CN109844027B - Liquid crystalline resin composition for surface mount relay and surface mount relay using same - Google Patents
Liquid crystalline resin composition for surface mount relay and surface mount relay using same Download PDFInfo
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- CN109844027B CN109844027B CN201780064270.0A CN201780064270A CN109844027B CN 109844027 B CN109844027 B CN 109844027B CN 201780064270 A CN201780064270 A CN 201780064270A CN 109844027 B CN109844027 B CN 109844027B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H45/00—Details of relays
- H01H45/02—Bases; Casings; Covers
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Abstract
Provided is a liquid crystal resin composition for surface mount relays, which provides a molded article having excellent heat resistance, in which the occurrence of blisters and the detachment of fillers are suppressed, and which can be bonded with an adhesive at a high bonding strength, and a surface mount relay component and a surface mount relay using the same. The liquid crystalline resin composition for a surface mount relay of the present invention comprises (A) a liquid crystalline polymer and (B) a fibrous filler, wherein the (A) liquid crystalline polymer is a wholly aromatic polyester amide which contains a predetermined amount of structural units (I) to (V) described below as essential structural components and exhibits optical anisotropy when melted, the (B) fibrous filler has a weight-average fiber length of 50to 170 [ mu ] m and a content of a component having a fiber length of 20 to 200 [ mu ] m of 70 mass% or more, and the surface mount relay is a surface mount relay which comprises a base and a terminal protruding from the base and is formed by soldering the terminal to a printed circuit board.
Description
Technical Field
The present invention relates to a liquid crystalline resin composition for a surface mount relay and a surface mount relay using the same.
Background
With the development of the electronics industry, the amount of production of relays has been steadily increasing, and the fields of use have been spread to communication devices, OA devices, home electric appliances, vending machines, and the like. Conventionally, as a relay mounted on a printed circuit board, a plug-in mounting type (through hole type) relay is known. The insertion-mounted relay includes a terminal vertically protruding from a relay main body, and the terminal is first inserted into a hole of a printed circuit board and mounted on one surface of the printed circuit board. Then, the terminal is soldered to the other surface of the printed circuit board, and the insertion-mounted relay is fixed to the printed circuit board so as to be electrically conductive.
In recent years, as a new relay mounted on a printed circuit board and used, a surface mounted (surface mounted) type relay has been developed (for example, patent document 1). In the surface mount relay, a terminal vertically protruding from a relay main body is bent at a right angle so that a soldering face is parallel to the relay main body. Therefore, in the surface mount relay, the terminal is mounted on the land provided on the conductor pattern on the surface of the printed circuit board, and is electrically conductively fixed to the printed circuit board by performing solder reflow processing, instead of providing the hole in the printed circuit board.
Documents of the prior art
Patent document
Patent document 1 Japanese patent No. 3463310
Disclosure of Invention
Problems to be solved by the invention
As described above, since the surface mount relay is fixed to the printed circuit board by solder reflow processing, molded articles constituting the surface mount relay, such as a base, a case, and a bobbin, are required to have excellent heat resistance and to be able to withstand the solder reflow processing. In addition, the surface mount relay is also required to be able to maintain airtightness even after the solder reflow process. Therefore, the molded article, particularly the base and the case, are required to be adhered to each other with high adhesion strength by an adhesive.
Accordingly, liquid crystalline polymer compositions have attracted attention because of their excellent heat resistance, dimensional accuracy, flowability, and the like. However, the liquid crystalline polymer composition may have a problem of generating foaming. That is, a liquid crystalline polyester amide, which is a liquid crystalline polymer, is excellent in high temperature thermal stability and is often used for a material requiring heat treatment at a high temperature. But the following problems arise: if the molded article is left in air or liquid at a high temperature for a long time, fine expansion called blistering occurs on the surface. This phenomenon is caused by that decomposition gas or the like generated when the liquid crystalline polyester amide is in a molten state is taken into the inside of the molded article, and then, the gas expands and presses upward the surface of the molded article softened by heating when heat treatment at a high temperature is performed, and the portion pressed upward appears in the form of bubbles. The occurrence of foaming can also be reduced by sufficiently degassing from the vent hole at the time of melt extrusion of the material, not staying in the molding machine for a long time at the time of molding, and the like. However, the condition range is very narrow, and it is not sufficient to obtain a molded article in which the occurrence of blisters is suppressed, that is, a molded article having blister resistance. In order to fundamentally solve the problem of the occurrence of foaming, it is necessary to improve the quality of the liquid crystalline polyester amide itself, and the known liquid crystalline polyester amide and the method using the same are not sufficient for solving the problem of the occurrence of foaming. In addition, the liquid crystalline polymer composition may also cause the following problems: the filler protrudes from the surface of the molded article of the composition and then comes off, resulting in functional failure such as poor conduction of the product.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal resin composition for a surface mount relay which can provide a molded article having excellent heat resistance, in which the occurrence of blisters and the detachment of a filler are suppressed, and which can be bonded with an adhesive at a high bonding strength, a surface mount relay component formed from the composition, and a surface mount relay including the component.
Means for solving the problems
The present inventors have found that the above problems can be solved by combining a liquid crystalline polymer containing a specific structural unit in a predetermined amount with a fibrous filler, setting the weight-average fiber length of the fibrous filler to 50to 170 μm, and setting the content of a component having a fiber length of 20 to 200 μm in the fibrous filler to 70 mass% or more. Specifically, the present invention provides the following.
(1) A liquid crystalline resin composition for a surface mount relay comprising (A) a liquid crystalline polymer and (B) a fibrous filler,
the liquid crystalline polymer (A) is a wholly aromatic polyester amide containing the following structural units (I) to (V) as essential structural components and exhibiting optical anisotropy when melted,
the content of the structural unit (I) is 50to 69 mol% based on the total structural units,
the content of the structural unit (II) is 9.2 to 22.5 mol% relative to the total structural units,
the content of the structural unit (III) is 2.5 to 6.3 mol% based on the total structural units,
the content of the structural unit (IV) is 8.5 to 24 mol% relative to the total structural units,
the content of the structural unit (V) is 1 to 7 mol% relative to the total structural units,
the total molar number of the structural unit (II) and the structural unit (III) is 1 to 1.06 times the total molar number of the structural unit (IV) and the structural unit (V), or the total molar number of the structural unit (IV) and the structural unit (V) is 1 to 1.06 times the total molar number of the structural unit (II) and the structural unit (III),
the total content of the structural units (I) to (V) is 100 mol% based on the total structural units,
the weight-average fiber length of the fibrous filler (B) is 50to 170 μm,
the fibrous filler (B) has a content of a component having a fiber length of 20 to 200 μm of 70 mass% or more,
the liquid crystalline polymer (A) is 50to 70% by mass based on the whole liquid crystalline resin composition,
the fibrous filler (B) is 30 to 50% by mass based on the whole liquid crystalline resin composition,
the surface mount relay includes a base and a terminal protruding from the base, and is configured such that the terminal is soldered to a printed circuit board.
(2) The liquid crystalline resin composition according to (1), wherein the fibrous filler (B) is a ground fiber.
(3) A surface mount relay part formed from the composition of (1) or (2).
(4) A surface mount relay comprising the component according to (3).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided a liquid crystal resin composition for a surface mount relay which is excellent in heat resistance, is suppressed in the generation of blisters and the detachment of a filler, and can provide a molded article which can be bonded with an adhesive at a high bonding strength, a component for a surface mount relay comprising the composition, and a surface mount relay comprising the component.
Drawings
FIG. 1: fig. 1 (a) is a perspective view schematically showing an embodiment of the surface mount relay of the present invention, and fig. 1 (b) is a partial cross-sectional view showing an AA cross section of fig. 1 (a).
FIG. 2: fig. 2 (a) and 2 (b) are side views schematically showing a state in which the surface mount relay according to the embodiment of the present invention is mounted on a printed circuit board.
FIG. 3: fig. 3 (a) is a diagram for explaining a method of manufacturing a sample for evaluating adhesive strength, and fig. 3 (b) is a diagram for explaining a method of evaluating adhesive strength.
Detailed Description
The embodiments of the present invention will be specifically described below.
[ liquid Crystal resin composition for surface mounting Relay ]
The liquid crystalline resin composition for a surface mount relay of the present invention includes a specific liquid crystalline polymer and a fibrous filler in predetermined amounts, the fibrous filler having a weight-average fiber length of 50to 170 [ mu ] m and a content of a component having a fiber length of 20 to 200 [ mu ] m in the fibrous filler being 70 mass% or more, and the surface mount relay is a surface mount relay including a base and a terminal protruding from the base and having the terminal soldered to a printed circuit board. The components constituting the liquid crystalline resin composition of the present invention will be described below.
(liquid Crystal Polymer)
The composite resin composition of the present invention contains a liquid crystalline polymer which is the wholly aromatic polyester amide. Since the wholly aromatic polyester amide has a low melting point, the processing temperature can be lowered, and the generation of decomposition gas during melting can be suppressed. As a result, the foaming of the molded article obtained by molding the composite resin composition containing the wholly aromatic polyester amide is suppressed, and the foaming resistance is improved. The liquid crystalline polymer may be used alone in 1 kind or in combination of 2 or more kinds.
The wholly aromatic polyester amide in the present invention includes the following structural unit (I), the following structural unit (II), the following structural unit (III), the following structural unit (IV), and the following structural unit (V).
The structural unit (I) is derived from 4-hydroxybenzoic acid (hereinafter also referred to as "HBA"). The wholly aromatic polyester amide of the present invention contains 50to 69 mol% of the structural unit (I) with respect to the total structural units. When the content of the structural unit (I) is less than 50 mol% or exceeds 69 mol%, at least 1 of the heat resistance and the manufacturability tends to be insufficient.
The structural unit (II) is derived from 1, 4-phenylene dicarboxylic acid (hereinafter also referred to as "TA"). The wholly aromatic polyester amide of the present invention contains 9.2 to 22.5 mol% of the structural unit (II) with respect to the total structural units. When the content of the structural unit (II) is less than 9.2 mol% or exceeds 22.5 mol%, at least 1 of the heat resistance and the manufacturability tends to be insufficient.
The structural unit (III) is derived from 1, 3-phenylene dicarboxylic acid (hereinafter also referred to as "IA"). The wholly aromatic polyester amide of the present invention contains 2.5 to 6.3 mol% of the structural unit (III) with respect to the total structural units. When the content of the structural unit (III) is less than 2.5 mol% or exceeds 6.3 mol%, at least 1 of the heat resistance and the manufacturability tends to be insufficient.
The structural unit (IV) is derived from 4, 4' -dihydroxybiphenyl (hereinafter also referred to as "BP"). The wholly aromatic polyester amide of the present invention contains 8.5 to 24 mol% of the structural unit (IV) with respect to the total structural units. When the content of the structural unit (IV) is less than 8.5 mol% or exceeds 24 mol%, at least 1 of the heat resistance and the productivity tends to be insufficient.
The structural unit (V) is derived from N-acetyl p-aminophenol (hereinafter also referred to as "APAP"). The wholly aromatic polyester amide of the present invention contains 1 to 7 mol% of the structural unit (V) with respect to the total structural units. When the content of the structural unit (V) is less than 1 mol%, although the heat resistance is good, the manufacturability is liable to become insufficient. When the content of the structural unit (V) exceeds 7 mol%, at least 1 of the heat resistance and the manufacturability tends to be insufficient.
From the viewpoint of balancing heat resistance and manufacturability, the total mole number of the structural unit (II) and the structural unit (III) (hereinafter also referred to as "mole number 1A") is 1 to 1.06 times the total mole number of the structural unit (IV) and the structural unit (V) (hereinafter also referred to as "mole number 2A"), or the total mole number of the structural unit (IV) and the structural unit (V) is 1 to 1.06 times the total mole number of the structural unit (II) and the structural unit (III). Preferably, the molar number 1A is 1 to 1.025 times the molar number 2A, or the molar number 2A is 1 to 1.025 times the molar number 1A.
As described above, the wholly aromatic polyester amide of the present invention contains specific structural units (I) to (V) in a specific amount with respect to all the structural units, and the ratio of the number of moles 1A to the number of moles 2A is in a specific range, and therefore, the wholly aromatic polyester amide is excellent in balance between heat resistance and productivity. The wholly aromatic polyester amide of the present invention contains the structural units (I) to (V) in a total amount of 100 mol% based on the total structural units.
As an index for indicating the heat resistance, a difference between a melting point and a deflection temperature under load (hereinafter also referred to as "DTU L") is mentioned, and since the difference tends to improve the heat resistance when the difference is 110 ℃ or less, it is preferable that DTU L is a value measured in a state of a liquid crystalline resin composition obtained by melt-kneading 60 mass% of the wholly aromatic polyester amide and 40 mass% of abrasive fibers having an average fiber diameter of 11 μm and an average fiber length of 75 μm at the melting point +20 ℃ of the wholly aromatic polyester amide, and is measured in accordance with ISO75-1, 2, and from the viewpoint of balance between the heat resistance and the productivity, the difference is preferably more than 0 ℃ and 108 ℃ or less (for example, 65 ℃ or more and 108 ℃ or less), and more preferably 71 ℃ or more and 107 ℃ or less.
Next, a method for producing the wholly aromatic polyester amide of the present invention will be described. The wholly aromatic polyester amide in the present invention can be polymerized by a direct polymerization method, an ester exchange method, or the like. In the polymerization, a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, or the like, or a combination of 2 or more of these methods is used, and preferably a melt polymerization method or a combination of a melt polymerization method and a solid phase polymerization method is used.
In the present invention, an acylating agent for a monomer to be polymerized and a monomer having a terminal activated in the form of an acid chloride derivative can be used for the polymerization. Examples of the acylating agent include fatty acid anhydrides such as acetic anhydride.
In the polymerization, various catalysts can be used, and typical catalysts include dialkyltin oxide, diaryltin oxide, titanium dioxide, alkoxytitanosilicate, titanium alkoxide, fatty acid metal salt, and BF3Such as Lewis acidsSalts, etc., preferably fatty acid metal salts. The amount of the catalyst used is usually about 0.001 to 1% by mass, particularly preferably about 0.003 to 0.2% by mass, based on the total mass of the monomers.
In addition, in the case of performing solution polymerization or slurry polymerization, liquid paraffin, highly heat-resistant synthetic oil, inert mineral oil, or the like can be used as a solvent.
The reaction conditions include, for example, a reaction temperature of 200 to 380 ℃ and a final pressure of 0.1 to 760Torr (i.e., 13 to 101,080 Pa). In particular, the reaction temperature during the melting reaction is, for example, 260 to 380 ℃, preferably 300 to 360 ℃, and the final pressure is 1 to 100Torr (i.e., 133 to 13,300Pa), preferably 1 to 50Torr (i.e., 133 to 6,670 Pa).
The reaction may be started by charging all of the raw material monomers (HBA, TA, IA, BP, and APAP), the acylating agent, and the catalyst into the same reaction vessel (one-stage method), or may be started by acylating the hydroxyl groups of the raw material monomers HBA, BP, and APAP with the acylating agent and then reacting the acylated hydroxyl groups with the carboxyl groups of TA and IA (two-stage method).
In the melt polymerization, after the temperature in the reaction system reaches a predetermined temperature, the pressure is reduced to a predetermined reduced pressure, and the melt polymerization is carried out. After the torque of the stirrer reached a predetermined value, an inert gas was introduced into the reactor to bring the reactor from a reduced pressure state to a predetermined pressurized state through a normal pressure, and the wholly aromatic polyester amide was discharged from the reaction system.
The wholly aromatic polyester amide produced by the above polymerization method can be subjected to solid phase polymerization by heating in an inert gas under normal pressure or reduced pressure to increase the molecular weight. The preferable conditions for the solid-phase polymerization are a reaction temperature of 230 to 350 ℃, preferably 260 to 330 ℃ and a final pressure of 10to 760Torr (i.e., 1,330 to 101,080 Pa).
The method for producing a wholly aromatic polyester amide according to the present invention preferably includes the steps of: acylating 4-hydroxybenzoic acid, 4' -dihydroxybiphenyl and N-acetyl-p-aminophenol with a fatty acid anhydride in the presence of a fatty acid metal salt, further transesterifying with 1, 4-phenylene dicarboxylic acid and 1, 3-phenylene dicarboxylic acid,
it is preferable that: with respect to all monomers comprising 4-hydroxybenzoic acid, 1, 4-phenylene dicarboxylic acid, 1, 3-phenylene dicarboxylic acid, 4' -dihydroxybiphenyl, and N-acetyl p-aminophenol,
the using amount of the 4-hydroxybenzoic acid is 50-69 mol%,
The dosage of the 1, 4-phenylene dicarboxylic acid is 9.2-22.5 mol%,
The dosage of the 1, 3-phenylene dicarboxylic acid is 2.5-6.3 mol%,
The dosage of the 4, 4' -dihydroxybiphenyl is 8.5-24 mol%,
The dosage of the N-acetyl-p-aminophenol is 1 to 7 mol percent
Preferably, the total mole number of 1, 4-phenylene dicarboxylic acid and 1, 3-phenylene dicarboxylic acid (hereinafter also referred to as "mole number 1B") is 1 to 1.06 times the total mole number of 4,4 '-dihydroxybiphenyl and N-acetyl-p-aminophenol (hereinafter also referred to as "mole number 2B"), or the total mole number of 4, 4' -dihydroxybiphenyl and N-acetyl-p-aminophenol is 1 to 1.06 times the total mole number of 1, 4-phenylene dicarboxylic acid and 1, 3-phenylene dicarboxylic acid,
the amount of the fatty acid anhydride is preferably 1.02 to 1.04 times the total hydroxyl equivalent of 4-hydroxybenzoic acid, 4' -dihydroxybiphenyl, and N-acetyl-p-aminophenol. More preferably, the fatty acid metal salt is acetic acid metal salt, and the fatty acid anhydride is acetic anhydride. Further, it is more preferable that the molar number 1B is 1 to 1.025 times the molar number 2B, or the molar number 2B is 1 to 1.025 times the molar number 1B.
Next, the properties of the wholly aromatic polyester amide will be described. The wholly aromatic polyester amide of the present invention exhibits optical anisotropy when melted. The optical anisotropy exhibited upon melting means that: the wholly aromatic polyester amide in the present invention is a liquid crystalline polymer.
In the present invention, it is essential for the wholly aromatic polyester amide to be a liquid crystalline polymer that has both thermal stability and easy processability. The wholly aromatic polyester amide composed of the structural units (I) to (V) may be of a type that does not form an anisotropic melt phase depending on the structural components and the sequence distribution in the polymer, but the polymer of the present invention is limited to wholly aromatic polyester amides that exhibit optical anisotropy when melted.
More specifically, the melt anisotropy was confirmed by melting a sample placed on a heating stage made by L inkam using a polarizing microscope made by olympus, and observing the melt anisotropy at a magnification of 150 times in a nitrogen atmosphere.
Since a nematic liquid crystalline polymer undergoes a significant viscosity drop above the melting point, it generally exhibits liquid crystallinity at a temperature at or above the melting point, which is an indicator of processability. From the viewpoint of heat resistance, the melting point is preferably as high as possible, and in view of thermal deterioration in melt processing of the polymer, heating capacity of a molding machine, and the like, a melting point exceeding 340 ℃ and 370 ℃ or lower is a preferable standard. More preferably, the temperature is 345 to 365 ℃.
The liquid crystalline resin composition of the present invention contains 50to 70 mass% of the liquid crystalline polymer with respect to the whole liquid crystalline resin composition. If the content of the liquid crystalline polymer is less than 50% by mass based on the whole liquid crystalline resin composition, the fluidity of the liquid crystalline resin composition is liable to deteriorate, and there is a fear that the warp deformation of a molded article such as a surface mount relay component obtained from the liquid crystalline resin composition becomes large, which is not preferable. When the content of the liquid crystalline polymer exceeds 70% by mass of the entire liquid crystalline resin composition, the flexural modulus and the crack resistance of a molded article such as a surface mount relay part obtained from the liquid crystalline resin composition are undesirably reduced. The liquid crystalline resin composition of the present invention preferably contains the liquid crystalline polymer in an amount of 55 to 65 mass%, more preferably 58 to 62 mass%, based on the whole liquid crystalline resin composition.
(fibrous Filler)
The liquid crystalline resin composition of the present invention comprises the liquid crystalline polymer and a fibrous filler, wherein the fibrous filler has a weight-average fiber length of 50to 170 [ mu ] m and a content of a component having a fiber length of 20 to 200 [ mu ] m in the fibrous filler is 70% by mass or more, and therefore a molded article obtained by molding the liquid crystalline resin composition is excellent in heat resistance, is inhibited from generating bubbles and from being detached from the filler, and can be bonded with a high adhesive strength by an adhesive. The fibrous filler may be used alone in 1 kind or in combination of 2 or more kinds. The fibrous filler in the present invention is not particularly limited, and examples thereof include glass fibers, milled fibers, carbon fibers, asbestos fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, and potassium titanate fibers. In order to maintain high bonding strength between molded articles obtained from the liquid crystalline resin composition and to easily suppress the separation of the filler from the molded articles, the fibrous filler in the present invention is preferably ground fibers.
In the liquid crystalline resin composition of the present invention, the fibrous filler has a weight average fiber length of 50to 170 μm, preferably 70 to 150 μm, more preferably 80 to 140 μm, and still more preferably 100to 140 μm. When the weight-average fiber length is less than 50 μm, the high-temperature rigidity of the molded article obtained from the liquid crystalline resin composition is not likely to become sufficient, and the warpage of the molded article may become large, which is not preferable. When the weight-average fiber length exceeds 170 μm, it is difficult to suppress the separation of the filler from the molded article of the liquid crystalline resin composition obtained, which is not preferable. When the weight-average fiber length is within the range of 50to 170 μm, the surface roughness (Ra) of the molded article of the liquid crystalline resin composition obtained is moderately improved, and the adhesion strength between the molded articles can be easily maintained high within an appropriate range. In the present specification, the weight-average fiber length of the fibrous filler means a value measured as follows: the liquid crystalline resin composition was heated at 600 ℃ for 2 hours to ash the composition, thereby obtaining an ash residue, the ash residue was dispersed in a 5 mass% aqueous polyethylene glycol solution to obtain a dispersion, and the weight average fiber length of the dispersion was measured with an image measuring instrument.
The content of the component having a fiber length of 20 to 200 μm in the fibrous filler is 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more, in order to suppress the detachment of the filler from the molded article of the liquid crystalline resin composition and to maintain the mechanical strength of the molded article such as weld strength and high-temperature rigidity in a highly balanced manner. The upper limit of the content is not particularly limited, and may be 100 mass% or less, or 95 mass% or less. In the present specification, the content is measured as follows: the liquid crystalline resin composition was heated at 600 ℃ for 2 hours to ash and obtain an ash residue, and the ash residue was dispersed in a 5 mass% aqueous polyethylene glycol solution to obtain a dispersion, and the fiber length distribution of the dispersion was measured by an image measuring instrument.
The fiber diameter of the fibrous filler in the present invention is not particularly limited, and a fibrous filler having a fiber diameter of about 5to 15 μm is generally used.
The liquid crystalline resin composition of the present invention contains 30 to 50 mass% of a fibrous filler with respect to the entire liquid crystalline resin composition. When the content of the fibrous filler is less than 30% by mass based on the whole liquid crystalline resin composition, the load deflection temperature of a molded article such as a surface mount relay part obtained from the liquid crystalline resin composition is low and the high-temperature rigidity is insufficient, which is not preferable. If the content of the fibrous filler exceeds 50 mass% based on the whole liquid crystalline resin composition, the flowability of the liquid crystalline resin composition may be deteriorated, and warpage of a molded article may be increased, which is not preferable. The fibrous filler in the present invention is contained in the liquid crystalline resin composition preferably in an amount of 35 to 45% by mass, more preferably 38 to 42% by mass, based on the whole liquid crystalline resin composition.
(other Components)
In addition to the above components, the liquid crystalline resin composition of the present invention may further contain 1 or more of a plate-like filler, a nucleating agent, a pigment such as carbon black or an inorganic firing pigment, an antioxidant, a stabilizer, a plasticizer, a lubricant, a release agent, a flame retardant and a known inorganic filler.
The method for producing the liquid crystalline resin composition of the present invention is not particularly limited as long as the components in the liquid crystalline resin composition can be mixed uniformly, the weight-average fiber length of the fibrous filler is 50to 170 μm, and the content of the component having a fiber length of 20 to 200 μm in the fibrous filler is 70 mass% or more, and can be selected suitably from conventionally known methods for producing resin compositions. Examples thereof include the following methods: the components are melt-kneaded and extruded using a melt-kneading apparatus such as a single-screw or twin-screw extruder, and the obtained liquid crystalline resin composition is processed into a desired form such as powder, flake, pellet, or the like.
The liquid crystalline resin composition of the present invention has excellent fluidity, and therefore, the minimum filling pressure during molding is not likely to become excessive, and it can be preferably molded into a surface mount relay component or the like.
The melt viscosity of the liquid crystalline resin composition is 1 × 10 measured according to ISO11443 at a temperature 10-30 ℃ higher than the melting point of the liquid crystalline polymer and a shear rate of 1000/s5Pa · s or less (more preferably 5Pa · s or more and 1 × 10Pa · s or less)2Pa · s or less), which is preferable in terms of ensuring the fluidity of the liquid crystalline resin composition at the time of molding of the surface mount relay part and avoiding an excessive filling pressure.
(surface mounting Relay parts and surface mounting relays)
The liquid crystalline resin composition of the present invention is molded to obtain a surface mount relay component of the present invention. The surface mount relay component of the present invention has excellent heat resistance, is inhibited from generating bubbles and from being detached from a filler, and can be bonded with an adhesive at high bonding strength. The surface mount relay of the present invention includes the above-described components, and therefore (1) is excellent in heat resistance and can withstand solder reflow treatment; (2) in particular, the base and the case can be bonded together with a high bonding strength by an adhesive, and airtightness can be maintained even after solder reflow treatment, and (3) generation of blister and separation of filler are suppressed, and malfunction such as poor conduction is less likely to occur.
The surface mount relay component of the present invention and the surface mount relay of the present invention will be explained. Fig. 1 (a) is a perspective view schematically showing an embodiment of the surface mount relay of the present invention, and fig. 1 (b) is a partial cross-sectional view showing an AA cross section of fig. 1 (a). The surface mount relay 1 includes a base 2, a case 3, a coil block 4, an armature block 5, and a terminal 6.
The base 2 includes terminals 6 protruding from the base 2. A housing 3 is disposed on the outer periphery of the upper surface of the base 2. A coil block 4 and an armature block 5 are disposed in this order in the center portion of the upper surface of the base 2.
The housing 3 is disposed so as to cover the outer peripheral portion of the upper surface of the base 2, and the coil block 4 and the armature block 5. A coil block 4 and an armature block 5 are housed in a hollow container-like space formed by the base 2 and the case 3.
The coil unit 4 includes a bobbin 41, a coil 42, and a core 43, and is disposed in the center of the upper surface of the base 2. The bobbin 41 has a cylindrical portion penetrating in the longitudinal direction, a coil 42 electrically connected to one end of a part of the terminal 6 is wound around the outer periphery of the bobbin 41, and an iron core 43 is inserted into the cylindrical portion of the bobbin 41.
The armature assembly 5 includes an armature connection portion 51 and an armature 52, and is disposed on the coil assembly 4, and the armatures 52 extend from the armature connection portion 51 in directions opposite to each other along the longitudinal direction of the bobbin 41. The armature 52 is electrically connected to one end of the other portion of the terminal 6. When an electromagnet is formed by conduction with the coil 42, the tip of the armature 52 moves to the coil block 4 side due to the magnetic force. As a result, a signal from the input side including the coil 42 is transmitted to the output side including the armature 52.
One end of the terminal 6 is electrically connected to the coil 42 or the armature 52, and the other end is electrically conductively connected to a printed circuit board 7 described later. The terminals 6 protrude from the base 2 to be soldered to a printed board 7 as described later.
The base 2, the case 3, and the bobbin 41 among the above components are preferably formed of the liquid crystal resin composition of the present invention, in view of the fact that a molded product having excellent heat resistance, suppressed occurrence of blisters, suppressed detachment of fillers, and capable of being bonded with an adhesive at a high bonding strength can be formed. That is, examples of the surface mount relay component of the present invention include a base, a case, and a bobbin.
The surface mount relay 1 can be manufactured, for example, as follows: the coil block 4 and the armature block 5 are sequentially disposed in the center portion of the upper surface of the base 2, the case 3 is disposed in the outer peripheral portion of the upper surface of the base 2, and the base 2 and the case 3 are bonded together with an adhesive.
A method of mounting the surface mount relay 1 on the printed circuit board 7 will be described. As shown in fig. 2 (a), in the surface mount relay 1, the terminal 6 perpendicularly protruding from the surface mount relay 1 is bent at a right angle so that the soldering face is parallel to the surface mount relay 1. Therefore, in the surface mount relay 1, the terminal 6 is mounted on a land (not shown) provided on the conductor pattern 8 on the surface of the printed board 7, and solder reflow processing is performed, instead of providing a hole in the printed board 7, thereby being conductively fixed to the printed board 7.
In the above description, the case where the tip of the terminal 6 vertically protruding from the surface mount relay 1 is bent at right angles to the outside of the surface mount relay 1 as shown in fig. 2 (a) is shown. On the other hand, as shown in fig. 2 (b), the tip of the terminal 6 projecting perpendicularly from the surface-mount relay 1 may be bent at a right angle toward the inside of the surface-mount relay 1.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
< Synthesis example 1 >
The following raw material monomers, fatty acid metal salt catalyst and acylating agent were charged into a polymerization vessel equipped with a stirrer, reflux column, monomer inlet, nitrogen gas inlet, and decompression/outflow line, and nitrogen substitution was started.
(I) 10.6 mol (64 mol%) (HBA) of 4-hydroxybenzoic acid
(II) terephthalic acid 2.4 mol (14.5 mol%) (TA)
(III) isophthalic acid 0.6 mol (3.5 mol%) (IA)
(IV)4, 4' -Dihydroxybiphenyl 2.7 mol (16 mol%) (BP)
(V) N-acetyl para-aminophenol 0.3 mole (2 mole%) (APAP)
Potassium acetate catalyst 110mg
1715g of acetic anhydride (1.03 times the total hydroxyl equivalent of HBA, BP and APAP)
After the charge of the raw materials, the temperature of the reaction system was raised to 140 ℃ and the reaction was carried out at 140 ℃ for 1 hour. Then, the temperature was raised to 360 ℃ over 5.5 hours, and the pressure was reduced to 10Torr (1330 Pa) over 20 minutes, and melt polymerization was carried out while distilling off acetic acid, excess acetic anhydride, and other low boiling components. After the stirring torque reached a predetermined value, nitrogen gas was introduced, and the pressure was increased from a reduced pressure state through normal pressure, and the polymer was discharged from the bottom of the polymerization vessel.
< evaluation >
The wholly aromatic polyester amide of synthesis example 1 was evaluated for melting point, DTU L and productivity by the following methods, and the evaluation results are shown in table 1.
[ melting Point ]
After an endothermic peak temperature (Tm1) observed when a polymer was measured under a temperature raising condition of 20 ℃/min from room temperature was observed by DSC (TA Instrument Co., Ltd.), the polymer was held at a temperature of (Tm1+40) ° C for 2 minutes, and then cooled down to room temperature under a temperature lowering condition of 20 ℃/min, and then the temperature of the endothermic peak observed when measured under a temperature raising condition of 20 ℃/min was measured again.
[DTUL]
60% by mass of a polymer and 40% by mass of a glass fiber (EFH 75-01, manufactured by Mitsui Kabushiki Kaisha, milled fiber, average fiber diameter 11 μm, and average fiber length 75 μm) were melt-kneaded by a twin-screw extruder (TEX 30 α, manufactured by Nippon Steel Co., Ltd.) at a cylinder temperature of +20 ℃ of the melting point of the polymer, to obtain pellets of a liquid crystalline resin composition.
The pellets of the liquid crystalline resin composition were molded by a molding machine (SE 100DU, manufactured by Sumitomo heavy machinery industries Co., Ltd.) under the following molding conditions to obtain a test piece (4mm × 10mm × 80mm) for measurement, and the deflection temperature under load was measured by a method according to ISO75-1, 2 using the test piece, and the results are shown in Table 1 using 1.8MPa as the bending stress.
[ Forming Condition ]
Barrel temperature: melting Point of the Polymer +20 deg.C
Temperature of the die: 80 deg.C
Back pressure: 2MPa of
Injection speed: 33 mm/sec
[ manufacturability ]
The above-mentioned behavior when the polymer was discharged from the lower part of the polymerization vessel was observed, and the productivity was evaluated according to the following criteria. The results are shown in tables 1 to 4.
○, the productivity was evaluated as good when the polymer could be discharged as a strand without any problem and the strand could be cut into pellets.
×, when the polymer was not discharged because of solidification in the vessel during the polymerization or when the polymer could not be cut even if it could be discharged as a strand, the productivity was evaluated as poor.
< Synthesis examples 2 to 16, comparative Synthesis examples 1 to 8 >
Polymers were obtained in the same manner as in synthesis example 1 except that the types and feed ratios (mol%) of the raw material monomers were as shown in tables 1 to 3. The same evaluation as in synthesis example 1 was performed. The evaluation results are shown in tables 1 to 3.
[ Table 1]
[ Table 2]
[ Table 3]
< examples 1 and 2, and comparative examples 1 to 3 >
In the following examples and comparative examples, the liquid crystalline polymer 1 was the liquid crystalline polymer obtained in synthesis example 1. The liquid crystalline polymer 2 is produced as follows.
In the present example, the melting point and the melt viscosity of the pellets were measured under the following conditions.
[ measurement of melting Point ]
After an endothermic peak temperature (Tm1) observed when a liquid crystalline polymer is measured under a temperature rise condition of 20 ℃/min from room temperature was observed by DSC manufactured by TA instruments, the liquid crystalline polymer was held at a temperature of (Tm1+40) ° C for 2 minutes, then cooled down to room temperature under a temperature decrease condition of 20 ℃/min, and then the temperature of the endothermic peak observed when measured under a temperature rise condition of 20 ℃/min was measured again.
[ measurement of melt viscosity ]
The melt viscosity of the liquid crystalline polymer was measured at a shear rate of 1000/sec based on ISO11443 using Capirograph model 1B manufactured by Toyo Seiki Seisaku-Sho K.K., at a temperature of 10to 30 ℃ higher than the melting point of the liquid crystalline polymer, using an orifice having an inner diameter of 1mm and a length of 20 mm. The measurement temperature was 360 ℃ for the liquid crystalline polymer 1 and 380 ℃ for the liquid crystalline polymer 2.
(method for producing liquid Crystal Polymer 2)
The following raw material monomers, metal catalyst and acylating agent were charged into a polymerization vessel equipped with a stirrer, reflux column, monomer inlet, nitrogen inlet and pressure reduction/outflow line, and nitrogen substitution was started.
(I) 4-hydroxybenzoic acid: 1040g (48 mol%) (HBA)
(II) 6-hydroxy-2-naphthoic acid: 89g (3 mol%) (HNA)
(III) terephthalic acid: 547g (21 mol%) (TA)
(IV) isophthalic acid: 91g (3.5 mol%) (IA)
(V)4, 4' -dihydroxybiphenyl: 716g (24.5 mol%) (BP)
Potassium acetate catalyst: 110mg
Acetic anhydride: 1644g
After charging the raw materials into the polymerization vessel, the temperature of the reaction system was raised to 140 ℃ and the reaction was carried out at 140 ℃ for 1 hour. Then, the temperature was raised to 360 ℃ over 5.5 hours, and the pressure was reduced to 5Torr (667 Pa) over 20 minutes, and melt polymerization was carried out while distilling off acetic acid, excess acetic anhydride, and other low boiling components. After the stirring torque reached a predetermined value, nitrogen gas was introduced, the pressure was increased from a reduced pressure state through normal pressure, and the polymer was discharged from the lower part of the polymerization vessel, and the strand was pelletized to be pelletized. The obtained pellets had a melting point of 355 ℃ and a melt viscosity of 10 pas.
(Components other than liquid crystalline Polymer)
The liquid crystalline polymer obtained above and the following components were mixed by a twin screw extruder to obtain a liquid crystalline resin composition. The amounts of the respective components are shown in table 4. In the following tables, "%" represents mass%.
(B) Fibrous filler
Glass fiber: ECS03T-786H, a chopped strand of 10 μm in fiber diameter and 3mm in length, manufactured by Nippon Denshoku K.K
Grinding fiber 1: PF70E001 manufactured by Nindon textile Co., Ltd., fiber diameter of 10 μm, average fiber length of 70 μm (manufacturer's nominal value)
Grinding fiber 2: EPH-80M manufactured by Nippon Denko K.K., fiber diameter 10.5 μ M, and average fiber length 80 μ M (manufacturer's nominal value)
The manufacturer nominal values are different from the values in table 4, which are measured values of the composition.
The extrusion conditions for obtaining the liquid crystalline resin composition are as follows.
[ extrusion Condition ]
[ examples 1 and 2, comparative examples 1 and 3]
The temperature of the cylinder provided at the main feed port was set to 250 ℃ and the temperatures of all the other cylinders were set to 360 ℃. The liquid crystalline polymer is supplied from the main inlet. The filler was supplied from a side inlet.
[ comparative example 2]
The temperature of the cylinder provided at the main feed port was set to 250 ℃ and the temperatures of all the other cylinders were set to 380 ℃. The liquid crystalline polymer is supplied from the main inlet. The filler was supplied from a side inlet.
The weight average fiber length of the fibrous filler in the liquid crystalline resin composition was measured by the following method.
[ measurement of weight-average fiber Length ]
The liquid crystal resin composition pellets 5g were heated at 600 ℃ for 2 hours to ash, the ash residue was dispersed sufficiently in a 5 mass% polyethylene glycol aqueous solution, the resultant was transferred to a petri dish by a dropper, and the fibrous filler was observed under a microscope, and the weight-average fiber length of the fibrous filler was measured by an image measuring instrument (L UZEXFS, NIRECO Co., Ltd.).
The content of the component having a fiber length of 20 to 200 μm in the fibrous filler in the liquid crystalline resin composition is measured by the following method.
[ measurement of content of component having fiber length of 20 to 200 μm ]
The liquid crystalline resin composition pellets 5g were heated at 600 ℃ for 2 hours to be ashed, the ashed residue was sufficiently dispersed in a 5 mass% polyethylene glycol aqueous solution, the mixture was transferred to a petri dish by a dropper, and the fiber length distribution of a fibrous filler was measured by an image measuring instrument (L UZEXFS manufactured by NIRECO Co., Ltd.) and the proportion of a component having a fiber length of 20 to 200 μm was read in the fiber length distribution as the content.
(measurement of melt viscosity of liquid Crystal resin composition)
The melt viscosity of the liquid crystalline resin composition was measured at a shear rate of 1000/sec based on ISO11443 using Capirograph model 1B manufactured by Toyo Seiki Seisaku-Sho K.K., using an orifice having an inner diameter of 1mm and a length of 20mm at a temperature of 10to 30 ℃ higher than the melting point of the liquid crystalline polymer. The measurement temperature was 360 ℃ for the liquid crystalline resin composition using liquid crystalline polymer 1 and 380 ℃ for the liquid crystalline resin composition using liquid crystalline polymer 2. The results are shown in Table 4.
The physical properties of the molded article molded from the liquid crystalline resin composition were measured by the following methods. The evaluation results are shown in table 4.
(bending test)
The liquid crystalline resin composition was injection-molded under the following molding conditions to obtain a 0.8mm thick molded article, and the flexural strength, the strain at break, and the flexural modulus were measured in accordance with ASTM D790.
[ Molding conditions ]
A forming machine: sumitomo heavy machinery industry, SE100DU
Barrel temperature: 360 deg.C (examples 1 and 2, comparative examples 1 and 3)
370 deg.C (comparative example 2)
Temperature of the die: 80 deg.C
Injection speed: 33 mm/sec
(deflection temperature under load)
The liquid crystalline resin composition was injection-molded under the following molding conditions to obtain a molded article, and the deflection temperature under load was measured in accordance with ISO75-1, 2, and evaluated in accordance with the following criteria.
○ (preferably), the deflection temperature under load is 260 ℃ or higher.
× (bad). The deflection temperature under load is less than 260 ℃.
[ Molding conditions ]
A forming machine: sumitomo heavy machinery industry, SE100DU
Barrel temperature: 360 deg.C (examples 1 and 2, comparative examples 1 and 3)
370 deg.C (comparative example 2)
Temperature of the die: 80 deg.C
Injection speed: 33 mm/sec
(foaming temperature)
A liquid crystalline resin composition was injection-molded under the following molding conditions to obtain a 12.5mm × 120mm × 0.8.8 mm molded article having a weld portion, and a piece obtained by dividing the molded article into two parts at the weld portion was held in a hot press at a predetermined temperature for 5 minutes as 1 test piece, and then, whether or not foaming occurred on the surface of the test piece was visually checked.
○ (good), the foaming temperature is 270 ℃ or higher.
× (poor). The foaming temperature is less than 270 ℃.
[ Molding conditions ]
A forming machine: sumitomo heavy machinery industry, SE100DU
Barrel temperature: 360 deg.C (examples 1 and 2, comparative examples 1 and 3)
370 deg.C (comparative example 2)
Temperature of the die: 90 deg.C
Injection speed: 33 mm/sec
(Filler releasing Property)
A molded article of 12.5mm × 120mm × 0.8.8 mm having a weld portion was obtained by injection molding a liquid crystalline resin composition under the following molding conditions, and the molded article obtained by dividing the molded article into two parts at the weld portion was subjected to IR reflow under the following conditions, and then the state of detachment of the fibrous filler was observed and evaluated according to the following criteria.
○ (good), the fibrous filler was prevented from coming off without change.
× (bad), fibrous filler detached.
[ Molding conditions ]
A forming machine: sumitomo heavy machinery industry, SE100DU
Barrel temperature: 360 deg.C (examples 1 and 2, comparative examples 1 and 3)
370 deg.C (comparative example 2)
Temperature of the die: 90 deg.C
Injection speed: 33 mm/sec
[ IR reflow soldering Condition ]
A measuring machine: japanese pulse technology research corporation large desk type reflow soldering device RF-300 (using far infrared heater)
Sample feeding speed: 140 mm/sec
Passing time of the reflow oven: 5 minutes
Temperature conditions in the preheating zone: 150 ℃ C
Temperature conditions of the reflow soldering zone: 190 deg.C
Peak temperature: 251 deg.C
(surface roughness (Ra))
The liquid crystalline resin composition was injection-molded under the following molding conditions to obtain a test piece (ISO test piece type 1A, thickness 4 mm). The surface roughness Ra of the central portion of the molded article was measured with an ultra-deep color 3D shape measuring microscope VK-9500 (manufactured by KEYENCE).
[ Molding conditions ]
A forming machine: sumitomo heavy machinery industry, SE100DU
Barrel temperature: 360 deg.C (examples 1 and 2, comparative examples 1 and 3)
370 deg.C (comparative example 2)
Temperature of the die: 90 deg.C
Injection speed: 33 mm/sec
(adhesive Strength)
The liquid crystalline resin composition was injection-molded under the following molding conditions to obtain a test piece (ISO test piece type 1A, thickness 4 mm). the test piece was divided into 2 parts, and bonded with an epoxy adhesive (L OCTITE 3128NH, manufactured by HENKE L, Inc.) (curing condition: × 30 minutes at 80 ℃) as shown in FIG. 3 (a). thereafter, the bonded test piece was set as shown in FIG. 3 (b), and a load was applied in the direction of the arrow with a tensile tester to evaluate the adhesive strength from the load when peeling occurred.
[ Molding conditions ]
A forming machine: sumitomo heavy machinery industry, SE100DU
Barrel temperature: 360 deg.C (examples 1 and 2, comparative examples 1 and 3)
370 deg.C (comparative example 2)
Temperature of the die: 90 deg.C
Injection speed: 33 mm/sec
[ tensile test conditions ]
The testing machine is ORIENTEC, TENSI L ON RTC-1325A
Test speed: 10 mm/min
[ Table 4]
The pigment contains the following specific components: a component having a fiber length of 20 to 200 μm in the fibrous filler
As shown in table 4, the molded article obtained by molding the liquid crystalline resin composition for surface mount relays of the present invention has excellent heat resistance, is inhibited from generating blisters and from being detached from the filler, and can be bonded with an adhesive at high bonding strength. Therefore, the liquid crystalline resin composition can be suitably used for the production of a surface mount relay component and a surface mount relay.
Description of the reference numerals
1 surface mounting relay
2 base
3 case
4 coil assembly
41 coil rack
42 coil
43 iron core
5 armature assembly
51 armature connection
52 armature
6 terminal
7 printed circuit board
8 conductor pattern
Claims (4)
1. A liquid crystalline resin composition for a surface mount relay comprising (A) a liquid crystalline polymer and (B) a fibrous filler,
the liquid crystalline polymer (A) is a wholly aromatic polyester amide composed only of the following structural units (I) to (V) and exhibiting optical anisotropy when molten,
the content of the structural unit (I) is 50to 69 mol% based on the total structural units,
the content of the structural unit (II) is 9.2 to 22.5 mol% relative to the total structural units,
the content of the structural unit (III) is 2.5 to 6.3 mol% based on the total structural units,
the content of the structural unit (IV) is 8.5 to 24 mol% relative to the total structural units,
the content of the structural unit (V) is 1 to 7 mol% relative to the total structural units,
the total molar number of the structural unit (II) and the structural unit (III) is 1 to 1.06 times the total molar number of the structural unit (IV) and the structural unit (V), or the total molar number of the structural unit (IV) and the structural unit (V) is 1 to 1.06 times the total molar number of the structural unit (II) and the structural unit (III),
the total content of the structural units (I) to (V) is 100 mol% based on the total structural units,
the weight-average fiber length of the fibrous filler (B) is 80 to 140 μm,
the fibrous filler (B) has a content of a component having a fiber length of 20 to 200 μm of 70 mass% or more,
the liquid crystalline polymer (A) is 50-70% by mass relative to the whole liquid crystalline resin composition,
the fibrous filler (B) is 30 to 50 mass% based on the whole liquid crystalline resin composition,
the surface mount relay includes a base and a terminal protruding from the base, and is soldered to a printed circuit board,
(I)
(II)
(III)
(IV)
(V)
2. the liquid crystalline resin composition according to claim 1, wherein the fibrous filler (B) is a milled fiber.
3. A surface mount relay component formed from the composition of claim 1 or 2.
4. A surface mount relay provided with the component according to claim 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2016-250106 | 2016-12-22 | ||
| JP2016250106 | 2016-12-22 | ||
| PCT/JP2017/044425 WO2018116889A1 (en) | 2016-12-22 | 2017-12-11 | Liquid crystalline resin composition for surface-mounted relays and surface-mounted relay using same |
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| Publication Number | Publication Date |
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| CN109844027A CN109844027A (en) | 2019-06-04 |
| CN109844027B true CN109844027B (en) | 2020-08-04 |
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| JP (1) | JP6416443B1 (en) |
| CN (1) | CN109844027B (en) |
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| KR102501091B1 (en) * | 2020-05-13 | 2023-02-17 | 포리프라스틱 가부시키가이샤 | Liquid crystalline resin composition for surface mount relay and surface mount relay using the same |
| WO2022168706A1 (en) * | 2021-02-05 | 2022-08-11 | ポリプラスチックス株式会社 | Fan impeller liquid crystal resin composition and fan impeller which uses same |
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| CN103093944A (en) * | 2011-10-31 | 2013-05-08 | 住友化学株式会社 | High-voltage coil |
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| JPH06263857A (en) * | 1993-03-17 | 1994-09-20 | Dainippon Ink & Chem Inc | Copolyester and its production |
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| JP5909508B2 (en) * | 2012-01-31 | 2016-04-26 | Ｊｘエネルギー株式会社 | Liquid crystal polyester amide, liquid crystal polyester amide resin composition and molded article |
| CN105273366A (en) * | 2014-06-09 | 2016-01-27 | 住友化学株式会社 | Liquid crystal polyester resin composition, connector, and method for producing liquid crystal polyester resin composition |
| WO2017068869A1 (en) * | 2015-10-21 | 2017-04-27 | ポリプラスチックス株式会社 | Fully aromatic polyester amide, and production method therefor |
| CN108026270B (en) * | 2015-10-21 | 2019-03-26 | 宝理塑料株式会社 | Wholly aromatic polyester amide and its manufacturing method |
| JP6357634B1 (en) | 2017-10-30 | 2018-07-18 | 株式会社クローバー・ネットワーク・コム | Telephone number investigation device, method, program, information provision system |
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2017
- 2017-12-11 JP JP2018520209A patent/JP6416443B1/en active Active
- 2017-12-11 CN CN201780064270.0A patent/CN109844027B/en active Active
- 2017-12-11 WO PCT/JP2017/044425 patent/WO2018116889A1/en active Application Filing
- 2017-12-19 TW TW106144573A patent/TWI716656B/en active
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| US4748229A (en) * | 1986-08-28 | 1988-05-31 | Basf Aktiengesellschaft | Fully aromatic thermotropic polyesters |
| EP0919363A1 (en) * | 1997-06-13 | 1999-06-02 | Nippon Petrochemicals Company, Limited | Bonded composite and sealing composition for use in the same |
| JP2005060455A (en) * | 2003-08-20 | 2005-03-10 | Toray Ind Inc | Liquid crystalline polyester amide and its production method |
| CN101519498A (en) * | 2007-02-26 | 2009-09-02 | 住友化学株式会社 | Resin molded article and method for producing the same |
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| CN103093944A (en) * | 2011-10-31 | 2013-05-08 | 住友化学株式会社 | High-voltage coil |
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| CN109844027A (en) | 2019-06-04 |
| JP6416443B1 (en) | 2018-10-31 |
| TW201840715A (en) | 2018-11-16 |
| WO2018116889A1 (en) | 2018-06-28 |
| JPWO2018116889A1 (en) | 2018-12-20 |
| TWI716656B (en) | 2021-01-21 |
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