Polymer alloy and molded article

Abstract

To provide a polymer alloy that enables production of a molded article exhibiting superior dielectric characteristics (a reduced dielectric loss tangent with the dielectric constant kept low).SOLUTION: A polymer alloy according to the present invention comprises a liquid crystal polymer having a reactive group at its terminal, a non-liquid crystal polymer having a reactive group capable of reacting with the reactive group at the terminal of the liquid crystal polymer, and a reaction product of the liquid crystal polymer and the non-liquid crystal polymer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a polymer alloy, more particularly to a polymer alloy having excellent dielectric properties, and to a molded article containing the polymer alloy. [Background technology]

[0002] Conventionally, liquid crystal polymers have excellent moldability and heat resistance, and thus molded products (e.g., injection molded products) manufactured using liquid crystal polymers have been used in various electronic components. In recent years, with the increase in the amount of information communication in the field of communication, the use of signals having frequencies in the high frequency band has increased in electronic devices and communication devices, and in particular, signals having frequencies in the 10 9 Signals with frequencies in the gigahertz (GHz) range, which is above 100 Hz, are widely used. However, as the frequencies of the signals used increase, risks arise when sending and receiving signals via devices. The most typical example is a decrease in the quality of the output signal, which can lead to misinterpretation of information, i.e., an increase in transmission loss. One known way to reduce this risk is to use "low-dielectric materials" with low relative permittivity and dielectric loss tangent as insulators. Liquid crystal polymers are superior among engineering plastics in that they have low relative permittivity and dielectric loss tangent in the GHz range, and their use for this purpose is expanding. Transmission loss is expressed as the sum of loss in the conductor and loss in the insulator (dielectric loss), and dielectric loss is proportional to the dielectric loss tangent. Therefore, lowering the dielectric loss tangent effectively reduces transmission loss, but provides little benefit to the device in other respects. On the other hand, lowering the dielectric constant offers several advantages for device design. Lowering the dielectric constant of an insulator not only reduces transmission loss, but also offers several other benefits, such as reduced signal transmission delay and easier impedance matching between devices (improving circuit design flexibility). Ideally, insulators, such as liquid crystal polymers used in high-frequency devices, would be desired to have lower both the dielectric constant and the dielectric loss tangent. However, achieving this while maintaining the basic properties required for components, such as mechanical properties and heat resistance, is technically challenging. Therefore, in reality, 1) lower dielectric loss tangent is generally required for insulating components with large surface areas, such as circuit boards, and 2) lower dielectric constant is generally required for insulators with small surface areas, such as connectors, or for connecting devices.

[0003] In recent years, attempts have been made to improve various physical properties by mixing liquid crystal polymers with other resins. Polyphenylene ether (polyphenylene oxide) has a bulky repeating structure made up of 2,6-dimethylbenzene, which increases the free space volume within the polymer, making it known as an engineering polymer with a low dielectric constant. However, because polyphenylene ether is an amorphous polymer, its dielectric loss tangent in the GHz range is higher than that of liquid crystal polymers. From this perspective, studies are being conducted to create an excellent material with low dielectric constant and dielectric loss tangent by combining liquid crystal polymers with polyphenylene ether. For example, Patent Document 1 proposes a resin composition having excellent electrical properties, which contains (A) polyphenylene ether and (B) liquid crystalline polyester, and is blended with (C) an epoxy-modified aromatic vinyl block copolymer and / or an epoxy-modified partially hydrogenated aromatic vinyl block copolymer. Because polyphenylene ether and liquid crystal polymers are incompatible, simple blends result in macrophase separation, resulting in large, fragile interfaces. It is widely known that it is difficult to achieve material properties that improve specific properties without lowering the main properties of the individual polymers used in the blend. This is largely due to the difference in phase between the liquid crystal polymer and the non-liquid crystallinity polymer, which is an isotropic phase, and is a problem that becomes apparent when blending liquid crystal polymers with non-liquid crystallinity polymers. Therefore, attempts have been made to solve this problem by adding a compatibilizer that has affinity with both the liquid crystal polymer and the non-liquid crystal polymer. For example, Patent Document 2 discloses a resin composition containing (A) polyphenylene ether and (B) liquid crystalline polyester, in which component (A) forms a dispersed phase and component (B) forms a continuous phase. It proposes that by adding (C) a copolymer of a styrene compound and another compound as an additive to components (A) and (B) and kneading them, the composition has an excellent balance between mechanical strength and heat resistance and also has improved flame retardancy. Patent Document 3 discloses a polymer alloy obtained by blending a polyphenylene ether resin and a liquid crystal polyester using a compatibilizer for polymer alloys so that the blending ratio of the polyphenylene ether resin is greater than the blending ratio of the liquid crystal polyester. It proposes that the mechanical and electrical properties can be improved by using a block copolymer having a segment (A) consisting only of polyglycidyl methacrylate and a segment (B) consisting only of polystyrene as the compatibilizer. Patent Document 4 discloses a polymer alloy containing polyarylene sulfide, a liquid crystal polymer, and a compatibilizer. It is proposed to improve mechanical strength by using a compatibilizer that is a copolymer formed when polyarylene sulfide and a liquid crystal polymer are mixed, and that contains a first unit of polyarylene sulfide and a second unit of the liquid crystal polymer that are copolymerized with each other. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-121377 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-030044 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-202690 [Patent Document 4] Japanese Patent Application Laid-Open No. 2014-534278 Summary of the Invention [Problem to be solved by the invention]

[0005] In the resin compositions of Patent Documents 1 to 3, when a liquid crystal polymer is mixed with another resin, a third component is required to improve the affinity between the two resins and provide the associated compatibilizing effect. However, the third component used in these resin compositions has a molecular skeleton different from that of the liquid crystal polyester or polyphenylene ether. Therefore, in terms of the affinity for each polymer expected of a compatibilizer, it is inferior to compatibilizers with at least a partial identical structure and cannot be considered optimal. Furthermore, Patent Document 4 uses a compatibilizer consisting of a liquid crystal polyester and a crystalline polymer, polyarylene sulfide. However, to generate this compatibilizer, a compound that reacts with polyarylene sulfide must be introduced, which increases production costs and imposes design constraints on the polymer alloy. Therefore, it is desirable to produce molded products with excellent properties using existing processes without adding other compatibilizers or compounds for generating the compatibilizer in the system, or without adding new reaction or processing processes.

[0006] Therefore, an object of the present invention is to provide a polymer alloy containing a compound that acts as a compatibilizer that improves the affinity between a liquid crystal polymer and a non-liquid crystal polymer during the polymerization and processing of conventional liquid crystal polymers, without adding other compatibilizers or compounds for generating compatibilizers in the system, and without adding additional reaction or processing processes. Furthermore, when polyphenylene ether is used, the object is to provide a polymer alloy that can produce molded articles with excellent dielectric properties (low and excellent relative dielectric constant and dielectric dissipation factor). Another object of the present invention is to provide molded articles containing this liquid crystal polymer and electrical and electronic components equipped with the molded articles. [Means for solving the problem]

[0007] The present inventors have found that a polymer alloy containing a liquid crystal polymer having a terminal reactive group, a non-liquid crystal polymer having a reactive group capable of reacting with the terminal reactive group of the liquid crystal polymer, and a reaction product of the liquid crystal polymer and the non-liquid crystal polymer can produce a molded product with excellent dielectric properties (low and excellent relative dielectric constant and dielectric loss tangent) compared to conventional polymer blends obtained by kneading a liquid crystal polymer and a non-liquid crystal polymer. The present invention was completed based on this finding.

[0008] That is, according to the present invention, the following inventions are provided. [1] A liquid crystal polymer having a reactive group at its terminal; a non-liquid crystal polymer having a reactive group capable of reacting with the reactive group at the terminal of the liquid crystal polymer; a reaction product of the liquid crystalline polymer and the non-liquid crystalline polymer; A polymer alloy comprising: [2] The polymer alloy according to [1], wherein the reactive group at the terminal of the liquid crystal polymer includes at least one selected from the group consisting of a carboxy group, a hydroxy group, an amide group, an acetyl group, and an amino group. [3] The polymer alloy according to [1] or [2], wherein the liquid crystal polymer contains a structural unit derived from a hydroxycarboxylic acid. [4] The polymer alloy according to any one of [1] to [3], wherein the reactive group of the non-liquid crystal polymer includes at least one selected from the group consisting of a carboxy group, a hydroxy group, an amide group, an acetyl group, and an amino group. [5] The polymer alloy according to any one of [1] to [4], wherein the non-liquid crystal polymer is an amorphous polymer. [6] The polymer alloy according to any one of [1] to [5], wherein the non-liquid crystal polymer contains polyphenylene ether. [7] The polymer alloy according to any one of [1] to [6], wherein the non-liquid crystal polymer contains polyphenylene ether having a hydroxy group at a polymer terminal. [8] The polymer alloy according to any one of [1] to [7], wherein the polymer alloy has a morphology separated into three layers: sea, islands, and lakes. [9] The polymer alloy according to [8], wherein in the morphology, the sea and the lake are composed of the liquid crystal polymer.

[10] The polymer alloy according to any one of [1] to [9], wherein the blending amount of the non-liquid crystal polymer is 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the liquid crystal polymer.

[11] The polymer alloy according to any one of [1] to

[10] , wherein the reaction product is obtained by a polymerization reaction between a raw material monomer of the liquid crystal polymer and the non-liquid crystal polymer.

[12] A method for producing a polymer alloy according to any one of [1] to

[11] , a polymerization step of obtaining the reaction product by a polymerization reaction between the raw material monomer of the liquid crystal polymer and the non-liquid crystal polymer; A method for producing a polymer alloy, comprising:

[13] A molded article comprising the polymer alloy according to any one of [1] to

[11] .

[14] An electric / electronic component comprising the molded article according to

[13] . [Effects of the Invention]

[0009] The present inventors have succeeded in producing a polymer alloy by adding a non-liquid crystal polymer having a reactive group at the terminal of the liquid crystal polymer to a raw material monomer of the liquid crystal polymer and carrying out a polymerization process in the state where the polymer is polymerized. This has enabled the production of a polymer alloy containing three types of polymers: a liquid crystal polymer having a reactive group at the terminal, a non-liquid crystal polymer having a reactive group at the terminal of the liquid crystal polymer, and a reaction product of the liquid crystal polymer and the non-liquid crystal polymer. Such a polymer alloy can produce molded products with excellent dielectric properties (a reduction in the relative permittivity while maintaining a dielectric loss tangent as low as that of the liquid crystal polymer alone) compared to conventional polymer blends.

[0010] That is, according to the present invention, it is possible to provide a polymer alloy from which a molded article having excellent dielectric properties (a reduction in the relative dielectric constant while maintaining the dielectric loss tangent as low as that of the liquid crystal polymer alone) can be obtained. Also, according to the present invention, it is possible to provide a molded article having excellent dielectric properties (a reduction in the relative dielectric constant while maintaining the dielectric loss tangent as low as that of the liquid crystal polymer alone). [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 shows a photomicrograph of a cross section of a polymer alloy according to the present invention. [Figure 2] 1 is a photomicrograph of a cross section of a bending test piece prepared in Example 1-1. [Figure 3] 1 is a photomicrograph of a cross section of a bending test piece prepared in Comparative Example 1-1. [Figure 4] 1 is a microscopic infrared spectrum chart of a cross section of a bending test piece prepared in Example 1-3. [Figure 5] 1 is a proton NMR spectrum chart showing a component analysis of the composition prepared in Example 2-1 after washing and hydrolysis. Modes for carrying out the invention

[0012] [Polymer alloy] The polymer alloy according to the present invention comprises a liquid crystal polymer having a reactive group at its terminal, a non-liquid crystal polymer having a reactive group capable of reacting with the reactive group at the terminal of the liquid crystal polymer, and a reaction product of the liquid crystal polymer and the non-liquid crystal polymer.

[0013] The polymer alloy according to the present invention preferably has a morphology (salami structure) separated into three layers: sea, islands, and lakes. As an example of such a morphology (salami structure), a micrograph of a cross section of the polymer alloy is shown in FIG. 1. In such a morphology (salami structure), the sea and lake are preferably composed of a liquid crystalline polymer, and the islands are preferably composed of a non-liquid crystalline polymer. Furthermore, in the present invention, a reaction product between the liquid crystalline polymer and the non-liquid crystalline polymer is preferably present at the interface between each layer. The presence of a reaction product between the liquid crystalline polymer and the non-liquid crystalline polymer at the interface between each layer improves the interaction between the different interfaces, forming a morphology (salami structure) separated into three layers: sea, islands, and lakes. In such a morphology (salami structure) separated into three layers: sea, islands, and lakes, the affinity of each component is improved and finely dispersed, making it easier to significantly exhibit the properties derived from the liquid crystalline polymer and the non-liquid crystalline polymer. In the present invention, by using a polymer alloy that has a morphology (salami structure) separated into three layers: sea, island, and lake, it is possible to obtain a molded product with excellent dielectric properties (a reduction in the relative dielectric constant while maintaining the dielectric tangent as low as that of the liquid crystal polymer alone).

[0014] In the polymer alloy of the present invention, the blending amount of the non-liquid crystal polymer is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less, per 100 parts by mass of the liquid crystal polymer. By adjusting the blending amount of the non-liquid crystal polymer relative to the liquid crystal polymer within the above numerical range, a morphology separated into three layers of sea-island-lake is easily formed, and the dielectric properties can be further improved.

[0015] The dielectric constant of the polymer alloy of the present invention is preferably smaller than that of the liquid crystal polymer alone used in the polymer alloy. For example, the dielectric constant of the polymer alloy is preferably 3.50 or less, more preferably 3.45 or less, even more preferably 3.40 or less, still more preferably 3.35 or less, and most preferably 3.30 or less. The dielectric loss tangent of the liquid crystal polymer is preferably smaller than that of a simple mixture of the liquid crystal polymer and the non-liquid crystal polymer used in the polymer alloy. For example, the dielectric loss tangent of the polymer alloy is preferably 2.50×10 -3 or less, and more preferably 2.30 × 10 -3 or less, and more preferably 2.00 × 10 -3 and even more preferably 1.80 x 10 -3 The following is the result. By setting the relative dielectric constant and dielectric loss tangent of the polymer alloy within the above numerical ranges, it is possible to produce a molded product having the desired dielectric properties, and therefore, when used as a product, it is possible to prevent a decrease in the quality of the output signal in electrical and electronic equipment and communication equipment that use high-frequency signals. In this specification, the dielectric constant and dielectric loss tangent of the polymer alloy can be measured using a flat test piece of 30 mm (flow direction) × 30 mm × 0.4 mm (thickness) obtained by heating and melting the polymer alloy at a temperature between the melting point of the liquid crystal polymer and the melting point + 20°C (for example, 310°C). The dielectric constant and dielectric loss tangent can be measured by a cavity resonator method in accordance with IEC standard IEC62562, and the specific measurement conditions are as follows. The relative permittivity (Er) and dielectric loss tangent (tanδ) in the in-plane direction of the above-mentioned flat test specimen can be measured using a Keysight Technologies network analyzer M9805A by the split post dielectric resonator method (SPDR method) at 23°C, 55% humidity, and a frequency of 10 GHz.

[0016] Considering heat resistance, the lower limit of the melting point of the polymer alloy may be preferably 270°C or higher, more preferably 275°C or higher, and even more preferably 280°C or higher, and the upper limit is not particularly limited, but may be 360°C or lower, 350°C or lower, 340°C or lower, or 330°C or lower. By setting the melting point of the polymer alloy within the above numerical range, the heat resistance of molded articles produced using the polymer alloy to heat processing can be improved. In this specification, the melting point of the polymer alloy is a value measured by a differential scanning calorimeter (DSC). Specifically, the temperature is raised from 30°C to 350-400°C at a rate of 10°C / min to completely melt the polymer alloy, then the temperature is lowered to 30°C at a rate of 10°C / min, and the temperature is raised again at a rate of 10°C / min to the same temperature as in the first cycle. The temperature at the apex of the endothermic peak in the second cycle of the temperature rise process is defined as Tm2, ​​and Tm2 is defined as the melting point (°C).

[0017] At the melting point of the polymer alloy to the melting point + 30°C, the shear rate (100 s -1 The lower limit of the melt viscosity measured under the conditions of (1) above is preferably 10 Pa·s or more, and preferably 15 Pa·s or more, and the upper limit is preferably 500 Pa·s or less, more preferably 400 Pa·s or less, even more preferably 300 Pa·s or less, and still more preferably 150 Pa·s or less. By setting the melt viscosity of the polymer alloy within the above numerical range, the dielectric loss tangent can be further reduced, and the mechanical strength of the molded article can be improved. In this specification, the melt viscosity of the polymer alloy can be measured using a capillary rheometer viscometer in accordance with JIS K7199.

[0018] (liquid crystal polymer) The liquid crystal polymer used in the polymer alloy according to the present invention has a reactive group at its terminal. The reactive group at the terminal of the liquid crystal polymer preferably contains at least one selected from the group consisting of a carboxy group, a hydroxy group, an amide group, an acetyl group, and an amino group, and more preferably contains a carboxy group. In one embodiment of the present invention, these reactive groups can be introduced into the terminal of the liquid crystal polymer by polymerization using raw material monomers having these reactive groups.

[0019] In a preferred embodiment of the present invention, the liquid crystal polymer preferably contains a structural unit (I) derived from a hydroxycarboxylic acid, and may further contain a structural unit (II) derived from a diol and a structural unit (III) derived from a dicarboxylic acid, and may further contain a structural unit (IV) derived from an aromatic monomer having two functional groups (excluding the structural units (I) to (III)). Each structural unit is described in detail below.

[0020] The melting point of the liquid crystal polymer is not particularly limited, but in consideration of heat resistance, it is generally required to be 250°C or higher. The lower limit of the melting point of the liquid crystal polymer is preferably 270°C or higher, more preferably 280°C or higher, even more preferably 300°C or higher, and even more preferably 310°C or higher. The upper limit of the melting point of the liquid crystal polymer may be, for example, 370°C or lower. By setting the melting point of the liquid crystal polymer within the above numerical range, it is possible to improve the heat resistance of molded articles made using the liquid crystal polymer against heat processing while maintaining moldability within a practical temperature range. In this specification, the melting point of the liquid crystal polymer is a value measured by a differential scanning calorimeter (DSC). Specifically, the temperature is raised from 30°C to 350-400°C at a rate of 10°C / min to completely melt the liquid crystal polymer, then the temperature is lowered to 30°C at a rate of 10°C / min, and the temperature is raised again at a rate of 10°C / min to the same temperature as in the first cycle. The temperature at the apex of the endothermic peak in the second cycle of the temperature rise process is defined as Tm2, ​​and Tm2 is defined as the melting point (°C).

[0021] The liquid crystal polymer preferably has a relative dielectric constant of 3.50 or less, more preferably 3.45 or less, even more preferably 3.40 or less, even more preferably 3.35 or less, and most preferably 3.30 or less. The dielectric loss tangent of the liquid crystal polymer is preferably 2.50×10 -3 or less, and more preferably 2.30 × 10 -3 or less, and more preferably 2.00 × 10 -3 and even more preferably 1.80 x 10 -3 The following is the result. By setting the dielectric constant and dielectric dissipation factor of the liquid crystal polymer within the above numerical ranges, it is possible to manufacture molded products having the desired dielectric properties, and therefore when used as products, it is possible to prevent a decrease in the quality of output signals in electrical and electronic equipment and communication equipment that use high-frequency signals. In this specification, the dielectric constant and dielectric loss tangent of a liquid crystal polymer can be measured using a 30 mm (flow direction) × 30 mm × 0.4 mm (thickness) flat test piece obtained by heating and melting the liquid crystal polymer at a temperature between the melting point and the melting point + 20°C (for example, 310°C). The dielectric constant and dielectric loss tangent can be measured by a cavity resonator method in accordance with IEC standard IEC62562, and the specific measurement conditions are as follows: The relative permittivity (Er) and dielectric loss tangent (tanδ) in the in-plane direction of the above-mentioned flat test specimen can be measured using a Keysight Technologies network analyzer M9805A by the split post dielectric resonator method (SPDR method) at 23°C, 55% humidity, and a frequency of 10 GHz.

[0022] The liquid crystallinity of the liquid crystal polymer can be confirmed by using a polarizing microscope (product name: ECLIPSE E600 POL) manufactured by Nikon Corporation equipped with a large specimen cooling and heating stage for microscopes (product name: 10083L) manufactured by Japan High Tech Co., Ltd., to heat and melt the liquid crystal polymer on the microscope heating stage, and then observing whether or not it has optical anisotropy.

[0023] Each of the structural units contained in the liquid crystal polymer according to the present invention will be described in detail below.

[0024] (Structural unit (I) derived from hydroxycarboxylic acid) The structural unit (I) derived from a hydroxycarboxylic acid is preferably a structural unit derived from an aromatic hydroxycarboxylic acid, and more preferably a structural unit derived from an aromatic hydroxycarboxylic acid represented by the following formula (1): Only one type of structural unit (I) may be contained, or two or more types may be contained.

[0025] [ka] In the above formula, Ar 1 is a structure derived from an aromatic hydrocarbon, and may have a substituent or a hetero element as desired. Examples of the structure derived from an aromatic hydrocarbon include those having a skeleton derived from a monocyclic benzene, an aromatic polycyclic compound such as biphenyl or 4,4'-isopropylidenediphenyl, or a condensed compound such as naphthalene, anthracene, or phenanthrene. Examples of the substituent include a hydrogen atom, an alkyl group, an alkoxy group, and a fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. The alkyl group may be a linear or branched alkyl group. The alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

[0026] Examples of raw material monomers that provide the structural unit represented by formula (I) include 6-hydroxy-2-naphthoic acid (HNA), p-hydroxybenzoic acid (HBA), m-hydroxybenzoic acid (m-HBA), and acylated products, ester derivatives, and acid halides thereof.

[0027] From the viewpoint of dielectric properties (reduction in relative dielectric constant while maintaining the dielectric loss tangent as low as that of the liquid crystal polymer alone), the composition ratio (mol %) of the structural unit (I) in the liquid crystal polymer has a lower limit of preferably 30 mol % or more, more preferably 35 mol % or more, and particularly preferably 40 mol % or more, and an upper limit of 80 mol % or less, or 70 mol % or less.

[0028] (Diol-derived structural unit (II)) The diol-derived structural unit (II) is preferably a structural unit derived from an aromatic diol, and is preferably a structural unit derived from an aromatic diol represented by the following formula (2): Only one type of structural unit (II) may be contained, or two or more types may be contained.

[0029] [ka] In the above formula, Ar 2 is a structure derived from an aromatic hydrocarbon, and may have a substituent or a hetero element as desired. Examples of the structure derived from an aromatic hydrocarbon include those having a skeleton derived from a monocyclic benzene, an aromatic polycyclic compound such as biphenyl or 4,4'-isopropylidenediphenyl, or a condensed compound such as naphthalene, anthracene, or phenanthrene. Examples of the substituent include a hydrogen atom, an alkyl group, an alkoxy group, and a fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. The alkyl group may be a linear or branched alkyl group. The alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

[0030] Examples of raw material monomers that provide the structural unit (II) include 4,4'-dihydroxybiphenyl (BP), hydroquinone (HQ), methylhydroquinone (MeHQ), 4,4'-isopropylidenediphenol (BisPA), and their acylated derivatives, ester derivatives, and acid halides.

[0031] The composition ratio (mol%) of the structural unit (II) in the liquid crystal polymer is preferably 10 mol% or more and 40 mol% or less from the viewpoint of dielectric properties (reduction in dielectric loss tangent while maintaining a low relative dielectric constant). The lower limit of the composition ratio (mol%) of the structural unit (II) is more preferably 12.5 mol% or more, even more preferably 15 mol% or more, still more preferably 17.5 mol% or more, and particularly preferably 20 mol% or more. Furthermore, the upper limit of the composition ratio (mol%) of the structural unit (II) is more preferably 37.5 mol% or less, even more preferably 35 mol% or less, still more preferably 32.5 mol% or less, and particularly preferably 30 mol% or less.

[0032] (Structural unit (III) derived from dicarboxylic acid) The structural unit (III) derived from a dicarboxylic acid is preferably a structural unit derived from an aromatic dicarboxylic acid, and is preferably a structural unit derived from an aromatic dicarboxylic acid represented by the following formula (3): Only one type of structural unit (III) may be contained, or two or more types may be contained.

[0033] [ka] In the above formula, Ar 3 is a structure derived from an aromatic hydrocarbon, and may have a substituent or a hetero element as desired. Examples of the structure derived from an aromatic hydrocarbon include those having a skeleton derived from a monocyclic benzene, an aromatic polycyclic compound such as biphenyl or 4,4'-isopropylidenediphenyl, or a condensed compound such as naphthalene, anthracene, or phenanthrene. Examples of the substituent include a hydrogen atom, an alkyl group, an alkoxy group, and a fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. The alkyl group may be a linear or branched alkyl group. The alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

[0034] Examples of raw material monomers that provide the structural unit (III) include terephthalic acid (TPA), isophthalic acid (IPA), 2,6-naphthalenedicarboxylic acid (NADA), and acylated products, ester derivatives, and acid halides thereof.

[0035] The composition ratio (mol%) of the structural unit (II) in the liquid crystal polymer is preferably 10 mol% or more and 40 mol% or less from the viewpoint of dielectric properties (reduction in dielectric loss tangent while maintaining a low relative dielectric constant). The lower limit of the composition ratio (mol%) of the structural unit (II) is more preferably 12.5 mol% or more, even more preferably 15 mol% or more, still more preferably 17.5 mol% or more, and particularly preferably 20 mol% or more. Furthermore, the upper limit of the composition ratio (mol%) of the structural unit (II) is more preferably 37.5 mol% or less, even more preferably 35 mol% or less, still more preferably 32.5 mol% or less, and particularly preferably 30 mol% or less.

[0036] (Structural unit (IV) derived from an aromatic monomer having two functional groups) In addition to the above-mentioned structural units (I) to (III), the liquid crystal polymer may also contain a structural unit (IV) derived from an aromatic monomer having two functional groups. The two functional groups in the structural unit (IV) are selected from the group consisting of a hydroxy group, a carboxy group, and an amino group, and preferably contain at least one amino group. Examples of aromatic monomers having two functional groups include aromatic hydroxy monoamines and aromatic diamines.

[0037] An example of a structural unit derived from an aromatic hydroxymonoamine is a structural unit represented by the following formula (4): Raw material monomers that provide this structural unit include acetaminophen (AAP), p-aminophenol, etc. [ka]

[0038] An example of a structural unit derived from an aromatic diamine is a structural unit represented by the following formula (5): Raw material monomers that provide this structural unit include 4,4'-diaminodiphenyl ether (ODA) and the like. [ka]

[0039] The composition ratio (mol%) of the structural unit (IV) in the liquid crystal polymer can be appropriately adjusted according to the composition ratios of the other structural units. The composition ratio (mol%) of the structural unit (IV) is preferably 10 mol% or less, more preferably 7 mol% or less, even more preferably 5 mol% or less, still more preferably 3 mol% or less, and may be 0 mol%.

[0040] (Non-liquid crystal polymer) The non-liquid crystal polymer is a resin other than the liquid crystal polymer described above, which has a reactive group capable of reacting with the reactive group at the terminal of the liquid crystal polymer. The reactive group of the non-liquid crystal polymer preferably contains at least one selected from the group consisting of a carboxy group, a hydroxy group, an amide group, an acetyl group, and an amino group, and more preferably contains a hydroxy group.

[0041] The non-liquid crystal polymer is preferably an amorphous polymer. Examples of amorphous polymers having reactive groups include polyphenylene ether, polyvinyl alcohol, amorphous polyarylate, poly(meth)acrylate, and polycarbonate. Among these, polyphenylene ether having a hydroxy group at the polymer terminal is preferred. These amorphous polymers may be used alone or in combination of two or more.

[0042] In the present invention, it is preferable to use polyphenylene ether as the polyether. In the present invention, conventionally known polyphenylene ethers can be used as the polyphenylene ether. Polyphenylene ether (PPE) is a compound having a polyphenylene ether chain in the molecule. The polyphenylene ether of the present invention also includes its modified product, modified polyphenylene ether (m-PPE). The modified polyphenylene ether of the present invention also includes an alloy of polyphenylene ether (PPE) with other synthetic resins. Examples of other synthetic resins include polystyrene (PS), polyphenylene sulfide (PPS), polypropylene (PP), polyamide (PA), and polyacetal (POM).

[0043] The non-liquid crystal polymer may also include another polymer that is compatible with the amorphous polymer having a reactive group, such as polystyrene and polystyrene-hydrogenated polybutadiene (SEBS).

[0044] (Reaction products) The reaction product is obtained by reacting the reactive groups of the liquid crystal polymer with the reactive groups of the non-liquid crystal polymer. The reaction method is not particularly limited and can be appropriately set depending on the types of reactive groups of the liquid crystal polymer and the non-liquid crystal polymer.

[0045] In a preferred embodiment of the present invention, in the polymerization process of the liquid crystal polymer, a reaction product is preferably obtained by polymerization of a raw material monomer of the liquid crystal polymer with a non-liquid crystal polymer. This method produces a polymer alloy containing three types of materials: a liquid crystal polymer, a non-liquid crystal polymer, and the reaction product. This polymer alloy is preferred because it has a morphology (salami structure) separated into the above-mentioned three layers: sea, islands, and lake.

[0046] [Method of manufacturing polymer alloy] The method for producing a polymer alloy according to the present invention preferably includes a polymerization step for obtaining a polymer alloy and further includes a step of kneading the polymer alloy. Although the polymerization step and the kneading step are described below as separate steps, the polymerization step and the kneading step may be performed simultaneously. Therefore, the polymerization reaction of the polymer may proceed during kneading, and a morphology separated into three layers, i.e., sea-island-lake, may be formed in the polymer alloy.

[0047] (Polymerization process) The polymerization step is a step of introducing a non-liquid crystal polymer into a polymerization reaction system of raw material monomers for a liquid crystal polymer to obtain a polymer alloy. The polymer alloy can be produced by polymerizing the raw material monomers for the liquid crystal polymer and the non-liquid crystal polymer using a conventionally known method. In one embodiment of the present invention, the polymer alloy can be produced solely by melt polymerization. Alternatively, the polymer alloy can be produced by a method (two-stage polymerization) that includes a step of obtaining a polymer by melt polymerization and a step of obtaining a polymer alloy by solid-state polymerization of the polymer. In this polymerization step, a morphology separated into three layers, namely, sea, island, and lake, is formed.

[0048] From the viewpoint of efficiently obtaining a polymer alloy, the melt polymerization is preferably carried out under reflux of acetic acid in the presence of 1.03 to 1.15 molar equivalents of acetic anhydride relative to the total hydroxyl groups possessed by all raw material monomers of the liquid crystal polymer.

[0049] The reaction temperature for melt polymerization is preferably in the range of the melting point to (melting point + 70)°C, more preferably in the range of (melting point + 20)°C to (melting point + 50)°C.

[0050] The melt polymerization is preferably carried out in the presence of a catalyst without a solvent. As the catalyst, a conventionally known catalyst for polymer polymerization can be used. Examples of the catalyst include metal salt catalysts such as potassium acetate, magnesium acetate, stannous acetate, lead acetate, sodium acetate, tetrabutyl titanate, and antimony trioxide, nitrogen-containing heterocyclic compounds such as N-methylimidazole, and organic compound catalysts. The amount of catalyst used is not particularly limited, but is preferably the total number of moles of monomers × (10 to 100) mg / mol.

[0051] When performing solid-state polymerization, the polymer obtained by melt polymerization may be cooled and solidified, and then pulverized into powder or flakes. Alternatively, the polymer strands obtained by melt polymerization may be pelletized. The reaction temperature for solid-state polymerization is preferably the melting point or lower, and is preferably (melting point - 30)°C to (melting point - 10)°C. Solid-state polymerization may be performed with stirring, or may be performed in a stationary state without stirring.

[0052] The polymerization reactor is not particularly limited, but a reactor generally used for reactions of high-viscosity fluids is preferably used. Examples of such reactors include stirred tank-type polymerization reactors having stirrers with stirring blades of various shapes, such as anchor-type, multi-stage-type, spiral belt-type, and spiral shaft-type, or modified versions of these, as well as mixing devices generally used for kneading resins, such as kneaders, roll mills, and Banbury mixers.

[0053] (Kneading process) The kneading step is a step of kneading the polymer alloy obtained in the polymerization step. Methods for finely dispersing the non-liquid crystal polymer in the liquid crystal polymer include adjusting the melt viscosity of the liquid crystal polymer and adjusting the kneading conditions of the polymer alloy (kneading temperature, kneading time, etc.). In the present invention, it is preferable to knead the polymer alloy using an extruder equipped with a twin-screw kneader.

[0054] [Molded products] The molded article according to the present invention contains the above-mentioned polymer alloy. By containing the above-mentioned polymer alloy, the molded article has excellent dielectric properties (a reduction in the dielectric loss tangent while maintaining a low relative dielectric constant).

[0055] (filler) The molded article may further contain a filler. Examples of fillers include carbon fiber, graphite, glass fiber, talc, mica, glass flakes, clay, sericite, calcium carbonate, calcium sulfate, calcium silicate, silica, alumina, aluminum hydroxide, calcium hydroxide, graphite, potassium titanate, titanium oxide, fluorocarbon resin fiber, fluorocarbon resin, barium sulfate, and various whiskers. These fillers may be used alone or in combination of two or more.

[0056] The content of the filler in the molded article is preferably 1% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, even more preferably 10% by mass or more and 50% by mass or less, and even more preferably 15% by mass or more and 45% by mass or less, based on the total amount of the molded article. When two or more fillers are contained, it is preferable that the total content thereof is within the above range. If the content of the filler in the molded article is within the above range, it is preferable because a molded article having excellent mechanical properties can be obtained.

[0057] (other resins) The molded article may further contain other resins in addition to the polymer alloys described above, provided that the resin does not deviate from the spirit of the present invention. Examples of such resins include polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polyarylate, polycyclohexylene dimethylene terephthalate, and polybutylene terephthalate; polyolefin resins such as polyethylene and polypropylene; cycloolefin polymers; vinyl resins such as polyvinyl chloride; (meth)acrylic resins such as polyacrylate, polymethacrylate, and polymethyl methacrylate; imide resins such as polyacetal resins, polyamide resins, polyimides, and polyetherimides; polystyrene resins such as polystyrene, high-impact polystyrene, AS resin, and ABS resin; thermosetting resins such as epoxy resins; cellulose resins, polyether ether ketone resins, fluororesins, and polycarbonate resins. These resins may be used alone or in combination of two or more.

[0058] The content of the resin other than the polymer alloy in the molded article is preferably 5 parts by mass or more and preferably 20 parts by mass or less based on the non-liquid crystal polymer introduced into the system.

[0059] (Other additives) The molded article may contain other additives, such as colorants, dispersants, plasticizers, antioxidants, curing agents, flame retardants, heat stabilizers, ultraviolet absorbers, antistatic agents, and surfactants, within the scope of the present invention.

[0060] The shape of the molded product is not particularly limited and may be changed appropriately depending on the application, and may be, for example, a plate, sheet, film, fiber, powder, or the like.

[0061] The molded article can be produced by a conventionally known molding method using a mixture containing the above-mentioned polymer alloy and, if desired, fillers, other resins, other additives, etc. The mixture can be obtained by melt-kneading the above-mentioned polymer alloy, etc. using a Banbury mixer, kneader, single-screw or twin-screw extruder, etc. In addition, examples of molding methods for molded articles include press molding, foam molding, injection molding, melt spinning, solution spinning, calendar molding, and punch molding.

[0062] [Electrical and electronic components] The electric / electronic component according to the present invention comprises a molded article (e.g., a fibrous molded article or an injection-molded article) containing a polymer alloy. Examples of electric / electronic components comprising the molded article include antennas used in electronic devices and communication devices such as ETC, GPS, wireless LAN, and mobile phones, high-speed transmission connectors, CPU sockets, circuit boards, flexible printed circuit boards (FPCs), laminated circuit boards, millimeter-wave and quasi-millimeter-wave radars such as collision prevention radars, RFID tags, capacitors, inverter components, insulating films, cable covering materials, insulating materials for secondary batteries such as lithium-ion batteries, and speaker diaphragms. [Example]

[0063] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0064] [Test Example 1] <Production of polymer alloys> (Example 1-1) A polymerization vessel equipped with a stirring blade was charged with 27 mol% 6-hydroxy-2-naphthoic acid (HNA) and 73 mol% p-hydroxybenzoic acid (HBA) as raw material monomers for the liquid crystal polymer. Furthermore, poly(2,6-dimethyl-1,4-phenylene ether) (containing terminal hydroxy groups, Mw: 47600, Mn: 17300, manufactured by SABIC Corporation, product name: NORYL PPO630) was charged as a non-liquid crystal polymer, and magnesium acetate and potassium acetate were charged as catalysts. The amount of non-liquid crystal polymer added was 40 parts by mass per 100 parts by mass of liquid crystal polymer. Subsequently, the polymerization vessel was subjected to three cycles of vacuum decompression and nitrogen injection. Then, acetic anhydride (1.05 molar equivalents relative to the hydroxyl groups) was further added, and the temperature was raised to 160 °C. The acetylation reaction was carried out under reflux for 2 hours.

[0065] After the acetylation was completed, the polymerization vessel, which had been in a state of acetic acid distillation, was heated to 320°C at a rate of 0.5°C / min. During this time, acetic acid as a by-product was distilled off as the esterification reaction progressed. After reaching 320°C, the vessel was stirred for 20 minutes, and then the system was depressurized while maintaining the temperature at 320°C to promote the distillation of acetic acid as a by-product. In this state, the pressure was gradually reduced to 200 hPa over 20 minutes. After that, the viscosity of the polymer was measured based on the power consumption and torque of the agitator. -1 When the viscosity reached approximately 20 Pa·s, the polymer was extracted and cooled to solidify. If the target viscosity was not reached after maintaining the pressure at 200 hPa for more than an hour, the pressure was further reduced to 10 hPa. After the reaction, the amount of acetic acid distilled was measured and found to be 99-100% of the theoretical reaction standard. The resulting polymer was pulverized to a size that could pass through a sieve with 2.0 mm openings.

[0066] The polymer was then allowed to cool naturally at room temperature to obtain a polymer alloy. The polymer was heated and melted on a heating stage of a polarizing microscope (product name: ECLIPSE E600 POL) manufactured by Nikon Corporation equipped with a large cooling and heating stage for microscopes (product name: 10083L) manufactured by Japan High Tech Co., Ltd., and the liquid crystallinity was confirmed based on the presence or absence of optical anisotropy.

[0067] Next, the obtained polymer alloy was kneaded at 340°C using a twin-screw kneader (Labo Plastomill Micro, small extrusion segment 2D15W, manufactured by Toyo Seiki Co., Ltd.).

[0068] (manufacturing of molded products) The resulting kneaded material was heated and melted at 310°C using an injection molding machine and injected into a mold at 80°C to prepare flat test pieces measuring 30 mm (inflow direction) x 30 mm x 0.4 mm (thickness) and bending test pieces measuring 80 mm (inflow direction) x 12 mm x 2 mm (thickness).

[0069] (Comparative Example 1-1) A liquid crystal polymer was produced in the same manner as in Example 1-1, except that the non-liquid crystal polymer was not added in the polymerization step. Next, 100 parts by mass of the obtained liquid crystal polymer and 40 parts by mass of poly(2,6-dimethyl-1,4-phenylene ether) (PPO630) as a non-liquid crystal polymer were kneaded at 340°C using a twin-screw kneader. Using the obtained kneaded product, flat test pieces and bending test pieces were prepared in the same manner as in Example 1-1.

[0070] (Example 1-2) A polymer alloy was obtained in the same manner as in Example 1-1, except that the amount of the non-liquid crystal polymer added in the polymerization step was changed to 31 parts by mass per 100 parts by mass of the liquid crystal polymer. Next, the obtained polymer alloy was kneaded at 340°C using a twin-screw kneader. Using the obtained kneaded product, flat test pieces and bending test pieces were prepared in the same manner as in Example 1-1.

[0071] (Comparative Example 1-2) A liquid crystal polymer was produced in the same manner as in Example 1-1, except that the non-liquid crystal polymer was not added in the polymerization step. Next, 100 parts by mass of the obtained liquid crystal polymer and 31 parts by mass of poly(2,6-dimethyl-1,4-phenylene ether) (PPO630) as a non-liquid crystal polymer were kneaded at 340°C using a twin-screw kneader. Using the obtained kneaded product, flat test pieces and bending test pieces were prepared in the same manner as in Example 1-1.

[0072] (Examples 1-3) A polymer alloy was obtained in the same manner as in Example 1-1, except that the amount of the non-liquid crystal polymer added in the polymerization step was changed to 15 parts by mass per 100 parts by mass of the liquid crystal polymer. Next, the obtained polymer alloy was kneaded at 340°C using a twin-screw kneader. Using the obtained kneaded product, flat test pieces and bending test pieces were prepared in the same manner as in Example 1-1.

[0073] (Comparative Examples 1-3) A liquid crystal polymer was produced in the same manner as in Example 1-1, except that the non-liquid crystal polymer was not added in the polymerization step. Next, 100 parts by mass of the obtained liquid crystal polymer and 15 parts by mass of poly(2,6-dimethyl-1,4-phenylene ether) (PPO630) as a non-liquid crystal polymer were kneaded at 340°C using a twin-screw kneader. Using the obtained kneaded product, flat test pieces and bending test pieces were prepared in the same manner as in Example 1-1.

[0074] (Examples 1-4) A polymer alloy was obtained in the same manner as in Example 1-1, except that the amount of the non-liquid crystal polymer added in the polymerization step was changed to 7 parts by mass per 100 parts by mass of the liquid crystal polymer. Next, the obtained polymer alloy was kneaded at 340°C using a twin-screw kneader. Using the obtained kneaded product, flat test pieces and bending test pieces were prepared in the same manner as in Example 1-1.

[0075] (Examples 1-5) A polymer alloy was obtained in the same manner as in Example 1-1, except that the amount of non-liquid crystal polymer added in the polymerization process was changed to 5 parts by mass per 100 parts by mass of liquid crystal polymer, and after extraction, the pulverized polymer was heated from room temperature to 270°C under a reduced pressure of 100 kPa in a vacuum oven (Yamato Scientific Co., Ltd., square vacuum dryer DP23), and then held at 270°C for 6 hours to carry out solid-state polymerization. Next, the obtained polymer alloy was kneaded at 340°C using a twin-screw kneader. Using the obtained kneaded product, flat test pieces and bending test pieces were prepared in the same manner as in Example 1-1.

[0076] (Comparative Examples 1-4) A liquid crystal polymer was produced in the same manner as in Example 1-1, except that the non-liquid crystal polymer was not added in the polymerization step. Next, 100 parts by mass of the obtained liquid crystal polymer and 5 parts by mass of poly(2,6-dimethyl-1,4-phenylene ether) (PPO630) as a non-liquid crystal polymer were kneaded at 340°C using a twin-screw kneader. Using the obtained kneaded product, flat test pieces and bending test pieces were prepared in the same manner as in Example 1-1.

[0077] (Comparative Examples 1-5) A liquid crystal polymer was produced in the same manner as in Example 1-1, except that the non-liquid crystal polymer was not added in the polymerization step. Next, 100 parts by mass of the obtained liquid crystal polymer was kneaded at 340°C using a twin-screw kneader. Using the obtained kneaded product, flat test pieces and bending test pieces were prepared in the same manner as in Example 1-1.

[0078] <Cross-section observation of molded product> Each bending test specimen prepared above was cut using a jigsaw at a point 20 mm from the mold end point in the flow direction. The cut specimens were embedded in epoxy resin and epoxy curing agent (manufactured by HERZOG). After the epoxy cured, the test specimens were cross-sectioned using mechanical polishing (abrasive: Baikalox alumina manufactured by BAIKOWSKI, finishing grit size 0.05 μm). The exposed cross sections were examined using a digital macroscope (magnification: 200-700x, Keyence Corporation, product name: VHX-8000). As a result, in Examples 1-1 to 1-5, a morphology separated into three layers (sea, islands, and lake) consisting only of islands with different components (salami structure) was formed. On the other hand, in Comparative Examples 1-1 to 1-5, a morphology separated into three layers (sea, islands, and lake) (salami structure) was not formed. The presence or absence of a salami structure is shown in Table 1. Micrographs of Example 1-1 and Comparative Example 1-1 are shown in Figures 2 and 3, respectively.

[0079] In addition, the components of the cross-sectioned morphology were identified by microscopic infrared spectroscopy (FT-IR, JASCO FT / IR-4600). After measuring the IR spectrum of the polyphenylene ether (PPO630) alone, IR measurements were carried out on the sea, island, and lake of the cross-sectioned sample. As a result, the island part showed the IR peak characteristic of the polyphenylene ether alone (e.g., 2920 cm -1 The methyl group CH stretching vibration of the methyl group (HBA73 / HNA27) was observed, and the sea and lake regions were confirmed to have spectra similar to those of the liquid crystal polymer (HBA73 / HNA27). Therefore, the island regions were identified as polyphenylene ether, and the sea and lake regions were identified as liquid crystal polymer. This is a reasonable result, considering that the ratio of liquid crystal polymer in the polymer alloy exceeds half. Figure 4 shows the microscopic infrared spectrum charts of the sea, island, and lake regions of Examples 1-3, as well as the comparative liquid crystal polymer (HBA73 / HNA27) and the liquid crystal polymer (HBA73 / HNA27).

[0080] <Measurement of relative permittivity and dielectric loss tangent (10GHz)> The dielectric constant and dielectric loss tangent of each of the flat test specimens prepared above were measured using the cavity resonator method in accordance with IEC standard IEC62562. Specifically, the in-plane dielectric constant (Er) and dielectric loss tangent (tanδ) of the above flat test specimens were measured using a Keysight Technologies network analyzer N5247A by the split post dielectric resonator method (SPDR method) at 23°C, 55% humidity, and a frequency of 10 GHz. Each type of sample was measured in quadruplicate, and the average values ​​for the four measurements are shown in Table 1.

[0081] <Melt point measurement> The melting points of each of the kneaded materials obtained above were measured. Specifically, using a differential scanning calorimeter (DSC), the kneaded materials were heated from 30°C to 350-400°C at a rate of 10°C / min until they were completely melted, then cooled to 30°C at a rate of 10°C / min, and heated again at a rate of 10°C / min to the same temperature as in the first cycle. The temperature at the apex of the endothermic peak in the second cycle of the heating process was taken as Tm2, ​​and Tm2 was taken as the melting point (°C). The measurement results are shown in Table 1.

[0082] <Melt viscosity measurement> Each of the kneaded materials obtained above was subjected to a shear rate of 100 s at the temperature shown in Table 1. -1 The melt viscosity (Pa·s) under these conditions was measured in accordance with JIS K7199 using a capillary rheometer viscometer (Capillograph 1D, Toyo Seiki Seisakusho Co., Ltd.) and a capillary with an inner diameter of 1 mm and a length of 40 mm. The measurement results are shown in Table 1.

[0083] [Table 1]

[0084] In Table 1, "internal addition" in the method of adding non-liquid crystal polymer refers to placing the non-liquid crystal polymer in a reactor together with the raw material monomer during the liquid crystal polymer polymerization process, polymerizing the liquid crystal polymer, mixing the non-liquid crystal polymer, and then chemically reacting the non-liquid crystal polymer with the liquid crystal polymer simultaneously. "External addition" refers to cooling and pulverizing the liquid crystal polymer after polymerization, adding the non-liquid crystal polymer to the pulverized liquid crystal polymer, and then mixing the liquid crystal polymer and non-liquid crystal polymer using a twin-screw mixer without causing a chemical reaction. By the internal addition method, a chemical reaction between the raw monomers and the non-liquid crystal polymer occurred simultaneously with the polymerization between the raw monomers, resulting in a reaction product of the liquid crystal polymer and the non-liquid crystal polymer. This reaction product has an affinity with both the liquid crystal polymer and the amorphous polymer, and therefore has a sea-island-lake structure. On the other hand, polymer blends produced by the external addition method, which does not induce a chemical reaction, have the traditional sea-island structure. The results in Table 1 show that when the amount of non-liquid crystal polymer added to the liquid crystal polymer is the same, the polymer alloys of Examples 1-1 to 1-5 can have the same or a lower dielectric constant than mixtures of liquid crystal polymer and non-liquid crystal polymer such as Comparative Examples 1-1 to 1-4, and can have a lower dielectric constant than the liquid crystal polymer alone in Comparative Example 1-5. Furthermore, when the amount of non-liquid crystal polymer added to the liquid crystal polymer is the same, it was found that polymer alloys containing reaction products of liquid crystal polymer and non-liquid crystal polymer, such as those in Examples 1-1 to 1-5, can reduce the dielectric tangent compared to mixtures of liquid crystal polymer and non-liquid crystal polymer, such as those in Comparative Examples 1-1 to 1-4.

[0085] [Test Example 2] <Production of polymer alloys> Example 2-1 A polymer alloy was obtained in the same manner as in Example 1-3, except that the type of non-liquid crystal polymer in the polymerization process was changed to a low molecular weight poly(2,6-dimethyl-1,4-phenylene ether) (containing terminal hydroxy groups, Mw: 6300, Mn: 2350, manufactured by SABIC, trade name: SA120). Next, the obtained polymer alloy was kneaded at 340°C using a twin-screw kneader. Using the obtained kneaded product, flat test pieces and bending test pieces were prepared in the same manner as in Example 1-1.

[0086] (Comparative Example 2-2) A liquid crystal polymer was produced in the same manner as in Example 1-1, except that the non-liquid crystal polymer was not added in the polymerization step. Next, 100 parts by mass of the obtained liquid crystal polymer and 15 parts by mass of poly(2,6-dimethyl-1,4-phenylene ether) (SA120) as a non-liquid crystal polymer were kneaded at 340°C using a twin-screw kneader. Using the obtained kneaded product, flat test pieces and bending test pieces were prepared in the same manner as in Example 1-1.

[0087] <Cross-section observation of molded product> Using each of the bending test pieces prepared above, the presence or absence of a salami structure was observed in the same manner as in Test Example 1. The observation results are shown in Table 2.

[0088] <Measurement of relative permittivity and dielectric loss tangent (10GHz)> The relative permittivity and dielectric loss tangent of each of the flat plate test pieces prepared above were measured in the same manner as in Test Example 1. Each type of sample was measured four times, and the average values ​​of the four measurements are shown in Table 2.

[0089] <Melt point measurement> The melting point of each of the kneaded products obtained above was measured in the same manner as in Test Example 1. The measurement results are shown in Table 2.

[0090] <Melt viscosity measurement> The melt viscosity of each of the kneaded products obtained above was measured at the temperatures shown in Table 2 in the same manner as in Test Example 1. The measurement results are shown in Table 3.

[0091] [Table 2]

[0092] The results in Table 2 show that when the amount of non-liquid crystal polymer added to the liquid crystal polymer is the same, the polymer alloy of Example 2-1 can reduce the dielectric constant compared to a mixture of liquid crystal polymer and non-liquid crystal polymer such as Comparative Example 2-1, and can reduce the dielectric constant compared to the liquid crystal polymer alone in Comparative Example 1-5. Furthermore, when the amount of non-liquid crystal polymer added to the liquid crystal polymer is the same, it was found that a polymer alloy containing a reaction product of a liquid crystal polymer and a non-liquid crystal polymer, such as in Example 2-1, can reduce the dielectric tangent compared to a mixture of a liquid crystal polymer and a non-liquid crystal polymer, such as in Comparative Example 2-1.

[0093] [Test Example 3] <Production of polymer alloys> Example 3-1 In the polymerization process, the raw material monomers for the liquid crystal polymer were changed to 60 mol% HNA, 20 mol% 4,4'-dihydroxybiphenyl (BP), 15.5 mol% terephthalic acid (TPA), and 4.5 mol% 2,6-naphthalenedicarboxylic acid (NADA), and the final temperature reached during melt polymerization was changed to 350°C. A polymer alloy was obtained in the same manner as in Example 2-1. Next, the obtained polymer alloy was kneaded at 340°C using a twin-screw kneader. Using the obtained kneaded product, a bending test piece was prepared in the same manner as in Example 1-1.

[0094] (Example 3-2) A polymer alloy was obtained in the same manner as in Example 3-1, except that the type of non-liquid crystal polymer in the polymerization step was changed to poly(2,6-dimethyl-1,4-phenylene ether) (PPO630). Next, the obtained polymer alloy was kneaded at 340°C using a twin-screw kneader. Using the obtained kneaded product, flat test pieces and bending test pieces were prepared in the same manner as in Example 1-1.

[0095] (Comparative Example 3-1) A liquid crystal polymer was produced in the same manner as in Example 3-1, except that the non-liquid crystal polymer was not added in the polymerization step. Next, 100 parts by mass of the obtained liquid crystal polymer and 15 parts by mass of poly(2,6-dimethyl-1,4-phenylene ether) (SA120) as a non-liquid crystal polymer were kneaded at 340°C using a twin-screw kneader. Using the obtained kneaded product, flat test pieces and bending test pieces were prepared in the same manner as in Example 1-1.

[0096] (Comparative Example 3-2) In Comparative Example 3-1, no non-liquid crystal polymer was added during kneading. Using the obtained liquid crystal polymer alone, flat test pieces and bending test pieces were prepared in the same manner as in Example 1-1.

[0097] <Cross-section observation of molded product> Using each of the bending test pieces prepared above, the presence or absence of a salami structure was observed in the same manner as in Test Example 1. The observation results are shown in Table 3.

[0098] <Measurement of relative permittivity and dielectric loss tangent (10GHz)> The relative permittivity and dielectric loss tangent of each of the flat plate test pieces prepared above were measured in the same manner as in Test Example 1. Each type of sample was measured four times, and the average values ​​of the four measurements are shown in Table 3.

[0099] <Melt point measurement> The melting point of each of the kneaded products obtained above was measured in the same manner as in Test Example 1. The measurement results are shown in Table 3.

[0100] <Melt viscosity measurement> The melt viscosity of each of the kneaded products obtained above was measured at the temperatures shown in Table 3 in the same manner as in Test Example 1. The measurement results are shown in Table 3.

[0101] [Table 3]

[0102] The results in Table 3 show that when the amount of non-liquid crystal polymer added to the liquid crystal polymer is the same, the polymer alloy of Example 3-1 has the same dielectric constant as a mixture of liquid crystal polymer and non-liquid crystal polymer such as Comparative Example 3-1, and can reduce the dielectric constant compared to the liquid crystal polymer alone in Comparative Example 3-2. Furthermore, when the amount of non-liquid crystal polymer added to the liquid crystal polymer is the same, it was found that a polymer alloy containing a reaction product of a liquid crystal polymer and a non-liquid crystal polymer, such as in Example 3-1, can reduce the dielectric tangent compared to a mixture of a liquid crystal polymer and a non-liquid crystal polymer, such as in Comparative Example 3-1. In all of the Examples 1 to 3, despite the same composition ratio, the polymer alloys with a salami structure in the Examples tended to have lower dielectric dissipation factors than the polymer blends without a salami structure in the Comparative Examples. Liquid crystal polymers have an oriented, high-order structure that restricts the polar motion of molecules, resulting in a particularly low dielectric dissipation factor among polyesters. The added polyphenylene ether is amorphous and lacks orientation, resulting in a high dielectric dissipation factor. However, the bulky 2,6-dimethyl structure increases the free volume and lowers the relative dielectric constant. In polymer blends, if the affinity between the liquid crystal polymer and the non-liquid crystal polymer can be enhanced, it is believed that the orientation of the liquid crystal polymer and its low dielectric dissipation factor can be transferred to the non-liquid crystal polymer. The sea-island-lake structure shown in the Examples is thought to allow the liquid crystal polymer to transfer its orientation from inside and outside the amorphous polymer islands, resulting in the low dielectric dissipation factor in the polymer alloys with a salami structure.

[0103] To understand the state of polyphenylene ether in the polymer alloy with a salami structure, a composition analysis was performed using Example 2-1 according to the following procedure. First, the sample of Example 2-1 after melt polymerization was ground in a mortar to obtain a uniform and fine powder particle size. This was then subjected to Soxhlet extraction for 6 hours using toluene, a good solvent for polyphenylene ether but a poor solvent for liquid crystal polymers, to wash and separate the unreacted polyphenylene ether from the system. The solvent was then removed from the collected washings using an evaporator, and the weight of the remaining solid was measured, revealing that approximately 60% by mass of the polyphenylene ether introduced into the system had been washed and removed as unreacted polyphenylene ether. Next, the remaining solid after washing was thoroughly dried, and 20 mg was weighed out. Deuterium oxide (0.6 mL), deuterated toluene (0.8 mL), and sodium hydroxide (0.2 g) were added, and the mixture was stirred at 80 °C under a nitrogen atmosphere for 4 hours to hydrolyze the ester groups. After heating and stirring, the liquid crystal polymer portion was hydrolyzed to a monomer and obtained as a heavy water solution. Meanwhile, the heavy toluene layer above the heavy water layer was extracted and subjected to proton NMR (Agilent, DD-2, 600 MHz) measurement. The NMR chart (also measured using heavy toluene) of the polyphenylene ether used as the raw material in Example 2-1 (Figure 5) was identical to that of the polyphenylene ether used in Example 2-1 (Figure 5). This suggests that some of the polyphenylene ether introduced in Example 2-1 reacted with the liquid crystal polymer during the reaction and became insoluble in toluene, which was originally a good solvent. However, rehydrolysis reverted it to the original polyphenylene ether, which was soluble in toluene. Therefore, in the example system, the presence of a reaction product between the liquid crystal polymer and polyphenylene ether strengthened the interfacial interaction between the liquid crystal polymer phase and the polyphenylene ether phase, which is thought to have resulted in the development of a salami structure. In the comparative example not having a salami structure, almost all of the polyphenylene ether introduced into the system was isolated by Soxhlet extraction using toluene using the above procedure, and the presence of a reaction product between the liquid crystal polymer and the polyphenylene ether was not suggested.

Claims

1. a liquid crystal polymer having a reactive group at its terminal; a non-liquid crystal polymer having a reactive group capable of reacting with the reactive group at the terminal of the liquid crystal polymer; a reaction product of the liquid crystalline polymer and the non-liquid crystalline polymer; A polymer alloy comprising:

2. 2. The polymer alloy according to claim 1, wherein the reactive terminal group of the liquid crystal polymer comprises at least one selected from the group consisting of a carboxy group, a hydroxy group, an amide group, an acetyl group, and an amino group.

3. The polymer alloy according to claim 1 , wherein the liquid crystal polymer contains constitutional units derived from a hydroxycarboxylic acid.

4. 2. The polymer alloy according to claim 1, wherein the reactive group of the non-liquid crystal polymer comprises at least one selected from the group consisting of a carboxy group, a hydroxy group, an amide group, an acetyl group, and an amino group.

5. The polymer alloy according to claim 1 , wherein the non-liquid crystal polymer is an amorphous polymer.

6. The polymer alloy of claim 1 , wherein the non-liquid crystal polymer comprises a polyphenylene ether.

7. 2. The polymer alloy according to claim 1, wherein the non-liquid crystal polymer comprises a polyphenylene ether having a hydroxy group at a polymer terminal.

8. 2. The polymer alloy of claim 1, wherein the polymer alloy has a sea-island-lake three-layer separated morphology.

9. The polymer alloy of claim 8 , wherein in the morphology, the sea and the lake are composed of the liquid crystal polymer.

10. 2. The polymer alloy according to claim 1, wherein the blending amount of the non-liquid crystal polymer is 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the liquid crystal polymer.

11. The polymer alloy according to claim 1 , wherein the reaction product is obtained by a polymerization reaction between raw material monomers of the liquid crystal polymer and the non-liquid crystal polymer.

12. A method for producing the polymer alloy according to any one of claims 1 to 11, a polymerization step of obtaining the reaction product by a polymerization reaction between the raw material monomer of the liquid crystal polymer and the non-liquid crystal polymer; A method for producing a polymer alloy, comprising:

13. A molded article comprising the polymer alloy according to any one of claims 1 to 11.

14. An electric / electronic component comprising the molded article according to claim 13.

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