Resin compositions, pellets, and molded articles

Abstract

To provide a resin composition capable of forming molded products with fewer wrinkles. [Solution] A resin composition comprising a liquid crystal polyester and an amorphous polyarylate, wherein the liquid crystal polyester comprises a first monomer unit having a condensed aromatic ring, the content of the first monomer unit is 20 mol% or more relative to the total amount of monomer units constituting the liquid crystal polyester, and the glass transition temperature (Tg) of the amorphous polyarylate is 200°C or higher.

Description

[Technical Field]

[0001] This disclosure relates to resin compositions, pellets, and molded articles. [Background technology]

[0002] Liquid crystal polyester is used in a variety of applications due to its high fluidity and heat resistance, as well as the high dimensional accuracy of the resulting molded products.

[0003] For example, Patent Document 1 proposes an aromatic liquid crystal polyester film for capacitors that has excellent heat resistance and dielectric constant and low dielectric loss, using an aromatic polyester whose main component is a repeating structural unit derived from parahydroxybenzoic acid. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2002-359145 [Overview of the project] [Problems that the invention aims to solve]

[0005] In recent years, there has been a growing demand for improved molding accuracy in resin molded products, driven by the need for wider applications and the ability to manufacture more intricate parts.

[0006] Conventional liquid crystal polyester compositions tended to develop wrinkles on the surface of their molded products (especially films).

[0007] The object of this disclosure is to provide a resin composition capable of forming molded articles with fewer wrinkles. Another object of this disclosure is to provide pellets and molded articles containing the resin composition. [Means for solving the problem]

[0008] This disclosure provides, for example, the following: [1] It contains liquid crystal polyester and amorphous polyarylate, The liquid crystal polyester comprises a first monomer unit having a condensed aromatic ring, The content of the first monomer unit is 20 mol% or more relative to the total amount of all monomer units constituting the liquid crystal polyester. A resin composition wherein the amorphous polyarylate has a glass transition temperature (Tg) of 200°C or higher. [2] The resin composition according to [1], wherein the liquid crystal polyester content is 80% by mass or more. [3] The resin composition according to [1] or [2], wherein the content of the amorphous polyarylate is 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the liquid crystal polyester. [4] A resin composition according to any one of [1] to [3], further comprising a carbodiimide compound having a carbodiimide group. [5] It is a melt-mixed raw material containing liquid crystal polyester and amorphous polyarylate. The liquid crystal polyester comprises a first monomer unit having a condensed aromatic ring, The content of the first monomer unit is 20 mol% or more relative to the total amount of all monomer units constituting the liquid crystal polyester. A resin composition wherein the amorphous polyarylate has a glass transition temperature (Tg) of 200°C or higher. [6] The resin composition according to [5], wherein the content of the liquid crystal polyester in the raw material components is 80% by mass or more. [7] The resin composition according to [5] or [6], wherein the content of amorphous polyarylate in the raw material components is 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the liquid crystal polyester. [8] The resin composition according to any one of [5] to [7], wherein the raw material component further contains a carbodiimide compound having a carbodiimide group. [9] The resin composition according to any one of [1] to [8], wherein the difference (Tm-Tg) between the melting point (Tm) of the liquid crystal polyester and the glass transition temperature (Tg) of the amorphous polyarylate is 100°C or less.

[10] The resin composition according to any one of [1] to [9], wherein the condensed aromatic ring is a naphthalene ring.

[11] A resin composition according to any one of [1] to

[10] , having a melting point of 300°C or higher.

[12] A pellet comprising the resin composition described in any one of [1] to

[11] .

[13] A molded article containing any one of the resin compositions described in [1] to

[11] .

[14] A film, the molded article described in

[13] . [Effects of the Invention]

[0009] This disclosure provides a resin composition capable of forming molded articles with fewer wrinkles. Furthermore, this disclosure provides pellets and molded articles containing the resin composition. [Modes for carrying out the invention]

[0010] Preferred embodiments of this disclosure are described in detail below.

[0011] The resin composition of this embodiment comprises a liquid crystal polyester and an amorphous polyarylate. The liquid crystal polyester contains a first monomer unit having a condensed aromatic ring, and the content of the first monomer unit is 20 mol% or more of the total amount of all monomer units constituting the liquid crystal polyester. The glass transition temperature (Tg) of the amorphous polyarylate is 200°C or higher.

[0012] According to the resin composition of this embodiment, the occurrence of wrinkles during the molding of molded products (e.g., films) is suppressed, and molded products (e.g., films) with fewer wrinkles can be obtained.

[0013] The reason for the above effects is not entirely clear, but it is thought to be as follows: Liquid crystal polyester having condensed aromatic rings is prone to orientation due to the interaction of the condensed aromatic rings, and anisotropy occurs during molding, making it prone to wrinkle formation. Since the resin composition of this embodiment contains amorphous polyarylate, the orientation of the liquid crystal polyester is suppressed, the anisotropy during molding is mitigated, and the occurrence of wrinkles is suppressed. In addition, since the glass transition temperature (Tg) of amorphous polyarylate is 200°C or higher, solidification during molding becomes uniform, and the occurrence of wrinkles is suppressed.

[0014] In the resin composition of this embodiment, the liquid crystal polyester and amorphous polyarylate may each react with other components (for example, the carbodiimide compounds described later) in part or in whole to form a reaction product.

[0015] In this specification, "the resin composition comprises liquid crystal polyester and amorphous polyarylate" also includes cases where the resin composition comprises a reaction product of liquid crystal polyester and other components, and / or a reaction product of amorphous polyarylate and other components. In this case, "liquid crystal polyester content" refers to the total amount of unreacted liquid crystal polyester and the portion derived from liquid crystal polyester in the reaction product. Furthermore, "amorphous polyarylate content" refers to the total amount of unreacted amorphous polyarylate and the portion derived from amorphous polyarylate in the reaction product.

[0016] The resin composition of this embodiment can also be described as a mixture of raw material components containing liquid crystal polyester and amorphous polyarylate. The resin composition of this embodiment may also be a molten and kneaded product of the said raw material components.

[0017] Liquid crystal polyester can be any polyester that exhibits liquid crystal properties in a molten state. Liquid crystal polyester may be a single polymer or a mixture of two or more polymers. When liquid crystal polyester is a mixture of two or more polymers, the content of each monomer unit described below represents the total amount of each monomer unit in the mixture. Also, when liquid crystal polyester is a mixture of two or more polymers, the parameters related to liquid crystal polyester described below represent the parameters of the mixture (parameters measured using the mixture). The mixture used for measurement may be, for example, a mixture of powders of two or more polymers that have been granulated and pelletized. Furthermore, the total number of monomer units represents the total number of monomer units constituting each polymer.

[0018] Liquid crystal polyesters have constituent units (monomer units) derived from raw material monomers. In liquid crystal polyesters, the main monomer units (for example, monomer units that make up 90 mol% or more, 95 mol% or more, or 99 mol% or more of the total number of monomer units, preferably all monomer units) may be monomer units having an aromatic ring, i.e., monomer units derived from aromatic compounds. Liquid crystal polyesters in which all monomer units are monomer units derived from aromatic compounds are also called all-aromatic liquid crystal polyesters.

[0019] In this specification, "derived from" means that in the monomer units of the liquid crystal polyester formed by the polymerization of the raw material monomers, the chemical structure of the functional groups that contribute to polymerization of the raw material monomers has changed, while no other structural changes have occurred. Here, "derived from" is a concept that also includes cases where the product is derived from polymerizable derivatives of the raw material monomers (for example, compounds obtained by converting the functional groups that contribute to polymerization of the raw material monomers into other polymerizable groups).

[0020] Aromatic compounds are compounds having an aromatic ring. Suitable aromatic compounds as starting monomers may have an aromatic ring and two or more polymerizable groups (for example, a hydroxyl group, an amino group, or a carboxyl group, preferably a hydroxyl group or a carboxyl group) bonded to the aromatic ring.

[0021] The aromatic compound may be, for example, a compound represented by the following formula (1-1) (hereinafter also referred to as monomer (1-1)), a compound represented by the following formula (1-2) (hereinafter also referred to as monomer (1-2)), or a compound represented by the following formula (1-3) (hereinafter also referred to as monomer (1-3)). X 1 -Ar 1 -Y 1 (1-1) X 2 -Ar 2 -X 3 (1-2) Y 2 -Ar 3 -Y 3 (1-3) [In the formula, Ar 1 , Ar 2 and Ar 3 each independently represents a phenylene group, a biphenylylene group, a condensed polycyclic aromatic hydrocarbon group, or a group represented by the formula (Z-1). Ar 3 represents a phenylene group, a biphenylylene group, a condensed polycyclic aromatic hydrocarbon group, or a group represented by the formula (Z-1). Ar 1 , Ar 2 and Ar 3 Some or all of the hydrogen atoms they have may be substituted with a halogen atom, an alkyl group or an aryl group. X 1 , X 2 and X 3 each independently represents a hydroxy group or an amino group. Y 1 , Y 2 and Y 3 represent a carboxy group.] -Ar 4 -Z 1 -Ar 5 - (Z-1) [In the formula, Ar 4 and Ar 5 each independently represents a phenylene group or a condensed polycyclic aromatic hydrocarbon group. Z 1 represents an oxygen atom (-O-), a sulfur atom (-S-), a carbonyl group (-CO-), a sulfonyl group (-SO2-), or an alkanediyl group.]

[0022] Monomeric units derived from aromatic compounds may be, for example, the monomer unit represented by formula (2-1) below (hereinafter also referred to as monomer unit (2-1)), the constituent unit represented by formula (2-2) below (hereinafter also referred to as monomer unit (2-2)), or the constituent unit represented by formula (2-3) below (hereinafter also referred to as monomer unit (2-3)). It can be said that monomer unit (2-1) is a monomer unit derived from monomer (1-1), monomer unit (2-2) is a monomer unit derived from monomer (1-2), and monomer unit (2-3) is a monomer unit derived from monomer (1-3). -X 11 -Ar 1 -Y 11 - (2-1) -X 12 -Ar 2 -X 13 - (2-2) -Y 12 -Ar 3 -Y 13 - (2-3) [In the formula, Ar 1 Ar 2 and Ar 3 This is synonymous with the above. X 11 , X 12 and X 13 These represent either an oxygen atom (-O-) or an imino group (-NH-) independently. 11 , Y 12 and Y 13 This represents a carbonyl group (-CO-).

[0023] The phenylene group may be, for example, a 1,4-phenylene group or a 1,3-phenylene group, and is preferably a 1,4-phenylene group.

[0024] The biphenylylene group may be, for example, a 4,4'-biphenylylene group.

[0025] A condensed polycyclic aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from a condensed polycyclic aromatic hydrocarbon. Examples of condensed polycyclic aromatic hydrocarbons include naphthalene, anthracene, phenanthrene, tetracene, pyrene, triphenylene, perylene, and fluorene. Of these, naphthalene is preferred from the viewpoint of availability and price.

[0026] The condensed polycyclic aromatic hydrocarbon group may be a naphthylene group. The naphthylene group may be, for example, a 2,6-naphthylene group, a 2,7-naphthylene group, or a 1,5-naphthylene group, and is preferably a 2,6-naphthylene group.

[0027] Examples of halogen atoms as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The halogen atom as substituent may be a fluorine atom, a chlorine atom, or a bromine atom, or it may be a fluorine atom or a chlorine atom, or it may be a fluorine atom.

[0028] The alkyl group as a substituent may be linear, branched, or cyclic. The alkyl group may be, for example, an alkyl group having 1 to 10 carbon atoms. Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group, and the like.

[0029] The aryl group as a substituent may be a monocyclic or fused ring. The aryl group may be, for example, an aryl group having 6 to 20 carbon atoms. Examples of aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl, 1-naphthyl, and 2-naphthyl groups. The aryl group may also be a group in which a hydrogen atom of the aromatic ring is substituted with an alkyl group, such as the tolyl group.

[0030] Ar 1 Ar 2 and Ar 3 The number of substituents it has may be, for example, 0 to 2, 0 or 1, or 0.

[0031] Z 1 The alkanediyl group in may be linear or branched. The alkanediyl group may be an alkanediyl group having 1 to 10 carbon atoms. Examples of alkanediyl groups include methylene group, ethanediyl group, propanediyl group (e.g., propane-2,2-diyl group), butanediyl group, octanediyl group (e.g., octane-3,3-diyl group), etc.

[0032] Z 1 The group is preferably an oxygen atom, a sulfur atom, a methylene group, an ethanediyl group, or a propanediyl group, and more preferably an oxygen atom.

[0033] X 1 , X 2 and X 3 is preferably a hydroxyl group, X 11 , X 12 and X 13 Preferably, this is an oxygen atom (-O-). That is, monomer (1-1) may be an aromatic hydroxycarboxylic acid, monomer (1-2) may be an aromatic diol, and monomer (1-3) may be an aromatic dicarboxylic acid.

[0034] The liquid crystal polyester contains a first monomer unit having a condensed aromatic ring.

[0035] Examples of condensed aromatic rings possessed by the first monomer unit include naphthalene rings, anthracene rings, phenanthrene rings, tetracene rings, pyrene rings, triphenylene rings, perylene rings, and fluorene rings. Of these, naphthalene rings are preferred from the viewpoint of availability and price.

[0036] The first monomer unit may be a monomer unit corresponding to monomer unit (2-1), a monomer unit corresponding to monomer unit (2-2), or a monomer unit corresponding to monomer unit (2-3). For example, the first monomer unit may be a monomer unit corresponding to monomer unit (2-1) or monomer unit (2-3).

[0037] The first monomer unit is, for example, Ar 1 It may also be a monomer unit (2-1) (hereinafter also referred to as monomer unit (2-1-1)) which is a condensed polycyclic aromatic hydrocarbon group, and Ar 2 It may also be a monomer unit (2-2) (hereinafter also called monomer unit (2-2-1)) which is a condensed polycyclic aromatic hydrocarbon group, and Ar 3 The monomer unit (2-3) (hereinafter also referred to as monomer unit (2-3-1)) may be a condensed polycyclic aromatic hydrocarbon group. In the first monomer unit, the condensed polycyclic aromatic hydrocarbon group is preferably a naphthylene group, and more preferably a 2,6-naphthylene group.

[0038] The first monomer unit can also be described as a monomer unit derived from the first monomer having a condensed aromatic ring.

[0039] The first monomer may be the monomer corresponding to monomer (1-1), the monomer corresponding to monomer (1-2), or the monomer corresponding to monomer (1-3). The first monomer may be, for example, the monomer corresponding to monomer (1-1) or monomer (1-3).

[0040] The first monomer is, for example, Ar 1 It may also be a monomer (1-1) (hereinafter also referred to as monomer (1-1-1)) in which Ar is a condensed polycyclic aromatic hydrocarbon group, 2 It may also be a monomer (1-2) (hereinafter also called monomer (1-2-1)) in which condensed polycyclic aromatic hydrocarbon group, Ar 3 The monomer (1-3) (hereinafter also referred to as monomer (1-3-1)) may be a condensed polycyclic aromatic hydrocarbon group. In the first monomer, the condensed polycyclic aromatic hydrocarbon group is preferably a naphthylene group, and more preferably a 2,6-naphthylene group.

[0041] Examples of the first monomer include 2-hydroxy-6-naphthoic acid, 2,6-naphthalenedicarboxylic acid, 2,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2-hydroxy-3-naphthoic acid, 1-hydroxy-5-naphthoic acid, and 2,7-naphthalenediol. 2-hydroxy-6-naphthoic acid and 2,6-naphthalenedicarboxylic acid are preferred as the first monomer.

[0042] The polyester of this embodiment may further contain a second monomer unit having a benzene ring but not a condensed aromatic ring.

[0043] The second monomer unit may be a monomer unit corresponding to monomer unit (2-1), a monomer unit corresponding to monomer unit (2-2), or a monomer unit corresponding to monomer unit (2-3).

[0044] The second monomer unit is, for example, Ar 1 is a phenylene group, a biphenylylene group, or a group represented by formula (Z-1) (where Ar 4 and Ar 5 The monomer unit (2-1) (hereinafter also referred to as monomer unit (2-1-2)) is a phenylene group, and Ar 2 is a phenylene group, a biphenylylene group, or a group represented by formula (Z-1) (where Ar 4 and Ar 5 The monomer unit (2-2) (hereinafter also referred to as monomer unit (2-2-2)) is a phenylene group, and Ar 3 is a phenylene group, a biphenylylene group, or a group represented by formula (Z-1) (where Ar 4 and Ar 5 The monomer unit (2-3) (hereinafter also referred to as monomer unit (2-3-2)) is a phenylene group. In the second monomer unit, Ar 1 Ar 2 and Ar 3The group is preferably a phenylene group or a biphenylylene group, more preferably a 1,4-phenylene group, a 1,3-phenylene group or a 4,4'-biphenylylene group, and even more preferably a 1,4-phenylene group or a 4,4'-biphenylylene group.

[0045] The second monomer unit can also be described as a monomer unit derived from a second monomer that has a benzene ring but lacks a condensed aromatic ring.

[0046] The second monomer may be the monomer corresponding to monomer (1-1), the monomer corresponding to monomer (1-2), or the monomer corresponding to monomer (1-3).

[0047] The second monomer is, for example, Ar 1 is a phenylene group, a biphenylylene group, or a group represented by formula (Z-1) (where Ar 4 and Ar 5 It may also be a monomer (1-1) (hereinafter also called monomer (1-1-2)) which is a phenylene group, Ar 2 is a phenylene group, a biphenylylene group, or a group represented by formula (Z-1) (where Ar 4 and Ar 5 It may also be a monomer (1-2) (hereinafter also called monomer (1-2-2)) which is a phenylene group, Ar 3 is a phenylene group, a biphenylylene group, or a group represented by formula (Z-1) (where Ar 4 and Ar 5 The monomer (1-3) (hereinafter also referred to as monomer (1-3-2)) is a phenylene group. In the second monomer, Ar 1 Ar 2 and Ar 3 The group is preferably a phenylene group or a biphenylylene group, more preferably a 1,4-phenylene group, a 1,3-phenylene group or a 4,4'-biphenylylene group, and even more preferably a 1,4-phenylene group or a 4,4'-biphenylylene group.

[0048] Examples of the second monomer include p-hydroxybenzoic acid, m-hydroxybenzoic acid, hydroquinone, 4,4'-biphenol, terephthalic acid, and isophthalic acid. The second monomer is preferably p-hydroxybenzoic acid, hydroquinone, 4,4'-biphenol, or terephthalic acid.

[0049] Liquid crystal polyester may contain monomer units other than monomer units (2-1), monomer units (2-2), and monomer units (2-3), but the content of these other units may be, for example, 10 mol% or less, 5 mol% or less, 3 mol% or less, or 1 mol% or less, or even 0 mol%, relative to the total amount of all monomer units. In other words, in liquid crystal polyester, the total content of monomer units (2-1), monomer units (2-2), and monomer units (2-3) may be, for example, 90 mol% or more, 95 mol% or more, 97 mol% or more, or 99 mol% or more, or even 100 mol%, relative to the total amount of all monomer units.

[0050] Liquid crystal polyester may contain monomers other than the first monomer unit and the second monomer unit, but the content of these monomers may be, for example, 10 mol% or less, 5 mol% or less, 3 mol% or less, or 1 mol% or less, or 0 mol%, relative to the total of all monomer units. That is, in liquid crystal polyester, the total content of the first monomer unit and the second monomer unit may be, for example, 90 mol% or more, 95 mol% or more, 97 mol% or more, or 99 mol% or more, or 100 mol%, relative to the total of all monomer units.

[0051] Liquid crystal polyester may be composed mainly of monomer units (2-1), for example, or may include monomer units (2-1), monomer units (2-2), and monomer units (2-3).

[0052] When liquid crystal polyester is mainly composed of monomer units (2-1), the content of monomer units (2-1) may be, for example, 90 mol% or more, 95 mol% or more, 97 mol% or more, or 99 mol% or more, or 100 mol%, relative to the total amount of all monomer units.

[0053] When the liquid crystal polyester contains monomer units (2-1), monomer units (2-2), and monomer units (2-3), the total content of monomer units (2-1), monomer units (2-2), and monomer units (2-3) may be, for example, 90 mol% or more, 95 mol% or more, 97 mol% or more, or 99 mol% or more, or 100 mol%, relative to the total amount of all monomer units.

[0054] When the liquid crystal polyester contains monomer units (2-1), (2-2), and (2-3), the content of monomer unit (2-2) and the content of monomer unit (2-3) may be approximately the same (for example, the difference may be 3 mol% or less, 1 mol% or less, 0.5 mol% or less, or 0.1 mol% or less).

[0055] When the liquid crystal polyester contains monomer units (2-1), monomer units (2-2), and monomer units (2-3), the content of monomer unit (2-1) may be, for example, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol% or more, relative to the total of all monomer units. Furthermore, when the liquid crystal polyester contains monomer (2-1), monomer units (2-2), and monomer units (2-3), the content of monomer unit (2-1) may be, for example, 99 mol% or less, 95 mol% or less, or 90 mol% or less, relative to the total of all monomer units.

[0056] When the liquid crystal polyester contains monomer units (2-1), monomer units (2-2), and monomer units (2-3), the content of monomer unit (2-2) and the total content of monomer units (2-3) may be, for example, 1 mol% or more, 5 mol% or more, or 10 mol% or more, relative to the total of all monomer units. Furthermore, when the liquid crystal polyester contains monomers (2-1), monomer units (2-2), and monomer units (2-3), the content of monomer unit (2-2) and the total content of monomer units (2-3) may be, for example, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, or 30 mol% or less, relative to the total of all monomer units.

[0057] The content of the first monomer unit in the liquid crystal polyester is 20 mol% or more, and may be 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol% or more, relative to the total amount of all monomer units. A higher content of the first monomer unit tends to improve dielectric properties. Furthermore, liquid crystal polyester with a high content of the first monomer unit has high orientation and is prone to wrinkle formation when formed into a film on its own. In the resin composition of this embodiment, even when using liquid crystal polyester with a high content of the first monomer unit, the occurrence of wrinkles is significantly suppressed for the reasons mentioned above. The content of the first monomer unit may be, for example, 90 mol% or less, 85 mol% or less, or 80 mol% or less, relative to the total amount of all monomer units. This tends to result in better moldability and processability at low temperatures.

[0058] When liquid crystal polyester contains a second monomer unit, the content of the second monomer unit may be, for example, 10 mol% or more, 15 mol% or more, or 20 mol% or more, relative to the total amount of all monomer units. A higher content of the second monomer unit tends to result in better moldability and processability at low temperatures. The content of the second monomer unit may be 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, or 30 mol% or less, relative to the total amount of all monomer units.

[0059] The liquid crystal polyester may contain, as the first monomer unit, at least one selected from the group consisting of monomer unit (2-1-1), monomer unit (2-2-1), and monomer unit (2-3-1), and may also contain at least one selected from the group consisting of monomer unit (2-1-1) and monomer unit (2-3-1). Furthermore, it is preferable that the liquid crystal polyester contains at least monomer unit (2-1-1) as the first monomer unit.

[0060] The proportion of monomer units (2-1-1) in the first monomer unit may be, for example, 50 mol% or more, and may be 60 mol% or more, 70 mol% or more, or 75 mol% or more. The proportion of monomer units (2-1-1) in the first monomer unit may also be 100 mol%.

[0061] In the first embodiment, the liquid crystal polyester may include monomer unit (2-1-1) and monomer unit (2-3-1) as the first monomer unit.

[0062] In the first embodiment, the proportion of monomer units (2-1-1) in the first monomer unit may be, for example, 50 mol% or more, and may be 60 mol% or more, 70 mol% or more, or 75 mol% or more. Alternatively, the proportion of monomer units (2-1-1) in the first monomer unit may be, for example, 99 mol% or less, and may be 97 mol% or less, 95 mol% or less, or 90 mol% or less.

[0063] In the first embodiment, the proportion of monomer units (2-3-1) in the first monomer unit may be, for example, 1 mol% or more, and may be 3 mol% or more, 5 mol% or more, or 10 mol% or more. Alternatively, the proportion of monomer units (2-3-1) in the first monomer unit may be, for example, 50 mol% or less, and may be 40 mol% or less, 30 mol% or less, or 25 mol% or less.

[0064] The liquid crystal polyester may include, as a second monomer unit, at least one selected from the group consisting of monomer unit (2-1-2), monomer unit (2-2-2), and monomer unit (2-3-2).

[0065] In the first embodiment, the liquid crystal polyester may include monomer unit (2-1-2), monomer unit (2-2-2), and monomer unit (2-3-2) as second monomer units.

[0066] In the first embodiment, the proportion of monomer units (2-1-2) in the second monomer unit may be, for example, 0 mol% or more, 10 mol% or more, or 20 mol% or more, relative to the total amount of monomer units. Alternatively, the proportion of monomer units (2-1-2) in the second monomer unit may be, for example, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less, relative to the total amount of monomer units.

[0067] In the first embodiment, the proportion of monomer units (2-2-2) in the second monomer unit may be, for example, 0 mol% or more, 10 mol% or more, or 20 mol% or more, relative to the total amount of monomer units. Alternatively, the proportion of monomer units (2-2-2) in the second monomer unit may be, for example, 70 mol% or less, 60 mol% or less, or 50 mol% or less, relative to the total amount of monomer units.

[0068] In the first embodiment, the proportion of monomer units (2-3-2) in the second monomer unit may be, for example, 0 mol% or more, 5 mol% or more, or 10 mol% or more, relative to the total amount of monomer units. Alternatively, the proportion of monomer units (2-3-2) in the second monomer unit may be, for example, 40 mol% or less, 30 mol% or less, or 20 mol% or less, relative to the total amount of monomer units.

[0069] In this specification, the number of each monomer unit in a liquid crystal polyester is determined by the analytical method described in Japanese Patent Application Publication No. 2000-19168. Specifically, the number of each monomer unit relative to the total number of monomer units can be calculated by depolymerizing the liquid crystal polyester by reacting it with a lower alcohol in a supercritical state and quantifying the depolymerization product (monomers that induce each monomer unit) by liquid chromatography.

[0070] Liquid crystal polyester can be produced by polymerizing raw material monomers corresponding to the monomer units that constitute it. For example, it can be produced according to the method described in Japanese Patent No. 6439027.

[0071] The flow initiation temperature of the liquid crystal polyester may be, for example, 250°C or higher, and may also be 260°C or higher, 270°C or higher, or 280°C or higher. The flow initiation temperature of the liquid crystal polyester may be, for example, 400°C or lower, and may also be 360°C or lower, 350°C or lower, or 340°C or lower.

[0072] In this specification, the flow initiation temperature of the liquid crystal polyester is measured using a flow tester, where the liquid crystal polyester is melted under a load of 9.8 MPa while being heated at a rate of 4°C / min, and the molten liquid crystal polyester is extruded from a nozzle with an inner diameter of 1 mm and a length of 10 mm, and the viscosity is 4800 Pa·s.

[0073] The melting point (Tm) of the liquid crystal polyester may be, for example, 250°C or higher, and may also be 260°C or higher, 270°C or higher, 280°C or higher, or 285°C or higher. Alternatively, the melting point (Tm) of the liquid crystal polyester may be, for example, 400°C or lower, and may also be 360°C or lower, 350°C or lower, or 340°C or lower.

[0074] In this specification, the melting point of liquid crystal polyester is measured using a differential scanning calorimeter DSC-60 Plus (manufactured by Shimadzu Corporation) in accordance with JIS K7121. Specifically, 10 mg of liquid crystal polyester is placed in a sample container and heated from room temperature at a rate of 10°C / min to 350°C, where it is held for 10 minutes. Then, it is cooled at a rate of 10°C / min to 50°C and held for 10 minutes. The position of the endothermic peak that appears when the temperature is then heated again at a rate of 10°C / min is defined as the melting point (Tm) of the liquid crystal polyester.

[0075] The dielectric loss tangent of the liquid crystal polyester at 10 GHz may be, for example, 0.002 or less, and may also be 0.0015 or less, 0.0012 or less, or 0.0010 or less. This makes it easier to obtain a liquid crystal polyester composition having a suitable dielectric loss tangent as described later.

[0076] The relative permittivity of the liquid crystal polyester at 10 GHz may be, for example, 4.0 or less, or 3.8 or less. The relative permittivity of the liquid crystal polyester at 28 GHz may be, for example, 2.8 or more, or 3.0 or more.

[0077] In this specification, the dielectric loss tangent and relative permittivity of liquid crystal polyester at 10 GHz are measured by the following method. For thin-walled specimens of liquid crystal polyester, the relative permittivity and dielectric loss tangent at 10 GHz are measured using a vector network analyzer (Keysight Technologies, Inc., N529A) and a split-cylinder resonator (EM Labs, Inc., CR710). The thin-walled specimens may be, for example, injection-molded products, molten extruded films, or press sheets. The measurement environment is 23°C and 50% RH.

[0078] In the resin composition of the present embodiment, the content of the liquid crystal polyester may be, for example, 80% by mass or more, 85% by mass or more, 90% by mass or more, 92% by mass or more, 94% by mass or more, 96% by mass or more, or 98% by mass or more based on the total amount of the resin composition. Also, the content of the liquid crystal polyester may be, for example, 99.5% by mass or less, 99% by mass or less, 98.5% by mass or less, or 98% by mass or less based on the total amount of the resin composition.

[0079] Note that the upper limit of the content of the liquid crystal polyester may be an amount such that the total with the lower limit of the content of components other than the liquid crystal polyester is 100% by mass. For example, when the liquid crystal polyester of the present embodiment contains an amorphous polyarylate of A% by mass or more and a carbodiimide compound of B% by mass or more, the content of the liquid crystal polyester may be (100 - (A + B))% by mass or less.

[0080] The amorphous polyarylate may be, for example, an amorphous aromatic polyester having a divalent phenol residue (also referred to as a monomer unit derived from a divalent phenol) and a dibasic acid residue (also referred to as a monomer unit derived from a dibasic acid). The amorphous polyarylate can also be, for example, a polycondensate of a divalent phenol and a dibasic acid.

[0081] The amorphous polyarylate may have one or more kinds of divalent phenol residues. Also, the amorphous polyarylate may have one or more kinds of dibasic acid residues.

[0082] The divalent phenol residue may be, for example, a compound represented by the following formula (i).

Chemical formula

[0083] In formula (i), R 1 represents a divalent group, and R 2 , R 3 , R 4 and R 5Each independently represents a hydrogen atom, a halogeno group, a hydrocarbon group or a nitro group.

[0084] R 2 、R 3 、R 4 and R 5 The halogeno groups in R

[0085] R 2 、R 3 、R 4 and R 5 may be, for example, an aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms.

[0086] R 1 is, for example, a group represented by an oxygen atom (-O-), an oxygen atom (-O-), a sulfur atom (-S-), a carbonyl group (-CO-), a sulfonyl group (-SO2-) or -C(R 11 )(R 12 )-, and preferably a group represented by -C(R 11 )(R 12 )-.

[0087] R 11 and R 12 each independently represent a hydrogen atom, a halogeno group, or a hydrocarbon group which may have a substituent, and R 11 and R 12 may be bonded to each other by a direct bond, an ether bond, a carbonyl group, an ester bond or an amide bond to form a ring.

[0088] R 11 and R 12 The halogeno groups in may be, for example, a fluoro group (-F), a chloro group (-Cl), a bromo group (-Br) or an iodo group (-I), may be a fluoro group or a chloro group, or may be a fluoro group.

[0089] R11 and R 12 The hydrocarbon group in this may be, for example, an aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms.

[0090] R 11 and R 12 Examples of substituents that the hydrocarbon group in the compound may have include halogen groups, hydrocarbon groups, and nitro groups. Examples of halogen groups and hydrocarbon groups include the same groups as described above.

[0091] R 11 and R 12 The bond forming the ring is preferably a direct bond or an amide bond, and may be a direct bond.

[0092] A divalent phenol residue can be described as a monomeric unit derived from divalent phenol.

[0093] The divalent phenol may be, for example, a compound represented by the following formula (ii). [ka]

[0094] In formula (ii), R 1 , R 2 , R 3 , R 4 and R 5 These are R in equation (i), respectively. 1 , R 2 , R 3 , R 4 and R 5 It is synonymous with [the above].

[0095] Examples of divalent phenols represented by formula (ii) include 4,4'-dihydroxydiphenylmethane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-(4-hydroxyphenyl)propane (also known as bisphenol A), 2,2-(4-hydroxyphenyl)butane, 2,2-(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)butane, and 2,2-bis(4-hydroxy-3-methylphenyl)-4-methylpentane. Pentane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)butane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)-4-pentane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)propane, 9,9-bis(4-hydroxy-3,5-dichlorophenyl) Methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 3,3-bis(4-hydroxyphenyl)phthalimidine, N-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine, N-methyl-3,3-bis(4-hydroxyphenyl)phthalimidine, N-ethyl-3,3-bis(4-hydroxyphenyl)phthalimidine, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl) -3,5-dimethylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclopentane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclopentane, 1,1-bis(4-hydroxy-3-phenylphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane, 1,1-Bis(4-hydroxy-3,5-dimethylphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3-phenylphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)phenylmethane, bis Examples include (4-hydroxy-3-methylphenyl)phenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)phenylmethane, bis(4-hydroxy-3-phenylphenyl)phenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-1-phenylethane, and 1,1-bis(4-hydroxy-3-phenylphenyl)-1-phenylethane.

[0096] Amorphous polyarylates may have diol residues other than the divalent phenol residues mentioned above. Examples of diol residues include dihydroxybenzene residues and aliphatic glycol residues.

[0097] Examples of dihydroxybenzenes include hydroquinone, resorcinol, and catechol. Examples of aliphatic glycols include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, nonanediol, decanediol, cyclohexanedimethanol, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, and ethylene oxide adducts of bisphenol S.

[0098] Aromatic dicarboxylic acid residues are preferred as dibasic acid residues. Aromatic dicarboxylic acid residues can be described as monomeric units derived from aromatic dicarboxylic acids.

[0099] Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, methylterephthalic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfondicarboxylic acid, 4,4'-diphenylisopropylidenedicarboxylic acid, 1,2-bis(4-carboxyphenoxy)ethane, and 5-sodium sulfisophthalic acid.

[0100] As aromatic dicarboxylic acids, terephthalic acid and isophthalic acid are preferred, and it is more preferable to use a mixture of terephthalic acid and isophthalic acid. The proportion of terephthalic acid to the total of terephthalic acid and isophthalic acid may be, for example, 20 to 80 mol%, 25 to 70 mol%, or 30 to 60 mol%.

[0101] The dibasic acid residue may contain an aliphatic dicarboxylic acid residue. The aliphatic dicarboxylic acid residue can be considered a monomeric unit derived from an aliphatic dicarboxylic acid. Examples of aliphatic dicarboxylic acids include dicarboxymethylcyclohexane, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, glutaric acid, and dodecanediic acid.

[0102] Amorphous polyarylates may further contain monofunctional carboxylic acid residues, monofunctional phenol residues, monofunctional alcohol residues, etc. Monofunctional carboxylic acids, monofunctional phenols, and monofunctional alcohols are used as molecular weight modifiers.

[0103] Examples of monofunctional carboxylic acids include acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, p-tert-butylbenzoic acid, and p-methoxyphenylacetic acid. Examples of monofunctional phenols include phenol, cresol, p-tert-butylphenol, nonylphenol, o-phenylphenol, and cumylphenol. Examples of monofunctional alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, and phenethyl alcohol.

[0104] The glass transition temperature (Tg) of amorphous polyarylate is 200°C or higher, and may be 215°C or higher, 230°C or higher, or 250°C or higher, or 270°C or higher, from the viewpoint of obtaining the above-mentioned effects more significantly. The glass transition temperature (Tg) of amorphous polyarylate may be, for example, 320°C or lower, 300°C or lower, or 290°C or lower.

[0105] In this specification, the glass transition temperature of amorphous polyarylate is measured by the method specified in JIS K 7121.

[0106] The difference between the melting point (Tm) of the liquid crystal polyester and the glass transition temperature (Tg) of the amorphous polyarylate (Tm-Tg) may be, for example, 120°C or less, and may also be 100°C or less, 80°C or less, 60°C or less, 50°C or less, or 40°C or less. When the difference (Tm-Tg) is small, the effect of suppressing the occurrence of wrinkles described above tends to be more pronounced.

[0107] In the resin composition of this embodiment, the content of amorphous polyarylate may be, for example, 0.1 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, or 1.5 parts by mass or more, per 100 parts by mass of liquid crystal polyester. A higher content of amorphous polyarylate tends to result in a more pronounced effect of suppressing the occurrence of wrinkles as described above. Alternatively, the content of amorphous polyarylate may be, for example, 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, or 6 parts by mass or less, per 100 parts by mass of liquid crystal polyester. A lower content of amorphous polyarylate tends to result in better dielectric properties of the resin composition.

[0108] The resin composition of this embodiment may further contain a carbodiimide compound. The carbodiimide compound may, in whole or in part, react with a liquid crystal polyester and / or amorphous polyarylate to form a reactant.

[0109] In this specification, "the resin composition contains a carbodiimide compound" also includes cases where the resin composition contains a reaction product of the carbodiimide compound and other components. In this case, "carbodiimide compound content" refers to the total amount of unreacted carbodiimide compound and the portion derived from the carbodiimide compound in the reaction product.

[0110] When the resin composition of this embodiment contains a carbodiimide compound, the occurrence of wrinkles is suppressed more significantly.

[0111] The reason for these effects is not entirely clear, but it is thought to be as follows: When the resin composition of this embodiment contains liquid crystal polyester, amorphous polyarylate, and a carbodiimide compound, the carbodiimide compound improves the affinity between the liquid crystal polyester and the amorphous polyarylate, and the liquid crystal polyester and amorphous polyarylate solidify more uniformly, which is thought to more significantly suppress the occurrence of wrinkles during molding.

[0112] Carbodiimide compounds are compounds having a carbodiimide group (-N=C=N-). Carbodiimide compounds may have one carbodiimide group or may have multiple carbodiimide groups.

[0113] Carbodiimide compounds may further have polar groups other than the carbodiimide group. For example, carbodiimide compounds may have an isocyanate group. The aliphatic carbodiimide compounds described later may have an isocyanate group, for example, and may have isocyanate groups at both ends.

[0114] Examples of carbodiimide compounds include aliphatic carbodiimide compounds, aromatic carbodiimide compounds, and cyclic carbodiimide compounds.

[0115] Aliphatic carbodiimide compounds are compounds having an aliphatic hydrocarbon group and a carbodiimide group bonded to the aliphatic hydrocarbon group. Aliphatic carbodiimide compounds may have a chain-like structure in which carbodiimide groups and aliphatic hydrocarbon groups are alternately bonded.

[0116] Examples of aliphatic carbodiimide compounds include compounds having the structure represented by the following formula (A). [ka] [In the formula, R a [where represents an alkanediyl group, and n represents an integer greater than or equal to 1.]

[0117] The alkanediyl group may be, for example, an alkanediyl group having 1 to 10 carbon atoms, or an alkanediyl group having 1 to 4 carbon atoms. Examples of alkanediyl groups include a methylene group, an ethylene group, a 1,3-propanediyl group, and a 1,4-butanediyl group.

[0118] n represents an integer greater than or equal to 1, and may be, for example, 2 or greater, 5 or greater, 10 or greater, or 15 or greater. n may also be, for example, 50 or less, 40 or less, or 30 or less.

[0119] The aliphatic carbodiimide compound may be, for example, a compound represented by the following formula (A-1). [ka] [In the formula, R a And n is synonymous with the above.

[0120] As the aliphatic carbodiimide compound, commercially available products may be used, for example. Examples of aliphatic carbodiimide compounds that may be used include Carbodilite HMV-15CA (manufactured by Nisshinbo Chemical Co., Ltd.), Carbodilite HMV-8CA (manufactured by Nisshinbo Chemical Co., Ltd.), Carbodilite LA-1 (manufactured by Nisshinbo Chemical Co., Ltd.), Carbodilite V-02B (manufactured by Nisshinbo Chemical Co., Ltd.), Carbodilite V-03 (manufactured by Nisshinbo Chemical Co., Ltd.), Carbodilite V-04K (manufactured by Nisshinbo Chemical Co., Ltd.), Carbodilite V-07 (manufactured by Nisshinbo Chemical Co., Ltd.), Carbodilite V-09 (manufactured by Nisshinbo Chemical Co., Ltd.), etc.

[0121] Aromatic carbodiimide compounds are compounds having an aromatic ring and a carbodiimide group bonded to the aromatic ring. Aromatic carbodiimide compounds may have a structure in which carbodiimide groups and aromatic hydrocarbon groups are alternately bonded.

[0122] The aromatic ring in the aromatic carbodiimide compound is preferably a benzene ring.

[0123] Aromatic carbodiimide compounds include, for example, compounds having a structure represented by the following formula (B). [ka] [In the formula, Ar brepresents a phenylene group, and m represents an integer greater than or equal to 1. b Some or all of the hydrogen atoms in the compound may be substituted with halogen atoms, alkyl groups, or aryl groups.

[0124] The phenylene group may be, for example, a 1,3-phenylene group or a 1,4-phenylene group, and preferably a 1,3-phenylene group. These may have substituents.

[0125] Examples of halogen atoms as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The halogen atom as substituent may be a fluorine atom, a chlorine atom, or a bromine atom, or it may be a fluorine atom or a chlorine atom, or it may be a fluorine atom.

[0126] The alkyl group as a substituent may be linear, branched, or cyclic. The alkyl group may be, for example, an alkyl group having 1 to 10 carbon atoms. Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group, and the like.

[0127] The aryl group as a substituent may be a monocyclic or fused ring. The aryl group may be, for example, an aryl group having 6 to 20 carbon atoms. Examples of aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl, 1-naphthyl, and 2-naphthyl groups. The aryl group may also be a group in which a hydrogen atom of the aromatic ring is substituted with an alkyl group, such as the tolyl group.

[0128] Ar b The number of substituents it has may be, for example, 0 to 3.

[0129] Ar b Examples include the 2,4,6-triisopropyl-1,3-phenylene group.

[0130] As the aromatic carbodiimide compound, commercially available products may be used, for example. Examples of aromatic carbodiimide compounds that may be used include Stavaxol® P (manufactured by LANXESS K.K.), Stavaxol® P100 (manufactured by LANXESS K.K.), Stavaxol® P400 (manufactured by LANXESS K.K.), Stavaxol® I (manufactured by LANXESS K.K.), Carbodilite V-05 (manufactured by Nisshinbo Chemical Co., Ltd.), etc.

[0131] A cyclic carbodiimide compound is a compound that has a cyclic structure, and a portion of that cyclic structure is a carbodiimide group. In other words, a cyclic carbodiimide compound can also be described as a compound that has a cyclic structure containing a carbodiimide group.

[0132] Examples of cyclic carbodiimide compounds include the compound represented by the following formula (C-1) and the compound represented by the following formula (C-2). [ka] [ka]

[0133] As the cyclic carbodiimide compound, commercially available products may be used, for example. As the cyclic carbodiimide compound, Carbodista® TCC-NP (manufactured by Teijin Limited) may be used.

[0134] In the resin composition of this embodiment, the content of the carbodiimide compound may be, for example, 0.01 parts by mass or more, 0.03 parts by mass or more, 0.05 parts by mass or more, 0.07 parts by mass or more, 0.09 parts by mass or more, or 0.1 parts by mass or more, per 100 parts by mass of liquid crystal polyester. When the content of the carbodiimide compound is high, the effect of suppressing the occurrence of wrinkles described above tends to be more pronounced. Also, the content of the carbodiimide compound may be, for example, 5 parts by mass or less, 4 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, 1 part by mass or less, or 0.5 parts by mass or less, per 100 parts by mass of liquid crystal polyester. When the content of the carbodiimide compound is low, the dielectric properties tend to be further improved.

[0135] The resin composition of this embodiment may further contain other organic components not mentioned above.

[0136] The resin composition of this embodiment may further contain resins other than, for example, liquid crystal polyester and amorphous polyarylate. Examples of such resins include polyolefins, cyclic polyolefins, polyvinyl chloride, polysulfones, (meth)acrylic resins, polyphenylene ether resins, polyacetal resins, polyamide resins, imide resins, cellulose resins, polyether ether ketone resins, fluororesins, polycarbonate resins, styrene resins, thermosetting resins, and the like.

[0137] The resin composition of this embodiment may further contain colorants, dispersants, plasticizers, antioxidants, curing agents, flame retardants, heat stabilizers, ultraviolet absorbers, antistatic agents, surfactants, lubricants, mold release agents, and the like.

[0138] The content of other organic components in the resin composition of this embodiment may be, for example, 15% by mass or less, 10% by mass or less, 5% by mass or less, 3% by mass or less, or 1% by mass or less, and may also be 0% by mass.

[0139] The resin composition of this embodiment may further contain an inorganic filler. Examples of inorganic fillers include titanium dioxide and silica.

[0140] The content of inorganic filler in the resin composition of this embodiment is not particularly limited and can be adjusted as appropriate depending on the application. The content of inorganic filler in the resin composition of this embodiment may be, for example, 15% by mass or less, 10% by mass or less, 5% by mass or less, 3% by mass or less, or 1% by mass or less, or even 0% by mass.

[0141] The resin composition of this embodiment may be a mixture of raw material components containing liquid crystal polyester and amorphous polyarylate. The resin composition of this embodiment may also be a melted and kneaded product of raw material components containing liquid crystal polyester and amorphous polyarylate.

[0142] The raw material components may further contain a carbodiimide compound, in which case the liquid crystal polyester and the carbodiimide compound may react in the mixture and molten kneaded product to form a crosslinked structure.

[0143] The raw material components may further contain other organic components other than liquid crystal polyester, amorphous polyarylate, and carbodiimide compounds. The raw material components may further contain inorganic fillers. Examples of other organic components and inorganic fillers that the raw material components may contain are the same as those that the resin compositions described above may contain.

[0144] The range of content of each component in the raw material can be exemplified by the same range as the content of each component in the resin composition described above.

[0145] The method of mixing the raw material components is not particularly limited, and known methods can be used without particular restriction. Examples of mixing methods include melt kneading. In particular, when the raw material components contain a carbodiimide compound, melt kneading is preferred from the viewpoint that the reaction between the terminal groups of the liquid crystal polyester and the carbodiimide groups of the carbodiimide compound proceeds easily, and a suitable crosslinked structure is easily formed by this reaction.

[0146] The molten mixture of raw material components can be obtained, for example, by kneading the raw material components at a temperature T1 that is above the flow initiation temperature (FT) of liquid crystal polyester.

[0147] The difference between the liquid crystal polyester flow start temperature FT (°C) and temperature T1 (°C) (T1-FT) may be, for example, 5°C or more, and from the viewpoint of more uniform mixing of raw material components, it may be 10°C or more, or 20°C or more. The above difference (T1-FT) may be, for example, 80°C or less, and from the viewpoint of suppressing the decomposition of raw material components, it may be 70°C or less, 60°C or less, or 50°C or less.

[0148] The resin composition of this embodiment has excellent fluidity when melted and can therefore be suitably used as a molding material. The resin composition of this embodiment may be used, for example, as pellets.

[0149] The melting point of the resin composition in this embodiment may be, for example, 250°C or higher, and may also be 260°C or higher, 270°C or higher, 280°C or higher, or 285°C or higher. A higher melting point of the resin composition improves heat resistance. The melting point of the resin composition in this embodiment may be, for example, 400°C or lower, and may also be 360°C or lower, 350°C or lower, or 340°C or lower. A lower melting point of the resin composition makes molding easier.

[0150] The molded article of this embodiment contains the above-described liquid crystal polyester composition.

[0151] The molded article of this embodiment may be a molded article formed by a molding method that generates flow directions (MD) and perpendicular directions (TD). Since the molded article of this embodiment contains the above-mentioned liquid crystal polyester composition, wrinkle formation is suppressed even if it is formed by a molding method that generates flow directions (MD) and perpendicular directions (TD). Examples of such molding methods include injection molding, inflation molding, T-die molding, blow molding, and calendering.

[0152] The molded products of this embodiment may be, for example, connectors, sockets, films, relay components, coil bobbins, optical pickups, oscillators, semiconductor packages, IC trays, wafer carriers, household electrical appliance components, lighting fixture components, audio product components, ferrules for optical cables, telephone components, facsimile components, modem components, separation claws, heater holders, impellers, fan gears, gears, bearings, motor components, motor cases, engine components, engine room components, electrical components, automotive interior components, microwave cooking pots, heat-resistant tableware, flooring materials, wall materials, beams, columns, roofing materials, aircraft components, spacecraft components, space equipment components, nuclear reactors, marine facility components, cleaning jigs, optical instrument components, valves, pipes, nozzles, filters, medical equipment components, medical materials, sensor components, sanitary fixtures, sports equipment, or leisure goods.

[0153] The molded product in this embodiment may be, for example, a film. Films are molded products that are prone to wrinkles during molding, but in this embodiment, even if the molded product is a film, the occurrence of wrinkles during molding can be sufficiently suppressed.

[0154] While preferred embodiments of this disclosure have been described above, this disclosure is not limited to the embodiments described above. [Examples]

[0155] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0156] (Example 1) (a) Manufacturing of liquid crystal polyester (a-1) In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser, 1035.0 g (5.5 mol) of 6-hydroxy-2-naphthoic acid, 255.2 g (2.3 mol) of hydroquinone, 378.3 g (1.75 mol) of 2,6-naphthalenedicarboxylic acid, 83.1 g (0.5 mol) of terephthalic acid, 1226.87 g (12 mol) of acetic anhydride, and 0.175 g of 1-methylimidazole as a catalyst were added. The mixture was stirred at room temperature for 15 minutes, and then heated to 140°C over 30 minutes while stirring under a nitrogen gas stream. The mixture was then refluxed at the same temperature for 1 hour. Next, the temperature was raised from 140°C to 310°C over 4 hours and 35 minutes while distilling off the distilled by-product acetic acid and unreacted acetic anhydride. The reaction was considered complete when an increase in torque was observed, and the contents were removed. The obtained solid was cooled to room temperature and ground in a pulverizer to obtain aromatic polyester powder (particle size approximately 0.1 mm to 1 mm). The flow onset temperature (FT) of this powder was measured using a flow tester and was found to be 270°C. The obtained powder was heated from room temperature to 225°C over 1 hour, then heated from 225°C to 250°C over 1 hour and 40 minutes, and then heated from 250°C to 306°C over 9 hours and 20 minutes, followed by solid-phase polymerization at 306°C for 6 hours. After solid-phase polymerization, the powder was cooled to obtain liquid crystal polyester (a-1). The flow start temperature (FT) of the obtained liquid crystal polyester (a-1) was 330°C.

[0157] (b) Manufacturing of liquid crystal polyester (a-2) In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser, 1511.1 g (8.03 mol) of 6-hydroxy-2-naphthoic acid, 410.2 g (2.97 mol) of p-hydroxybenzoic acid, 1291.4 g (12.65 mol) of acetic anhydride, and 0.058 g of 1-methylimidazole as a catalyst were added. The mixture was stirred at room temperature for 15 minutes, and then heated to 140°C over 30 minutes while stirring under a nitrogen gas stream. The mixture was then refluxed at the same temperature for 1 hour. Next, the temperature was raised from 140°C to 275°C over 2 hours and 50 minutes while distilling off the distilled by-product acetic acid and unreacted acetic anhydride. The reaction was considered complete when an increase in torque was observed, and the contents were removed. The obtained solid was cooled to room temperature and ground in a pulverizer to obtain aromatic polyester powder (particle size approximately 0.1 mm to 1 mm). The flow onset temperature (FT) of this powder was measured using a flow tester and was found to be 217°C. The obtained powder was heated from room temperature to 190°C over 1 hour and 10 minutes, then heated from 190°C to 258°C over 9 hours and 50 minutes, and held at 258°C for 10 hours to allow solid-phase polymerization. After solid-phase polymerization, the powder was cooled to obtain liquid crystal polyester (a-2). The flow start temperature (FT) of the obtained liquid crystal polyester (a-2) was 318°C.

[0158] (c) Preparation of liquid crystal polyester (A) 60 parts by mass of liquid crystal polyester (a-1) and 40 parts by mass of liquid crystal polyester (a-2) were dry blended and granulated in a twin-screw extruder at a cylinder temperature of 360°C to obtain liquid crystal polyester (A). The melting point (Tm) of the obtained liquid crystal polyester was 313°C.

[0159] (d) Preparation of resin composition 98 parts by mass of liquid crystal polyester (A) and 2 parts by mass of amorphous polyarylate (B-1) (U Polymer® G-L4, manufactured by Unitika Ltd., glass transition temperature (Tg): 220°C) were mixed and granulated in a twin-screw extruder at a cylinder temperature of 360°C to obtain a resin composition.

[0160] (Example 2) 98 parts by mass of liquid crystal polyester (A) and 2 parts by mass of amorphous polyarylate (B-2) (U Polymer (registered trademark) G-D10, manufactured by Unitika Ltd., glass transition temperature (Tg): 275°C) were mixed and granulated in a twin-screw extruder at a cylinder temperature of 360°C to obtain a resin composition.

[0161] (Example 3) A resin composition was obtained by mixing 95 parts by mass of liquid crystal polyester (A) and 5 parts by mass of amorphous polyarylate (B-2) (U Polymer® G-D10, manufactured by Unitika Ltd., glass transition temperature (Tg): 275°C) and granulating the mixture in a twin-screw extruder at a cylinder temperature of 360°C.

[0162] (Example 4) A resin composition was obtained by mixing 97.9 parts by mass of liquid crystal polyester (A), 2 parts by mass of amorphous polyarylate (B-2) (U Polymer® G-D10, manufactured by Unitika Ltd., glass transition temperature (Tg): 275°C), and 0.1 parts by mass of a cyclic carbodiimide compound (Carbodista TCC-NP, manufactured by Teijin Limited), and granulating the mixture in a twin-screw extruder at a cylinder temperature of 360°C.

[0163] (Comparative Example 1) Only liquid crystal polyester (A) was used as the resin composition.

[0164] (Comparative Example 2) 98 parts by mass of liquid crystal polyester (A) and 2 parts by mass of amorphous polyarylate (B-3) (U Polymer® POWDER RK, manufactured by Unitika Ltd., glass transition temperature (Tg): 193°C) were mixed and granulated in a twin-screw extruder at a cylinder temperature of 360°C to obtain a resin composition.

[0165] The resin compositions obtained in Examples 1-4 and Comparative Examples 1-2 were evaluated by the following method. The results are shown in Tables 1 and 2.

[0166] <Manufacturing of molded products> A film was manufactured using an inflation method with a resin composition. Specifically, the resin composition was introduced into the cylinder of a single-screw extruder with a cylinder inner diameter of 20 mm, kneaded under conditions of a cylinder heating temperature of 320°C and a screw rotation speed of 90 rpm, and then extruded through an annular die with a die heating temperature of 300°C, a die inner diameter of 20 mm, and a die gap of 1.15 mm using an inflation method to produce a tubular film with a folded width of approximately 190 mm and a thickness of approximately 30 μm.

[0167] <Wrinkle evaluation> For the obtained tubular film, an arbitrary point was designated as the starting point 1 for thickness measurement. Using a spline micrometer SPM-MX (manufactured by Mitutoyo Corporation), the thickness was measured around the entire circumference at 5 mm intervals in the TD direction (direction perpendicular to the flow direction) from the starting point 1. Next, a point 150 mm from the starting point 1 in the MD direction (flow direction) was designated as the starting point 2, and the thickness was measured around the entire circumference at 5 mm intervals in the TD direction from the starting point 2. The average thickness of all measurement points was measured, and measurement points with a value of more than twice the average thickness were judged as "wrinkles". The total number of measurement points judged as wrinkles was defined as the "number of wrinkles", and the ratio of the number of wrinkles to the total number of measurement points was calculated and evaluated as follows. AA: The number of wrinkles is less than 3% of all measurement points. A: The number of wrinkles is between 3% and 5% of all measurement points. B: The number of wrinkles is between 5% and 7% of all measurement points. C: The number of wrinkles is 7% or more of all measurement points.

[0168] [Table 1]

[0169] [Table 2]

Claims

1. It contains liquid crystal polyester and amorphous polyarylate, The liquid crystal polyester comprises a first monomer unit having a condensed aromatic ring, The content of the first monomer unit is 20 mol% or more of the total amount of all monomer units constituting the liquid crystal polyester. A resin composition wherein the amorphous polyarylate has a glass transition temperature (Tg) of 200°C or higher.

2. The resin composition according to claim 1, wherein the content of the liquid crystal polyester is 80% by mass or more.

3. The resin composition according to claim 1, wherein the content of the amorphous polyarylate is 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the liquid crystal polyester.

4. The resin composition according to claim 1, further comprising a carbodiimide compound having a carbodiimide group.

5. It is a melt-mixed raw material containing liquid crystal polyester and amorphous polyarylate. The liquid crystal polyester comprises a first monomer unit having a condensed aromatic ring, The content of the first monomer unit is 20 mol% or more of the total amount of all monomer units constituting the liquid crystal polyester. A resin composition wherein the amorphous polyarylate has a glass transition temperature (Tg) of 200°C or higher.

6. The resin composition according to claim 5, wherein the content of the liquid crystal polyester in the raw material components is 80% by mass or more.

7. The resin composition according to claim 5, wherein the content of amorphous polyarylate in the raw material components is 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the liquid crystal polyester.

8. The resin composition according to claim 5, wherein the raw material component further contains a carbodiimide compound having a carbodiimide group.

9. The resin composition according to any one of claims 1 to 8, wherein the difference (Tm-Tg) between the melting point (Tm) of the liquid crystal polyester and the glass transition temperature (Tg) of the amorphous polyarylate is 100°C or less.

10. The resin composition according to any one of claims 1 to 8, wherein the condensed aromatic ring is a naphthalene ring.

11. A resin composition according to any one of claims 1 to 8, having a melting point of 300°C or higher.

12. A pellet comprising the resin composition according to any one of claims 1 to 8.

13. A molded article comprising the resin composition according to any one of claims 1 to 8.

14. A molded article according to claim 13, which is a film.

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