined aromatic diol, aromatic hydroxyamine or aromatic diamine.

  As the aromatic diol, the aromatic hydroxyamine or the aromatic diamine, for example, 4,4′-dihydroxybiphenyl, hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenyl ether, bis (4- (4 Hydroxyphenyl) methane, 1,2-bis (4-hydroxyphenyl) ethane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl thioether, 2,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, Examples include 4-aminophenol, 1,4-phenylenediamine, 4-amino-4′-hydroxybiphenyl, and 4,4′-diaminobiphenyl.

  The aromatic diol, the aromatic hydroxyamine or the aromatic diamine may be used alone or in combination of two or more in the production of the liquid crystalline polyester resin.

As the repeating unit (3), a unit in which Ar ³ is a 1,4-phenylene group (for example, a repeating unit derived from hydroquinone, 4-aminophenol or 1,4-phenylenediamine), and Ar ³ in 4, 4 A unit which is a '-biphenylylene group (for example, a repeating unit derived from 4,4'-dihydroxybiphenyl, 4-amino-4'-hydroxybiphenyl or 4,4'-diaminobiphenyl) is preferred, and 4,4'-biphenylylene is Units which are groups are more preferred.

  As the repeating unit (3), a unit in which X and Y are each an oxygen atom is preferable.

  In addition, when the molded object obtained from the liquid-crystal polyester resin composition of this embodiment requires especially favorable heat resistance and thermal stability, the number of the substituents which repeating unit (1)-(3) has Is preferred. In addition, when a molded article obtained from the liquid crystal polyester resin composition of the present embodiment is required to have particularly good heat resistance and thermal stability, it does not have a substituent (for example, an alkyl group) that is susceptible to heat. Is preferred.

  In the present embodiment, the heat resistance of the molded article refers to the property that the resin that is a forming material of the molded article is not easily softened under a high temperature environment. In the present embodiment, the heat resistance of the molded body can be clarified by measuring the load deflection temperature of the resin. The deflection temperature under load in this embodiment is measured under a load of 1.82 MPa in accordance with ASTM D648. It can be said that the heat resistance of the molded article is higher as the load deflection temperature of the resin measured in this manner is higher.

  Further, in the present embodiment, the thermal stability of the molded article refers to the property that decomposition and deterioration of the resin are less likely to occur when the molded article is held at a temperature (melting temperature) at which the resin is molded and processed.

  Next, a liquid crystal polyester resin particularly suitable for application to the present embodiment will be described in detail based on the examples of the structural units described above, for combinations of the structural units.

As a specific example of the preferable liquid-crystal polyester resin used for this embodiment, resin which consists of a structural unit (repeating unit) originating in the following monomer is mentioned, for example.
(A) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid copolymer (b) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer (c) 4-hydroxybenzoic acid / Terephthalic acid / isophthalic acid / 4,4'-dihydroxybiphenyl copolymer (d) 4-hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4,4'-dihydroxybiphenyl / hydroquinone copolymer (e) 4-hydroxy Benzoic acid / terephthalic acid / hydroquinone copolymer (f) 2-hydroxy-6-naphthoic acid / terephthalic acid / hydroquinone copolymer (g) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer (h) 2-hydroxy-6-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer (i) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / hydroquinone copolymer (j) 4-hydroxybenzoic acid / 2-hydroxy-6- Naphthoic acid / terephthalic acid / hydroquinone / 4,4'-dihydroxybiphenyl copolymer (k) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / 4,4'-dihydroxybiphenyl copolymer (I) 4- Hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer (m) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer (n) 4-hydroxybenzoic acid / 2 -Hydroxy-6-naphthoic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer o) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone / 4,4'-dihydroxybiphenyl copolymer (p) 4-hydroxybenzoic acid / terephthalic acid / 4-aminophenol copolymer (Q) 2-hydroxy-6-naphthoic acid / terephthalic acid / 4-aminophenol copolymer (r) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / 4-aminophenol copolymer (S) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / 4-aminophenol copolymer (t) 4-hydroxybenzoic acid / terephthalic acid / ethylene glycol copolymer (u) 4-hydroxy Benzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / ethylene glycol copolymer ( ) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / ethylene glycol copolymer (w) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / 4,4'- Dihydroxybiphenyl / ethylene glycol copolymer (x) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / 4,4'-dihydroxybiphenyl copolymer.

Among the above examples, (b) and (c) are preferable, and (c) is more preferable. That is, the Ar ¹ is a 1,4-phenylene group, the Ar ² is a 1,4-phenylene group and a 1,3-phenylene group, the Ar ³ is a biphenylylene group, and the X and the Y are More preferably each is an oxygen atom.

  The content of the repeating unit (1) of the liquid crystal polyester resin is preferably 30 mol% or more, more preferably 30 mol% to 80 mol%, further preferably 30% by mol or more, with respect to the total amount of all the repeating units constituting the liquid crystal polyester resin. Preferably, it is 30 mol% or more and 70 mol% or less, and particularly preferably 35 mol% or more and 65 mol% or less. The total amount of all repeating units constituting the liquid crystal polyester resin is obtained by dividing the mass of each repeating unit constituting the liquid crystal polyester resin by the formula weight of each repeating unit to obtain the equivalent amount (mol) of the substance amount of each repeating unit. It is the value which calculated | required and added them.

  The heat resistance and hardness of the molded object obtained using the liquid-crystal polyester resin composition of this embodiment as the content rate of the repeating unit (1) of liquid-crystal polyester resin is 30 mol% or more are easy to improve. Moreover, melt viscosity can be made low as the content rate of repeating unit (1) is 80 mol% or less. Therefore, the temperature required for molding the liquid crystal polyester resin tends to be low.

  The content of the repeating unit (2) of the liquid crystal polyester resin is preferably 35 mol% or less, more preferably 10 mol% to 35 mol%, further preferably, based on the total amount of all repeating units constituting the liquid crystal polyester resin. Preferably, it is 15 mol% or more and 35 mol% or less, particularly preferably 17.5 mol% or more and 32.5 mol% or less.

  The content of the repeating unit (3) of the liquid crystal polyester resin is preferably 35 mol% or less, more preferably 10 mol% to 35 mol%, further preferably, based on the total amount of all repeating units constituting the liquid crystal polyester resin. Preferably, it is 15 mol% or more and 35 mol% or less, particularly preferably 17.5 mol% or more and 32.5 mol% or less.

  In the liquid crystal polyester resin, the ratio of the content of the repeating unit (2) to the content of the repeating unit (3) is [content of repeating unit (2)] / [content of repeating unit (3)] ( It is preferably 0.9 or more and 1.1 or less, more preferably 0.95 or more and 1.05 or less, and still more preferably 0.98 or more and 1.02 or less, in terms of mol / mol).

  In the liquid crystal polyester resin, the ratio of the content of the repeating unit (3) to the content of the repeating unit (1) is [content of repeating unit (3)] / [content of repeating unit (1)] ( It is preferably 0.2 or more and 1.0 or less, more preferably 0.25 or more and 0.85 or less, and still more preferably 0.3 or more and 0.75 or less, in terms of mol / mol).

In the liquid crystal polyester resin, the molar ratio y / x of the repeating unit (2) is preferably more than 0 and 1 or less, more preferably 0.1 or more and 0.9 or less, and more preferably 0.2 or more. More preferably, it is 8 or less.
x represents the molar content of repeating units in which Ar ² is a 1,4-phenylene group.
y represents the molar content of repeating units in which Ar ² is a 1,3-phenylene group.

  The liquid crystal polyester resin may have repeating units (1) to (3) independently of one another, or two or more of them. The liquid crystal polyester resin may have one or more repeating units other than the repeating units (1) to (3), but the content is preferably based on the total amount of all repeating units. It is 10 mol% or less, more preferably 5 mol% or less.

[Liquid crystal polyester resin mixture]
In the present embodiment, it is also possible to use a liquid crystal polyester resin mixture in which a plurality of liquid crystal polyester resins are mixed. Thereby, the melt flowability of the liquid crystal polyester resin composition of the present embodiment can be further improved, and the warpage of the obtained molded article can be sufficiently suppressed.
Here, as the liquid crystal polyester resin mixture, a mixture of liquid crystal polyester resins having different flow start temperatures is assumed. In the liquid crystal polyester resin mixture, one having a higher flow start temperature is taken as a first liquid crystal polyester resin, and one having a lower flow start temperature is taken as a second liquid crystal polyester resin.

  300 degreeC or more is preferable, as for the flow start temperature of said 1st liquid crystal polyester resin, 310 degreeC or more is more preferable, and 315 degreeC or more is more preferable. Moreover, 400 degrees C or less is preferable, as for the flow start temperature of said 1st liquid-crystal polyester resin, 360 degrees C or less is more preferable, and 345 degrees C or less is more preferable. The upper limit value and the lower limit value can be arbitrarily combined.

  When the flow start temperature of the first liquid crystal polyester resin is within the above range, the melt flowability of the resin and the heat resistance of the resulting molded article tend to be compatible.

  On the other hand, 260 degreeC or more is preferable, as for the flow start temperature of said 2nd liquid crystalline polyester resin, 270 degreeC or more is more preferable, and 285 degreeC or more is more preferable. Moreover, 350 degrees C or less is preferable, as for the flow start temperature of said 2nd liquid crystal polyester resin, 320 degrees C or less is more preferable, and 315 degrees C or less is more preferable. The upper limit value and the lower limit value can be arbitrarily combined.

  When the flow start temperature of the second liquid crystal polyester resin is within the above range, the flowability (thin flowability) of the thin-walled portion of the mold tends to be good, and the deflection temperature under load of the resulting molded article becomes sufficiently high. Tend.

  In the liquid crystal polyester resin mixture, the content of the second liquid crystal polyester resin is preferably 10 to 150 parts by mass, more preferably 30 to 120 parts by mass with respect to 100 parts by mass of the first liquid crystal polyester resin. And 50 to 100 parts by mass.

  The content of the second liquid crystal polyester resin relative to the first liquid crystal polyester resin may be appropriately set so that the balance between the deflection temperature under load and the thin-walled fluidity of the liquid crystal polyester resin mixture is in a desired state.

  The liquid crystal polyester resin mixture can also contain a liquid crystal polyester resin other than the first liquid crystal polyester resin and the second liquid crystal polyester resin. In that case, in the resin mixture, the resin having the highest flow start temperature may be the first liquid crystal polyester resin, and the resin having the lowest flow start temperature may be the second liquid crystal polyester resin. A liquid crystal polyester resin mixture substantially consisting of a first liquid crystal polyester resin and a second liquid crystal polyester resin is preferred.

In the liquid crystal polyester resin mixture, α / β is preferably in the range of 0.1 to 0.6, and more preferably in the range of 0.3 to 0.6.
α represents the molar ratio y / x of the first liquid crystal polyester resin.
β represents a molar ratio y / x of the second liquid crystal polyester resin.
x represents the molar content of repeating units in which Ar ² is a 1,4-phenylene group.
y represents the molar content of repeating units in which Ar ² is a 1,3-phenylene group.

[Method of producing liquid crystalline polyester resin]
Next, an example of a method for producing a liquid crystal polyester resin according to the present embodiment will be described.

  The liquid crystal polyester resin of the present embodiment is preferably produced by the following acylation step and polymerization step.

  The acylation step is a step of obtaining an acylated product by acylating the phenolic hydroxy group of the raw material monomer with a fatty acid anhydride (such as acetic anhydride).

  In the polymerization step, a liquid crystal polyester is obtained by polymerizing the acyl group of the acylated product obtained in the acylation step and the carboxy group of the acylated product of aromatic dicarboxylic acid and aromatic hydroxycarboxylic acid so as to cause transesterification. It is good to get resin.

  The acylation step and the polymerization step may be carried out in the presence of a heterocyclic organic base compound as represented below.

In the above formula (5), R _{1 to} R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxymethyl group, a cyano group, or a cyanoalkyl having 1 to 4 carbon atoms in the alkyl group. And a cyanoalkoxy group having 1 to 4 carbon atoms of an alkoxy group, a carboxy group, an amino group, an aminoalkyl group having 1 to 4 carbon atoms, an aminoalkoxy group having 1 to 4 carbon atoms, a phenyl group, a benzyl group, a phenyl propiyl group It represents a leu group or a formyl group.

The heterocyclic organic base compound of the above formula (5) is preferably an imidazole derivative in which R ₁ is an alkyl group having 1 to 4 carbon atoms and R _{2 to} R ₄ are each a hydrogen atom.
This can further improve the reactivity of the acylation reaction in the acylation step and the transesterification reaction in the polymerization step. Moreover, the color tone of the molded object obtained using the liquid-crystal polyester resin composition of this embodiment can be made more favorable.

  Among the heterocyclic organic base compounds, one or both of 1-methylimidazole and 1-ethylimidazole are particularly preferable because they are easily available.

  The amount of the heterocyclic organic base compound used is 0.005, based on 100 parts by mass of the raw material monomers (i.e., aromatic dicarboxylic acid, aromatic diol and aromatic hydroxycarboxylic acid) of the liquid crystal polyester resin. Preferably, the amount is about 1 part by mass. Moreover, it is more preferable to set it as 0.05-0.5 mass part with respect to 100 mass parts of raw material monomers from a color tone of a molded object, and a viewpoint of productivity.

  The heterocyclic organic base compound may be present at any time during the acylation reaction and the transesterification reaction, and the addition time thereof may be immediately before the initiation of the acylation reaction, or during the acylation reaction. Or between the acylation reaction and the transesterification reaction. The liquid crystal polyester resin thus obtained has very high melt flowability and is excellent in heat stability.

  The amount of fatty acid anhydride (e.g., acetic anhydride) to be used should be determined in consideration of the amounts of the raw material monomers, aromatic diol and aromatic hydroxycarboxylic acid. Specifically, it is preferable that the total amount of the phenolic hydroxy groups contained in these raw material monomers be 1.0 or more equivalents and 1.2 or less equivalents, preferably 1.0 or more equivalents and 1.15 or more equivalents. It is more preferable to set it as follows, 1.03 times equivalent or more and 1.12 times equivalent or less is more preferable, and 1.05 times equivalent or more and 1.1 times equivalent or less is particularly preferable.

  When the amount of fatty acid anhydride used is 1.0-fold equivalent or more with respect to the total of phenolic hydroxy groups contained in the raw material monomer, the acylation reaction easily proceeds, and the raw material monomer unreacted in the subsequent polymerization step Is difficult to remain, and as a result, polymerization proceeds efficiently. In addition, when the acylation reaction proceeds sufficiently, the raw material monomers which are not acylated sublime, and there is little possibility that the fractionator used at the time of polymerization is clogged. On the other hand, when the amount of use of the fatty acid anhydride is 1.2 times equivalent or less, the obtained liquid crystal polyester resin is less likely to be colored.

  The acylation reaction in the above-mentioned acylation step is preferably performed in a temperature range of 130 ° C. to 180 ° C. for 30 minutes to 20 hours, and more preferably performed at 140 ° C. to 160 ° C. for 1 to 5 hours.

  The aromatic dicarboxylic acid used in the above-mentioned polymerization step may be present in the reaction system during the acylation step. That is, in the acylation step, the aromatic diol, the aromatic hydroxycarboxylic acid and the aromatic dicarboxylic acid may be present in the same reaction system. This is because any of the carboxy group and the optionally substituted substituent in the aromatic dicarboxylic acid is not affected at all by the fatty acid anhydride.

  Therefore, after the aromatic diol, the aromatic hydroxycarboxylic acid and the aromatic dicarboxylic acid are charged into the reactor, the acylation step and the polymerization step may be sequentially performed, or the aromatic diol and the aromatic dicarboxylic acid may be used in the reactor. After carrying out the acylation step by charging, the aromatic dicarboxylic acid may be further charged into the reactor to carry out the polymerization step. From the viewpoint of simplifying the production process, the former method is preferred.

  It is preferable to carry out the transesterification in the above-mentioned polymerization step while raising the temperature from 130 ° C. to 400 ° C. at a temperature rising rate of 0.1 to 50 ° C./min, 150 at a temperature rising rate of 0.3 to 5 ° C./min. It is more preferable to carry out while raising the temperature from ° C to 350 ° C.

  In addition, when carrying out the transesterification in the polymerization step, in order to shift the equilibrium, the by-produced fatty acid (for example, acetic acid etc.) and the unreacted fatty acid anhydride (for example acetic anhydride etc.) are evaporated to the outside of the system. It is preferable to distill off. At this time, by partially refluxing the fatty acid to be distilled back to the reactor, it is possible to condense or reversely sublimate the raw material monomer or the like which is vaporized or sublimated along with the fatty acid and returned to the reactor.

  In the acylation reaction of the acylation step and the transesterification reaction of the polymerization step, a batch apparatus may be used as a reactor, or a continuous apparatus may be used. The liquid crystal polyester resin that can be used in the present embodiment can be obtained by using any reaction device.

  After the above-mentioned polymerization step, a step for polymerizing the liquid crystal polyester resin obtained in this polymerization step may be carried out. For example, if the liquid crystalline polyester resin obtained in the polymerization step is cooled and then pulverized to prepare a powdered liquid crystalline polyester resin, and further, if this powder is heated, the high molecular weight of the liquid crystalline polyester resin Is possible.

  Also, pelletized liquid crystalline polyester resin is prepared by granulating a powdery liquid crystalline polyester resin obtained by cooling and crushing, and then the pelletized liquid crystalline polyester resin is heated to obtain a high molecular weight of the liquid crystalline polyester resin. May be carried out. High molecular weight polymerization using these methods is referred to in the art as solid phase polymerization.

Solid phase polymerization is particularly effective as a method of increasing the molecular weight of the liquid crystal polyester resin.
By polymerizing the liquid crystalline polyester resin, it becomes easy to obtain a liquid crystalline polyester resin having a suitable flow start temperature as described later.

  As a reaction condition of the solid phase polymerization, a method of heat treating a resin in a solid state in an inert gas atmosphere or under reduced pressure for 1 to 20 hours is usually employed. The polymerization conditions relating to this solid phase polymerization can be optimized as appropriate after obtaining the flow start temperature of the resin obtained by the melt polymerization. In addition, as an apparatus used for the said heat processing, a well-known dryer, a reactor, an inert oven, an electric furnace is mentioned, for example.

  The flow start temperature of the liquid crystalline polyester resin is preferably 270 ° C. or more, more preferably 270 to 400 ° C., and still more preferably 280 to 380 ° C. By using a liquid crystal polyester resin in which the flow initiation temperature is in such a range, the heat resistance of a molded article obtained using the liquid crystal polyester resin composition of the present embodiment can be further improved. In addition, in melt molding when obtaining a molded body from the liquid crystal polyester resin composition, the heat stability of the liquid crystal polyester resin is improved, and heat deterioration can be avoided.

  The flow start temperature is also called flow temperature or flow temperature, and the liquid crystal polyester resin is melted while raising the temperature at a rate of 4 ° C./min under a load of 9.8 MPa using a capillary rheometer, and the inner diameter It is a temperature at which a viscosity of 4800 Pa · s (48000 poises) is exhibited when it is extruded from a nozzle of 1 mm and a length of 10 mm, which is a measure of the molecular weight of a liquid crystal polyester resin. Synthesis, molding, application-, pp. 95-105, CMC, published on June 5, 1987).

  The liquid crystal polyester resin of the above-mentioned suitable flow start temperature can be easily obtained by optimizing the structural unit which constitutes the above-mentioned liquid crystal polyester resin suitably. That is, when the linearity of the molecular chain of the liquid crystal polyester resin is improved, the flow start temperature tends to increase.

  For example, structural units derived from terephthalic acid improve the linearity of liquid crystal polyester resin molecular chains. On the other hand, the structural unit derived from isophthalic acid improves the flexibility of the liquid crystal polyester resin molecular chain (reduces the linearity). Therefore, by controlling the copolymerization ratio of terephthalic acid and isophthalic acid, it is possible to obtain a liquid crystal polyester resin having a desired flow initiation temperature.

  When the liquid crystal polyester resin mixture described above is used, the at least one liquid crystal polyester resin is preferably a polymer obtained by polymerizing a raw material monomer containing an aromatic hydroxycarboxylic acid in the presence of an imidazole compound. The liquid crystalline polyester resin thus obtained has very high fluidity at the time of melting, and is excellent in thermal stability.

  Further, in the liquid crystal polyester resin used in the present embodiment, it is preferable to optimize the copolymerization ratio of terephthalic acid and isophthalic acid. Thereby, the linearity of the molecular chain of the liquid crystal polyester resin can be controlled as described above. As a result, a plurality of liquid crystal polyester resins having different flow start temperatures can be produced.

[Glass composition]
The glass component contained in the liquid crystal polyester resin composition of this embodiment may be referred to as glass fiber having a length of more than 50 μm and glass fine powder having a length of 4 to 50 μm (hereinafter simply referred to as “fine powder” And a glass-made ultrafine powder (hereinafter sometimes referred to simply as "ultrafine powder") having a length of less than 4 μm.

  The length of the glass component contained in the liquid crystal polyester resin composition of the present embodiment is the circumscribed rectangular major axis of the glass component in the binarized scanning electron microscope (SEM) image. The circumscribed rectangle major axis means the length of the long side when the particle is surrounded by the circumscribed rectangle. The analysis method of the glass component using SEM is mentioned later.

(Glass fiber)
The number average fiber length of the glass fiber contained in the liquid crystal polyester resin composition of the present embodiment is 200 μm or more and 400 m or less.

  The mechanical strength of the molded object using a virgin material can be made high enough as the number average fiber length of glass fiber is 200 micrometers or more. In addition, when the number average fiber length of the glass fiber of the present embodiment is 400 μm or less, physical destruction of the glass fiber at the time of regrind hardly occurs. As a result, the reduction in mechanical strength due to the physical destruction of the glass fiber is suppressed. Therefore, the maintenance rate of mechanical strength at the time of regrind can be made sufficiently high.

  The number average fiber length of the glass fiber is preferably 210 μm or more, more preferably 220 μm or more, and still more preferably 230 μm or more. Moreover, it is preferable that it is 380 micrometers or less, and, as for the number average fiber length of the said glass fiber, it is more preferable that it is 350 micrometers or less.

  It is preferable that the glass fiber contained in the liquid-crystal polyester resin composition of this embodiment is a substantially circular cross-sectional shape in radial direction. It can be confirmed by SEM that the cross-sectional shape of the glass component in the radial direction is substantially circular. The diameter of the glass fiber is preferably 5 μm or more and 17 μm or less, more preferably 6 μm or more and 15 μm or less, and still more preferably 9 μm or more and 12 μm or less.

(Fine powder)
The fine powder contained in the liquid crystal polyester resin composition of the present embodiment preferably has a substantially circular cross-sectional shape in the radial direction. In the present specification, the radial direction of the fine powder is the circumscribed rectangular minor axis direction of the fine powder in the binarized SEM image. The circumscribed rectangle minor axis means the length of the short side when the particle is surrounded by the circumscribed rectangle. It can be confirmed by SEM that the cross-sectional shape in the radial direction of the fine powder is substantially circular. The diameter of the fine powder is preferably 5 μm or more and 17 μm or less, more preferably 6 μm or more and 15 μm or less, and still more preferably 9 μm or more and 12 μm or less.

The aspect ratio (length / diameter) of the fine powder contained in the liquid crystal polyester resin composition of the present embodiment is preferably 0.3 or more, and more preferably 0.5 or more. Further, the aspect ratio of the fine powder is preferably 5.6 or less, more preferably 5.3 or less.
As one aspect, it is preferable that the aspect ratio (length / diameter) of the fine powder contained in the liquid crystal polyester resin composition of the present embodiment is 0.3 or more and 5.6 or less.

  The fine powder contained in the liquid crystal polyester resin composition of the present embodiment has a length of 40 μm to 50 μm and a first fine powder having a length of 4 μm or more and 40 μm or less (hereinafter, may be simply referred to as “first fine powder”). The following 2nd fine powder (Hereafter, it may only be called "2nd fine powder.") And.

(Content ratio)
The liquid crystal polyester resin composition of the present embodiment contains 5 parts by mass or more and 100 parts by mass or less of the glass component with respect to 100 parts by mass of the liquid crystal polyester. When the content of the glass component is 5 parts by mass or more and 100 parts by mass or less, the moldability of the liquid crystal polyester resin composition and the mechanical strength of the molded body can be compatible.

The liquid crystal polyester resin composition preferably contains 10 parts by mass to 70 parts by mass and more preferably 20 parts by mass to 60 parts by mass with respect to 100 parts by mass of the liquid crystal polyester.

  The liquid crystal polyester resin composition of this embodiment contains 20% or more and 95% or less of fine powder with respect to the total number of glass components.

  In the liquid crystal polyester resin composition of the present embodiment, when the content ratio of the fine powder to the total number of glass components is 20% or more, the influence of physical destruction of the glass components at the time of regrind can be reduced. Therefore, the maintenance rate of mechanical strength at the time of regrind can be made sufficiently high.

  In the liquid crystal polyester resin composition of the present embodiment, the content of the fine powder with respect to the total number of glass components is preferably 50% or more, and more preferably 70% or more.

  Further, in the liquid crystal polyester resin composition of the present embodiment, when the content ratio of the fine powder to the total number of the glass components is 95% or less, the mechanical strength of the molded article of the virgin material can be sufficiently high.

  In the liquid crystal polyester resin composition of the present embodiment, the content ratio of the fine powder to the total number of glass components is preferably 90% or less.

  In one aspect, the content of the fine powder relative to the total number of glass components is more preferably 70% or more and 90% or less.

  The liquid crystal polyester resin composition of the present embodiment preferably contains 40% to 90% of the first fine powder with respect to the total number of glass components.

  When the content of the first fine powder is 40% or more with respect to the total number of glass components, the influence of physical destruction of the glass components at the time of regrind can be reduced. Therefore, the maintenance rate of mechanical strength at the time of regrind can be made sufficiently high.

  Moreover, the mechanical strength of the molded object of a virgin material can be made high enough as the content rate of a 1st fine powder is 90% or less with respect to the total of a glass component.

  Therefore, the maintenance rate of mechanical strength at the time of regrind can be made high as the content rate of the 1st fine powder is 40% or more and 90% or less with respect to the total of a glass component.

  In the liquid crystal polyester resin composition of the present embodiment, the upper limit value and the lower limit value of the content ratio of the first fine powder can be combined with the upper limit value and the lower limit value of the content ratio of the fine powder in a possible range.

(Analytical method of glass component)
The measuring method of the length of a glass component is demonstrated. First, 5 g of pellets made of the liquid crystal polyester resin composition of the present embodiment are heated at 600 ° C. for 4 hours in an air atmosphere in a muffle furnace (“FP 410” manufactured by Yamato Scientific Co., Ltd.) to remove the resin and remove glass To obtain an ashing residue containing 0.3 g of an ashed sample is added to 50 mL of pure water, and 0.5% by volume of micro-90 (Sigma Aldrich) is used as a surfactant to improve dispersibility.
An aqueous solution is added to obtain a mixed solution. The ashed sample is uniformly dispersed in pure water for 5 minutes with respect to the obtained mixed solution for 5 minutes to obtain a sample solution.

  Next, a sample solution in which the glass component is dispersed in pure water is pipetted into a 5 mL sample cup, and diluted 5 times with pure water to obtain a sample solution. Using the particle shape image analyzer ("PITA3" manufactured by Seishin Enterprise Co., Ltd.) under the following conditions, the obtained sample solution is passed through a flow cell to image the glass components moving in the solution one by one. In the measurement method described above, the point in time when the number of glass components integrated from the start of measurement reaches 5000 is taken as the end of measurement.

[conditions]
Measurement number: 5000 pieces Dispersion solvent: Water Dispersion conditions: As carrier liquid 1 and carrier liquid 2, a micro-90 0.5 volume% aqueous solution is used.
Sample liquid velocity: 2.08 μL / sec Carrier liquid 1 velocity: 333.33 μL / sec Carrier liquid 2 velocity: 333.33 μL / sec Observation magnification: 10 × objective

  The obtained image is binarized, the circumscribed rectangle major axis of the glass component in the processed image is measured, and the average value of the 5000 measured values is taken as the length of the glass component.

  The number average fiber length of the glass fiber of this embodiment adopts an average value of the measured values of the glass fiber having a length of more than 50 μm.

  The content ratio of the fine powder to the total number of glass components of the present embodiment was calculated by dividing the number of fine powders having a length of 4 μm or more and 50 μm or less in the image after the processing described above by the total number of glass components.

  The content ratio of the first fine powder to the total number of glass components of the present embodiment was calculated by dividing the number of first fine powders having a length of 4 μm or more and 40 μm or less in the image after the processing described above by the total number of glass components. .

  The measuring method of the diameter of the glass fiber of this embodiment is demonstrated. The diameter of the glass fiber of the present embodiment is as follows: the ashing residue containing the above-mentioned glass component is observed at a magnification of 1000 times with SEM, and the diameters of 100 glass fibers randomly selected from the SEM image are measured. The average value of 100 measured values is adopted.

  The measuring method of the diameter of the fine powder of this embodiment is demonstrated. First, the ashing residue containing the above-mentioned glass component is observed by SEM at a magnification of 1000 times. The obtained image is binarized, and the radial length (that is, the circumscribed rectangular minor axis) of 100 powders randomly selected in the processed image is measured, and the average of 100 measured values is measured. Let the value be the diameter of the fines.

  Regarding the aspect ratio of the fine powder of this embodiment, in the image obtained by the above-described particle shape image analysis apparatus, the length direction substantially matching the diameter of the glass component measured by the above-described method is the radial direction of the fine powder. The calculated value of length / diameter is adopted.

[Method of preparing glass component]
The number average fiber length of the glass fibers contained in the liquid crystal polyester resin composition can be prepared by adjusting the conditions of melt kneading at the time of production of the liquid crystal polyester resin composition. For example, in order to reduce the number average fiber length of glass fibers contained in a liquid crystal polyester resin composition, increase the rotational speed of the screw used, lower the cylinder temperature, increase the melt viscosity of the molten resin, and Means for increasing the

  The fine powder contained in the liquid crystal polyester resin composition of the present embodiment can be produced by pulverizing a commercially available glassy fibrous filler (hereinafter, may be referred to as a "fibril"). In the present embodiment, fine powder may be blended with the liquid crystal polyester resin so that the content ratio of the fine powder to the total number of glass components contained in the liquid crystal polyester resin composition is in the range of 20% to 95%. In the method for producing a liquid crystal polyester resin composition described later, the content of the fine powder is controlled to be in the range of 20% to 95% with respect to the total number of glass components by appropriately changing the production conditions. It is also good.

  The fibrils used in the present embodiment are not particularly limited, and include fillers produced by various methods such as chopped glass fibers of long fiber type and milled glass fibers of short fiber type. Among these, chopped glass fiber is preferable as the above-mentioned fibril. The fibrils may be used alone or in combination of two or more.

  Examples of the type of the above-mentioned fibrils include E-glass, A-glass, C-glass, D-glass, AR-glass, R-glass, S-glass, and mixtures thereof. Among them, E-glass is preferable because it is excellent in strength and easy to obtain.

  As the above-mentioned fibril, a weakly alkaline fiber is excellent in mechanical strength (tensile strength and Izod impact strength) and can be preferably used. In particular, glass fibers having a silicon oxide content of 50% by mass to 80% by mass with respect to the total mass of the glass fibers are preferably used, and glass fibers of 65% by mass to 77% by mass are more preferably used.

  The fibril may be a fiber treated with a coupling agent such as a silane coupling agent or a titanium coupling agent, if necessary.

  The fibrils may be coated with a thermoplastic resin such as urethane resin, acrylic resin, ethylene / vinyl acetate copolymer, or a thermosetting resin such as epoxy resin. The fibrils may also be treated with a focusing agent.

The number average fiber length of the fibrils is preferably 20 μm or more and 6000 μm or less.
When the number average fiber length of the fibrils is 20 μm or more, the reinforcing effect on the obtained molded article is sufficiently high. When the number average fiber length of the fibrils is 6000 μm or less, the number average fiber length of glass fibers contained in the liquid crystal polyester resin composition after melt-kneading can be easily adjusted to 400 μm or less.

  The number average fiber length of the fibrils to be subjected to the melt-kneading is more preferably 1000 μm or more, and still more preferably 2000 μm or more. The number average fiber length of the fibrils is more preferably 5,000 μm or less, and still more preferably 4500 μm or less.

  The fiber diameter (single fiber diameter) of the fibrils to be subjected to the melt-kneading is preferably 5 μm or more and 17 μm or less. When the fiber diameter of the fibrils is 5 μm or more, the reinforcing effect on the obtained molded article is sufficiently high. When the fiber diameter of the fibrils is 17 μm or less, the melt flowability of the liquid crystal polyester resin composition is sufficiently high.

  The fiber diameter of the raw fiber to be subjected to the melt-kneading is more preferably 6 μm or more, and still more preferably 9 μm or more. Further, the fiber diameter of the fibrils is more preferably 15 μm or less, and still more preferably 12 μm or less.

  The fiber diameter of the fibrils does not substantially change after melt-kneading.

(Method of measuring number average fiber length and fiber diameter of fibrils)
In the present specification, “number average fiber length of fibrils” means values measured by the method described in “7.8 Length of chopped strand” according to JIS R 3420, unless otherwise noted.
Further, in the present specification, “fiber diameter of fibril” means the value measured by “Method A” among the methods described in JIS R 3420 “7.6 Single fiber diameter” unless otherwise noted. Do.

[Other ingredients]
The liquid crystal polyester composition may contain one or more other components such as a filler other than the glass component of the present embodiment, an additive, and a resin other than the liquid crystal polyester resin, as long as the effects of the present invention are exhibited.

  The filler may be a fibrous filler, may be a plate-like filler, or may be a spherical or other particulate filler other than fibrous and plate-like. The filler may be an inorganic filler or an organic filler.

  Examples of fibrous fillers that are inorganic fillers include carbon fibers such as bread-based carbon fibers and pitch-based carbon fibers; ceramic fibers such as silica fibers, alumina fibers and silica-alumina fibers; and metal fibers such as stainless steel fibers It can be mentioned. In addition, whiskers such as potassium titanate whisker, barium titanate whisker, wollastonite whisker, aluminum borate whisker, silicon nitride whisker, silicon carbide whisker and the like can also be mentioned.

  Examples of fibrous fillers that are organic fillers include polyester fibers, aramid fibers, and cellulose fibers.

  Examples of plate fillers which are inorganic fillers include talc, mica, graphite, wollastonite, glass flakes, barium sulfate and calcium carbonate. Mica may be muscovite, phlogopite, fluorophlogite, or tetrasilicon mica.

  Examples of particulate fillers that are inorganic fillers include silica, alumina, titanium oxide, glass beads, glass balloons, boron nitride, silicon carbide and calcium carbonate.

  As an example of an additive, the additive normally used for resin composition is mentioned. Examples of such additives include stabilizers, UV absorbers, plasticizers, flame retardants, flame retardant aids, antistatic agents, surfactants, colorants, lubricants, and mold release agents.

  Examples of the stabilizer include hindered phenols, hydroquinones, phosphites, and substituted products thereof.

  Examples of the ultraviolet absorber include resorcinol, salicylate, benzotriazole, benzophenone and the like.

  Coloring agents include materials including dyes such as nitrocin and pigments such as cadmium sulfide, phthalocyanines, carbon black and the like.

  As the lubricant, for example, stearic acid, montanic acid, esters thereof, half esters thereof with polyhydric alcohols, stearyl alcohol, stearamide, polyethylene wax and the like can be mentioned.

  The moldability of the liquid crystal polyester resin composition of the present embodiment can be improved by further adding a mold release agent. Examples of the mold release agent include montanic acid, a salt thereof, an ester thereof, a half ester thereof with a polyhydric alcohol, stearyl alcohol, stearamide, polyethylene wax and the like, and preferably a fatty acid ester of pentaerythritol.

  The compounding amount of the release agent is preferably 0.1 parts by mass or more and 0.5 parts by mass or less, more preferably 0.2 parts by mass or more and 0.4 parts by mass or less with respect to 100 parts by mass of the liquid crystal polyester resin. It is. When the compounding amount of the release agent is in the range of 0.1 parts by mass or more and 0.5 parts by mass or less, there is a tendency that contamination of molds to be used and blisters of molded articles do not easily occur, and It is easy to obtain.

  Examples of resins other than liquid crystal polyesters include thermoplastic resins other than liquid crystal polyesters such as polypropylene, polyamide, polyesters other than liquid crystal polyester, polysulfone, polyethersulfone, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene ether, polyetherimide, etc. And thermosetting resins such as phenol resin, epoxy resin, polyimide resin, and cyanate resin. The content of the resin other than the liquid crystal polyester is usually 0 to 20 parts by mass with respect to 100 parts by mass of the liquid crystal polyester.

<Production Method of Liquid Crystalline Polyester Resin Composition>
The liquid crystalline polyester resin composition is preferably prepared by melt-kneading a liquid crystalline polyester resin, a glass component and other components used as needed using an extruder, and extruding in the form of pellets.

  The glass component to be used may be previously prepared so that the content ratio of fine powder is in the range of 20% to 95% with respect to the total number of glass components. Moreover, using the glass-made fibrous filler as marketed as a raw material, this fibrous filler is broken at the time of manufacture of a liquid-crystal polyester resin composition, and the total number of the glass component contained in a liquid-crystal polyester resin composition It may be controlled so that the content ratio of the fine powder with respect to is in the range of 20% to 95%.

  The extruder preferably includes a cylinder, one or more screws disposed in the cylinder, and one or more supply ports provided in the cylinder, and one or more vents provided in the cylinder. It is more preferable to have

  Furthermore, in the present embodiment, it is known that the fine powder is less likely to be physically broken compared to the glass fiber because extremely large energy is required to break the fine powder having a length of 4 μm to 50 μm. ing. Therefore, in the regrind material to which the liquid crystal polyester resin composition of the present embodiment is applied, it is expected that the fine powder does not change even in melting in the screw at the time of injection molding.

  According to the liquid crystal polyester resin composition having the above-described configuration, a liquid crystal polyester resin composition having a high mechanical strength maintenance rate at the time of regrind can be obtained.

<Molded body>
The molded object of this embodiment uses the liquid crystal polyester resin composition mentioned above as a forming material.

  As a molding method of the liquid crystal polyester composition of the present embodiment, a melt molding method is preferable. Examples thereof include an injection molding method, an extrusion molding method such as a T-die method and an inflation method, a compression molding method, a blow molding method, a vacuum molding method and a press molding. Among them, injection molding is preferred.

  Examples of products and parts which are molded articles of liquid crystal polyester composition include bobbins such as an optical pickup bobbin and a transformer bobbin; relay parts such as a relay case, a relay base, a relay sprue, and a relay armature; RIMM, DDR, CPU socket , S / O, DIMM, Board to Board connector, FPC connector, connector such as card connector; reflector such as lamp reflector, LED reflector; holder such as lamp holder, heater holder; diaphragm such as speaker diaphragm; for copying machine Separating claws such as separating claws, separating claws for printers, etc .; Camera module parts; Switch parts; Motor parts; Sensor parts; Hard disk drive parts; Tableware such as ovenware; Vehicle parts; Aircraft parts; And sealing members such as sealing members for coils and the like.

  In addition, as examples other than these, copiers such as separation claws and heater holders, printing machine related parts; impellers, fan gears, gears, bearings, motor parts, mechanical parts such as cases; automotive mechanical parts, fuel relations Exhaust and intake pipes, exhaust gas, coolant, oil temperature sensors, thermostat base for air conditioners, motor insulators for air conditioners, brush holders for radiator motors, wiper motor related parts, duplexers, starter switches, starter relays , Wire harness for transmission, air conditioner panel switch board, coil for fuel related electromagnetic valve, connector for fuse, ECU connector, horn terminal, electrical component insulating plate, lamp socket, lamp reflector, lamp housing, brake Automobile and vehicle related parts such as pistons, solenoid bobbins, engine oil filters, igniter cases etc. Cooking appliances such as microwave cooking pots and heat resistant dishes; materials for insulation or sound insulation such as floorings and walls, beams or columns Support materials such as roof materials, construction materials such as roof materials or materials for civil engineering and construction; parts for aircrafts, space machines, space equipments; radiation facilities members such as nuclear reactors; marine facilities members; cleaning jigs; optical equipment parts; Pipes, nozzles, filters, membranes, medical equipment parts and materials, sensors parts, sanitary equipment, sports equipment, leisure equipment and the like.

[Method of evaluating mechanical strength of molded body]
The mechanical strength of the shaped body is evaluated by measuring the tensile strength and the Izod impact strength.

  The tensile strength of a molded object is measured according to ASTM D638 using an ASTM No. 4 test piece produced by an injection molding machine using a liquid crystal polyester resin composition.

  The Izod impact strength of the molded product is obtained by dividing a test specimen of 127 mm in length, 12.7 mm in width, and 6.4 mm in thickness prepared by an injection molding machine using a liquid crystal polyester resin composition into two equal parts in the longitudinal direction. The test pieces are used and measured in accordance with ASTM D256.

  According to the molded article having the above-described structure, since the above-described liquid crystal polyester resin composition is used, a molded article having a high retention rate of mechanical strength at the time of regrind can be obtained.

  EXAMPLES The present invention will be described by way of examples, but the present invention is not limited to these examples. Each measurement was performed as follows.

<Flow start temperature of liquid crystalline polyester resin>
Using a flow tester (“CFT-500EX type” manufactured by Shimadzu Corporation), approximately 2 g of liquid crystal polyester is filled in a cylinder equipped with a die having a nozzle with an inner diameter of 1 mm and a length of 10 mm under a load of 9.8 MPa The liquid crystal polyester was melted while raising the temperature at a rate of 4 ° C./min, and was extruded from a nozzle, and a temperature showing a viscosity of 4800 Pa · s (48000 poise) was measured.

<Measurement 1 of Glass Component in Liquid Crystalline Polyester Resin Composition>
First, 5 g of pellets made of the liquid crystal polyester resin composition of this example are heated at 600 ° C. for 4 hours in an air atmosphere in a muffle furnace (“FP 410” manufactured by Yamato Scientific Co., Ltd.) to remove the resin, and the glass component is removed. An ashing residue containing 0.3 g of the ashed sample is added to 50 mL of pure water, and 0.5 vol% of micro-90 (manufactured by Sigma-Aldrich Japan GK Co., Ltd.) aqueous solution is added as a surfactant to improve dispersibility. The mixture is obtained. The ashed sample was uniformly dispersed in pure water over 5 minutes with ultrasonic waves for the obtained mixture to obtain a sample solution.

  Next, the sample solution in which the glass component was dispersed was pipetted into a 5 mL sample cup, and diluted 5-fold with pure water to obtain a sample solution. The sample solution obtained was passed through a flow cell using a particle shape image analyzer ("PITA-3" manufactured by Seishin Enterprise Co., Ltd.) under the following conditions, and glass components moving in the solution were imaged one by one. .

[conditions]
Measurement number: 5000 pieces Dispersion solvent: Water Dispersion conditions: micro-90 0.5 vol% aqueous solution as carrier liquid 1 and carrier liquid Sample liquid velocity: 2.08 μl / sec Carrier liquid 1 Velocity: 333.33 μl / sec Carrier liquid 2 Speed: 333.33 μl / sec Observation magnification: 10 × objective

(Glass component length)
The obtained image was binarized, the circumscribed rectangular major axis of the glass component in the image after processing was measured, and the average value of the 5000 measured values was taken as the length of the glass component.

(Content ratio of fine powder to the total number of glass components)
The amount of fine powder relative to the total number of glass components was calculated by dividing the number of fine particles having a length of 4 μm or more and 50 μm or less in the image after the processing described above by the total number of glass components.

(Content ratio of the first fine powder to the total number of glass components)
The content ratio of the first fine powder to the total number of glass components was calculated by dividing the number of first fine particles having a length of 4 μm or more and 40 μm or less in the image after the processing described above by the total number of glass components.

<Measurement 2 of Glass Component in Liquid Crystalline Polyester Resin Composition> (Diameter of Fine Powder)
The ashing residue obtained in the above <Measurement 1> was observed at a magnification of 1000 using a SEM (“S-4700” manufactured by Hitachi, Ltd.). The obtained image is binarized, and the radial length (that is, the circumscribed rectangular minor axis) of 100 powders randomly selected in the processed image is measured, and the average of 100 measured values is measured. The value was taken as the diameter of the fine powder.

(Aspect ratio of fine powder)
In the image obtained in <Measurement 1> above, the length direction that almost matches the diameter of the glass component obtained in <Measurement 2> is taken as the diameter direction of the fine powder, and the length / diameter of this fine powder is calculated. It was adopted.

(Number average fiber length of glass fibers with a length of more than 50 μm)
The number average fiber length of glass fiber was calculated using the measured value of the glass fiber whose length in the image after the process mentioned above is more than 30 micrometers.

<(A) Production of Liquid Crystalline Polyester Resin>
Production Example 1 (Liquid Crystalline Polyester Resin (A-1))
In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer and reflux condenser, 994.5 g (7.2 mol) of 4-hydroxybenzoic acid and 446.9 g of 4,4'-dihydroxybiphenyl ( 2.4 mol), 299.0 g (1.8 mol) of terephthalic acid, 99.7 g (0.6 mol) of isophthalic acid and 1347.6 g (13.2 mol) of acetic anhydride, and 1-methylimidazole as a catalyst 0.2 g was added, and the inside of the reactor was sufficiently replaced with nitrogen gas.

  Thereafter, while stirring under a nitrogen gas flow, the temperature was raised from room temperature to 150 ° C. over 30 minutes, and the same temperature was maintained to reflux for 30 minutes.

  Then, 2.4 g of 1-methylimidazole was added. Thereafter, while distilling off by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 150 ° C. to 320 ° C. over 2 hours and 50 minutes, and maintained at 320 ° C. for 30 minutes. After holding, the contents were taken out and cooled to room temperature.

  The resulting solid is crushed to a particle size of 0.1 to 1 mm with a grinder, and then heated from room temperature to 250 ° C. in one hour under a nitrogen atmosphere, and heated from 250 ° C. to 296 ° C. for 5 hours Solid phase polymerization was carried out by holding at 296 ° C. for 3 hours. After solid phase polymerization, the resultant was cooled to obtain a powdery liquid crystal polyester resin (A-1). The flow start temperature of the obtained liquid crystal polyester resin (A-1) was 328 ° C.

[Production Example 2 (Liquid Crystalline Polyester Resin (A-2))]
In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer and reflux condenser, 994.5 g (7.2 mol) of 4-hydroxybenzoic acid and 446.9 g of 4,4'-dihydroxybiphenyl ( 2.4 mol), 239.2 g (1.44 mol) of terephthalic acid, 159.5 g (0.96 mol) of isophthalic acid and 1347.6 g (13.2 mol) of acetic anhydride, and 1-methylimidazole as a catalyst 0.2 g was added, and the inside of the reactor was sufficiently replaced with nitrogen gas.

  Thereafter, while stirring under a nitrogen gas flow, the temperature was raised from room temperature to 150 ° C. over 30 minutes, and the same temperature was maintained to reflux for 1 hour.

  Next, 0.9 g of 1-methylimidazole was added, and the temperature was raised from 150 ° C. to 320 ° C. over 2 hours and 50 minutes while distilling off by-product acetic acid and unreacted acetic anhydride, and maintained at 320 ° C. for 30 minutes . After holding, the contents were removed and cooled to room temperature.

  The resulting solid is crushed to a particle size of 0.1 to 1 mm with a grinder, and then heated from room temperature to 220 ° C. in 1 hour under a nitrogen atmosphere, and taken from 220 ° C. to 241 ° C. over 0.5 hour Solid-phase polymerization was carried out by raising the temperature and maintaining the temperature at 241 ° C. for 10 hours. After solid phase polymerization, the resultant was cooled to obtain a powdery liquid crystal polyester resin (A-2). The flow start temperature of the obtained liquid crystal polyester resin (A-2) was 292 ° C.

Moreover, in the following examples, the following commercial item was used as a glass component. However, the following number average fiber length is a maker nominal value and is a value which does not consider fine powder. In addition, the shape described by each filler represents the shape of the cross section in the radial direction of each filler.
Filler A: CS3J260S (manufactured by Nitto Boseki Co., Ltd., substantially circular, diameter 10 μm, number average fiber length 3 mm)
Filler B: PF20E-001 (manufactured by Nitto Boseki Co., Ltd., substantially circular, diameter 10 μm, number average fiber length 20 μm)

Moreover, the following raw materials were used in the following examples.
Release agent: Roxyol VPG 861 (manufactured by Emery Oleo Chemicals Japan KK, a mixture of a full ester (tetrastearate) and a partial ester of pentaerythritol and stearic acid, 5% weight loss temperature 310 ° C.)

<Production of Liquid Crystalline Polyester Resin Composition (Virgin Material)>
[Examples 1 to 4, Comparative Examples 1 to 4]
A glass component was prepared in advance by mixing glass fibers having a length of more than 30 μm, fine powder, and extremely fine powder. The liquid crystal polyester resin, the glass component and the release agent are melt-kneaded at a cylinder temperature of 340 ° C. using a twin-screw extruder (“PCM-30HS” manufactured by Ikegai Iron Works Co., Ltd.) in the proportions shown in Table 1 and Table 2. Thus, a pellet-like liquid crystal polyester resin composition was obtained. In addition, manufacture of a liquid-crystal polyester resin composition was performed degassing with the vacuum vent with which the twin-screw extruder was equipped using the water ring type vacuum pump ("SW-25" by Shinko Seiki Co., Ltd.). In the following evaluation, this was made into a virgin material, and the physical property value of this virgin material was made into the physical property value of the initial stage.

Comparative Example 4
Production of a liquid crystal polyester resin composition was examined in the same manner as in Comparative Example 1 except that 122 parts by mass of the glass component was blended with 100 parts by mass of the liquid crystal polyester resin. However, the viscosity at the time of melt-kneading increased too much, and the strand could not be manufactured.

<Manufacture of regrind material>
A runner or a sprue generated when using the pellet-like liquid crystal polyester resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4 and producing test pieces described later was granulated using a granulator (Harmo Co., Ltd., "SPCII 750H ) And crushed to obtain regrind material. In the following evaluation, the physical property value of this regrind material was taken as the physical property value after regrind.

  After hot-air drying of the virgin materials and regrind materials of Examples 1 to 4 and Comparative Examples 1 to 4 at 130 ° C. for 4 hours, evaluation was performed according to the following method. The results are shown in Tables 3 and 4.

<Maintenance rate of mechanical strength>
The retention rate of mechanical strength of a molded article using the liquid crystal polyester resin composition was evaluated by determining the retention rate of tensile strength and the retention rate of Izod impact strength.

[Tensile strength]
The tensile strength of the liquid crystal polyester resin composition is determined using an injection molding machine ("PNX40-5A" manufactured by Nissei Resin Industry Co., Ltd.) under molding conditions of 350 ° C molding temperature, 130 ° C mold temperature, and 75 mm / sec injection speed. It measured based on ASTMD638 using the produced ASTM No. 4 test piece.

  The tensile strength of the virgin material and the regrind material was determined respectively, and the result of calculating the tensile strength of the regrind material with respect to the tensile strength of the virgin material was taken as the retention ratio of the tensile strength.

[Izod impact strength]
A length of 127 mm and a width of 12.7 mm produced using an injection molding machine (“PNX40-5A” manufactured by Nissei Plastic Industry Co., Ltd.) at a molding temperature of 350 ° C., a mold temperature of 130 ° C. and an injection speed of 75 mm / sec. A test piece having a thickness of 6.4 mm was bisected in the lengthwise direction, and the obtained test piece was used to measure in accordance with ASTM D256.

  The Izod impact strength of the virgin material and the regrind material was determined, and the Izod impact strength of the regrind material was calculated relative to the Izod impact strength of the virgin material as the Izod impact strength retention ratio.

From the results of the tensile strength retention rate and the Izod impact strength retention rate, the maintenance rate of mechanical strength of a molded article using a liquid crystal polyester resin composition was evaluated based on the following criteria.
○: The retention rate of tensile strength is 90% or more, and the retention rate of Izod impact strength is 90% or more. ×: The condition of “○” is not satisfied.

<Heat resistance>
The heat resistance of the liquid crystal polyester resin composition was evaluated by determining the maintenance rate of deflection temperature under load.

[Load deflection temperature]
A length of 127 mm and a width of 12.7 mm produced using an injection molding machine (“PNX40-5A” manufactured by Nissei Plastic Industry Co., Ltd.) at a molding temperature of 350 ° C., a mold temperature of 130 ° C. and an injection speed of 75 mm / sec. A test piece having a thickness of 6.4 mm was used, and the load was measured at a temperature increase rate of 2 ° C./min at a load of 1.82 MPa according to ASTM D648.

  The load deflection temperature of the virgin material and the regrind material was respectively determined, and the load deflection temperature of the regrind material with respect to the load deflection temperature of the virgin material was calculated.

  As shown in Table 3, the liquid crystal polyester resin compositions of Examples 1 to 4 to which the present invention was applied had high mechanical strength retention rates.

  It is considered that physical destruction of the glass fiber was unlikely to occur because the number average fiber length of the glass fiber was in the range of 200 μm to 400 μm. As a result, it is considered that the decrease in mechanical strength due to the physical destruction of the glass fiber is suppressed.

  In addition, since the content ratio of the fine powder to the total number of glass components contained in the liquid crystal polyester resin composition is in the range of 20% to 95%, the influence of physical destruction of the glass components at the time of regrind can be reduced. It is considered possible.

  From the above, it is considered that the liquid crystal polyester resin compositions of Examples 1 to 4 were able to increase the maintenance rate of mechanical strength at the time of regrind.

  Moreover, the liquid crystal polyester resin composition of Examples 1-4 also had the high maintenance factor of deflection temperature under load. From this, it can be said that the liquid crystal polyester resin compositions of Examples 1 to 4 are excellent in heat resistance at the time of regrind.

  On the other hand, the liquid crystal polyester resin compositions of Comparative Examples 1 to 4 shown in Table 4 had a high maintenance rate of deflection temperature under load as in Examples 1 to 4. From this, it can be said that the heat resistance at the time of regrind is excellent. However, the liquid crystal polyester resin compositions of Comparative Examples 1 to 4 had low mechanical strength retention rates.

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

Claims (10)

100 parts by mass of liquid crystal polyester resin,
5 parts by mass or more and 100 parts by mass or less of the glass component,
The glass component includes glass fibers having a length of more than 50 μm and glass powder having a length of 4 to 50 μm,
The number average fiber length of the glass fiber is 200 μm or more and 400 μm or less,
The liquid crystal polyester resin composition whose content rate of the said fine powder is 20% or more and 95% or less with respect to the total of the said glass component. The fine powder is composed of a first fine powder made of glass having a length of 4 μm to 40 μm and a second fine powder of more than 40 μm and 50 μm or less,
The liquid-crystal polyester resin composition of Claim 1 which contains 40% or more and 90% or less of the said 1st fine powder with respect to the total of the said glass component.   The liquid crystal polyester resin composition according to claim 1 or 2, wherein the content ratio of the fine powder is 70% or more and 90% or less with respect to the total number of the glass components.   The liquid crystal polyester resin composition according to any one of claims 1 to 3, wherein the diameter of the fine powder is 9 μm to 12 μm, and the aspect ratio of the fine powder is 0.3 to 5.6. The liquid crystal polyester resin composition according to any one of claims 1 to 4, wherein the liquid crystal polyester resin contains a repeating unit represented by the following formulas (1) to (3).
(1) ^-O-Ar 1 -CO-
(2) ^-CO-Ar 2 -CO-
(3) ^-X-Ar 3 -Y-
[Ar ¹ represents a phenylene group, a naphthylene group or a biphenylylene group.
Ar ² and Ar ³ each independently represent a phenylene group, a naphthylene group, a biphenylylene group or a group represented by the following formula (4).
X and Y each independently represent an oxygen atom or an imino group (-NH-).
One or more hydrogen atoms in the group represented by Ar ¹ , Ar ² or Ar ³ are each independently substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms It may be done. ]
^{(4) -Ar 4 -Z-Ar} 5 -
[Ar ⁴ and Ar ⁵ each independently represent a phenylene group or a naphthylene group. Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group or an alkylidene group having 1 to 10 carbon atoms.
At least one hydrogen atom in the group represented by Ar ⁴ or Ar ⁵ is independently substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. It is also good. ] Ar ¹ is a 1,4-phenylene group, Ar ² is a 1,4-phenylene group and a 1,3-phenylene group, Ar ³ is a biphenylylene group, and each of X and Y is oxygen The liquid crystal polyester resin composition according to claim 5, which is an atom. The molar ratio (3) / (1) of the repeating unit represented by the formula (1) to the repeating unit represented by the formula (3) is 0.2 or more and 1.0 or less,
The molar ratio (2) / (3) of the repeating unit represented by the formula (3) to the repeating unit represented by the formula (2) is 0.9 or more and 1.1 or less. The liquid-crystal polyester resin composition as described in-. The liquid crystal polyester resin composition according to any one of claims 5 to 7, wherein a molar ratio y / x of the repeating unit represented by the formula (2) is more than 0 and 1 or less.
[X represents a molar content of a repeating unit in which Ar ² is a 1,4-phenylene group.
y represents the molar content of the repeating unit in which Ar ² is a 1,3-phenylene group. ] The liquid crystal polyester resin composition according to claim 8, wherein the liquid crystal polyester resin contains a first liquid crystal polyester resin and a second liquid crystal polyester resin, and α / β is 0.1 or more and 0.6 or less.
[Α represents a molar ratio y / x of the first liquid crystal polyester resin.
β represents a molar ratio y / x of the second liquid crystal polyester resin. ]   The molded object which uses the liquid-crystal polyester resin composition of any one of Claims 1-9 as a formation material.