Polymer alloy, method for producing the same, and molded article

Abstract

To provide a polymer alloy that enables production of a molded article exhibiting higher Izod impact strength than the liquid crystal polymer alone, while keeping flexural modulus, flexural strength, and flexural elongation comparable to those of the liquid crystal polymer alone.SOLUTION: A polymer alloy according to the present invention is a polymer alloy comprising a liquid crystal polymer and a non-liquid crystal polymer, the polymer alloy having a morphology separated into three phases of sea-island-lake structure, wherein the maximum area of the island phase is 300 μm2 or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] Conventionally, liquid crystal polymers have been excellent in moldability, heat resistance, and mechanical properties, and therefore molded products (for example, injection molded products) made using liquid crystal polymers have been used in various electronic components.

[0003] In recent years, attempts have been made to improve various physical properties by mixing a liquid crystal polymer with other resins such as a non-liquid crystal polymer. For example, Patent Document 1 proposes a heat-resistant resin composition comprising 99 to 1% by weight of a liquid crystal polyester (A) that forms an anisotropic melt phase with a heat distortion temperature of 160 to 280°C, a liquid crystal onset temperature of 330°C or less, and a melt viscosity of 10,000 poise or less, and 1 to 99% by weight of a polyarylene oxide (B).

[0004] However, when a liquid crystalline polymer is mixed with a non-liquid crystalline polymer, the incompatibility between the two polymers leads to macrophase separation, resulting in a large, fragile interface between the two polymers, resulting in poorer physical properties than the liquid crystalline polymer alone. To address this issue, resin compositions have been proposed in which a third component is added to a liquid crystalline polymer and a non-liquid crystalline polymer. For example, Patent Document 2 proposes a resin composition obtained by blending 100 parts by weight of a resin component consisting of 1 to 70 parts by weight of (A) a polyphenylene ether resin and 30 to 99 parts by weight of (B) a liquid crystalline polyester with 0.01 to 10 parts by weight of (C) an organic compound containing an isocyanate group. Patent Document 3 also proposes the further addition of a (C) metal compound or a (D) silane compound to a resin composition consisting of (A) polyphenylene ether and (B) a liquid crystalline polyester, in which component (A) forms a dispersed phase and component (B) forms a continuous phase. Furthermore, Patent Document 4 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. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2-97555 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-38003 [Patent Document 3] Japanese Patent Application Laid-Open No. 2007-182480 [Patent Document 4] Japanese Patent Application Laid-Open No. 2009-030044 Summary of the Invention [Problem to be solved by the invention]

[0006] However, in the resin composition described in Patent Document 1, the heat distortion temperature, liquid crystal onset temperature, and melt viscosity of the liquid crystal polyester must satisfy specific conditions, which places restrictions on the design of the polymer alloy and is insufficient for improving physical properties (particularly Izod impact strength). Furthermore, in the resin compositions described in Patent Documents 2 to 4, it is necessary to add a third component to the liquid crystal polymer and the non-liquid crystal polymer, which places restrictions on the design of the polymer alloy and is insufficient for improving physical properties (particularly Izod impact strength).

[0007] Therefore, an object of the present invention is to provide a polymer alloy and a method for producing the same, which can provide a molded article having a superior Izod impact strength to that of a liquid crystal polymer alone while maintaining the same levels of flexural modulus, flexural strength, and flexural elongation as those of the liquid crystal polymer alone. Another object of the present invention is to provide a molded article having a superior Izod impact strength to that of a liquid crystal polymer alone while maintaining the same levels of flexural modulus, flexural strength, and flexural elongation as those of the liquid crystal polymer alone. [Means for solving the problem]

[0008] The inventors have discovered that in a polymer alloy containing a liquid crystal polymer and a non-liquid crystal polymer and having a morphology separated into three layers of sea-island-lake, by adjusting the maximum area of ​​the islands in the cross section of the polymer alloy, it is possible to obtain a molded product having an Izod impact strength superior to that of the liquid crystal polymer alone, while maintaining the flexural modulus, flexural strength, and flexural elongation at the same level as that of the liquid crystal polymer alone.

[0009] That is, according to the present invention, the following inventions are provided. [1] A liquid crystal polymer; a non-liquid crystal polymer; A polymer alloy comprising: The polymer alloy has a morphology separated into three layers of sea-island-lake, The maximum area of ​​the island is 300 μm 2 The following are polymer alloys: [2] The liquid crystal polymer has a reactive group at its terminal, The polymer alloy according to [1], wherein the non-liquid crystal polymer has a reactive group capable of reacting with a reactive group at the end of the liquid crystal polymer. [3] The polymer alloy according to [2], further comprising a reaction product of the liquid crystal polymer and the non-liquid crystal polymer. [4] The average area of ​​the islands is 10 μm 2 The polymer alloy according to any one of [1] to [3] below. [5] The maximum area of ​​the island is 100 μm 2 The polymer alloy according to any one of [1] to [4] below. [6] The polymer alloy according to any one of [1] to [5], wherein the morphology is such that the sea and the lake are composed of the liquid crystal polymer, and the islands are composed of a non-liquid crystal polymer. [7] The polymer alloy according to [2], wherein the reactive group at the terminal of the liquid crystal polymer 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. [8] The polymer alloy according to any one of [1] to [7], wherein the liquid crystal polymer contains a structural unit derived from a hydroxycarboxylic acid. [9] The polymer alloy according to [2], 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.

[10] The polymer alloy according to any one of [1] to [9], wherein the non-liquid crystal polymer has a structural unit derived from an aromatic monomer.

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

[10] , wherein the non-liquid crystal polymer contains an ether group in the repeating bond.

[12] The polymer alloy according to

[11] , wherein the non-liquid crystal polymer comprises polyphenylene ether.

[13] The polymer alloy according to

[12] , wherein the non-liquid crystal polymer comprises polyphenylene ether having a hydroxy group at the polymer terminal.

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

[13] , wherein the amount of the non-liquid crystal polymer blended is 1 part by mass or more and 40 parts by mass or less per 100 parts by mass of the liquid crystal polymer.

[15] The polymer alloy according to [3], 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.

[16] The polymer alloy has an Izod impact strength of 40 kJ / m 2 The polymer alloy according to any one of [1] to

[15] , wherein

[17] The polymer alloy is subjected to a shear rate of 100 s -1 The polymer alloy according to any one of [1] to

[16] , which has a melt viscosity of 1 Pa·s or more as measured by a method.

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

[17] , a polymerization step of introducing the non-liquid crystal polymer into a polymerization reaction system of raw material monomers of the liquid crystal polymer to obtain a polymer alloy; A method for producing a polymer alloy, comprising:

[19] A process for kneading the polymer alloy obtained in the polymerization process, wherein the maximum area of ​​the islands in the morphology separated into three layers of sea, islands, and lakes is 300 μm 2 A kneading process to finely disperse the material until it becomes The method for producing a polymer alloy according to

[18] , further comprising:

[20] The average area of ​​the islands is 10 μm 2 The method for producing a polymer alloy according to

[18] or

[19] , wherein the polymer alloy is:

[21] The maximum area of ​​the island is 100 μm 2 The method for producing a polymer alloy according to any one of

[18] to

[20] , which is as follows:

[22] The method for producing a polymer alloy according to

[19] , wherein in the morphology, the sea and the lake are composed of the liquid crystal polymer, and the islands are composed of a non-liquid crystal polymer.

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

[17] .

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

[23] . [Effects of the Invention]

[0010] According to the present invention, a polymer alloy and a method for producing the same can be provided, which can produce a molded article having a superior Izod impact strength to that of a liquid crystal polymer alone while maintaining the same flexural modulus, flexural strength, and flexural elongation as that of the liquid crystal polymer alone. Furthermore, according to the present invention, a molded article having a superior Izod impact strength to that of a liquid crystal polymer alone while maintaining the same flexural modulus, flexural strength, and flexural elongation as that of the liquid crystal polymer alone can be provided. [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 microscopic infrared spectrum chart of a cross section of a bending test piece prepared in Comparative Example 1-5. [Figure 3] FIG. 1 is a view showing micrographs of the cross sections of test pieces of Example 1-1 and Comparative Example 1-6. [Figure 4] FIG. 1 is a view showing micrographs of cross sections of test pieces of Example 1-4 and Comparative Example 2-1. [Figure 5] FIG. 1 is a view showing micrographs of cross sections of test pieces of Example 1-1 and Comparative Example 2-2. Modes for carrying out the invention

[0012] [Polymer alloy] The polymer alloy according to the present invention contains a liquid crystalline polymer and a non-liquid crystalline polymer. The polymer alloy according to the present invention 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. Here, the sea refers to the continuous phase formed by the main polymer of the polymer alloy, the islands refer to a phase (first dispersed phase) formed by a non-main polymer of the polymer alloy that has separated from the continuous phase and dispersed thereon, and the lake refers to a phase (second dispersed phase) formed by the main polymer of the polymer alloy that has separated from the first dispersed phase and dispersed therein. In such a morphology (sea-islands-lake structure or salami structure), the sea (continuous phase) and the lake (second dispersed phase) are preferably composed of liquid crystalline polymers, and the islands (first dispersed phase) are preferably composed of non-liquid crystalline polymers. In the present invention, it is also preferable that a reaction product between a liquid crystalline polymer and a non-liquid crystalline polymer is present at the interface of each layer. The presence of a reaction product between a liquid crystalline polymer and a non-liquid crystalline polymer at the interface of each layer improves the interaction between the different interfaces, allowing for the formation of a morphology (salami structure) separated into three layers: sea, islands, and lake. In such a morphology (salami structure) separated into three layers: sea, islands, and lake, 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, compared to the two-layer morphology (sea-island mixture) obtained by conventional simple kneading. In the present invention, by using a polymer alloy having a morphology (salami structure) separated into three layers: sea, islands, and lake, it is possible to obtain a molded product having a flexural modulus, flexural strength, and flexural elongation comparable to those of the liquid crystalline polymer alone, while having an Izod impact strength superior to that of the liquid crystalline polymer alone.

[0013] The maximum area of ​​the islands in the morphology is 300 μm 2 less than 200 μm, preferably 2 or less, more preferably 150 μm 2 or less, and more preferably 100 μm 2Less than or equal to 80 μm 2 The lower limit may be 0.1 μm or less. 2 It may be more than 0.5 μm 2 It may be 1.0 μm or more. 2 May be more than 5 μm 2 It may be more than 10 μm 2 It may be more than 20 μm 2 That's all I can say. The upper limit of the average area of ​​the islands in the morphology is preferably 10 μm 2 More preferably, 9.0 μm or less 2 or less, and more preferably 7.0 μm 2 and even more preferably 6.0 μm or less. 2 The lower limit is 0.1 μm or less. 2 It may be 0.2 μm or more. 2 It may be more than 0.5 μm 2 It may be 0.7 μm or more. 2 It may be 1.0 μm or more. 2 It may be 1.5 μm or more. 2 It may be more than that. By setting the maximum area and average area of ​​the islands in the morphology within the above ranges, the non-liquid crystal polymer is sufficiently finely dispersed in the liquid crystal polymer in the polymer alloy, improving the affinity between the liquid crystal polymer and the non-liquid crystal polymer and making it difficult for separation to occur at the interface between the liquid crystal polymer and the non-liquid crystal polymer, thereby improving the impact resistance of molded articles obtained from the polymer alloy. In the present invention, the area of ​​the islands in the morphology is a value calculated from a micrograph of the cross section of a molded article obtained from the polymer alloy. Specifically, the maximum area and average area of ​​the islands in the morphology can be measured by the following method. First, a molded product is prepared by heating and melting the liquid crystal polymer used in the polymer alloy at 20°C above its melting point and injecting it into a mold at 80°C. A bending test piece measuring 80 mm (flow direction) x 12 mm x 2 mm (thickness) is used. The bending test piece is cut with a jigsaw at a point 20 mm from the end point of the mold in the flow direction, and the cross section of the bending test piece is exposed. Osmium metal is vapor-deposited on the exposed cross section using a vapor deposition device (Meiwafosis, model number: Neoc-Pro, vacuum level 10 Pa, vapor deposition time 10 seconds), and the cross section is examined with a scanning electron microscope (SEM, JEOL, model number: JSM-IT500HR). Next, the micrographs of the cross sections observed with the SEM are processed using image processing software (Image-Pro10, manufactured by Media Cybernetics) to detect the island portions. The detection of the island portions and calculation of their areas are carried out according to the following procedure. Step 1. When observing with a scanning electron microscope, first adjust the magnification to 600-2500x, and then use a magnification that will allow 50-1000 islands of morphology to fit within a single image. Step 2. Import the image into Image-Pro and use the "Spatial Calibration" function to scan the scale bar on the SEM image. This will set the length standard for image processing, allowing you to set an absolute standard for measuring island size and compare analysis results using SEM images with different magnifications. Step 3. Adjust the contrast of the captured image using the "Adjust" function. Adjust the brightness and contrast of the image appropriately to make the island areas darker and the sea areas brighter, and make the difference between them clearer. Step 4. Use the "Select" function to select the area to be processed. Use the rectangular tool to select the entire sample observation surface of the SEM image, excluding the area containing image information. Step 5. In the "Count / Size" function, set the measurement item to "Area: Area." Also, in order to remove noise from the object to be detected, set the effective detection range for "Area: Area" in "Measurement" - "Selection Settings." This effective detection range determines the lower limit of detection based on the reference distance shown on the scale bar on the image. The lower limit at this time is the island area whose converted diameter is 0.025 times the length of the scale bar of the image to be analyzed. Here, the converted diameter is the diameter calculated using the measured area when the observed island is considered to be a perfect circle. (Example: In the case of a magnification of 2500x and a scale bar length of 10μm, the island area whose converted diameter is 0.025 times that, or 0.25μm, is 0.05μm.) 2 is the detection limit for the island.) Step 6. Using "Smart Target Extraction," select multiple islands to calculate their area. Also, select the ocean area to distinguish them from the islands as the background, and perform machine learning on the detected areas. In this state, use "Count" to detect the islands. Step 7. Measure the area of ​​each detected island. Step 8. Repeat steps 1 to 7 using SEM images taken at different locations on the same observation sample until the total number of islands detected reaches 600 to 2,000, and calculate the maximum and average areas of all the detected islands.

[0014] (Izod impact strength) The polymer alloy preferably has an Izod impact strength of 40 kJ / m 2 More preferably, 60 kJ / m 2 More preferably, it is 100 kJ / m or more. 2 or more, and even more preferably 110 kJ / m 2 That's all. If the Izod impact strength of the polymer alloy is within the above range, a molded product having excellent impact resistance can be obtained. In the present invention, the Izod impact strength of a polymer alloy refers to a value measured on a test piece obtained from the polymer alloy in accordance with JIS K 7110. Specifically, the Izod impact strength is measured on a bending test piece obtained from the polymer alloy, measuring 80 mm (flow direction) × 12 mm × 2 mm (thickness), using an IT-type impact tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.) at room temperature in accordance with JIS K 7110, by releasing a pendulum with a weighing capacity of 5.5 J and a pendulum tip radius of 0.8 mm from a lift angle of 150° and hitting the edge of the test piece fixed in a cantilevered position at a pendulum impact speed of 3.5 m / s.

[0015] Considering heat resistance, the lower limit of the melting point of the polymer alloy may be preferably 250°C or higher, more preferably 260°C or higher, and even more preferably 270°C or higher, and the upper limit is not particularly limited, but may be 370°C or lower, 365°C or lower, 360°C or lower, or 355°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).

[0016] Polymer alloy at 300℃ to 380℃ and a shear rate of 100 s -1The lower limit of the melt viscosity measured under the above conditions is preferably 1 Pa·s or more, preferably 10 Pa·s or more, more preferably 20 Pa·s or more, and even more preferably 30 Pa·s or more, and the upper limit is preferably 1000 Pa·s or less, more preferably 700 Pa·s or less, even more preferably 500 Pa·s or less, and even more preferably 350 Pa·s or less. By setting the melt viscosity of the polymer alloy within the above numerical range, the Izod impact strength can be further improved. In this specification, the melt viscosity of the polymer alloy can be measured using a capillary rheometer viscometer in accordance with JIS K7199.

[0017] (liquid crystal polymer) The liquid crystal polymer used in the polymer alloy according to the present invention preferably 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.

[0018] 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.

[0019] 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).

[0020] 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.

[0021] Each of the structural units contained in the liquid crystal polymer according to the present invention will be described in detail below.

[0022] (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.

[0023] [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.

[0024] 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.

[0025] From the viewpoint of impact resistance, the composition ratio (mol %) of the structural unit (I) in the liquid crystal polymer has a lower limit of preferably 10 mol % or more, more preferably 20 mol % or more, and even more preferably 25 mol % or more, and an upper limit of preferably 100 mol % or less, more preferably 95 mol % or less, and even more preferably 90 mol % or less.

[0026] (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.

[0027] [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.

[0028] 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.

[0029] From the viewpoint of impact resistance, the composition ratio (mol %) of the structural unit (II) in the liquid crystal polymer has a lower limit of preferably 2.5 mol % or more, more preferably 5 mol % or more, and an upper limit of preferably 45 mol % or less, more preferably 40 mol % or less, and even more preferably 37.5 mol % or less.

[0030] (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.

[0031] [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.

[0032] 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.

[0033] From the viewpoint of impact resistance, the composition ratio (mol %) of the structural unit (III) in the liquid crystal polymer has a lower limit of preferably 2 mol % or more, more preferably 2.5 mol % or more, and an upper limit of preferably 45 mol % or less, more preferably 40 mol % or less, and even more preferably 37.5 mol % or less.

[0034] (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.

[0035] 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]

[0036] 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]

[0037] (Structural unit (V) derived from a monomer other than those listed above) In addition to the above-mentioned structural units (I) to (IV), the liquid crystal polymer may contain a structural unit (V) derived from a monomer other than an aromatic monomer. An example of such a monomer is a structural unit represented by the following formula (6). Examples of monomers that provide this structural unit include 1,4-cyclohexanedicarboxylic acid (CHDA). [ka]

[0038] The composition ratio (mol %) of the structural unit (V) in the liquid crystal polymer can be adjusted appropriately depending on the composition ratios of the other structural units. The composition ratio (mol %) of the structural unit (V) 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 even be 0 mol %.

[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 above-mentioned liquid crystal polymer, and is not particularly limited, and conventionally known non-liquid crystal polymers can be used. The non-liquid crystal polymer preferably 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 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, and more preferably includes a hydroxy group. Furthermore, the non-liquid crystal polymer preferably has a structural unit derived from an aromatic monomer. Furthermore, the non-liquid crystal polymer preferably includes an ether group in the repeating bond.

[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. Conventionally known polyphenylene ethers can be used as the polyphenylene ether in the present invention. Polyphenylene ether (PPE) is a compound having a polyphenylene ether chain in the molecule. The polyphenylene ether in the present invention also includes its modified product, modified polyphenylene ether (m-PPE). The modified polyphenylene ether in the present invention also includes alloys 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). Furthermore, when polyphenylene ether is heated at 340°C or higher and 380°C or lower and at a shear rate of 100 s -1 The lower limit of the melt viscosity measured under the above conditions is preferably 1 Pa·s or more, more preferably 10 Pa·s or more, even more preferably 20 Pa·s or more, and even more preferably 40 Pa·s or more, and the upper limit is preferably 10,000 Pa·s or less, more preferably 5,000 Pa·s or less, even more preferably 1,000 Pa·s or less, and even more preferably 500 Pa·s or less.

[0043] 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 is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, and still more preferably 20 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 Izod impact strength can be further improved.

[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] [Polymer alloy manufacturing method] 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, and is a step of kneading the polymer alloy obtained in the polymerization step. In the morphology separated into three layers of sea-island-lake, the maximum area of ​​the islands is 300 μm 2 This is a process of finely dispersing the non-liquid crystal polymer until the following occurs. 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 polymer alloy. By containing the polymer alloy, the molded article has a flexural modulus, flexural strength, and flexural elongation comparable to those of the liquid crystal polymer alone, while having an Izod impact strength superior to that of the liquid crystal polymer alone.

[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 resins other than the polymer alloy in the molded article is preferably 1 part by mass or more and preferably 10 parts by mass or less per 100 parts by mass of the polymer alloy.

[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% of 6-hydroxy-2-naphthoic acid (HNA) and 73 mol% of p-hydroxybenzoic acid (HBA) as raw material monomers for the liquid crystal polymer, and poly(2,6-dimethyl-1,4-phenylene ether) (containing terminal hydroxy groups, Mw: 47600, Mn: 17300, manufactured by SABIC Corporation, trade name: NORYL PPO630, melt viscosity: 128 Pa·s (350°C, 100 s)) as a non-liquid crystal polymer. -1)) and magnesium acetate and potassium acetate were charged as catalysts. The amount of non-liquid crystal polymer added was 6.3 parts by mass per 100 parts by mass of liquid crystal polymer (raw material monomer). Next, the polymerization vessel was depressurized and nitrogen was injected three times, after which acetic anhydride (1.05 molar equivalents relative to the hydroxyl groups) was further added, the temperature was raised to 160°C, and the acetylation reaction was carried out under reflux for 1.5 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 The polymer was extracted when the viscosity reached approximately 20 Pa·s 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 allowed to cool naturally at room temperature, then crushed to a size that could pass through a 2.0 mm mesh sieve, yielding a melt-polymerized polymer. The resulting melt-polymerized polymer was placed in a vacuum oven (Yamato Scientific Co., Ltd., square vacuum dryer DP23) and heated from room temperature to 250°C under reduced pressure of 100 kPa. The temperature was then maintained at 250°C for 10 hours to undergo solid-state polymerization, yielding Polymer Alloy A1.

[0066] The obtained polymer alloy A1 was heated and melted on the heating stage of a polarizing microscope manufactured by Nikon Corporation (product name: ECLIPSE E600 POL) equipped with a large specimen cooling and heating stage for microscopes manufactured by Japan High Tech (product name: 10083L). Optical anisotropy was confirmed, and it was determined that the polymer alloy A1 had liquid crystallinity.

[0067] The melting point of polymer alloy A1 was measured using a differential scanning calorimeter (DSC). Specifically, polymer alloy A1 was heated from 30°C to 350-400°C at a rate of 10°C / min until 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). As a result of the measurement, the melting point of polymer alloy A1 was 282°C.

[0068] Polymer alloy A1, 305°C, shear rate 100 s -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 showed that the melt viscosity of Polymer Alloy A1 was 125 Pa·s.

[0069] Next, the obtained polymer alloy A1 was kneaded using an extruder equipped with a twin-screw kneader (Laboplastomill Micro, small extrusion segment 2D15W, manufactured by Toyo Seiki Co., Ltd.) under conditions of a heating temperature of 340°C and a screw rotation of 40 rpm, to obtain a sample of Example 1-1.

[0070] (Example 1-2) In the polymerization step of Example 1-1, poly(2,6-dimethyl-1,4-phenylene ether) (containing terminal hydroxy groups, Mw: 56200, Mn: 19900, manufactured by SABIC Corporation, trade name: NORYL PPO640, melt viscosity: 274 Pa s (350°C, 100 s)) was used as the non-liquid crystal polymer. -1 )) was used to obtain a melt-polymerized polymer.

[0071] Next, Polymer Alloy A2 was produced in the same manner as Polymer Alloy A1, except that the heating conditions for solid-state polymerization of the obtained melt-polymerized polymer were changed to 250°C for 20 hours. The melting point and melt viscosity of the obtained Polymer Alloy A2 were measured in the same manner as above, and the melting point of Polymer Alloy A2 was 286°C and the melt viscosity was 244 Pa s. Furthermore, the obtained Polymer Alloy A2 was subjected to twin-screw kneading in the same manner as in Example 1-1, to obtain a sample of Example 1-2.

[0072] (Examples 1-3) In the polymerization step of Example 1-1, the amount of the non-liquid crystal polymer (PPO630) added was changed to 11 parts by mass, and a melt-polymerized polymer was obtained.

[0073] Next, Polymer Alloy A3 was produced in the same manner as Polymer Alloy A1, except that the heating conditions for solid-state polymerization of the obtained melt-polymerized polymer were changed to 250°C for 25 hours. The melting point and melt viscosity of the obtained Polymer Alloy A3 were measured in the same manner as above, and the melting point of Polymer Alloy A3 was 284°C and the melt viscosity was 259 Pa s. Furthermore, the obtained Polymer Alloy A3 was subjected to twin-screw kneading in the same manner as in Example 1-1, to obtain a sample of Example 1-3.

[0074] (Examples 1-4) In the polymerization step of Example 1-1, the amount of the non-liquid crystal polymer (PPO630) added was changed to 15.8 parts by mass, and a melt-polymerized polymer was obtained.

[0075] Next, Polymer Alloy A4 was produced in the same manner as Polymer Alloy A1, except that the heating conditions for solid-state polymerization of the obtained melt-polymerized polymer were changed to 250°C for 10 hours. The melting point and melt viscosity of the obtained Polymer Alloy A4 were measured in the same manner as above, and the melting point of Polymer Alloy A4 was 284°C and the melt viscosity was 79 Pa s. Furthermore, the obtained Polymer Alloy A4 was subjected to twin-screw kneading in the same manner as in Example 1-1, to obtain a sample of Example 1-4.

[0076] <Production of liquid crystal polymers with different viscosities> (Comparative Example 1-1) Liquid crystal polymer L1 was produced in the same manner as in Example 1-1, except that no non-liquid crystal polymer was added in the polymerization step and solid-state polymerization was not performed. The melting point and melt viscosity of the obtained liquid crystal polymer L1 were measured in the same manner as above, and the melting point of the liquid crystal polymer L1 was found to be 281°C and the melt viscosity was 25 Pa·s. This liquid crystal polymer L1 was used as a sample for Comparative Example 1-1.

[0077] (Comparative Example 1-2) Liquid crystal polymer L1 was heated in a Yamato Scientific Co., Ltd. (product name: DN411I) under nitrogen gas flow at a rate of 30 L / min or more for a certain period of time while gradually increasing the temperature to carry out solid-state polymerization. Specifically, solid-state polymerization was carried out at 200°C for 0.5 hours, 240°C for 1 hour, 250°C for 1 hour, 255°C for 1 hour, 260°C for 1 hour, and finally at 265°C for 3 hours to produce liquid crystal polymer L2. The melting point and melt viscosity of the resulting liquid crystal polymer L2 were measured in the same manner as above, and the melting point and melt viscosity of the liquid crystal polymer L2 were found to be 285°C and 149 Pa·s. This liquid crystal polymer L2 was designated as Comparative Example 1-2.

[0078] (Comparative Examples 1-3) Liquid crystal polymer L3 was produced in the same manner as liquid crystal polymer L2, except that the heating conditions for the solid-state polymerization were changed to 200°C for 0.5 hours, 240°C for 1 hour, 250°C for 1 hour, 255°C for 1 hour, 260°C for 1 hour, 265°C for 3 hours, 270°C for 2 hours, and finally 275°C for 0.5 hours. Next, the melting point and melt viscosity of the obtained liquid crystal polymer L3 were measured in the same manner as above. The melting point of liquid crystal polymer L3 was 284°C and the melt viscosity was 262 Pa·s. This liquid crystal polymer L3 was used as the sample of Comparative Example 1-3.

[0079] (Comparative Examples 1-4) Liquid crystal polymer L4 was produced in the same manner as liquid crystal polymer L2, except that the heating conditions for the solid-state polymerization were changed to 200°C for 0.5 hours, 240°C for 1 hour, 250°C for 1 hour, 255°C for 1 hour, 260°C for 1 hour, 265°C for 3 hours, 270°C for 2 hours, and finally 275°C for 1.5 hours. The melting point and melt viscosity of the obtained liquid crystal polymer L4 were measured in the same manner as above, and the melting point of liquid crystal polymer L4 was 284°C and the melt viscosity was 460 Pa·s. This liquid crystal polymer L4 was used as the sample of Comparative Example 1-4.

[0080] <Production of polymer alloys without twin-screw mixing> (Comparative Examples 1-5) In the polymerization step of Example 1-1, the amount of non-liquid crystal polymer (PPO630) added was changed to 15.8 parts by mass, resulting in a melt-polymerized polymer. This melt-polymerized polymer was not subjected to solid-state polymerization, resulting in Polymer Alloy A5. The melting point and melt viscosity were measured in the same manner as above, resulting in a melting point of 283°C and a melt viscosity of 56 Pa·s. Polymer Alloy A5 was not kneaded by twin-screw kneading, resulting in a sample of Comparative Example 1-5.

[0081] (Comparative Examples 1-6) The polymer alloy A1 produced in Example 1-1 was not subjected to twin-screw kneading, and this was used as a sample of Comparative Example 1-6.

[0082] (Comparative Examples 1-7) The polymer alloy A4 produced in Example 1-4 was not subjected to twin-screw kneading, and this was used as a sample of Comparative Example 1-7.

[0083] <Twin-screw compounding of low-viscosity polymer alloy> (Comparative Examples 1-8) Polymer Alloy A6 was obtained by melt polymerization in the same manner as for Polymer Alloy A5. The melting point and melt viscosity were measured in the same manner as above, and the melting point of Polymer Alloy A6 was 280°C and the melt viscosity was 18 Pa s. Polymer Alloy A6 was subjected to twin-screw kneading in the same manner as in Example 1-1, and a sample of Comparative Example 1-8 was obtained.

[0084] <Manufacturing of molded products> Using an injection molding machine, each polymer alloy and liquid crystal polymer obtained above was heated and melted at 310°C and injected into a mold at 80°C to prepare bending test pieces measuring 80 mm (flow direction) x 12 mm x 2 mm (thickness).

[0085] (Measurement of Izod impact strength) For each bending test piece obtained above, an IT-type impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used in accordance with JIS K7110. A pendulum with a weight of 5.5 J and a tip radius of 0.8 mm was lifted at a 150° angle and released at room temperature. The pendulum impact speed was 3.5 m / s and the Izod impact strength (kJ / m 2 ) was measured. The average value of N=5 measurements for each bending test piece is shown in Table 1.

[0086] (Measurement of flexural modulus, flexural strength, and flexural elongation) For each bending test piece obtained above, the flexural modulus (GPa), flexural strength (MPa), and flexural elongation (%) were measured at room temperature using a universal testing machine (Strograph VG, manufactured by Toyo Seiki Co., Ltd.) in accordance with JIS K7171 under the conditions of indenter radius = support table radius = 5.0 mm, support distance 50 mm, and test speed 2 mm / min. The average values ​​of N = 5 measurements for each bending test piece are shown in Table 1.

[0087] (Measurement of island area by cross-sectional observation) Each bending test specimen prepared above was cut using a jigsaw at a point 20 mm from the end of the mold in the flow direction. The cut specimens were embedded in epoxy resin and epoxy curing agent (Herzog). After the epoxy cured, the cross-sections of each bending test specimen were mechanically polished (abrasive: Baikalox alumina, BAIKOWSKI, 0.05 μm grit). Osmium metal was deposited on the exposed cross-sections using a vapor deposition system (Meiwafosis, Model: Neoc-Pro, 10 Pa, 10 s vacuum). The deposition time was 10 seconds. The cross-sections were then examined using a scanning electron microscope (SEM, JEOL, Model: JSM-IT500HR, 1200x magnification). The cross-sections of each bending test specimen made with the polymer alloy revealed a salami structure, with three distinct layers: a sea, an island, and a lake, where only the islands were composed of different components. The presence or absence of a salami structure is shown in Table 1.

[0088] Next, the micrographs of the cross sections observed with the SEM were processed using image processing software (Image-Pro10, manufactured by Media Cybernetics) to detect the island portions. The detection of the island portions and calculation of their areas were carried out as follows. Step 1. For observation using a scanning electron microscope, the magnification was adjusted in advance to 600-2500x, and a magnification was applied so that 50-1000 islands in the morphology could be captured in a single image. Step 2. The image was imported into Image-Pro, and the "Spatial Calibration" function was used to scan the scale bar on the SEM image. The length of the scanned scale bar was then matched to the length of the scale bar on the SEM image, establishing a length standard for image processing. This established an absolute standard for measuring island size, allowing comparison of analysis results using SEM images at different magnifications. Step 3. Using the "Adjust" function, the contrast of the captured image was adjusted. The brightness and contrast of the image were adjusted appropriately, making the island areas darker and the sea areas brighter, and the difference between them was made clearer. Step 4: The area to be processed was selected using the "Select" function. The rectangular tool was used to select the entire sample observation surface of the SEM image, excluding the area containing image information. Step 5. In the "Count / Size" function, the measurement item was set to "Area: Area." In addition, in order to remove noise from the object to be detected, the effective detection range of "Area: Area" was set in "Measurement" - "Selection Settings." The lower limit of detection for this effective detection range was determined based on the reference distance indicated on the scale bar on the image. The lower limit in this case was set to the island area whose converted diameter is 0.025 times the length of the scale bar of the image to be analyzed. Here, the converted diameter is the diameter calculated using the measured area when the observed island is considered to be a perfect circle. (Example: In the case of a magnification of 2500x and a scale bar length of 10 μm, the island area whose converted diameter is 0.025 times that, or 0.25 μm, is 0.05 μm.) 2 was set as the detection limit for the island.) Step 6: Using "Smart Object Extraction," multiple islands were selected as the area calculation targets. Additionally, the ocean area was selected as the background to distinguish them, and machine learning of the detected locations was performed. In this state, the islands were detected using "Count." Step 7: The area of ​​each detected island was measured. Step 8. Steps 1 to 7 were repeated using SEM images taken at different locations on the same observation sample until the total number of islands detected was between 600 and 2000. The maximum and average areas of all the detected islands are shown in Table 1.

[0089] 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 IR peak characteristics of the polyphenylene ether alone (e.g., 2920 cm -1The 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 single 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. As a representative example, Figure 2 shows the microscopic infrared spectrum charts of the sea, island, and lake regions of Comparative Examples 1-5, as well as the single liquid crystal polymer (HBA73 / HNA27) and single polyphenylene ether (PPO630) for comparison.

[0090] [Table 1]

[0091] From the results in Table 1, the polymer alloys having a salami structure of Examples 1-1 to 1-4 have the same melt viscosity range as the Examples, and compared to Comparative Examples 1-1 to 1-5, which are liquid crystal polymers without a salami structure, the Izod impact strength is significantly improved while maintaining the same level of flexural strength. This is consistent with the fact that the flexural modulus of the Examples tends to decrease compared to the Comparative Examples, and the toughness of the material is increased. Furthermore, biaxial kneading was carried out to set the maximum island area in the polymer alloy morphology to 300 μm 2 In Examples 1-1 and 1-4, which were adjusted as follows, the thickness was 300 μm without performing twin-screw kneading. 2 The Izod impact strength was significantly higher than that of Comparative Examples 1-5, 1-6, and 1-7, which contained coarse islands exceeding 1. These results demonstrate that the Izod impact strength of polymer alloys with a salami structure can be significantly improved by increasing the dispersion of non-liquid crystal polymers. In Comparative Example 1-8, even when biaxial kneading was applied, the maximum area of ​​the islands in the morphology of the polymer alloy was 300 μm 2 The results showed that the viscosity did not reach or exceed the specified value, and the impact strength was also low. This suggests that with low-viscosity polymer alloys, the fine dispersion of the non-liquid crystal polymer phase cannot be sufficiently promoted by twin-screw mixing, and high Izod impact strength cannot be achieved. FIG. 3 shows micrographs (magnification: 1200 times) of the cross sections of the test pieces of Comparative Example 1-6 and Example 1-1.

[0092] [Test Example 2] <Production of polymer blends> (Comparative Example 2-1) 100 parts by mass of liquid crystal polymer L3 and poly(2,6-dimethyl-1,4-phenylene ether) (PPE, Mw: 47600, Mn: 17300, manufactured by SABIC Corporation, trade name: NORYL PPO630, melt viscosity: 128 Pa·s (350°C, 100 s) -1 )) and 15.8 parts by mass of the hydroxybenzoate were mixed in an extruder equipped with a twin-screw mixer (Labo Plastomill Micro, small extrusion segment 2D15W, manufactured by Toyo Seiki Seisakusho, Ltd.) at a heating temperature of 340°C and a screw rotation speed of 40 rpm to obtain Polymer Blend B1. Polymer Blend B1 was used as the sample of Comparative Example 2-1.

[0093] (Comparative Example 2-2) In the preparation of the polymer blend, the liquid crystal polymer L4 was used as the liquid crystal polymer, and the amount of poly(2,6-dimethyl-1,4-phenylene ether) (PPO630) was changed to 6.3 parts by mass, but the same procedure as in Comparative Example 2-1 was repeated to obtain Polymer Blend B2. Polymer Blend B2 was used as the sample of Comparative Example 2-2.

[0094] <Manufacturing of molded products> Using an injection molding machine, each of the polymer blends obtained above was heated and melted at 310°C and injected into a mold at 80°C to prepare bending test specimens measuring 80 mm (flow direction) x 12 mm x 2 mm (thickness).

[0095] (Measurement of Izod impact strength) The Izod impact strength (kJ / m) of each of the bending test pieces obtained above was measured in the same manner as in [Test Example 1] above. 2 ) was measured. The average value of N=5 measurements for each bending test piece is shown in Table 2. For comparison, the results of Examples 1-1 and 1-4 are also shown.

[0096] (Measurement of flexural modulus, flexural strength, and flexural elongation) For each of the bending test pieces obtained above, the flexural modulus (GPa), flexural strength (MPa), and flexural elongation (%) were measured in the same manner as in Test Example 1. The average values ​​of N=5 measurements for each bending test piece are shown in Table 2. For comparison, the results of Examples 1-1 and 1-4 are also shown.

[0097] (Measurement of island area by cross-sectional observation) For each of the bending test pieces obtained above, cross-section observation was performed in the same manner as in [Test Example 1] above to detect island portions. The area of ​​each of the obtained island portions was measured, and the maximum area and average area of ​​the islands were calculated. The measurement results are shown in Table 2. For comparison, the results of Examples 1-1 and 1-4 are also shown.

[0098] [Table 2]

[0099] In Table 2, "internal addition" in the method of adding non-liquid crystal polymer refers to the process of adding the non-liquid crystal polymer together with the raw material monomer in the reaction furnace during the polymerization process of the liquid crystal polymer, and simultaneously polymerizing the liquid crystal polymer, mixing the non-liquid crystal polymer, and chemically reacting the non-liquid crystal polymer with the liquid crystal polymer. Furthermore, "external addition" refers to the process of 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 the non-liquid crystal polymer using a twin-screw kneader without causing a chemical reaction. By using 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 the production of a reaction product of a liquid crystal polymer and a non-liquid crystal polymer. This reaction product has affinity with both liquid crystal polymers and amorphous polymers, and therefore has a morphology separated into three layers: sea, islands, and lakes. On the other hand, polymer blends produced by the external addition method, which does not induce a chemical reaction, have the conventional morphology separated into two layers: sea and islands. The results in Table 2 show that Comparative Example 2-1 and Example 1-4 had similar maximum and average island areas and were favorably finely dispersed, but Example 1-4, which had a salami structure, exhibited significantly higher Izod impact strength. Similarly, Comparative Example 2-2 had smaller maximum and average island areas and a higher degree of dispersion than Example 1-1, but Example 1-1, which had a salami structure, exhibited significantly higher Izod impact strength. This suggests that the presence of a salami structure in a polymer alloy can achieve higher impact strength than a simple sea-island structure. FIG. 4 shows micrographs (magnification: 1200x) of the cross sections of the test pieces of Example 1-4 and Comparative Example 2-1, and FIG. 5 shows micrographs (magnification: 1200x) of the cross sections of the test pieces of Example 1-1 and Comparative Example 2-2.

Claims

1. A liquid crystal polymer, a non-liquid crystal polymer; A polymer alloy comprising: the polymer alloy has a morphology separated into three layers of sea-island-lake, The maximum area of ​​the island is 300 μm ２ The following is a polymer alloy.

2. the liquid crystal polymer has a reactive group at its terminal; 2. The polymer alloy according to claim 1, wherein the non-liquid crystal polymer has a reactive group capable of reacting with a terminal reactive group of the liquid crystal polymer.

3. The polymer alloy of claim 2 further comprising a reaction product of said liquid crystalline polymer and said non-liquid crystalline polymer.

4. The average area of ​​the islands is 10 μm ２ 2. The polymer alloy of claim 1, wherein:

5. The maximum area of ​​the island is 100 μm ２ 2. The polymer alloy of claim 1, wherein:

6. The polymer alloy of claim 1 , wherein in the morphology, the sea and lakes are composed of the liquid crystal polymer and the islands are composed of the non-liquid crystal polymer.

7. 3. The polymer alloy according to claim 2, 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.

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

9. 3. The polymer alloy according to claim 2, 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.

10. The polymer alloy according to claim 1 , wherein the non-liquid crystal polymer has structural units derived from aromatic monomers.

11. The polymer alloy according to claim 1 , wherein the non-liquid crystal polymer contains an ether group in the repeating bond.

12. 12. The polymer alloy of claim 11, wherein the non-liquid crystal polymer comprises a polyphenylene ether.

13. 13. The polymer alloy of claim 12, wherein the non-liquid crystal polymer comprises a polyphenylene ether having a hydroxy group at a polymer terminal.

14. 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 40 parts by mass or less per 100 parts by mass of the liquid crystal polymer.

15. The polymer alloy according to claim 3 , 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.

16. The polymer alloy has an Izod impact strength of 40 kJ / m ２ 2. The polymer alloy of claim 1, wherein

17. The polymer alloy is subjected to a shear rate of 100 s at 300 ° C or higher and 380 ° C or lower. －１ The polymer alloy according to claim 1, having a melt viscosity measured by a method of 1 Pa·s or more.

18. A method for producing the polymer alloy according to any one of claims 1 to 17, a polymerization step of introducing the non-liquid crystal polymer into a polymerization reaction system of raw material monomers of the liquid crystal polymer to obtain a polymer alloy; A method for producing a polymer alloy, comprising:

19. A step of kneading the polymer alloy obtained in the polymerization step, wherein the maximum area of ​​the islands in the morphology separated into three layers of sea-island-lake is 300 μm ２ A kneading process to finely disperse the material until it becomes The method for producing the polymer alloy of claim 18, further comprising:

20. The average area of ​​the islands is 10 μm ２ 19. The method for producing a polymer alloy according to claim 18, wherein:

21. The maximum area of ​​the island is 100 μm ２ 19. The method for producing a polymer alloy according to claim 18, wherein:

22. 20. The method for producing a polymer alloy according to claim 19, wherein in the morphology, the sea and the lake are made of the liquid crystal polymer, and the islands are made of a non-liquid crystal polymer.

23. A molded article comprising the polymer alloy according to any one of claims 1 to 17.

24. An electric / electronic component comprising the molded article according to claim 23.

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