Resin composition and molded article

Abstract

This resin composition contains a liquid crystalline polymer and a fluororesin, wherein the fluororesin has a peak area percentage of the CF3 group content to the CF2 group content in the fluororesin, as determined by the following [method for measuring the CF3 group content], of at least 0.05%.　[Method for measuring the CF3 group content] The ratio of the CF3 group content to the CF2 group content in the fluororesin is calculated, in terms of area percentage, from the peak area ICF3 corresponding to the CF3 group and the peak area ICF2 corresponding to the CF2 group, as measured by 19F solid-state NMR, and is determined by expression (f1).　(f1): CF3 group content (%)={(ICF3) / 3 / (ICF2) / 2}×100

Description

Technical Field

[0001] The present invention relates to a resin composition and a molded body. This application claims priority based on Japanese Patent Application No. 2021-014344 filed in Japan on February 1, 2021, and incorporates the content herein by reference.

Background Art

[0002] High molecular materials are used in various fields due to their ease of molding and processing and light weight. Among them, in recent years, high-performance polymer materials (engineering materials) that can replace metals and ceramics have been used in various fields such as electric, electronic, mechanical, optical equipment, automotive, aircraft, and medical fields.

[0003] Among these, in electrical and electronic components, in the trend of making components thinner, lighter, shorter, and smaller, further miniaturization of such components is being promoted. In addition, such components tend to require higher performance such as heat stability to the extent that they are compatible with surface mounting technology using lead-free solder. From the perspective of meeting these requirements, among the above-mentioned engineering materials, liquid crystalline polymers can be said to be particularly excellent materials. Liquid crystalline polymers are materials with good moldability such as thin-wall fluidity and low burr performance, excellent in high heat stability, high mechanical strength, and insulation, and have high flame retardancy without using additives with a high environmental load.

[0004] As a resin composition containing a liquid crystalline polymer, for example, Patent Document 1 discloses a liquid crystalline resin composition containing at least 1 hundred parts by weight of a liquid crystalline polyester resin and 10 to 100 parts by weight of glass fiber, wherein the weight average fiber length of the glass fiber is 30 to 100 μm, and 0.1 to 5.0% by weight of glass fiber with a fiber length of 300 to 500 μm is contained in all the glass fibers, and a pellet-shaped liquid crystalline polyester resin composition is disclosed.

Prior Art Documents

Patent Documents

[0005] [Patent Document 1] International Publication No. 2012 / 090410 [Summary of the Invention] [Problems to be Solved by the Invention]

[0006] However, in the conventional resin composition as described in Patent Document 1, the occurrence of die swell may be a problem. Here, die swell is a phenomenon in which the molten resin expands after exiting the extrusion die. When die swell occurs, the particle size of the obtained pellets becomes non-uniform, resulting in a decrease in productivity.

[0007] The present invention has been made in view of such circumstances, and an object thereof is to provide a resin composition having a good effect of suppressing die swell and a molded body produced using the resin composition. [Means for Solving the Problems]

[0008] In order to solve the above problems, the present invention employs the following configuration. [1] A resin composition containing a liquid crystalline polymer and a fluororesin, wherein the fluororesin has a peak area percentage of the CF3 group content with respect to the CF2 group content in the fluororesin of 0.05% or more, which is determined by the following [Measurement Method of CF3 Group Content]. [Measurement Method of CF3 Group Content] The content of the CF3 group with respect to the CF2 group content in the fluororesin is 19 Calculated as an area percentage from the peak area ICF3 corresponding to the CF3 group and the peak area ICF2 corresponding to the CF2 group measured by 19F solid-state NMR, and obtained by the following formula (f1). CF3 group content (%) = {(ICF3 / × 3 ) / (ICF2 / × 2 ) )} × 100 ··· (f1)

[0009] [2] The resin composition according to [1], further containing glass fibers. [3] The resin composition according to [1] or [2] further comprising a plate-like filler. [4] The resin composition according to any one of [1] to [3], wherein the resin decomposition initiation temperature of the fluororesin is 473°C or higher.

[0010] A molded article made using any one of the resin compositions described in [5], [1], to [4]. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a resin composition that has a good effect in suppressing die swell formation and a molded article made using the resin composition. [Brief explanation of the drawing]

[0012] [Figure 1] This is a schematic diagram showing the coil bobbin of this embodiment. [Modes for carrying out the invention]

[0013] (Resin composition) The resin composition of this embodiment contains a liquid crystalline polymer and a fluororesin.

[0014] <Liquid crystal polymer> The liquid crystalline polymer in the resin composition of this embodiment is a thermoplastic resin that exhibits liquid crystalline properties in which the linear chains of molecules are regularly arranged in the molten state. It is preferable that the resin composition containing the liquid crystalline polymer also exhibits liquid crystalline properties in the molten state, and the resin composition of this embodiment is preferably melted at a temperature of 450°C or lower. The resin composition of this embodiment contains a liquid crystalline polymer, resulting in high strength, high heat resistance, and high dimensional accuracy.

[0015] The liquid crystalline polymer in the resin composition of this embodiment may be a liquid crystalline polyester, a liquid crystalline polyesteramide, a liquid crystalline polyester ether, a liquid crystalline polyester carbonate, or a liquid crystalline polyester imide. In the resin composition of this embodiment, a liquid crystalline polymer is preferably a liquid crystalline polyester, and more preferably a fully aromatic liquid crystalline polyester obtained by using only aromatic compounds as raw material monomers.

[0016] Typical examples of liquid crystalline polymers in the resin composition of this embodiment include those obtained by polymerizing (polycondensing) aromatic hydroxycarboxylic acid with at least one compound selected from the group consisting of aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine, and aromatic diamine; those obtained by polymerizing multiple aromatic hydroxycarboxylic acids; those obtained by polymerizing aromatic dicarboxylic acid with at least one compound selected from the group consisting of aromatic diol, aromatic hydroxyamine, and aromatic diamine; and those obtained by polymerizing a polyester such as polyethylene terephthalate with an aromatic hydroxycarboxylic acid. Here, aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine, and aromatic diamine may each be independently replaced by polymerizable derivatives thereof, either partially or entirely.

[0017] Examples of polymerizable derivatives of compounds having a carboxyl group, such as aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids, include those obtained by converting the carboxyl group to an alkoxycarbonyl group or an aryloxycarbonyl group (esters), those obtained by converting the carboxyl group to a haloformyl group (acid halides), and those obtained by converting the carboxyl group to an acyloxycarbonyl group (acid anhydrides). Examples of polymerizable derivatives of compounds having a hydroxyl group, such as aromatic hydroxycarboxylic acids, aromatic diols, and aromatic hydroxyamines, include those obtained by acyling the hydroxyl group to an acyloxyl group (acylated compounds). Examples of polymerizable derivatives of compounds having an amino group, such as aromatic hydroxyamines and aromatic diamines, include those obtained by acyling the amino group to an acylamino group (acylated compounds).

[0018] In the resin composition of this embodiment, the liquid crystalline polymer preferably has a flow initiation temperature of, for example, 280°C or higher, more preferably 280°C to 420°C, and even more preferably 300°C to 400°C. In the resin composition of this embodiment, the higher the flow initiation temperature of the liquid crystalline polymer, the more likely it is that the heat resistance, strength, and rigidity will improve. On the other hand, when the flow initiation temperature of the liquid crystalline polymer exceeds 420°C, the melting temperature and melt viscosity of the resin composition containing the liquid crystalline polymer tend to increase. Therefore, the temperature required for molding the resin composition tends to increase.

[0019] The flow start temperature, also called the flow temperature or fluid temperature, is measured using a capillary rheometer at 9.8 MPa (100 kg / cm²). 2 This temperature, when a liquid crystalline polymer is melted under a load of ) while being heated at a rate of 4°C / min and extruded from a nozzle with an inner diameter of 1 mm and a length of 10 mm, exhibits a viscosity of 4800 Pa·s (48000 poise), and serves as an indicator of the molecular weight of the liquid crystalline polymer (see Naoyuki Koide (ed.), "Liquid Crystal Polymers - Synthesis, Molding, and Applications," CMC Corporation, June 5, 1987, p. 95).

[0020] As the liquid crystalline polymer in the resin composition of this embodiment, a liquid crystal polyester having a repeating unit (u1) represented by the following formula (1) (hereinafter also referred to as "repeating unit (u1)"), a repeating unit (u2) represented by the following formula (2) (hereinafter also referred to as "repeating unit (u2)"), and a repeating unit (u3) represented by the following formula (3) (hereinafter also referred to as "repeating unit (u3)") is particularly preferable. (1)-O-Ar 1 -CO- (2)-CO-Ar 2 -CO- (3)-X-Ar 3 -Y- (In the formula, Ar 1 represents a phenylene group. Ar 2 and Ar 3 each independently represent a phenylene group or a biphenylylene group. X and Y each independently represent an oxygen atom or an imino group (-NH-). The hydrogen atoms of the groups represented by Ar "" 1 , Ar 2 and Ar 3 may each independently be substituted with a halogen atom, an alkyl group having 1 to ""

[0021] ·Repeating unit (u1) The repeating unit (u1) is a repeating unit derived from monohydroxybenzoic acid.

[0022] In the above formula (1), Ar 1 is a phenylene group, and the hydrogen atom of the phenylene group may be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms.

[0023] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0024] Examples of the alkyl groups mentioned above include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, and n-decyl group.

[0025] Examples of the aforementioned aryl group include the phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 1-naphthyl group, and 2-naphthyl group.

[0026] Among the repeating units (u1) above, Ar 1 It is preferable that the group is a p-phenylene group (a repeating unit derived from p-hydroxybenzoic acid).

[0027] • Repeating unit (u2) The repeating unit (u2) is a repeating unit derived from a predetermined aromatic dicarboxylic acid. Ar 2 represents a phenylene group or a biphenylylene group, and the hydrogen atoms in the phenylene group and biphenylylene group may be substituted with halogen atoms, C1-C10 alkyl groups or C6-C20 aryl groups. Examples of halogen atoms, C1-C10 alkyl groups and C6-C20 aryl groups include Ar 1 Examples include halogen atoms which may be substituted for the hydrogen atom of the group represented by the above, alkyl groups having 1 to 10 carbon atoms, and aryl groups having 6 to 20 carbon atoms.

[0028] Among the repeating units (u2) above, Ar 2 Those in which the group is a p-phenylene group (a repeating unit derived from terephthalic acid), Ar 2 Those in which the m-phenylene group is (a repeating unit derived from isophthalic acid), and Ar 2 Preferably, the group is a diphenyl ether-4,4'-diyl group (a repeating unit derived from diphenyl ether-4,4'-dicarboxylic acid), and Ar 2 Those in which the group is a p-phenylene group (a repeating unit derived from terephthalic acid), Ar 2A more preferable option is one in which the group is an m-phenylene group (a repeating unit derived from isophthalic acid).

[0029] • Repeating unit (u3) The repeating unit (u3) is a repeating unit derived from a predetermined aromatic diol, aromatic hydroxylamine, or aromatic diamine. Ar 3 represents a phenylene group or a biphenylylene group, and the hydrogen atoms in the phenylene group and biphenylylene group may be substituted with halogen atoms, C1-C10 alkyl groups, or C6-C20 aryl groups. Examples of halogen atoms, C1-C10 alkyl groups, and C6-C20 aryl groups include Ar 1 Examples include halogen atoms which may be substituted for the hydrogen atom of the group represented by the above, alkyl groups having 1 to 10 carbon atoms, and aryl groups having 6 to 20 carbon atoms. X and Y are each independently an oxygen atom or an imino group (-NH-), and it is preferable that both are oxygen atoms.

[0030] Among the repeating units (u3) above, Ar 3 Those in which is a p-phenylene group (a repeating unit derived from hydroquinone, p-aminophenol, or p-phenylenediamine), and Ar 3 Preferably, the group is a 4,4'-biphenylylene group (a repeating unit derived from 4,4'-dihydroxybiphenyl, 4-amino-4'-hydroxybiphenyl, or 4,4'-diaminobiphenyl), and Ar 3 A more preferable configuration is one in which X is a 4,4'-biphenylylene group and X and Y are oxygen atoms (a repeating unit derived from 4,4'-dihydroxybiphenyl).

[0031] The number of repeating units (u1) is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more, of the total number of repeating units (100%). On the other hand, the number of repeating units (u1) is preferably 80% or less, more preferably 70% or less, and even more preferably 65% ​​or less, of the total number of repeating units. For example, the number of repeating units (u1) in liquid crystal polyester is preferably 30% to 80%, more preferably 40% to 70%, and even more preferably 50% to 65%.

[0032] The number of repeating units (u2) is preferably 7% or more, more preferably 10% or more, and even more preferably 15% or more, of the total number of repeating units. On the other hand, the number of repeating units (u2) is preferably 35% or less, more preferably 30% or less, and even more preferably 25% or less, of the total number of repeating units. For example, the number of repeating units (u2) in liquid crystal polyester is preferably 7% to 35%, more preferably 10% to 30%, and even more preferably 15% to 25%.

[0033] The number of repeating units (u3) is preferably 7% or more, more preferably 10% or more, and even more preferably 15% or more, of the total number of repeating units. On the other hand, the number of repeating units (u3) is preferably 35% or less, more preferably 30% or less, and even more preferably 25% or less, of the total number of repeating units. For example, the number of repeating units (u3) in liquid crystal polyester is preferably 7% to 35%, more preferably 10% to 30%, and even more preferably 15% to 25%.

[0034] In a liquid crystal polyester having repeating units (u1), repeating units (u2), and repeating units (u3), the sum of the number of repeating units (1), the number of repeating units (2), and the number of repeating units (3) does not exceed 100%.

[0035] In this specification, the number of each repeating unit can be determined, for example, by the analytical method described in Japanese Patent Application Publication No. 2000-19168. Specifically, by reacting a liquid crystal polyester resin with a supercritical lower alcohol (alcohol with 1 to 3 carbon atoms) to depolymerize the liquid crystal polyester resin to monomers that induce its repeating units, and then quantifying the monomers that induce each repeating unit obtained as a depolymerization product by liquid chromatography, the number of each repeating unit can be calculated. For example, if a liquid crystal polyester resin consists of repeating units (u1) to (u3), the number of repeating units (u1) can be determined by calculating the molar concentrations of the monomers that induce each of the repeating units (u1) to (u3) using liquid chromatography, and then calculating the ratio of the molar concentration of the monomer that induces each of the repeating units (u1) to (u3) when the sum of the molar concentrations of the monomers that induce each of the repeating units (u1) to (u3) is set to 100%.

[0036] Liquid crystal polyester having such a predetermined repeating unit composition exhibits excellent heat resistance and thermal stability. The more repeating units (u1) there are, the more easily the melt fluidity, heat resistance, thermal stability, strength, and rigidity improve. However, if there are too many repeating units, the melting temperature and melt viscosity tend to increase, and the temperature required for molding tends to increase.

[0037] In liquid crystal polyester, it is preferable that the number of repeating units (u2) and the number of repeating units (u3) are substantially equal. Specifically, the ratio of the number of repeating units (u2) to the number of repeating units (u3) is expressed as [number of repeating units (u2)] / [number of repeating units (u3)], and is, for example, 0.9 / 1 to 1 / 0.9, preferably 0.95 / 1 to 1 / 0.95, and more preferably 0.98 / 1 to 1 / 0.98.

[0038] The liquid crystal polyester may have two or more repeating units (u1) to (u3), each independently. Furthermore, the liquid crystal polyester may have repeating units other than (u1) to (u3), but the number of such units is, for example, 10% or less, preferably 5% or less, of the total number of repeating units.

[0039] As a specific example of a liquid crystalline polymer with high heat resistance and thermal stability in the resin composition of this embodiment, (i) For the total number of all repeating units, Ar 1 The repeating unit (u1) which is a p-phenylene group (i.e., a repeating unit derived from p-hydroxybenzoic acid) is preferably 40% to 80%, more preferably 45% to 75%, and even more preferably 50% to 70%. (ii)Ar 2 The compound preferably contains 1% to 30%, more preferably 10% to 25%, and even more preferably 15% to 20% of repeating units (u2) which are p-phenylene groups (i.e., repeating units derived from terephthalic acid). (iii)Ar 2 The compound preferably contains 1% to 15%, more preferably 1% to 10%, and even more preferably 1% to 5%, repeating units (u2) in which m-phenylene groups (i.e., repeating units derived from isophthalic acid). (iv)Ar 3 Examples of liquid crystal polyesters include those having repeating units (u3) (i.e., repeating units derived from 4,4'-dihydroxybiphenylene) where is a 4,4'-biphenylylene group and X and Y are oxygen atoms, preferably in amounts of 5% to 40%, more preferably 10% to 30%, and even more preferably 15% to 25%. In the liquid crystal polyester having repeating units (u1), repeating units (u2), and repeating units (u3), the sum of the number of repeating units (1), the number of repeating units (2), and the number of repeating units (3) does not exceed 100%.

[0040] The number of each repeating unit described above is an approximate value of the proportion (mol%) of each repeating unit calculated from the amount of raw monomer used. Therefore, the preferred proportion (mol%) of each repeating unit calculated from the amount of raw material monomer will be the same value as the preferred number (%) of each repeating unit described above.

[0041] In this embodiment, the liquid crystalline polymer is preferably produced by melt polymerization of raw material monomers corresponding to the repeating units that constitute it, and then solid-phase polymerization of the resulting polymer. This makes it possible to produce high molecular weight liquid crystalline polymers with high heat resistance, thermal stability, strength, and rigidity with good operability. Melt polymerization may be carried out in the presence of a catalyst. Examples of catalysts include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide, as well as nitrogen-containing heterocyclic compounds such as 4-(dimethylamino)pyridine and 1-methylimidazole, with nitrogen-containing heterocyclic compounds being preferred.

[0042] In this embodiment, the liquid crystalline polymer is preferably melt-kneaded using an extruder and then molded into pellets.

[0043] Preferably, the extruder has a cylinder, one or more screws arranged inside the cylinder, and one or more supply ports provided in the cylinder. Furthermore, it is more preferable for the extruder to have one or more vents provided in the cylinder. In addition, it is preferable to use an extruder equipped with a kneading section downstream of the supply port (or downstream of each supply port if multiple supply ports are provided). Here, the kneading section refers to a part provided on a part of the screw for efficient melting and kneading. Examples of the kneading section include a kneading disc (forward kneading disc, neutral kneading disc, reverse kneading disc), a mixing screw, etc.

[0044] It is preferable that the extruder has a vacuum system connected to a section with one or more vents. By using the vacuum system to degas the inside of the extruder cylinder during the melt-kneading of the liquid crystalline polymer, residual low molecular weight components can be removed from the liquid crystalline polymer.

[0045] The liquid crystalline polymer in the resin composition of this embodiment may be used alone or in combination of two or more types.

[0046] The content of the liquid crystalline polymer in the resin composition of this embodiment is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 55% by mass or more, based on the total amount of the resin composition. On the other hand, the content of the liquid crystalline polymer is preferably 95% by mass or less, more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less, based on the total amount of the resin composition. For example, the content of the liquid crystalline polymer is preferably 30% by mass or more and 95% by mass or less, more preferably 40% by mass or more and 70% by mass or less, and even more preferably 55% by mass or more and 65% by mass or less, based on the total amount of the resin composition.

[0047] <Fluororesin> The fluororesin in the resin composition of this embodiment is determined by the following [Method for measuring CF3 group content], and the peak area percentage of the CF3 group content relative to the CF2 group content in the fluororesin is 0.05% or more. [Method for measuring CF3 content] The CF3 group content relative to the CF2 group content in the aforementioned fluororesin is, 19 The area percentage is calculated from the peak area ICF3 corresponding to the CF3 group and the peak area ICF2 corresponding to the CF2 group, which are measured by 1F solid-state NMR, and is determined by the following formula (f1). CF3 group content (%)={(ICF3 / 3 ) / (ICF2 / 2 )} × 100···(f1)

[0048] The peak area percentages for the above CF3 group content were determined based on the information described in Macromolecules 2001, 34, 66-75.

[0049] Examples of NMR spectrometers for measuring solid samples include 400 MHz NMR spectrometers (manufactured by JEOL Ltd., Bruker, Agilent, Varian, etc.).

[0050] Calculate the CF3 content 19 1F solid-state NMR measurements are performed, for example, using the single-pulse method, under the following measurement conditions.

[0051] Measuring device: PS400WB (manufactured by Varian) Static magnetic field strength: 9.4 Tesla (Resonance frequency: 400 MHz (1H)) Magic angle rotation: 35kHz (35,000 revolutions per second) Repeat time: 15s Total number of times: 128 Temperature: 26℃ Chemical shift reference material: Hexafluorobenzene

[0052] The fluororesin in the resin composition of this embodiment has a peak area percentage of CF3 group content relative to CF2 group content in the fluororesin, determined by the [Method for Measuring CF3 Group Content] described above, which is 0.05% or more, preferably 0.05% to 1.0%, more preferably 0.05% to 0.20%, even more preferably 0.05% to 0.15%, and particularly preferably 0.05% to 0.10%.

[0053] In the resin composition of this embodiment, the fluororesin has a peak area percentage of 0.05% or more of the CF3 group content. Therefore, the resin composition of this embodiment containing this fluororesin has a good effect in suppressing die swell formation. On the other hand, if the peak area percentage of the CF3 group content is below the above preferred upper limit, thermal stability will be further improved.

[0054] In the resin composition of this embodiment, the fluororesin preferably has a resin decomposition initiation temperature of 450°C or higher, more preferably 470°C or higher, and even more preferably 473°C or higher. Here, the resin decomposition initiation temperature is defined as the temperature at which the weight loss rate becomes 0.1% when a fluororesin is heated from 25°C (room temperature) to 800°C at a heating rate of 10°C / min using a thermogravimetric analyzer (product name: TGA-50, manufactured by Shimadzu Corporation). The upper limit of the decomposition start temperature of the fluororesin in the resin composition of this embodiment is not particularly limited, but is, for example, 600°C or less. For example, the resin decomposition temperature of the fluororesin in the resin composition of this embodiment is preferably 450°C or more and 600°C or less, more preferably 470°C or more and 600°C or less, and even more preferably 473°C or more and 600°C or less.

[0055] The number-average molecular weight (Mn) of the fluororesin in the resin composition of this embodiment is preferably 100 to 5,000,000, more preferably 200 to 1,000,000, even more preferably 300 to 50,000, and particularly preferably 10,000 to 30,000. In this specification, the number-average molecular weight (Mn) is the number-average molecular weight (Mn) obtained by the method described in J.Appl.Polym.Sci.1973,17,3253. Specifically, it refers to the value calculated by the following formula (m-1) from the crystallization heat (ΔHc: cal / g) obtained using a differential scanning calorimetry device (product name: DSC-50, manufactured by Shimadzu Corporation). Here, the crystallization heat (ΔHc) is the heat quantity obtained from the area of ​​the crystallization peak in the DSC curve. Number average molecular weight (Mn)=2.1×10 10 ΔHc -5.16 ...(m-1)

[0056] If the number-average molecular weight (Mn) of the fluororesin in the resin composition of this embodiment is within the above preferred range, the thermal stability and the effect of suppressing die swell formation will be further improved.

[0057] The peak area percentage of CF3 group content, the resin decomposition initiation temperature, and the number-average molecular weight (Mn) of the fluororesin described above can be controlled by changing the manufacturing method of the fluororesin. For example, regarding the peak area percentage of CF3 group content in a fluororesin, a fluororesin with a peak area percentage of CF3 group content of 0.05% or more can be obtained by increasing the branching chain of the fluororesin, controlling the degree of polymerization of the fluororesin, or controlling the mixing ratio of the raw material monomers.

[0058] Specific examples of fluororesins in the resin composition of this embodiment include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polyvinylidene fluoride (PVDF), and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (perfluoroalkoxyalkane, PFA).

[0059] Among the fluororesins used in the resin composition of this embodiment, PTFE is preferred from the viewpoint of improving thermal stability and the effect of suppressing die swell formation.

[0060] In other words, as the fluororesin in the resin composition of this embodiment, PTFE is preferred in which the peak area percentage of the CF3 group content relative to the CF2 group content in PTFE, as determined by the above [Method for measuring CF3 group content], is 0.05% or more; PTFE is more preferred in which the peak area percentage of the CF3 group content is 0.05% or more and 1.0% or less; PTFE is more preferred in which the peak area percentage of the CF3 group content is 0.05% or more and 0.20% or less; and PTFE is even more preferred in which the peak area percentage of the CF3 group content is 0.05% or more and 0.10% or less.

[0061] Furthermore, as the fluororesin in the resin composition of this embodiment, PTFE with a resin decomposition initiation temperature of 450°C to 600°C is preferred, PTFE with a resin decomposition initiation temperature of 470°C to 600°C is more preferred, and PTFE with a resin decomposition initiation temperature of 473°C to 600°C is even more preferred.

[0062] Furthermore, as the fluororesin in the resin composition of this embodiment, PTFE with a number average molecular weight (Mn) of 100 to 5,000,000 is preferred, PTFE with a number average molecular weight (Mn) of 200 to 1,000,000 is more preferred, PTFE with a number average molecular weight (Mn) of 300 to 50,000 is even more preferred, and PTFE with a number average molecular weight (Mn) of 10,000 to 30,000 is particularly preferred.

[0063] The fluororesin in the resin composition of this embodiment may be used alone or in combination of two or more types.

[0064] The fluororesin content in the resin composition of this embodiment is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, and even more preferably 0.50% by mass or more, based on the total amount of the resin composition. On the other hand, the fluororesin content is preferably 5.0% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.0% by mass or less, based on the total amount of the resin composition. For example, the fluororesin content is preferably 0.05% by mass or more and 5.0% by mass or less, more preferably 0.10% by mass or more and 1.5% by mass or less, and even more preferably 0.50% by mass or more and 1.0% by mass or less, based on the total amount of the resin composition.

[0065] If the content of fluororesin in the resin composition of this embodiment relative to the total amount of the resin composition is within the above preferred range, the effect of suppressing die swell formation will be further improved.

[0066] Furthermore, the fluororesin content in the resin composition of this embodiment is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1.0 part by mass or more, per 100 parts by mass of the liquid crystalline polymer described above. On the other hand, the fluororesin content is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, and even more preferably 2.0 parts by mass or less, per 100 parts by mass of liquid crystalline polymer. For example, the fluororesin content is preferably 0.1 parts by mass or more and 5.0 parts by mass or less, more preferably 0.5 parts by mass or more and 3.0 parts by mass or less, and even more preferably 1.0 part by mass or more and 2.0 parts by mass or less.

[0067] If the content of fluororesin in the resin composition of this embodiment relative to 100 parts by mass of liquid crystalline polymer is within the above preferred range, the thermal stability and the effect of suppressing die swell formation will be further improved.

[0068] In the resin composition of this embodiment, when PTFE is used as the fluororesin, the fluororesin in the resin composition of this embodiment can be manufactured, for example, by the following method (manufacturing method (i) or (ii)).

[0069] Manufacturing method (i) Method (i) is a method for producing polytetrafluoroethylene (PTFE) using emulsion polymerization and suspension polymerization in combination. Specifically, tetrafluoroethylene is polymerized in the presence of a polymerization initiator (water-soluble peroxide) and an aqueous medium (for example, deionized high-purity pure water) to produce emulsion particles. Next, the emulsion particles are agglomerated to produce agglomerated powder. Then, tetrafluoroethylene is polymerized in the presence of the agglomerated powder, polymerization initiator, and aqueous medium to produce polytetrafluoroethylene (PTFE) in which the peak area percentage of the CF3 group content described above falls within the above range.

[0070] Manufacturing method (ii) Method (ii) is a method of polymerizing tetrafluoroethylene and at least one arbitrary comonomer in an aqueous polymerization medium. Specifically, tetrafluoroethylene and at least one copolymerizable fluorinated ethylenically unsaturated comonomer (e.g., perfluoro(propyl vinyl ether) (PPVE)) are mixed with a specific dispersant (e.g., perfluoroalkyl (C4~C)). 16 By adjusting the mixing ratio of each monomer and polymerizing them under a mixture of ammonium ethanesulfonate, polytetrafluoroethylene (PTFE) can be produced in which the peak area percentage of the CF3 group content described above falls within the above range. For example, the comonomer content in the PTFE is preferably between 0.005 mol% and 20 mol%.

[0071] In the resin composition of this embodiment, the fluororesin produced by the above method (ii) is preferred.

[0072] <Optional ingredients> The resin composition of this embodiment contains the above-mentioned liquid crystalline polymer and fluororesin, and may further contain components other than these components (optional components) to the extent that the effects of the present invention are achieved. Examples of such optional components include glass fibers, inorganic fillers other than glass fibers, pigments, and additives.

[0073] ≪Fiberglass≫ The type of glass fiber used in the resin composition of this embodiment is not particularly limited, and known types can be used, for example, E glass (i.e., alkali-free glass), C glass (i.e., glass for acid-resistant applications), AR glass (i.e., glass for alkali-resistant applications), S glass, or T glass. Among these, the glass fiber is preferably E-glass.

[0074] The glass fibers may be untreated or treated. Glass fibers can be treated with consolidators, silane coupling agents, boron compounds, etc. Examples of consolidators include aromatic urethane consolidators, aliphatic urethane consolidators, and acrylic consolidators.

[0075] The fiber diameter of the glass fibers in the resin composition of this embodiment is not particularly limited, but is preferably 1 to 40 μm, more preferably 3 to 35 μm, and even more preferably 5 to 15 μm.

[0076] The fiber length of the glass fibers in the resin composition of this embodiment is not particularly limited, but is preferably 10 to 150 μm, more preferably 30 to 125 μm, and even more preferably 50 to 100 μm.

[0077] The fiber diameter and fiber length of the glass fibers in the resin composition of this embodiment can be measured, for example, using a scanning electron microscope, an optical microscope, or the like.

[0078] The glass fibers in the resin composition of this embodiment may be used alone or in combination of two or more types.

[0079] The glass fiber content in the resin composition of this embodiment is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 35% by mass or more, based on the total amount of the resin composition. On the other hand, the glass fiber content is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 45% by mass or less, based on the total amount of the resin composition. For example, the glass fiber content is preferably 10% by mass or more and 70% by mass or less, more preferably 20% by mass or more and 60% by mass or less, and even more preferably 35% by mass or more and 45% by mass or less, based on the total amount of the resin composition.

[0080] If the glass fiber content in the resin composition of this embodiment is within the above preferred range, in addition to the effect of suppressing die swell formation, the mechanical strength of the molded article can be further improved.

[0081] Furthermore, if the resin composition of this embodiment contains glass fibers, the amount of fluororesin described above is preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more, and even more preferably 0.50 parts by mass or more, based on 100 parts by mass of the liquid crystalline polymer and glass fibers described above. On the other hand, the fluororesin content is preferably 5.0 parts by mass or less, more preferably 1.5 parts by mass or less, and even more preferably 1.0 part by mass or less, per 100 parts by mass of the liquid crystalline polymer and glass fiber mentioned above. For example, the fluororesin content is preferably 0.05 parts by mass or more and 5.0 parts by mass or less, more preferably 0.10 parts by mass or more and 1.5 parts by mass or less, and even more preferably 0.50 parts by mass or more and 1.0 part by mass or less, per 100 parts by mass of the liquid crystalline polymer and glass fiber described above.

[0082] If the content of fluororesin relative to the liquid crystalline polymer and glass fibers in the resin composition of this embodiment is within the above preferred range, a good balance is achieved between thermal stability, die swell suppression effect, and mechanical strength.

[0083] Inorganic fillers other than glass fibers The inorganic filler other than glass fibers in the resin composition of this embodiment may be a fibrous filler, a plate-shaped filler, or a granular filler other than fibrous or plate-shaped. In the resin composition of this embodiment, the inorganic filler is preferably a plate-shaped filler among the above.

[0084] Examples of plate-shaped fillers include talc and mica.

[0085] ·talc In the resin composition of this embodiment, pulverized hydrated magnesium silicate is preferred as the talc. The crystalline structure of hydrated magnesium silicate molecules is a pyrophyllite-type triple layer structure, and talc is formed by stacking these structures. As for the talc, flat talc in which the molecular crystals of hydrated magnesium silicate are finely ground to about a unit layer is more preferable.

[0086] The talc may be untreated or treated. Examples of treated talc include talc surface-treated with known surfactants. Examples of such surfactants include silane coupling agents, titanium coupling agents, higher fatty acids, higher fatty acid esters, higher fatty acid amides, and higher fatty acid salts.

[0087] The median diameter (D50) of the talc is preferably 5 to 30 μm, and more preferably 10 to 25 μm. The median diameter (D50) of talc can be measured, for example, using a known laser diffraction particle size distribution analyzer.

[0088] In the resin composition of this embodiment, talc may be used alone or in combination of two or more types. The talc content in the resin composition of this embodiment is preferably 5% by mass or more, more preferably 15% by mass or more, and even more preferably 25% by mass or more, based on the total amount of the resin composition. On the other hand, the talc content is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, based on the total amount of the resin composition. For example, the talc content is preferably 5% by mass or more and 80% by mass or less, more preferably 15% by mass or more and 70% by mass or less, and even more preferably 25% by mass or more and 60% by mass or less, based on the total amount of the resin composition. If the talc content in the resin composition of this embodiment is within the above range, the mechanical strength of the molded article made using the resin composition can be further improved.

[0089] · Mica Mica is a pulverized silicate mineral containing aluminum, potassium, magnesium, sodium, iron, etc. It has a structure in which an octahedral structure, composed of two or three metal oxides / hydroxides, is sandwiched between four tetrahedral structures formed by oxides of three silicon atoms (Si) and one aluminum atom (Al). The mica in this embodiment may be natural mica such as muscovite, phlogopite, fluorphlogopite, or tetrasilicate mica, or synthetic mica produced artificially.

[0090] The mica can be untreated or treated. Examples of treated mica include those surface-treated with known surfactants. Examples of such surfactants include silane coupling agents, titanium coupling agents, higher fatty acids, higher fatty acid esters, higher fatty acid amides, and higher fatty acid salts.

[0091] The median diameter (D50) of the mica is preferably 5 to 30 μm, and more preferably 10 to 25 μm. The median diameter (D50) of mica can be measured, for example, using a known laser diffraction particle size distribution analyzer.

[0092] The mica in the resin composition of this embodiment may be used alone or in combination of two or more types. The mica content in the resin composition of this embodiment is preferably 5% by mass or more, more preferably 15% by mass or more, and even more preferably 25% by mass or more, based on the total amount of the resin composition. On the other hand, the mica content is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, based on the total amount of the resin composition. For example, the mica content is preferably 5% by mass or more and 80% by mass or less, more preferably 15% by mass or more and 70% by mass or less, and even more preferably 25% by mass or more and 60% by mass or less, based on the total amount of the resin composition. If the mica content in the resin composition of this embodiment is within the above range, the mechanical strength of the molded article produced using the resin composition can be further improved.

[0093] Pigments Examples of pigments include alumina, iron oxide, cobalt oxide, chromium oxide, manganese oxide, titanium oxide, carbon black, and titanium yellow. Among these, carbon black and titanium oxide are preferred.

[0094] The pigment in the resin composition of this embodiment may be used alone or in combination of two or more types. The pigment content in the resin composition of this embodiment is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, based on the total amount of the resin composition. On the other hand, the pigment content is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less, based on the total amount of the resin composition. For example, the pigment content is preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 7% by mass or less, and even more preferably 0.5% by mass or more and 5% by mass or less, based on the total amount of the resin composition.

[0095] • Carbon Black The carbon black content in the resin composition of this embodiment is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, based on the total amount of the resin composition. On the other hand, the carbon black content is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1.5% by mass or less, based on the total amount of the resin composition. For example, the carbon black content is preferably 0.05% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less, and even more preferably 0.5% by mass or more and 1.5% by mass or less, based on the total amount of the resin composition.

[0096] The average particle size of the primary particles of carbon black may be, for example, 20-50 nm or 20-40 nm. The primary particle size of carbon black can be determined by the method described in Carbon Black Yearbook No. 48 (1998), p. 114, published by the Carbon Black Association. Specifically, it can be calculated by observing carbon black at a magnification of 20,000x using a transmission electron microscope, measuring the diameter of 1,000 primary carbon black particles, and calculating the average number of these particles.

[0097] The specific surface area of ​​carbon black is, for example, 30 to 200 m². 2 It may be / g, and may be 50-160m2 / g. The specific surface area of ​​carbon black refers to the nitrogen adsorption specific surface area. This nitrogen adsorption specific surface area can be measured by first removing any gases or other substances adhering to the sample surface, then adsorbing nitrogen onto the sample at liquid nitrogen temperature, and calculating the specific surface area from the amount of nitrogen adsorbed. Specifically, in accordance with JIS K6217-2:2001, nitrogen gas can be adsorbed at liquid nitrogen temperature using a BET specific surface area measuring instrument (for example, AccuSorb 2100E from Micromeritics), and the amount of adsorption can be measured and calculated using the BET method.

[0098] The oil absorption rate of carbon black may be 30 mL / 100g or more and 120 mL / 100g or less, and 40 mL / 100g or more and 80 mL / 100g or less. The oil absorption capacity of carbon black can be determined using a dibutyl phthalate absorbent meter according to the method described in JIS K6217-4:2001.

[0099] Titanium dioxide The titanium dioxide in the resin composition of this embodiment is not particularly limited, and known types can be used. The crystalline structure of titanium dioxide is not particularly limited and may be rutile, anatase, or a mixture of both.

[0100] Furthermore, titanium dioxide that has undergone surface treatment may be used. For example, surface treatment of titanium oxide with an inorganic metal oxide can improve properties such as dispersibility. Aluminum oxide is an example of an inorganic metal oxide.

[0101] The average particle size of titanium dioxide is preferably 0.1 to 1 μm, and more preferably 0.15 to 0.25 μm. The average particle size of titanium dioxide can be measured, for example, using a known laser diffraction particle size distribution analyzer.

[0102] In the resin composition of this embodiment, titanium dioxide may be used alone or in combination of two or more types. The titanium dioxide content in the resin composition of this embodiment is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, based on the total amount of the resin composition. On the other hand, the titanium dioxide content is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less, based on the total amount of the resin composition. For example, the titanium dioxide content is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 7% by mass or less, and even more preferably 2% by mass or more and 5% by mass or less, based on the total amount of the resin composition. If the titanium dioxide content in the resin composition of this embodiment is within the above range, the mechanical strength of the molded article made using the resin composition can be further improved.

[0103] ≪Additives≫ Additives include flame retardants, conductivity imparting agents, crystal nucleating agents, UV absorbers, antioxidants, vibration damping agents, antibacterial agents, insecticides, deodorants, color inhibitors, heat stabilizers, mold release agents, antistatic agents, plasticizers, lubricants, dyes, foaming agents, antifoaming agents, viscosity modifiers, and surfactants.

[0104] The resin composition of this embodiment described above contains a liquid crystalline polymer and a fluororesin, wherein the peak area percentage of the CF3 group content relative to the CF2 group content in the fluororesin, as determined by the [Method for Measuring CF3 Group Content] described above, is 0.05% or more. The resin composition of this embodiment can further improve the effect of suppressing die swell formation by using a liquid crystalline polymer in combination with a fluororesin in which the peak area percentage of the CF3 group content is 0.05% or more. Furthermore, the thermal stability of the resin composition of this embodiment can be further improved by using a combination of a liquid crystalline polymer and a fluororesin having a peak area percentage of CF3 group content of 0.05% or more.

[0105] The present invention has the following aspects.

[0106] "1" Contains a liquid crystalline polymer and a fluororesin, The fluororesin is a resin composition in which the peak area percentage of the CF3 group content relative to the CF2 group content in the fluororesin, as determined by the following [Method for measuring CF3 group content], is 0.05% or more, preferably 0.05% or more and 1.0%, more preferably 0.05% or more and 0.20%, and even more preferably 0.05% or more and 0.10%. [Method for measuring CF3 content] The ratio of CF3 group content to CF2 group content in the aforementioned fluororesin is calculated as an area percentage from the peak area ICF3 corresponding to CF3 groups and the peak area ICF2 corresponding to CF2 groups, measured by 19F solid-state NMR, and is determined by the following formula (f1). CF3 group content (%)={(ICF3 / 3 ) / (ICF2 / 2 )} × 100···(f1)

[0107] "2" The resin composition according to "1", wherein the liquid crystalline polymer is a liquid crystal polyester having a repeating unit (u1) represented by the following formula (1), a repeating unit (u2) represented by the following formula (2), and a repeating unit (u3) represented by the following formula (3). (1)-O-Ar 1 -CO- (2) New CO-Ar 2 -CO- (3)-X-Ar 3 -Y- (In the formula, Ar 1 represents the phenylene group. 2 and Ar 3 Each independently represents a phenylene group or a biphenylylene group. X and Y each independently represent an oxygen atom or an imino group (-NH-). 1 Ar 2 and Ar 3 The hydrogen atoms in the aforementioned group may each be independently substituted with a halogen atom, a C1-C10 alkyl group, or a C6-C20 aryl group.

[0108] "3" The content of the liquid crystalline polymer is preferably 30% by mass or more and 95% by mass or less, more preferably 40% by mass or more and 70% by mass or less, and even more preferably 55% by mass or more and 65% by mass or less, based on the total amount of the resin composition. The resin composition according to "1" or "2", wherein the fluororesin content is preferably 0.05% by mass or more and 5.0% by mass or less, more preferably 0.10% by mass or more and 1.5% by mass or less, and even more preferably 0.50% by mass or more and 1.0% by mass or less, based on the total amount of the resin composition.

[0109] "4" The resin composition according to any one of "1" to "3", wherein the fluororesin is polytetrafluoroethylene (PTFE).

[0110] "5" Furthermore, a resin composition according to any one of "1" to "4" that contains glass fibers.

[0111] "6" The resin composition according to "5", wherein the content of the glass fibers is preferably 10% by mass or more and 70% by mass or less, more preferably 20% by mass or more and 60% by mass or less, and even more preferably 35% by mass or more and 45% by mass or less, based on the total amount of the resin composition.

[0112] "7" The resin composition according to any one of "1" to "6", further comprising a plate-shaped filler.

[0113] "8" The resin composition according to any one of "1" to "7", wherein the resin decomposition initiation temperature of the fluororesin is 473°C or higher.

[0114] Using the resin composition described in any one of "9" or "1" to "8", a test specimen measuring 64 mm in width, 64 mm in length, and 3 mm in thickness was prepared by injection molding, and a colorimeter was used to measure the b immediately after the test specimen was prepared. * And, after heating the test piece at 300°C for 2 hours, b * When measuring, b immediately after specimen preparation * And, after heating the test piece at 300°C for 2 hours, b * A resin composition having the property that the rate of change is preferably 12% or less, more preferably 9% or less, even more preferably 5% or less, and particularly preferably less than 3.3%.

[0115] (Method for manufacturing resin compositions) The method for producing the resin composition of this embodiment includes the steps of producing a fluororesin in which the peak area percentage of the CF3 group content relative to the CF2 group content in the fluororesin is 0.05% or more, as determined by the following [Method for measuring CF3 group content], A method for producing a resin composition is provided, which includes the step of mixing the fluororesin and the liquid crystalline polymer. [Method for measuring CF3 content] The CF3 group content relative to the CF2 group content in the aforementioned fluororesin is, 19 The area percentage is calculated from the peak area ICF3 corresponding to the CF3 group and the peak area ICF2 corresponding to the CF2 group, which are measured by 1F solid-state NMR, and is determined by the following formula (f1). CF3 group content (%)={(ICF3 / 3 ) / (ICF2 / 2 )} × 100···(f1)

[0116] Specifically, the manufacturing methods (i) to (iv) described above are examples of the process for producing a fluororesin in which the peak area percentage of the CF3 group content is 0.05% or more, and among these, manufacturing methods (ii) to (iv) are preferred.

[0117] (Molded body) The molded article of this embodiment is a molded article made using the resin composition described above. The molded article of this embodiment can be obtained using a resin composition by a known molding method. The molding method for the resin composition of this embodiment is preferably a melt molding method, and examples include injection molding, extrusion molding methods such as the T-die method and inflation method, compression molding, blow molding, vacuum molding, and press molding. Among these, injection molding is preferred.

[0118] For example, when using the above-mentioned resin composition as a molding material and molding by injection molding, the resin composition is melted using a known injection molding machine, and the molten resin composition is injected into a mold to perform the molding. Here, when introducing the resin composition into the injection molding machine, each component may be introduced into the injection molding machine separately, or some or all of the components may be mixed in advance and introduced into the injection molding machine as a mixture. Examples of known injection molding machines include the TR450EH3 manufactured by Sodick Corporation and the PS40E5ASE hydraulic horizontal molding machine manufactured by Nissei Plastic Industrial Co., Ltd.

[0119] The injection molding temperature conditions are determined appropriately according to the type of liquid crystalline polymer, and it is preferable to set the cylinder temperature of the injection molding machine to a temperature 10 to 80°C higher than the flow start temperature of the liquid crystalline polymer used.

[0120] From the viewpoint of the cooling rate of the resin composition and productivity, it is preferable to set the mold temperature in the range of room temperature (25°C) to 180°C. Other injection conditions, such as screw rotation speed, back pressure, injection speed, holding pressure, and holding pressure time, can be adjusted as appropriate.

[0121] The molded article of this embodiment is generally applicable to any application where liquid crystalline polymers can be used. The molded bodies of this embodiment include, for example, electrical and electronic components such as connectors, sockets, relay components, coil bobbins, optical pickups, oscillators, printed circuit boards, circuit boards, semiconductor packages, and computer-related components; semiconductor manufacturing process-related components such as IC trays and wafer carriers; household electrical appliance components such as VTRs, televisions, irons, air conditioners, stereos, vacuum cleaners, refrigerators, rice cookers, and lighting fixtures; lighting fixture components such as lamp reflectors and lamp holders; audio product components such as compact discs, laser discs (registered trademark), and speakers; communication equipment components such as ferrules for optical cables, telephone components, facsimile components, and modems; separation claws, heater holders, Examples include parts for photocopiers and printers; mechanical parts such as impellers, fan gears, bearings, motor parts and cases; automotive parts such as mechanical parts, engine parts, engine compartment parts, electrical parts, and interior parts; cooking utensils such as microwave cooking pots and heat-resistant tableware; building materials such as flooring and wall coverings for insulation and soundproofing, beams and columns for support, roofing materials, or civil engineering and construction materials; parts for aircraft, spacecraft, and space equipment; radiation facility components such as nuclear reactors, marine facility components, cleaning jigs, optical instrument parts, valves, pipes, nozzles, filters, membranes, medical equipment parts and materials, sensor parts, sanitary fixtures, sports equipment, and leisure goods.

[0122] Among the above, the molded body of this embodiment is preferably used as a coil bobbin. The following details the coil bobbin, which is a suitable application.

[0123] Figure 1 is a schematic diagram showing a coil bobbin of this embodiment. As shown in the figure, the coil bobbin 1A has a main body portion 2 and a pair of flange portions 3.

[0124] In the following explanation, we will set up an xyz Cartesian coordinate system and describe the positional relationships of each member while referring to this xyz Cartesian coordinate system. Here, the extension direction of the main body 2 is the x-axis direction, the direction perpendicular to the x-axis direction in the horizontal plane is the y-axis direction, and the direction perpendicular to both the x-axis direction and the y-axis direction (i.e., the vertical direction) is the z-axis direction.

[0125] The main body portion 2 is a cylindrical member. The main body portion 2 has an axial hole 29 that penetrates the main body portion 2 in the x-axis direction. A winding is wound around the outer surface 2b of the main body portion 2 in the circumferential direction. The winding wound around the outer surface 2b forms a coil.

[0126] The flange portion 3 is provided at both ends of the shaft hole 29 of the main body portion 2 in the extending direction. The flange portion 3 has an annular shape that extends in the yz plane. The flange portion 3 may have a through hole for inserting the winding wire.

[0127] Coil bobbins, such as the coil bobbin 1A described above, are electrical and electronic components used as the core of a coil formed by winding wire. Since coils wound on bobbins tend to become hot due to the operating environment and heating caused by current, the molded body of this embodiment, which has high thermal stability, is useful as a coil bobbin.

[0128] As described above, the molded article of this embodiment uses the resin composition described above, so the pellet shape obtained from the resin composition is less likely to be irregular, and the variation when feeding the pellets into the molding machine, plasticizing them, and weighing them is reduced, thus making defects less likely to occur. [Examples]

[0129] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0130] [Measurement of the flow initiation temperature of liquid crystalline polymers] The flow initiation temperature of the liquid crystalline polymer was measured using a flow characteristics evaluation device (Shimadzu Corporation; product name "Flow Tester CFT-500"). Approximately 2g of the sample was packed into a capillary tube rheometer fitted with a die with an inner diameter of 1mm and a length of 10mm, and the test was conducted at 9.8MPa (100kgf / cm²). 2Under a load of ), when a liquid crystalline polymer was extruded from a nozzle at a heating rate of 4°C / min, the temperature at which the melt viscosity reached 4800 Pa·s (48000 Poise) was defined as the flow initiation temperature. The results are shown in Table 1 as "Flow Initiation Temperature (°C)".

[0131] [Example of manufacturing liquid crystalline polymer (resin A)] In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser, 994.5 g (7.2 mol) of p-hydroxybenzoic acid, 446.9 g (2.4 mol) of 4,4'-dihydroxybiphenyl, 365.4 g (2.2 mol) of terephthalic acid, 33.2 g (0.2 mol) of isophthalic acid, 1347.6 g (13.2 mol) of acetic anhydride, and 0.194 g of 1-methylimidazole as a catalyst were added. The mixture was stirred at room temperature for 15 minutes to thoroughly purge the reactor with nitrogen gas, and then the temperature was increased while stirring. When the internal temperature reached 145°C, the mixture was stirred for 1 hour while maintaining that temperature.

[0132] Subsequently, the mixture was heated to 320°C over 2 hours and 50 minutes while removing the distilled by-product acetic acid and unreacted acetic anhydride. The reaction was terminated when an increase in torque was observed, yielding the prepolymer. The prepolymer's flow initiation temperature was 263°C.

[0133] The obtained prepolymer was cooled to room temperature (25°C) and pulverized in a coarse grinder to obtain a liquid crystalline polymer (liquid crystal polyester) powder (particle size approximately 0.1-1 mm). Then, under a nitrogen atmosphere, the temperature was raised from room temperature (25°C) to 250°C over 1 hour, then from 250°C to 300°C over 5 hours, and held at 300°C for 3 hours to allow the polymerization reaction to proceed in a solid layer. The flow initiation temperature of the obtained liquid crystalline polymer (liquid crystal polyester; resin A) was 361°C.

[0134] The proportion of each repeating unit of resin A, calculated from the amount of raw material monomers used, is calculated as follows: Ar 1 The repeating unit (u1) which is a p-phenylene group (i.e., a repeating unit derived from p-hydroxybenzoic acid) is 60 mol%, Ar 2The repeating unit (u2) which is a p-phenylene group (i.e., a repeating unit derived from terephthalic acid) is 18 mol%, Ar 2 The repeating unit (u2) which is an m-phenylene group (i.e., a repeating unit derived from isophthalic acid) is 2 mol%, Ar 3 The compound contained 20 mol% of a repeating unit (u3) where X and Y are oxygen atoms (i.e., a repeating unit derived from 4,4'-dihydroxybiphenylene).

[0135] [Example of manufacturing liquid crystalline polymer (resin B)] In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer, and reflux condenser, 994.5 g (7.2 mol) of p-hydroxybenzoic acid, 446.9 g (2.4 mol) of 4,4'-dihydroxybiphenyl, 299.0 g (1.8 mol) of terephthalic acid, 99.7 g (0.6 mol) of isophthalic acid, and 1347.6 g (13.2 mol) of acetic anhydride were added. After replacing the gas in the reactor with nitrogen gas, 0.18 g of 1-methylimidazole was added, and the temperature was raised from room temperature to 150°C over 30 minutes while stirring under a nitrogen gas stream, and then refluxed at 150°C for 30 minutes.

[0136] Next, while distilling off the by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 150°C to 320°C over 2 hours and 50 minutes. When an increase in torque was observed, the contents were removed from the reactor and cooled to room temperature to obtain a solid prepolymer. Next, the prepolymer was pulverized using a pulverizer, and the resulting pulverized material was heated under a nitrogen atmosphere from room temperature to 250°C over 1 hour, then heated from 250°C to 295°C over 5 hours, and held at 295°C for 3 hours to carry out solid-phase polymerization. The resulting solid-phase polymer was cooled to room temperature to obtain powdered liquid crystal polyester (L3). The flow initiation temperature of the obtained liquid crystal polymer (liquid crystal polyester; resin B) was 327°C.

[0137] The proportion of each repeating unit of resin B, calculated from the amount of raw material monomers used, is calculated as follows: Ar 1The repeating unit (u1) which is a p-phenylene group (i.e., a repeating unit derived from p-hydroxybenzoic acid) is 60 mol%, Ar 2 The repeating unit (u2) which is a p-phenylene group (i.e., a repeating unit derived from terephthalic acid) is 15 mol%, Ar 2 The repeating unit (u2) which is an m-phenylene group (i.e., a repeating unit derived from isophthalic acid) is 5 mol%, Ar 3 The compound contained 20 mol% of a repeating unit (u3) where X and Y are oxygen atoms (i.e., a repeating unit derived from 4,4'-dihydroxybiphenylene).

[0138] [Examples of fluororesin manufacturing] <Example of resin F1 manufacturing> A 6L stainless steel autoclave, equipped with two stainless steel flat-plate agitators and a temperature control jacket, was filled with 2760g of deionized water and sealed. After removing oxygen from the system by repeatedly injecting and degassing with nitrogen gas, 1.8g of ethane was injected as a chain transfer agent using tetrafluoroethylene (TFE) to set the internal pressure to 0.10MPa. The internal temperature was raised under stirring at 700rpm, and when the internal temperature reached 85°C, TFE was injected again to adjust the internal pressure to 0.80MPa.

[0139] As polymerization initiators, aqueous solutions prepared by dissolving 700 mg of disuccinate peroxide (DSP) in 20 g of deionized water and aqueous solutions prepared by dissolving 700 mg of ammonium persulfate (APS) in 20 g of deionized water were injected into the tank under pressure using a TFE. As the decomposition of the polymerization initiators caused a decrease in the tank pressure, the TFE was continuously supplied to maintain the tank pressure at 0.80 ± 0.05 MPa. During the polymerization reaction, the tank temperature was adjusted to 85 ± 1 °C and the stirring speed was controlled to 350 rpm. Next, when 175g of TFE had been consumed, the stirring speed was changed to 700 rpm, and the polymerization reaction was continued until another 525g of TFE had been consumed. When the total consumption of TFE reached 700g, stirring was stopped and the pressure in the tank was released. The fluororesin in the wet state on the surface and in the liquid after polymerization was washed with deionized water and then filtered off. The filtered fluororesin was dried for 18 hours in a hot air circulating dryer at 160°C to obtain fluororesin (resin F1).

[0140] <Example of resin F2 manufacturing> In a 36L stainless steel autoclave with stirring blades, add 21.8 kg of deionized water, 50 g of ammonium carbonate buffer, and perfluoroalkyl (C4-C4) solution. 16 45 g of a mixture of ammonium ethanesulfonate (average C8) was added. The autoclave was closed and evacuated, then tetrafluoroethylene (TFE) was blown in three times and evacuated again. After introducing ethane into the autoclave until the pressure rose to 16.9 kPa, 98 mL of perfluoro(propyl vinyl ether) (PPVE) and 350 mL of Freon® F-113 (CCl2FCClF2) were injected into the autoclave. The autoclave was pressurized to 2.1 MPa using TFE, and at the same time, a solution of 1.5 g of ammonium persulfate (APS) dissolved in 500 mL of deionized water was pumped into the autoclave. After polymerization began (pressure dropped by 0.07 MPa), an additional PPVE and a solution of 1.2 g of APS dissolved in 1000 mL of deionized water were pumped into the autoclave at rates of 1.10 mL / min and 10 mL / min, respectively, relative to the polymerization residue. The stirrer speed was adjusted to control the reaction so that an additional 50 g of TFE per minute was needed to maintain a constant pressure of 2.2 MPa. After adding 7 kg of TFE from the start of the reaction, the supply of TFE and PPVE and the stirrer were stopped. The initiator solution (APS) was continued to be pumped until the unreacted material was removed from the autoclave. The aggregated polymer was removed from the autoclave, washed with deionized water, and dried at 150°C to obtain a fluoropolymer (resin F2).

[0141] <Example of resin F3 manufacturing> Except for changing the amounts of perfluoro(propyl vinyl ether) (PPVE) and Freon® F-113 (CCl2FCClF2) injected into the autoclave before the reaction started to 45 mL of perfluoro(propyl vinyl ether) (PPVE) and 350 mL of Freon® F-113 (CCl2FCClF2), the resin was manufactured in the same manner as resin F2 to obtain fluororesin (resin F3).

[0142] <Example of resin F4 manufacturing> Except for changing the amounts of perfluoro(propyl vinyl ether) (PPVE) and Freon® F-113 (CCl2FCClF2) injected into the autoclave before the reaction started to 75 mL of perfluoro(propyl vinyl ether) (PPVE) and 350 mL of Freon® F-113 (CCl2FCClF2), the resin was manufactured in the same manner as resin F2 to obtain fluororesin (resin F4).

[0143] <Example of resin F5 manufacturing> Except for changing the amounts of perfluoro(propyl vinyl ether) (PPVE) and Freon® F-113 (CCl2FCClF2) injected into the autoclave before the reaction started, to 165 mL of perfluoro(propyl vinyl ether) (PPVE) and 345 mL of Freon® F-113 (CCl2FCClF2), the resin was manufactured in the same manner as resin F2, and fluororesin (resin F5) was obtained.

[0144] [Evaluation of physical properties of fluororesins] For resins F1 to F5 obtained by the above manufacturing examples, the CF3 group content, resin decomposition initiation temperature, and number-average molecular weight (Mn) were measured using the method described later. The results are shown in Table 1.

[0145] [Measurement of CF3 group content] The ratio of CF3 group content to CF2 group content in resins F1 to F5 is: 19The area percentage was calculated from the peak area ICF3 corresponding to the CF3 group and the peak area ICF2 corresponding to the CF2 group, which were measured by 14-fluorine solid-state NMR, and then determined by the following formula (f1). CF3 group content (%)={(ICF3 / 3 ) / (ICF2 / 2 )} × 100···(f1)

[0146] The CF3 content was calculated. 19 1F solid-state NMR measurements were performed using the single-pulse method under the following conditions.

[0147] Measuring device: PS400WB (manufactured by Varian) Static magnetic field strength: 9.4 Tesla (Resonance frequency: 400 MHz (1H)) Magic angle rotation: 35kHz (35,000 revolutions per second) Repeat time: 15s Total number of times: 128 Temperature: 26℃ Chemical shift reference material: Hexafluorobenzene

[0148] [Measurement of the resin decomposition initiation temperature] Resins F1 to F5 were each filled into aluminum cells at a dose of 20 mg. Then, using a thermogravimetric analyzer (product name: TGA-50, manufactured by Shimadzu Corporation), the cells were heated from 25°C (room temperature) to 800°C at a rate of 10°C / min with a nitrogen gas flow rate of 50 mL / min. The temperature at which the weight loss rate reached 0.1% was measured, and this temperature was defined as the resin decomposition start temperature.

[0149] [Measurement of number-average molecular weight (Mn)] The number-average molecular weight (Mn) of resins F1 to F5 is determined by the method described in J.Appl.Polym.Sci.1973,17,3253. The crystallization heat (J / g) was determined using a differential scanning calorimetry device (product name: DSC-50, manufactured by Shimadzu Corporation), converted to crystallization heat (ΔHc;cal / g), and calculated using the following formula (m-1). Number average molecular weight (Mn)=2.1×1010 ΔHc -5.16 ...(m-1)

[0150] [Table 1]

[0151] [Example 1 of resin composition production] (Examples 1-4, Comparative Example 1) The liquid crystalline polymer, glass fibers, fluororesin, and pigment were granulated using a twin-screw extruder (Ikegai Co., Ltd., PCM-30) at a cylinder temperature of 340°C in the mixing ratios shown in Table 2 below to obtain the resin compositions (pellets) for each example.

[0152] [Assessment of the occurrence of Dicewell 1] In the above-mentioned manufacturing examples of the resin composition, the diameter of the die bore of the twin-screw extruder and the diameter of the cross-section of the resin composition (pellets) extruded from the die bore were visually compared, and the occurrence of die swells was evaluated according to the following criteria. A: The diameter of the die hole and the diameter of the pellet cross-section were approximately equal. B: The diameter of the pellet's cross-section is larger than the diameter of the die hole, causing cutting defects in the subsequent pellet cutting process.

[0153] [Table 2]

[0154] In Table 2, each abbreviation has the following meaning. The numbers in brackets [ ] represent the content (mass %). Resin A: A liquid crystalline polymer (liquid crystal polyester; Resin A) obtained by the manufacturing method described above. G1: Glass fiber (Product name: Milled Fiber EFH75-01, manufactured by Central Glass Co., Ltd., fiber diameter 11 μm, fiber length 75 μm) Resins F1-F5: Fluororesins obtained by the respective manufacturing methods described above. M1: Carbon black (Product name: #45LB, manufactured by Mitsubishi Chemical Corporation, primary particle size 24nm, specific surface area 125m²)2 / g, oil absorption 45mL / 100g)

[0155] As shown in Table 2, the resin compositions of Examples 1 to 4, which contain resins F1 to F4 with a peak area percentage of CF3 group content of 0.05% or more, showed a better effect in suppressing die swell formation compared to the resin composition of Comparative Example 1.

[0156] [Evaluation of thermal stability] * Measurement of rate of change > Using the resin composition of the example, test specimens measuring 64 mm in width, 64 mm in length, and 3 mm in thickness were prepared by injection molding. The prepared test specimens were measured using a spectrophotometer (product name: CM-3600d, manufactured by Konica Minolta) to determine the b color immediately after the test specimens were prepared. * And, after heating the test piece at 300°C for 2 hours, b * The values ​​were measured separately. The rates of change for each are shown in Table 3.

[0157] [Table 3]

[0158] As shown in Table 3, molded articles made using the resin compositions of Examples 1 to 4, which contain a liquid crystalline polymer and resins F1 to F4 having a peak area percentage of CF3 group content of 0.05% or more, are b * The rate of change was low, and yellowing was suppressed. From this, it was confirmed that the molded articles produced using the resin compositions of Examples 1 to 4 have high thermal stability. Furthermore, among the examples, the molded articles produced using the resin compositions of Examples 2 to 4 containing resins F2 to F4 are particularly b * The rate of change was low, and yellowing was suppressed.

[0159] As shown in Tables 2 and 3, the resin compositions of the examples were found to have high thermal stability and good die swell suppression effects.

[0160] [Example 2 of resin composition production] ​(Examples 5-8) The liquid crystalline polymer, plate-like filler, fluororesin, and pigment were granulated using a twin-screw extruder (Ikegai Co., Ltd., PCM-30) at a cylinder temperature of 340°C in the mixing ratios shown in Table 4 below to obtain the resin compositions (pellets) for each example.

[0161] [Evaluation of the occurrence of Dicewell 2] The die swell occurrence status of the resin compositions of Examples 5 to 8 was evaluated using the same method as described in [Evaluation of die swell occurrence status 1] above.

[0162] [Table 4]

[0163] In Table 4, each abbreviation has the following meaning. The numbers in brackets [ ] represent the content (mass %). Resin B: A liquid crystalline polymer (liquid crystal polyester; Resin B) obtained by the manufacturing method described above. T1: Talc (Product name: MS-KY, manufactured by Nippon Talc Co., Ltd., median diameter (D50) 21 μm) Resins F1-F4: Fluororesins obtained by the respective manufacturing methods described above. M2: Titanium Yellow (Product name: TY-70S, manufactured by Ishihara Sangyo Co., Ltd., average particle size 1.00 μm) M3: Carbon Black (Product name: BP4350, manufactured by Cabot, oil absorption capacity 66-77 mL / 100 g) M4: Titanium dioxide (Product name: CR-60, manufactured by Ishihara Sangyo Co., Ltd., average particle size 0.21 μm)

[0164] As shown in Table 4, the resin compositions of Examples 5 to 8 also showed good die swell suppression effects, similar to the resin compositions of Examples 1 to 4 described above.

[0165] While preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other modifications are possible without departing from the spirit of the invention. The present invention is not limited by the foregoing description, but only by the scope of the appended claims. [Explanation of Symbols]

[0166] 1A... Coil bobbin 2. Main body 3. Guard section

Claims

1. It contains a liquid crystalline polymer and a fluororesin. The fluororesin is as follows [CF ３ The CF in the fluororesin, determined by the method for measuring the group content. ２ CF relative to the amount of the group ３ A resin composition in which the peak area percentage of the group content is 0.05% or more and 0.20% or less. [CF ３ [Method for measuring the amount of the compound] CF in the fluororesin ２ The content of the CF ３ group with respect to the content of the CF １９ group is measured by F solid NMR and is calculated as the area percentage from the peak area ICF ３ corresponding to the CF ３ group and the peak area ICF ２ corresponding to the CF ２ group, and is obtained by the following formula (f1). CF ３ Base content (%) = { (ICF) ３ / 3) / (ICF) ２ / 2)}×100・・・(f1)

2. The resin composition according to claim 1, wherein the number average molecular weight (Mn) of the fluororesin is 10,000 or more.

3. Furthermore, the resin composition according to claim 1 or 2, further containing glass fibers.

4. Furthermore, the resin composition according to claim 1 or 2, further containing a plate-like filler.

5. The resin composition according to claim 4, wherein the plate-shaped filler is talc.

6. The resin composition according to claim 5, wherein the talc content is 5% by mass or more and 80% by mass or less with respect to the total amount of the resin composition.

7. The resin composition according to claim 1 or 2, further comprising a pigment.

8. The resin composition according to claim 7, wherein the pigment is carbon black.

9. The resin composition according to claim 8, wherein the pigment contains carbon black in an amount of 0.05% by mass or more and 10% by mass or less relative to the total amount of the resin composition.

10. The resin composition according to claim 1 or 2, wherein the resin decomposition initiation temperature of the fluororesin is 473°C or higher.

11. A molded article made using the resin composition described in any one of claims 1 to 10.

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