WO2021229931A1 - Liquid-crystalline resin composition for surface-mounted relays, and surface-mounted relay using same - Google Patents
Liquid-crystalline resin composition for surface-mounted relays, and surface-mounted relay using same Download PDFInfo
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- WO2021229931A1 WO2021229931A1 PCT/JP2021/012893 JP2021012893W WO2021229931A1 WO 2021229931 A1 WO2021229931 A1 WO 2021229931A1 JP 2021012893 W JP2021012893 W JP 2021012893W WO 2021229931 A1 WO2021229931 A1 WO 2021229931A1
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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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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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
- C08K7/10—Silicon-containing compounds
-
- 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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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
Definitions
- the present invention relates to a liquid crystal resin composition for a surface mount relay and a surface mount relay using the same.
- the through-hole relay has a terminal that protrudes vertically from the relay body, and is first mounted on one surface of the printed circuit board by inserting this terminal into a hole in the printed circuit board. Then, by soldering the terminals on the other surface of the printed circuit board, the through-hole relay is electrically conductively fixed to the printed circuit board.
- a surface mount type (surface mount type) relay has been developed as a new relay mounted on a printed circuit board and used (for example, Patent Document 1).
- surface mount relays terminals protruding vertically from the relay body are bent at right angles so that the soldering surface is parallel to the relay body. Therefore, the surface mount relay can be electrically conducted by placing the above terminals on a solder pad provided on the conductor pattern on the surface of the printed circuit board and performing a solder reflow process without providing holes in the printed circuit board. Is fixed to the printed circuit board.
- the surface mount relay is fixed to the printed circuit board by the solder reflow process
- the molded body constituting the surface mount relay for example, the base, the case, the bobbin, etc., is excellent so as to withstand the solder reflow process. Heat resistance is required. Further, the surface mount relay is also required to be able to maintain airtightness and shape even after the solder reflow process.
- liquid crystal resin compositions are attracting attention because of their excellent heat resistance, dimensional accuracy, fluidity, and the like.
- the filler protrudes from the surface of the molded product of the composition and further desorbs to cause a functional disorder such as poor continuity of the product.
- the liquid crystal resin composition is required to have good fluidity.
- the present invention has been made in view of such circumstances, and is a liquid crystal property for surface mount relays having excellent heat resistance and airtightness, providing a molded body in which deformation and desorption of filler are suppressed, and having good fluidity. It is an object of the present invention to provide a resin composition, a surface mount relay component made of the composition, and a surface mount relay including the component.
- the present inventors combine a liquid crystal resin containing a specific structural unit in a predetermined amount with a predetermined content, fibrous wollastonite, and mica, and set the aspect ratio of the fibrous wollastonite in a predetermined range. It was found that the above problem can be solved by doing so. Specifically, the present invention provides the following.
- a liquid crystal resin composition for a surface mount relay containing (A) a liquid crystal resin, (B) fibrous wollastonite, and (C) mica.
- the liquid crystal resin (A) is composed of the following structural units (I) to (VI) as essential constituents.
- the content of the constituent unit (I) is 50 to 70 mol% with respect to all the constituent units.
- the content of the constituent unit (II) is 0.5 mol% or more and less than 4.5 mol% with respect to all the constituent units.
- the content of the constituent unit (III) is 10.25 to 22.25 mol% with respect to all the constituent units.
- the content of the constituent unit (IV) is 0.5 mol% or more and less than 4.5 mol% with respect to all the constituent units.
- the content of the constituent unit (V) is 5.75 to 23.75 mol% with respect to all the constituent units.
- the content of the constituent unit (VI) is 1 to 7 mol% with respect to all the constituent units.
- the total content of the constituent unit (II) and the constituent unit (IV) with respect to all the constituent units is 1 mol% or more and less than 5 mol%.
- the total content of the constituent units (I) to (VI) is 100 mol% with respect to all the constituent units.
- the aspect ratio of the fibrous wollastonite (B) is 8 or more.
- the content of the liquid crystal resin (A) is 55 to 75% by mass.
- the content of the fibrous wollastonite (B) is 2.5 to 17.5% by mass.
- the content of (C) mica is 15 to 32.5% by mass,
- the total content of the (B) fibrous wollastonite and the (C) mica is 25 to 45% by mass.
- the surface mount relay is a liquid crystal resin composition which is a surface mount relay having a base and terminals protruding from the base, and the terminals are soldered to a printed circuit board.
- the total number of moles of the constituent unit (III) and the constituent unit (IV) is 1 to 1.1 times the total number of moles of the constituent unit (V) and the constituent unit (VI), or The description in (1), wherein the total number of moles of the constituent unit (V) and the constituent unit (VI) is 1 to 1.1 times the total number of moles of the constituent unit (III) and the constituent unit (IV).
- Liquid crystal resin composition Liquid crystal resin composition.
- a surface mount relay component made of the composition according to (1) or (2).
- the composition comprises a liquid crystal resin composition for a surface mount relay having excellent heat resistance and airtightness, providing a molded body in which deformation and desorption of a filler are suppressed, and having good fluidity.
- a component for a surface mount relay and a surface mount relay including the component can be provided.
- FIG. 1 (a) is a perspective view schematically showing an embodiment of a surface mount relay according to the present invention
- FIG. 1 (b) is a partial cross-sectional view showing an AA cross section of FIG. 1 (a).
- 2 (a) and 2 (b) are side views schematically showing a state in which the embodiment of the surface mount relay according to the present invention is mounted on a printed circuit board.
- 3A is a plan view showing a relay case molded in an embodiment
- FIG. 3B is a partial vertical sectional view showing a BB cross section of FIG. 3A.
- the unit of the numerical value in the figure is mm (hereinafter, the same applies to FIGS. 4 (a) to 5 (b)).
- FIG. 4 (a) is a plan view showing a pedestal mounted from the bottom surface side of the relay case shown in FIGS. 3 (a) and 3 (b), and FIG. 4 (b) is a plan view of FIG. 4 (a).
- FIG. 5A shows a relay case in which the pedestal shown in FIGS. 4A and 4B is attached and the inside is sealed in order to evaluate the swelling during reflow of the relay case and the airtightness of the relay case in the embodiment.
- FIG. 5B is a diagram showing measurement points in the evaluation of swelling during reflow of the relay case performed in the embodiment.
- FIG. 5B is a plan view showing a relay case as in FIG. 3A, and a plurality of positions indicated by black circles are measurement points.
- the liquid crystal resin composition for a surface mount relay contains a specific liquid crystal resin, fibrous wollastonite, and mica in predetermined amounts, and the aspect ratio of the fibrous wollastonite is 8 or more.
- the surface mount relay is a surface mount relay having a base and terminals protruding from the base, and the terminals are soldered to a printed circuit board.
- the liquid crystal resin composition according to the present invention contains the liquid crystal resin which is the above-mentioned total aromatic polyester amide. Since the total aromatic polyester amide has a low melting point, the processing temperature can be lowered and the generation of decomposition gas at the time of melting is suppressed.
- the liquid crystal resin can be used alone or in combination of two or more.
- the total aromatic polyesteramide in the present invention has the following structural unit (I), the following structural unit (II), the following structural unit (III), the following structural unit (IV), the following structural unit (V), and the following structural unit ( It consists of VI).
- the structural unit (I) is derived from 4-hydroxybenzoic acid (hereinafter, also referred to as "HBA").
- the total aromatic polyesteramide in the present invention contains 50 to 70 mol% of the constituent unit (I) with respect to all the constituent units.
- the content of the structural unit (I) is less than 50 mol% or more than 70 mol%, at least one of low melting point and heat resistance tends to be insufficient.
- the content of the structural unit (I) is preferably 54 to 67 mol%, more preferably 58 to 64 mol%.
- the structural unit (II) is derived from 6-hydroxy-2-naphthoic acid (hereinafter, also referred to as "HNA").
- the total aromatic polyesteramide in the present invention contains 0.5 mol% or more and less than 4.5 mol% of the constituent unit (II) with respect to all the constituent units.
- the content of the structural unit (II) is less than 0.5 mol% or 4.5 mol% or more, at least one of low melting point and heat resistance tends to be insufficient.
- the content of the structural unit (II) is preferably 0.75 to 3.75 mol%, more preferably 1 to 3 mol%.
- the structural unit (III) is derived from 1,4-phenylenedicarboxylic acid (hereinafter, also referred to as "TA").
- the total aromatic polyesteramide in the present invention contains 10.25 to 22.25 mol% of the constituent unit (III) with respect to all the constituent units.
- the content of the structural unit (III) is less than 10.25 mol% or more than 22.25 mol%, at least one of low melting point and heat resistance tends to be insufficient.
- the content of the structural unit (III) is preferably 12.963 to 20.75 mol%, more preferably 15.675 to 19.25 mol%.
- the structural unit (IV) is derived from 1,3-phenylenedicarboxylic acid (hereinafter, also referred to as "IA").
- the total aromatic polyesteramide in the present invention contains 0.5 mol% or more and less than 4.5 mol% of the constituent unit (IV) with respect to all the constituent units.
- the content of the structural unit (IV) is less than 0.5 mol% or 4.5 mol% or more, at least one of low melting point and heat resistance tends to be insufficient.
- the content of the structural unit (IV) is preferably 0.5 to 3.75 mol%, more preferably 0.5 to 3 mol%.
- the structural unit (V) is derived from 4,4'-dihydroxybiphenyl (hereinafter, also referred to as "BP").
- the total aromatic polyester amide in the present invention contains 5.75 to 23.75 mol% of the structural unit (V) with respect to all the structural units.
- the content of the structural unit (V) is less than 5.75 mol% or more than 23.75 mol%, at least one of low melting point and heat resistance tends to be insufficient.
- the content of the structural unit (V) is preferably 8.5 to 20.375 mol%, more preferably 11.25 to 17 mol% (for example, 11. 675 to 17 mol%).
- the structural unit (VI) is derived from N-acetyl-p-aminophenol (hereinafter, also referred to as "APAP").
- the total aromatic polyester amide in the present invention contains 1 to 7 mol% of constituent units (VI) with respect to all constituent units.
- the content of the structural unit (VI) is less than 1 mol% or more than 7 mol%, at least one of low melting point and heat resistance tends to be insufficient. From the viewpoint of achieving both a low melting point and heat resistance, the content of the structural unit (VI) is preferably 1.5 to 7 mol%, more preferably 2 to 7 mol%.
- the total aromatic polyesteramide in the present invention contains 1 mol% or more and less than 5 mol% of the total of the constituent units (II) and the constituent units (IV) with respect to all the constituent units.
- the flexible structural unit (II) having a naphthalene skeleton and the flexible structural unit (IV) having a benzene skeleton coexist in the total amount in the above range to lower the melting point. It is easy to achieve both heat resistance and heat resistance. If the total content is less than 1 mol%, the proportion of the flexible constituent units becomes too small, so that the melting point tends to be insufficient.
- the total content is 5 mol% or more, the ratio of the flexible constituent units becomes too large, so that the heat resistance tends to be insufficient.
- the total content is preferably 1.75 to 4.75 mol%, more preferably 2.5 to 4.5 mol%.
- the molar ratio of the constituent unit (VI) to the total of the constituent units (V) and the constituent units (VI) is 0.04 to 0.37.
- the molar ratio is less than 0.04, the proportion of the constituent units having a biphenyl skeleton increases, so that the crystallinity of the total aromatic polyesteramide becomes low, and the compatibility between the low melting point and the heat resistance becomes insufficient.
- Cheap when the molar ratio exceeds 0.37, heterogeneous bonds other than ester bonds increase, so that the crystallinity of the total aromatic polyesteramide becomes low, and it tends to be insufficient to achieve both low melting point and heat resistance. ..
- the molar ratio is preferably 0.07 to 0.36, more preferably 0.11 to 0.35.
- the total number of moles of the structural unit (III) and the structural unit (IV) (hereinafter, also referred to as “mol number 1A”) is referred to as the structural unit (V). It is 1 to 1.1 times the total number of moles with the structural unit (VI) (hereinafter, also referred to as “molar number 2A”), or the number of moles 2A is 1 to 1.1 times the number of moles 1A. Is preferable. It is more preferable that the number of moles 1A is 1.02 to 1.06 times the number of moles 2A, or the number of moles 2A is 1.02 to 1.06 times the number of moles 1A. It is even more preferable that the number of moles 1A is 1.024 to 1.056 times the number of moles 2A, or the number of moles 2A is 1.024 to 1.056 times the number of moles 1A.
- each of the specific constituent units (I) to (VI) and the total of the constituent units (II) and the constituent units (IV) is converted into all the constituent units.
- it contains a specific amount and the molar ratio of the structural unit (VI) to the total of the structural unit (V) and the structural unit (VI) is within a specific range, both low melting point and heat resistance are compatible. Is enough.
- the total aromatic polyesteramide of the present invention contains 100 mol% of the constituent units (I) to (VI) in total with respect to all the constituent units.
- the total aromatic polyester amide in the present invention is polymerized by using a direct polymerization method, a transesterification method, or the like.
- a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, etc., or a combination of two or more of these is used, and a melt polymerization method or a combination of the melt polymerization method and the solid phase polymerization method is used. Is preferably used.
- an acylating agent for a polymerization monomer or a monomer having an activated terminal can be used as an acid chloride derivative during polymerization.
- the acylating agent include fatty acid anhydrides such as acetic anhydride.
- Various catalysts can be used for these polymerizations, and typical ones are potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and tris (2).
- 4-Pentandionato) Metal salt-based catalysts such as cobalt (III) and organic compound-based catalysts such as 1-methylimidazole and 4-dimethylaminopyridine can be mentioned.
- the reaction conditions are, for example, a reaction temperature of 200 to 380 ° C. and a final ultimate pressure of 0.1 to 760 Torr (that is, 13 to 101,080 Pa).
- the reaction temperature is 260 to 380 ° C., preferably 300 to 360 ° C.
- the final ultimate pressure is 1 to 100 Torr (that is, 133 to 13,300 Pa), preferably 1 to 50 Torr (that is, 133 to 6,670 Pa). ).
- all raw material monomers HBA, HNA, TA, IA, BP, and APAP
- an acylating agent HBA, HNA, TA, IA, BP, and APAP
- a catalyst can be charged in the same reaction vessel to initiate the reaction (one-stage method), or the raw material monomer HBA.
- HNA, BP, and APAP can be acylated with an acylating agent and then reacted with the carboxyl groups of TA and IA (two-stage method).
- melt polymerization is carried out by starting depressurization to a predetermined decompression degree.
- an inert gas is introduced, and the pressure is changed from a reduced pressure state to a normal pressure state to a predetermined pressure state, and the total aromatic polyesteramide is discharged from the reaction system.
- the total aromatic polyesteramide produced by the above polymerization method can further increase its molecular weight by solid-phase polymerization in which it is heated under normal pressure, reduced pressure, or in an inert gas.
- Preferred conditions for the solid phase polymerization reaction are a reaction temperature of 230 to 350 ° C., preferably 260 to 330 ° C., and a final ultimate pressure of 10 to 760 Torr (that is, 1,330 to 101,080 Pa).
- the total aromatic polyesteramide in the present invention exhibits optical anisotropy when melted. Exhibiting optical anisotropy when melted means that the total aromatic polyesteramide in the present invention is a liquid crystal resin.
- the fact that the total aromatic polyester amide is a liquid crystal resin is an indispensable element for the total aromatic polyester amide to have both thermal stability and easy processability.
- the total aromatic polyesteramide composed of the constituent units (I) to (VI) may not form an anisotropic molten phase depending on the constituent components and the sequence distribution in the polymer, but the liquid crystal in the present invention.
- the sex resin is limited to all aromatic polyesteramides that exhibit optical anisotropy when melted.
- melt anisotropy can be confirmed by a conventional polarization inspection method using an orthogonal polarizing element. More specifically, the confirmation of melt anisotropy can be carried out by melting a sample placed on a hot stage manufactured by Rinkamu using a polarizing microscope manufactured by Olympus and observing it at a magnification of 150 times in a nitrogen atmosphere.
- the liquid crystalline resin is optically anisotropic and transmits light when inserted between orthogonal polarizing elements. If the sample is optically anisotropic, polarized light is transmitted even in a molten static liquid state, for example.
- a nematic liquid crystal resin causes a significant decrease in viscosity above the melting point, generally, showing liquid crystallinity at a temperature above the melting point is an index of processability. It is preferable that the melting point is as high as possible from the viewpoint of heat resistance, but it is preferable that the melting point is 360 ° C. or lower in consideration of thermal deterioration during melt processing of the liquid crystal resin and the heating capacity of the molding machine. .. It is more preferably 300 to 360 ° C, and even more preferably 340 to 358 ° C.
- the melt viscosity of the total aromatic polyesteramide at a temperature 10 to 30 ° C. higher than the melting point of the total aromatic polyesteramide in the present invention and a shear rate of 1000 / sec is preferably 500 Pa ⁇ s or less, more preferably 0. It is .5 to 300 Pa ⁇ s, and even more preferably 1 to 100 Pa ⁇ s.
- the melt viscosity means the melt viscosity measured in accordance with ISO11443.
- the liquid crystal resin composition according to the present invention contains the above liquid crystal resin in an amount of 55 to 75% by mass based on the entire liquid crystal resin composition.
- the content of the liquid crystal resin is less than 55% by mass with respect to the entire liquid crystal resin composition, the fluidity of the liquid crystal resin composition tends to deteriorate, and the surface mount relay obtained from the liquid crystal resin composition is likely to deteriorate. It is not preferable because the airtightness of the molded body such as parts may decrease.
- the content of the liquid crystal resin is more than 75% by mass with respect to the entire liquid crystal resin composition, the effect of suppressing deformation of the molded body such as the surface mount relay component obtained from the liquid crystal resin composition, the airtightness, etc.
- the liquid crystal resin composition according to the present invention preferably contains the above liquid crystal resin in an amount of 57.5 to 72.5% by mass, more preferably 60 to 70% by mass, based on the entire liquid crystal resin composition. preferable.
- the aspect ratio of the fibrous wollastonite that is, the value of the average fiber length / average fiber diameter is 8 or more.
- the aspect ratio is preferably 10 to 25, more preferably 15 to 20, from the viewpoint of the effect of suppressing deformation of a molded body such as a surface mount relay component obtained from the liquid crystal resin composition according to the present invention. be.
- the fibrous wollastonite is not particularly limited, and for example, a known fibrous wollastonite can be used.
- the fibrous wollastonite may be used alone or in combination of two or more having different aspect ratios, average fiber lengths, average fiber diameters and the like.
- the average fiber diameter of the fibrous wollastonite is preferably 3.0 to 50 ⁇ m, and the more preferable average fiber diameter is 4.5 to 40 ⁇ m.
- a molded product such as a surface mount relay component obtained from the liquid crystal resin composition according to the present invention tends to have sufficient mechanical strength and deflection temperature under load.
- the average fiber diameter is 50 ⁇ m or less, the effect of suppressing raising of the surface of the molded product tends to be high.
- the average fiber diameter of (B) fibrous wollastonite in the liquid crystal resin composition is the fibrous state remaining after the liquid crystal resin composition is incinerated by heating at 600 ° C. for 2 hours. The wollastonite is observed with a scanning electron microscope, and the average of the measured fiber diameters of 100 fibrous wollastonite is adopted.
- the average fiber length of the fibrous wollastonite is preferably 30 to 800 ⁇ m, and the more preferable average fiber length is 50 to 600 ⁇ m.
- a molded product such as a surface mount relay component obtained from the liquid crystal resin composition according to the present invention tends to have sufficient mechanical strength and deflection temperature under load.
- the average fiber length is 800 ⁇ m or less, the effect of suppressing raising of the surface of the molded product tends to be high.
- the average fiber length of (B) fibrous wollastonite in the liquid crystal resin composition is the fibrous state remaining after the liquid crystal resin composition is incinerated by heating at 600 ° C. for 2 hours.
- the liquid crystal resin composition according to the present invention contains (B) fibrous wollastonite in an amount of 2.5 to 17.5% by mass based on the entire liquid crystal resin composition.
- the molded product such as a surface mount relay component obtained from the liquid crystal resin composition It is not preferable because the airtightness may decrease.
- the molded product such as a surface mount relay component obtained from the liquid crystal resin composition It is not preferable because the deformation suppressing effect may be reduced.
- the fibrous wollastonite (B) in the present invention is preferably contained in the liquid crystal resin composition in an amount of 3.5 to 14% by mass, preferably 5 to 10% by mass, based on the entire liquid crystal resin composition. Is more preferable.
- the liquid crystal resin composition according to the present invention contains mica. By containing mica in the liquid crystal resin composition according to the present invention, the fluidity of the liquid crystal resin composition can be easily improved, and a molded product in which deformation is suppressed can be obtained. Mica can be used alone or in combination of two or more.
- Mica is contained in an amount of 15 to 32.5% by mass based on the entire liquid crystal resin composition. If the content of mica is less than 15% by mass with respect to the entire liquid crystal resin composition, it is not preferable because the deformation of the molded product obtained from the liquid crystal resin composition is not sufficiently suppressed. When the content of mica is more than 32.5% by mass with respect to the entire liquid crystal resin composition, the fluidity of the liquid crystal resin composition tends to deteriorate, and molding of the liquid crystal resin composition may become difficult. It is not preferable because it has a property and may reduce the airtightness of a molded product such as a surface-mounted relay component obtained from a liquid crystal resin composition. Mica is preferably contained in the liquid crystal resin composition in an amount of 17 to 31.5% by mass, more preferably 20 to 30% by mass, based on the entire liquid crystal resin composition.
- Mica is a pulverized silicate mineral containing aluminum, potassium, magnesium, sodium, iron and the like.
- Examples of mica that can be used in the present invention include muscovite, phlogopite, biotite, artificial mica, and the like, and among these, muscovite is preferable in that it has a good hue and is inexpensive.
- a wet pulverization method and a dry pulverization method are known as methods for pulverizing minerals.
- the wet pulverization method is a method in which rough mica is roughly pulverized by a dry pulverizer, water is added, and the main pulverization is performed by wet pulverization in a slurry state, followed by dehydration and drying.
- the dry pulverization method is a low-cost and general method as compared with the wet pulverization method, it is easier to pulverize the mineral thinly and finely by using the wet pulverization method.
- It is preferable to use a thin and fine pulverized product in the present invention because mica having a preferable average particle size and thickness described later can be obtained. Therefore, in the present invention, it is preferable to use mica produced by the wet pulverization method.
- a coagulation sedimentation agent and / or a sedimentation aid is added to the object to be pulverized in order to improve the dispersion efficiency of the object to be pulverized.
- a coagulation sedimenting agent and the sedimentation aid that can be used in the present invention include polyaluminum chloride, aluminum sulfate, ferrous sulfate, ferric sulfate, copper chloride, polyiron sulfate, ferric chloride, and iron-silica inorganic high.
- coagulation sedimentation agents and sedimentation aids have an alkaline or acidic pH.
- the mica used in the present invention preferably does not use a coagulation sedimentation agent and / or a sedimentation aid during wet pulverization.
- the liquid crystal resin in the liquid crystal resin composition is less likely to be decomposed, and a large amount of gas is less likely to be generated or the molecular weight of the liquid crystal resin is less likely to decrease. Therefore, it is easy to maintain better performance of the obtained molded body such as a surface mount relay component.
- the mica that can be used in the present invention preferably has an average particle size of 10 to 100 ⁇ m measured by a microtrack laser diffraction method, and particularly preferably an average particle size of 20 to 80 ⁇ m.
- the average particle size of mica is 10 ⁇ m or more, the effect of improving the rigidity of the molded product is likely to be sufficient, which is preferable.
- the average particle size of mica is 100 ⁇ m or less, the rigidity of the molded product is likely to be sufficiently improved, and the weld strength is also likely to be sufficient, which is preferable.
- the average particle size of mica is 100 ⁇ m or less, it is easy to secure sufficient fluidity for molding the surface mount relay component of the present invention.
- the thickness of mica that can be used in the present invention is preferably 0.01 to 1 ⁇ m, particularly preferably 0.03 to 0.3 ⁇ m, as measured by observation with an electron microscope.
- the thickness of the mica is 0.01 ⁇ m or more, the mica is less likely to crack during the melt processing of the liquid crystal resin composition, and the rigidity of the molded product may be easily improved, which is preferable.
- the thickness of mica is 1 ⁇ m or less, the effect of improving the rigidity of the molded product is likely to be sufficient, which is preferable.
- the mica that can be used in the present invention may be surface-treated with a silane coupling agent or the like, and / or may be granulated with a binder to form granules.
- the total content of (B) fibrous wollastonite and (C) mica is 25 to 45% by mass with respect to the entire liquid crystal resin composition.
- the content is less than 25% by mass with respect to the entire liquid crystal resin composition, at least one of the effect of suppressing deformation of the molded body such as the surface mount relay component obtained from the liquid crystal resin composition, the airtightness, and the like. It is not preferable because there is a risk that the liquid crystal will drop.
- the content is preferably 27.5 to 37.5% by mass, more preferably 30 to 40% by mass, based on the entire liquid crystal resin composition.
- the liquid crystal resin composition according to the present invention includes other polymers, other fillers, and known substances generally added to synthetic resins, that is, antioxidants and ultraviolet rays, as long as the effects of the present invention are not impaired.
- Stabilizers such as absorbents, antistatic agents, flame retardants, colorants such as dyes and pigments, lubricants, mold release agents, crystallization accelerators, crystal nucleating agents and other other components are also added as appropriate according to the required performance. be able to.
- Other components may be used alone or in combination of two or more.
- liquid crystal resins other than (A) liquid crystal resin examples include liquid crystal resins other than (A) liquid crystal resin.
- the liquid crystal resin composition according to the present invention does not contain a liquid crystal resin other than (A) the liquid crystal resin, from at least any one of the deformation suppressing effect of the molded body and the airtightness.
- other polymers include epoxy group-containing copolymers.
- the liquid crystal resin composition according to the present invention is less likely to generate gas due to thermal decomposition of the epoxy group-containing copolymer and to cause the molded product such as a surface-mounted relay component to swell. Is preferably free of epoxy group-containing copolymers.
- the other filler means a filler other than fibrous talc talc having an aspect ratio of 8 or more, mica, and carbon black, and for example, a fibrous filler other than fibrous talc talc having an aspect ratio of 8 or more (for example). , Fibrous wollastonite with an aspect ratio of less than 8 and milled fiber), and plate-like fillers other than mica (for example, talc).
- the liquid crystal resin composition according to the present invention is a fibrous wollastonite having an aspect ratio of less than 8. It is preferable that it does not contain milled fiber and talc.
- the method for producing a liquid crystal resin composition according to the present invention is not particularly limited as long as the components in the liquid crystal resin composition can be uniformly mixed, and can be appropriately selected from the conventionally known methods for producing a resin composition.
- each component is melt-kneaded and extruded using a melt-kneading device such as a single-screw or twin-screw extruder, and then the obtained liquid crystal resin composition is processed into a desired form such as powder, flakes, and pellets. There is a way to do it.
- liquid crystal resin composition according to the present invention has excellent fluidity, the minimum filling pressure at the time of molding is unlikely to be excessive, and parts for surface mount relays and the like can be preferably molded.
- the melt viscosity of the liquid crystal resin composition measured according to ISO11443 at a temperature 10 to 30 ° C. higher than the melting point of the liquid crystal resin at a shear rate of 1000 / sec is 500 Pa ⁇ s or less (more preferably 5 Pa ⁇ s or more). It is preferable that the temperature is 100 Pa ⁇ s or less) because it is easy to secure the fluidity of the liquid crystal resin composition and the filling pressure is unlikely to become excessive at the time of molding the surface-mounted relay component.
- the surface mount relay component according to the present invention By molding the liquid crystal resin composition according to the present invention, the surface mount relay component according to the present invention can be obtained.
- the surface mount relay component according to the present invention is excellent in heat resistance and airtightness, and deformation and desorption of filler are suppressed. Since the surface mount relay according to the present invention includes the above parts, it can (1) have excellent heat resistance and can withstand solder reflow processing, and (2) can maintain airtightness and shape even after solder reflow processing. , (3) Desorption of filler is suppressed, and functional disorders such as poor continuity are less likely to occur.
- FIG. 1 (a) is a perspective view schematically showing an embodiment of a surface mount relay according to the present invention
- 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, a polaron block 5, and a terminal 6.
- the base 2 includes a terminal 6 protruding from the base 2.
- the case 3 is arranged on the outer peripheral portion of the upper surface of the base 2.
- the coil block 4 and the polaron block 5 are arranged in this order in the central portion of the upper surface of the base 2.
- the case 3 is arranged so as to cover the outer peripheral portion of the upper surface of the base 2 and the coil block 4 and the polaron block 5.
- the coil block 4 and the tangent block 5 are housed in a hollow container-shaped space formed by the base 2 and the case 3.
- the coil block 4 includes a bobbin 41, a coil 42, and an iron core 43, and is arranged at the center of the upper surface of the base 2.
- the bobbin 41 has a cylindrical portion penetrating in the long axis direction, and a coil 42 electrically connected to one end of a part of the terminal 6 is wound around the outer circumference of the bobbin 41, and the cylindrical portion of the bobbin 41 is wound.
- the iron core 43 is inserted in the.
- the polaron block 5 includes a polaron connecting portion 51 and a polaron 52 extending from the polaron connecting portion 51 in the opposite directions along the long axis direction of the bobbin 41, and is arranged on the coil block 4.
- the polaron 52 is electrically connected to one end of another portion of the terminal 6.
- One end of the terminal 6 is electrically connected to the coil 42 or the polaron 52, and the other end is electrically conductively connected to the printed circuit board 7 described later.
- the terminal 6 protrudes from the base 2 and is soldered to the printed circuit board 7 as described later.
- the base 2, the case 3, and the bobbin 41 are related to the present invention in consideration of the fact that they are excellent in heat resistance and airtightness and can be formed as a molded body in which deformation and desorption of filler are suppressed. It is preferably composed of a liquid crystal resin composition. That is, examples of the surface mount relay component according to the present invention include a base, a case, and a bobbin.
- the coil block 4 and the polaron block 5 are arranged in this order in the central portion of the upper surface of the base 2, and then the case 3 is arranged on the outer peripheral portion of the upper surface of the base 2, and the base 2 and the case are arranged. It can be manufactured by adhering 3 and 3 with an adhesive.
- the method of mounting the surface mount relay 1 on the printed circuit board 7 will be described.
- the terminal 6 protruding vertically from the surface mount relay 1 is bent at a right angle so that the soldering surface is parallel to the surface mount relay 1. Therefore, in the surface mount relay 1, the terminal 6 is placed on a solder pad (not shown) provided on the conductor pattern 8 on the surface of the printed circuit board 7 without providing a hole in the printed circuit board 7, and the solder reflow process is performed. By doing so, it is electrically conductively fixed to the printed circuit board 7.
- FIG. 2A the case where the tip of the terminal 6 protruding vertically from the surface mount relay 1 is bent at a right angle to the outside of the surface mount relay 1 is shown.
- FIG. 2B the tip of the terminal 6 protruding vertically from the surface mount relay 1 may be bent at a right angle to the inside of the surface mount relay 1.
- the liquid crystal resins LCP1 to LCP4 were manufactured as follows. At that time, the melting point and the melt viscosity of the pellets were measured under the following conditions.
- the temperature of the reaction system was raised to 140 ° C., and the reaction was carried out at 140 ° C. for 1 hour. Then, the temperature is further raised to 360 ° C. over 5.5 hours, and then the pressure is reduced to 5 Torr (that is, 667 Pa) over 20 minutes while distilling acetic acid, excess acetic anhydride, and other low boiling points. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to bring the polymer into a pressurized state from a reduced pressure state through a normal pressure state, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized and pelletized. The obtained pellet had a melting point of 355 ° C. and a melt viscosity of 10 Pa ⁇ s.
- the temperature is further raised to 360 ° C. over 5.5 hours, and then the pressure is reduced to 5 Torr (that is, 667 Pa) over 30 minutes while distilling acetic acid, excess acetic anhydride, and other low boiling points.
- Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to bring the polymer into a pressurized state from a reduced pressure state through a normal pressure state, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized and pelletized. The obtained pellets were heat-treated at 300 ° C. for 3 hours under a nitrogen stream. The melting point of the pellet was 348 ° C., and the melt viscosity was 9 Pa ⁇ s.
- Fibrous filler Fibrous wollastonite 1 NYGLOS 8 (manufactured by NYCO Materials, aspect ratio 17, average fiber length 136 ⁇ m, average fiber diameter 8 ⁇ m)
- Fibrous wollastonite 2 NYAD 325 (manufactured by NYCO Materials, aspect ratio 5, average fiber length 50 ⁇ m, average fiber diameter 5 ⁇ m)
- Glass fiber ECS03T-786H manufactured by Nippon Electric Glass Co., Ltd., chopped strand / plate-shaped filler mica with fiber diameter 10 ⁇ m and length 3 mm; AB-25S manufactured by Yamaguchi Mica Industry Co., Ltd., average particle diameter 25 ⁇ m Talc; Crown Talc PP manufactured by Matsumura Sangyo Co., Ltd., average particle size 10
- the extrusion conditions for obtaining the liquid crystal resin composition are as follows. [Extrusion conditions] The temperature of the cylinder provided in the main feed port was 250 ° C., and the temperatures of the other cylinders were all as follows. All liquid crystal resin was supplied from the main feed port. The filler was supplied from the side feed port. Other cylinder temperature: 360 ° C (Examples 1 to 3 and Comparative Examples 1 to 7 and 11) 350 ° C (Comparative Example 8) 370 ° C (Comparative Examples 9 and 10)
- the minimum injection filling pressure at which a good molded body could be obtained when the above relay case was injection molded was measured as the minimum filling pressure.
- the melt viscosity, the deflection temperature under load, the bending strength, the bending strain, and the flexural modulus show good values
- the minimum filling pressure of the relay case is 80 MPa or less
- the relay case The evaluations of deformation, swelling during reflow of the relay case, detachment of the relay case filler, and airtightness of the relay case were all good. Therefore, the liquid crystal resin composition according to the present invention has excellent fluidity, and the molded product such as a surface mount relay component obtained from this liquid crystal resin composition has excellent heat resistance and airtightness, and is deformed and filled. It was confirmed that desorption was suppressed. Therefore, the liquid crystal resin composition can be suitably used for manufacturing a surface mount relay component and a surface mount relay.
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Abstract
Description
前記(A)液晶性樹脂は、必須の構成成分として、下記構成単位(I)~(VI)からなり、
全構成単位に対して構成単位(I)の含有量は50~70モル%であり、
全構成単位に対して構成単位(II)の含有量は0.5モル%以上4.5モル%未満であり、
全構成単位に対して構成単位(III)の含有量は10.25~22.25モル%であり、
全構成単位に対して構成単位(IV)の含有量は0.5モル%以上4.5モル%未満であり、
全構成単位に対して構成単位(V)の含有量は5.75~23.75モル%であり、
全構成単位に対して構成単位(VI)の含有量は1~7モル%であり、
全構成単位に対して構成単位(II)と構成単位(IV)との合計の含有量は1モル%以上5モル%未満であり、
全構成単位に対して構成単位(I)~(VI)の合計の含有量は100モル%であり、
構成単位(V)と構成単位(VI)との合計に対する構成単位(VI)のモル比が0.04~0.37である、溶融時に光学的異方性を示す全芳香族ポリエステルアミドであり、
前記(B)繊維状ウォラストナイトのアスペクト比は、8以上であり、
前記液晶性樹脂組成物全体に対して、
前記(A)液晶性樹脂の含有量は、55~75質量%、
前記(B)繊維状ウォラストナイトの含有量は、2.5~17.5質量%、
前記(C)マイカの含有量は、15~32.5質量%、
前記(B)繊維状ウォラストナイト及び前記(C)マイカの合計の含有量は、25~45質量%
であり、
前記表面実装リレーは、ベースと、前記ベースから突出する端子とを備え、前記端子をプリント基板に半田付けするようにした表面実装リレーである液晶性樹脂組成物。
The liquid crystal resin (A) is composed of the following structural units (I) to (VI) as essential constituents.
The content of the constituent unit (I) is 50 to 70 mol% with respect to all the constituent units.
The content of the constituent unit (II) is 0.5 mol% or more and less than 4.5 mol% with respect to all the constituent units.
The content of the constituent unit (III) is 10.25 to 22.25 mol% with respect to all the constituent units.
The content of the constituent unit (IV) is 0.5 mol% or more and less than 4.5 mol% with respect to all the constituent units.
The content of the constituent unit (V) is 5.75 to 23.75 mol% with respect to all the constituent units.
The content of the constituent unit (VI) is 1 to 7 mol% with respect to all the constituent units.
The total content of the constituent unit (II) and the constituent unit (IV) with respect to all the constituent units is 1 mol% or more and less than 5 mol%.
The total content of the constituent units (I) to (VI) is 100 mol% with respect to all the constituent units.
A total aromatic polyesteramide exhibiting optical anisotropy when melted, wherein the molar ratio of the structural unit (VI) to the total of the structural unit (V) and the structural unit (VI) is 0.04 to 0.37. ,
The aspect ratio of the fibrous wollastonite (B) is 8 or more.
For the entire liquid crystal resin composition,
The content of the liquid crystal resin (A) is 55 to 75% by mass.
The content of the fibrous wollastonite (B) is 2.5 to 17.5% by mass.
The content of (C) mica is 15 to 32.5% by mass,
The total content of the (B) fibrous wollastonite and the (C) mica is 25 to 45% by mass.
And
The surface mount relay is a liquid crystal resin composition which is a surface mount relay having a base and terminals protruding from the base, and the terminals are soldered to a printed circuit board.
本発明に係る表面実装リレー用液晶性樹脂組成物は、特定の液晶性樹脂と、繊維状ウォラストナイトと、マイカとを所定量ずつ含み、繊維状ウォラストナイトのアスペクト比は、8以上であり、前記表面実装リレーは、ベースと、前記ベースから突出する端子とを備え、前記端子をプリント基板に半田付けするようにした表面実装リレーである。以下、本発明に係る液晶性樹脂組成物を構成する成分について説明する。 <Liquid crystal resin composition for surface mount relay>
The liquid crystal resin composition for a surface mount relay according to the present invention contains a specific liquid crystal resin, fibrous wollastonite, and mica in predetermined amounts, and the aspect ratio of the fibrous wollastonite is 8 or more. The surface mount relay is a surface mount relay having a base and terminals protruding from the base, and the terminals are soldered to a printed circuit board. Hereinafter, the components constituting the liquid crystal resin composition according to the present invention will be described.
本発明に係る液晶性樹脂組成物には、上記全芳香族ポリエステルアミドである液晶性樹脂が含まれる。上記全芳香族ポリエステルアミドは、融点が低いため、加工温度を低くすることができ、溶融時の分解ガスの発生が抑制される。液晶性樹脂は、1種単独で又は2種以上組み合わせて使用することができる。 [Liquid crystal resin]
The liquid crystal resin composition according to the present invention contains the liquid crystal resin which is the above-mentioned total aromatic polyester amide. Since the total aromatic polyester amide has a low melting point, the processing temperature can be lowered and the generation of decomposition gas at the time of melting is suppressed. The liquid crystal resin can be used alone or in combination of two or more.
(B)繊維状ウォラストナイトのアスペクト比、即ち、平均繊維長/平均繊維径の値は8以上である。上記アスペクト比は、本発明に係る液晶性樹脂組成物から得られる表面実装リレー用部品等の成形体の変形抑制効果等の観点から、好ましくは10~25であり、より好ましくは15~20である。 [(B) Fibrous Wollastonite]
(B) The aspect ratio of the fibrous wollastonite, that is, the value of the average fiber length / average fiber diameter is 8 or more. The aspect ratio is preferably 10 to 25, more preferably 15 to 20, from the viewpoint of the effect of suppressing deformation of a molded body such as a surface mount relay component obtained from the liquid crystal resin composition according to the present invention. be.
本発明に係る液晶性樹脂組成物には、マイカが含まれる。本発明に係る液晶性樹脂組成物にマイカが含まれることにより、液晶性樹脂組成物の流動性が向上しやすく、また、変形が抑制された成形体を得ることができる。マイカは、1種単独で又は2種以上組み合わせて使用することができる。 [(C) Mica]
The liquid crystal resin composition according to the present invention contains mica. By containing mica in the liquid crystal resin composition according to the present invention, the fluidity of the liquid crystal resin composition can be easily improved, and a molded product in which deformation is suppressed can be obtained. Mica can be used alone or in combination of two or more.
マイカとは、アルミニウム、カリウム、マグネシウム、ナトリウム、鉄等を含んだケイ酸塩鉱物の粉砕物である。本発明において使用できるマイカとしては、白雲母、金雲母、黒雲母、人造雲母等が挙げられ、これらのうち色相が良好であり、低価格であるという点で白雲母が好ましい。 [Mica]
Mica is a pulverized silicate mineral containing aluminum, potassium, magnesium, sodium, iron and the like. Examples of mica that can be used in the present invention include muscovite, phlogopite, biotite, artificial mica, and the like, and among these, muscovite is preferable in that it has a good hue and is inexpensive.
本発明に係る液晶性樹脂組成物には、本発明の効果を害さない範囲で、その他の重合体、その他の充填剤、一般に合成樹脂に添加される公知の物質、即ち、酸化防止剤や紫外線吸収剤等の安定剤、帯電防止剤、難燃剤、染料や顔料等の着色剤、潤滑剤、離型剤、結晶化促進剤、結晶核剤等のその他の成分も要求性能に応じ適宜添加することができる。その他の成分は1種単独で用いても2種以上を組み合わせて用いてもよい。 [Other ingredients]
The liquid crystal resin composition according to the present invention includes other polymers, other fillers, and known substances generally added to synthetic resins, that is, antioxidants and ultraviolet rays, as long as the effects of the present invention are not impaired. Stabilizers such as absorbents, antistatic agents, flame retardants, colorants such as dyes and pigments, lubricants, mold release agents, crystallization accelerators, crystal nucleating agents and other other components are also added as appropriate according to the required performance. be able to. Other components may be used alone or in combination of two or more.
本発明に係る液晶性樹脂組成物を成形することにより、本発明に係る表面実装リレー用部品を得ることができる。本発明に係る表面実装リレー用部品は、耐熱性及び気密性に優れ、変形とフィラーの脱離とが抑制されている。本発明に係る表面実装リレーは、上記部品を備えるため、(1)耐熱性に優れ、半田リフロー処理に耐えることができ、(2)半田リフロー処理後でも気密性及び形状を保持することができ、(3)フィラーの脱離が抑制され、導通不良等の機能障害が発生しにくい。 <Surface mount relay parts and surface mount relays>
By molding the liquid crystal resin composition according to the present invention, the surface mount relay component according to the present invention can be obtained. The surface mount relay component according to the present invention is excellent in heat resistance and airtightness, and deformation and desorption of filler are suppressed. Since the surface mount relay according to the present invention includes the above parts, it can (1) have excellent heat resistance and can withstand solder reflow processing, and (2) can maintain airtightness and shape even after solder reflow processing. , (3) Desorption of filler is suppressed, and functional disorders such as poor continuity are less likely to occur.
下記の実施例及び比較例において、液晶性樹脂LCP1~LCP4は、以下の通りにして製造した。その際、ペレットの融点及び溶融粘度の測定は、それぞれ下記の条件で行った。 <Examples 1 to 3 and Comparative Examples 1 to 11>
In the following Examples and Comparative Examples, the liquid crystal resins LCP1 to LCP4 were manufactured as follows. At that time, the melting point and the melt viscosity of the pellets were measured under the following conditions.
TAインスツルメント社製DSCにて、液晶性樹脂を室温から20℃/分の昇温条件で加熱した際に観測される吸熱ピーク温度(Tm1)の測定後、(Tm1+40)℃の温度で2分間保持した後、20℃/分の降温条件で室温まで一旦冷却した後、再度、20℃/分の昇温条件で加熱した際に観測される吸熱ピークの温度を測定した。 [Measurement of melting point]
After measuring the heat absorption peak temperature (Tm1) observed when the liquid crystal resin is heated from room temperature to 20 ° C./min with a DSC manufactured by TA Instruments, it is 2 at a temperature of (Tm1 + 40) ° C. After holding for 1 minute, the temperature of the heat absorption peak observed when the temperature was once cooled to room temperature under the condition of lowering temperature of 20 ° C./min and then heated again under the condition of raising temperature of 20 ° C./min was measured.
(株)東洋精機製作所製キャピログラフ1B型を使用し、液晶性樹脂の融点よりも10~30℃高い温度で、内径1mm、長さ20mmのオリフィスを用いて、剪断速度1000/秒で、ISO11443に準拠して、液晶性樹脂の溶融粘度を測定した。なお、測定温度は、LCP1については360℃、LCP2については350℃、LCP3については380℃、LCP4については380℃であった。 [Measurement of melt viscosity]
Using Capillograph 1B type manufactured by Toyo Seiki Seisakusho Co., Ltd., using an orifice with an inner diameter of 1 mm and a length of 20 mm at a temperature 10 to 30 ° C higher than the melting point of the liquid crystal resin, to ISO11443 at a shear rate of 1000 / sec. According to this, the melt viscosity of the liquid crystal resin was measured. The measured temperature was 360 ° C. for LCP1, 350 ° C. for LCP2, 380 ° C. for LCP3, and 380 ° C. for LCP4.
撹拌機、還流カラム、モノマー投入口、窒素導入口、減圧/流出ラインを備えた重合容器に、以下の原料モノマー、脂肪酸金属塩触媒、アシル化剤を仕込み、窒素置換を開始した。
(I)4-ヒドロキシ安息香酸:1385g(60モル%)(HBA)
(II)6-ヒドロキシ-2-ナフトエ酸:88g(2.8モル%)(HNA)
(III)1,4-フェニレンジカルボン酸:504g(18.15モル%)(TA)
(IV)1,3-フェニレンジカルボン酸:19g(0.7モル%)(IA)
(V)4,4’-ジヒドロキシビフェニル:415g(13.35モル%)(BP)
(VI)N-アセチル-p-アミノフェノール:126g(5モル%)(APAP)
酢酸カリウム触媒:120mg
無水酢酸:1662g
重合容器に原料を仕込んだ後、反応系の温度を140℃に上げ、140℃で1時間反応させた。その後、更に360℃まで5.5時間かけて昇温し、そこから20分かけて10Torr(即ち、1330Pa)まで減圧して、酢酸、過剰の無水酢酸、その他の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して減圧状態から常圧を経て加圧状態にして、重合容器の下部からポリマーを排出し、ストランドをペレタイズしてペレット化した。得られたペレットの融点は345℃、溶融粘度は10Pa・sであった。 (Manufacturing method of LCP1)
The following raw material monomers, fatty acid metal salt catalysts, and acylating agents were charged into a polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a depressurization / outflow line, and nitrogen substitution was started.
(I) 4-Hydroxybenzoic acid: 1385 g (60 mol%) (HBA)
(II) 6-Hydroxy-2-naphthoic acid: 88 g (2.8 mol%) (HNA)
(III) 1,4-phenylenedicarboxylic acid: 504 g (18.15 mol%) (TA)
(IV) 1,3-phenylenedicarboxylic acid: 19 g (0.7 mol%) (IA)
(V) 4,4'-Dihydroxybiphenyl: 415 g (13.35 mol%) (BP)
(VI) N-Acetyl-p-Aminophenol: 126 g (5 mol%) (APAP)
Potassium acetate catalyst: 120 mg
Acetic anhydride: 1662 g
After charging the raw materials into the polymerization vessel, the temperature of the reaction system was raised to 140 ° C., and the reaction was carried out at 140 ° C. for 1 hour. Then, the temperature is further raised to 360 ° C. over 5.5 hours, and then the pressure is reduced to 10 Torr (that is, 1330 Pa) over 20 minutes while distilling acetic acid, excess acetic anhydride, and other low boiling points. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to bring the polymer into a pressurized state from a reduced pressure state through a normal pressure state, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized and pelletized. The obtained pellet had a melting point of 345 ° C. and a melt viscosity of 10 Pa · s.
撹拌機、還流カラム、モノマー投入口、窒素導入口、減圧/流出ラインを備えた重合容器に、以下の原料モノマー、脂肪酸金属塩触媒、アシル化剤を仕込み、窒素置換を開始した。
(I)4-ヒドロキシ安息香酸1380g(60モル%)(HBA)
(II)6-ヒドロキシ-2-ナフトエ酸157g(5モル%)(HNA)
(III)1,4-フェニレンジカルボン酸484g(17.5モル%)(TA)
(V)4,4’-ジヒドロキシビフェニル388g(12.5モル%)(BP)
(VI)N-アセチル-p-アミノフェノール126g(5モル%)(APAP)
酢酸カリウム触媒110mg
無水酢酸1659g
重合容器に原料を仕込んだ後、反応系の温度を140℃に上げ、140℃で1時間反応させた。その後、更に340℃まで4.5時間かけて昇温し、そこから15分かけて10Torr(即ち、1330Pa)まで減圧して、酢酸、過剰の無水酢酸、その他の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して減圧状態から常圧を経て加圧状態にして、重合容器の下部からポリマーを排出し、ストランドをペレタイズしてペレット化した。得られたペレットの融点は336℃、溶融粘度は20Pa・sであった。 (Manufacturing method of LCP2)
The following raw material monomers, fatty acid metal salt catalysts, and acylating agents were charged into a polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a depressurization / outflow line, and nitrogen substitution was started.
(I) 4-Hydroxybenzoic acid 1380 g (60 mol%) (HBA)
(II) 157 g (5 mol%) of 6-hydroxy-2-naphthoic acid (HNA)
(III) 484 g (17.5 mol%) of 1,4-phenylenedicarboxylic acid (TA)
(V) 4,4'-Dihydroxybiphenyl 388 g (12.5 mol%) (BP)
(VI) N-Acetyl-p-Aminophenol 126 g (5 mol%) (APAP)
Potassium acetate catalyst 110 mg
Acetic anhydride 1659g
After charging the raw materials into the polymerization vessel, the temperature of the reaction system was raised to 140 ° C., and the reaction was carried out at 140 ° C. for 1 hour. Then, the temperature is further raised to 340 ° C. over 4.5 hours, and then the pressure is reduced to 10 Torr (that is, 1330 Pa) over 15 minutes while distilling acetic acid, excess acetic anhydride, and other low boiling points. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to bring the polymer into a pressurized state from a reduced pressure state through a normal pressure state, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized and pelletized. The obtained pellet had a melting point of 336 ° C. and a melt viscosity of 20 Pa · s.
撹拌機、還流カラム、モノマー投入口、窒素導入口、減圧/流出ラインを備えた重合容器に、以下の原料モノマー、脂肪酸金属塩触媒、アシル化剤を仕込み、窒素置換を開始した。
(I)4-ヒドロキシ安息香酸:1040g(48モル%)(HBA)
(II)6-ヒドロキシ-2-ナフトエ酸:89g(3モル%)(HNA)
(III)1,4-フェニレンジカルボン酸:547g(21モル%)(TA)
(IV)1,3-フェニレンジカルボン酸:91g(3.5モル%)(IA)
(V)4,4’-ジヒドロキシビフェニル:716g(24.5モル%)(BP)
酢酸カリウム触媒:110mg
無水酢酸:1644g (Manufacturing method of LCP3)
The following raw material monomers, fatty acid metal salt catalysts, and acylating agents were charged into a polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a depressurization / outflow line, and nitrogen substitution was started.
(I) 4-Hydroxybenzoic acid: 1040 g (48 mol%) (HBA)
(II) 6-Hydroxy-2-naphthoic acid: 89 g (3 mol%) (HNA)
(III) 1,4-phenylenedicarboxylic acid: 547 g (21 mol%) (TA)
(IV) 1,3-phenylenedicarboxylic acid: 91 g (3.5 mol%) (IA)
(V) 4,4'-Dihydroxybiphenyl: 716 g (24.5 mol%) (BP)
Potassium acetate catalyst: 110 mg
Acetic anhydride: 1644 g
撹拌機、還流カラム、モノマー投入口、窒素導入口、減圧/流出ラインを備えた重合容器に、以下の原料モノマー、脂肪酸金属塩触媒、アシル化剤を仕込み、窒素置換を開始した。
(I)4-ヒドロキシ安息香酸:37g(2モル%)(HBA)
(II)6-ヒドロキシ-2-ナフトエ酸:1218g(48モル%)(HNA)
(III)1,4-フェニレンジカルボン酸:560g(25モル%)(TA)
(V)4,4’-ジヒドロキシビフェニル:628g(25モル%)(BP)
酢酸カリウム触媒:165mg
無水酢酸:1432g
重合容器に原料を仕込んだ後、反応系の温度を140℃に上げ、140℃で1時間反応させた。その後、更に360℃まで5.5時間かけて昇温し、そこから30分かけて5Torr(即ち、667Pa)まで減圧して、酢酸、過剰の無水酢酸、その他の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して減圧状態から常圧を経て加圧状態にして、重合容器の下部からポリマーを排出し、ストランドをペレタイズしてペレット化した。得られたペレットについて、窒素気流下、300℃で3時間の熱処理を行った。ペレットの融点は348℃、溶融粘度は9Pa・sであった。 (Manufacturing method of LCP4)
The following raw material monomers, fatty acid metal salt catalysts, and acylating agents were charged into a polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a depressurization / outflow line, and nitrogen substitution was started.
(I) 4-Hydroxybenzoic acid: 37 g (2 mol%) (HBA)
(II) 6-Hydroxy-2-naphthoic acid: 1218 g (48 mol%) (HNA)
(III) 1,4-phenylenedicarboxylic acid: 560 g (25 mol%) (TA)
(V) 4,4'-Dihydroxybiphenyl: 628 g (25 mol%) (BP)
Potassium acetate catalyst: 165 mg
Acetic anhydride: 1432 g
After charging the raw materials into the polymerization vessel, the temperature of the reaction system was raised to 140 ° C., and the reaction was carried out at 140 ° C. for 1 hour. Then, the temperature is further raised to 360 ° C. over 5.5 hours, and then the pressure is reduced to 5 Torr (that is, 667 Pa) over 30 minutes while distilling acetic acid, excess acetic anhydride, and other low boiling points. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to bring the polymer into a pressurized state from a reduced pressure state through a normal pressure state, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized and pelletized. The obtained pellets were heat-treated at 300 ° C. for 3 hours under a nitrogen stream. The melting point of the pellet was 348 ° C., and the melt viscosity was 9 Pa · s.
・繊維状充填剤
繊維状ウォラストナイト1:NYGLOS 8(NYCO Materials社製、アスペクト比17、平均繊維長136μm、平均繊維径8μm)
繊維状ウォラストナイト2:NYAD 325(NYCO Materials社製、アスペクト比5、平均繊維長50μm、平均繊維径5μm)
ミルドファイバー:日東紡(株)製PF70E001、繊維径10μm、平均繊維長70μm(メーカー公称値)
ガラス繊維:日本電気硝子(株)製ECS03T-786H、繊維径10μm、長さ3mmのチョプドストランド
・板状充填剤
マイカ;(株)山口雲母工業製AB-25S、平均粒子径25μm
タルク;松村産業(株)製クラウンタルクPP、平均粒子径10μm (Ingredients other than liquid crystal resin)
Fibrous filler Fibrous wollastonite 1: NYGLOS 8 (manufactured by NYCO Materials, aspect ratio 17, average fiber length 136 μm,
Fibrous wollastonite 2: NYAD 325 (manufactured by NYCO Materials,
Mild fiber: PF70E001 manufactured by Nitto Boseki Co., Ltd., fiber diameter 10 μm, average fiber length 70 μm (manufacturer's nominal value)
Glass fiber: ECS03T-786H manufactured by Nippon Electric Glass Co., Ltd., chopped strand / plate-shaped filler mica with fiber diameter 10 μm and
Talc; Crown Talc PP manufactured by Matsumura Sangyo Co., Ltd., average particle size 10 μm
[押出条件]
メインフィード口に設けられたシリンダーの温度を250℃とし、他のシリンダーの温度はすべて下記の通りとした。液晶性樹脂はすべてをメインフィード口から供給した。また、充填剤はサイドフィード口から供給した。
他のシリンダー温度:
360℃(実施例1~3並びに比較例1~7及び11)
350℃(比較例8)
370℃(比較例9及び10) Each liquid crystal resin obtained above and a component other than the liquid crystal resin described above were mixed using a twin-screw extruder to obtain a liquid crystal resin composition. The blending amount of each component is as shown in Tables 1 and 2. In the following, "%" regarding the blending amount in the table indicates mass%. The extrusion conditions for obtaining the liquid crystal resin composition are as follows.
[Extrusion conditions]
The temperature of the cylinder provided in the main feed port was 250 ° C., and the temperatures of the other cylinders were all as follows. All liquid crystal resin was supplied from the main feed port. The filler was supplied from the side feed port.
Other cylinder temperature:
360 ° C (Examples 1 to 3 and Comparative Examples 1 to 7 and 11)
350 ° C (Comparative Example 8)
370 ° C (Comparative Examples 9 and 10)
(株)東洋精機製作所製キャピログラフ1B型を使用し、液晶性樹脂の融点よりも10~30℃高い温度で、内径1mm、長さ20mmのオリフィスを用いて、剪断速度1000/秒で、ISO11443に準拠して、液晶性樹脂組成物の溶融粘度を測定した。なお、測定温度は、LCP1を使用した液晶性樹脂組成物については360℃、LCP2を使用した液晶性樹脂組成物については350℃、LCP3を使用した液晶性樹脂組成物については380℃、LCP4を使用した液晶性樹脂組成物については380℃であった。結果を表1及び表2に示す。 (Measurement of melt viscosity of liquid crystal resin composition)
Using Capillograph 1B type manufactured by Toyo Seiki Seisakusho Co., Ltd., using an orifice with an inner diameter of 1 mm and a length of 20 mm at a temperature 10 to 30 ° C higher than the melting point of the liquid crystal resin, to ISO11443 at a shear rate of 1000 / sec. According to this, the melt viscosity of the liquid crystal resin composition was measured. The measurement temperature was 360 ° C. for the liquid crystal resin composition using LCP1, 350 ° C. for the liquid crystal resin composition using LCP2, 380 ° C. for the liquid crystal resin composition using LCP3, and LCP4. The temperature of the liquid crystal resin composition used was 380 ° C. The results are shown in Tables 1 and 2.
下記成形条件で、液晶性樹脂組成物を射出成形して成形体を得、ISO75-1,2に準拠して荷重たわみ温度を測定した。荷重たわみ温度を成形体の耐熱性を表す指標として用いた。
[成形条件]
成形機:住友重機械工業(株)、SE100DU
シリンダー温度:
360℃(実施例1~3並びに比較例1~7及び11)
350℃(比較例8)
370℃(比較例9及び10)
金型温度:90℃
射出速度:33mm/sec (Deflection temperature under load)
Under the following molding conditions, the liquid crystal resin composition was injection-molded to obtain a molded product, and the deflection temperature under load was measured in accordance with ISO75-1 and ISO75-1. The deflection temperature under load was used as an index showing the heat resistance of the molded product.
[Molding condition]
Molding machine: Sumitomo Heavy Industries, Ltd., SE100DU
Cylinder temperature:
360 ° C (Examples 1 to 3 and Comparative Examples 1 to 7 and 11)
350 ° C (Comparative Example 8)
370 ° C (Comparative Examples 9 and 10)
Mold temperature: 90 ° C
Injection speed: 33 mm / sec
下記成形条件で、液晶性樹脂組成物を射出成形して0.8mm厚の成形体を得、ASTM D790に準拠し、曲げ強度、曲げ歪、及び曲げ弾性率を測定した。
[成形条件]
成形機:住友重機械工業(株)、SE100DU
シリンダー温度:
360℃(実施例1~3並びに比較例1~7及び11)
350℃(比較例8)
370℃(比較例9及び10)
金型温度:90℃
射出速度:33mm/sec (Bending test)
The liquid crystal resin composition was injection-molded under the following molding conditions to obtain a molded product having a thickness of 0.8 mm, and the bending strength, bending strain, and bending elastic modulus were measured according to ASTM D790.
[Molding condition]
Molding machine: Sumitomo Heavy Industries, Ltd., SE100DU
Cylinder temperature:
360 ° C (Examples 1 to 3 and Comparative Examples 1 to 7 and 11)
350 ° C (Comparative Example 8)
370 ° C (Comparative Examples 9 and 10)
Mold temperature: 90 ° C
Injection speed: 33 mm / sec
下記成形条件で、液晶性樹脂組成物を射出成形し(ゲート:ピンゲート、ゲートサイズ:φ0.3mm)、図3(a)及び図3(b)に示すような、リレーケースを得た。
[成形条件]
成形機:住友重機械工業(株)、SE30DUZ
シリンダー温度:
360℃(実施例1~3並びに比較例1~7及び11)
350℃(比較例8)
370℃(比較例9及び10)
金型温度:90℃
射出速度:200mm/sec (Minimum filling pressure in relay case)
The liquid crystal resin composition was injection-molded under the following molding conditions (gate: pin gate, gate size: φ0.3 mm) to obtain a relay case as shown in FIGS. 3 (a) and 3 (b).
[Molding condition]
Molding machine: Sumitomo Heavy Industries, Ltd., SE30DUZ
Cylinder temperature:
360 ° C (Examples 1 to 3 and Comparative Examples 1 to 7 and 11)
350 ° C (Comparative Example 8)
370 ° C (Comparative Examples 9 and 10)
Mold temperature: 90 ° C
Injection speed: 200 mm / sec
上述の通りにして得た図3(a)及び図3(b)に示すリレーケースの底面の寸法をミツトヨ製クイックビジョン404PROCNC画像測定機により測定した。測定は、下記条件で行ったリフローの前後で行い、以下の基準に従って評価した。
○(良好):リフロー前後の寸法変化の絶対値がリフロー前の寸法の0.6%未満であった。
×(不良):リフロー前後の寸法変化の絶対値がリフロー前の寸法の0.6%以上であった。
[リフロー条件]
測定機:(株)二葉科学製コンベア式熱風循環乾燥機DFC-27-022S
試料送り速度:0.45mm/min
リフロー炉通過時間:5分
プレヒートゾーンの温度条件:185℃
リフローゾーンの温度条件:295℃
ピーク温度:257℃ (Relay case deformation)
The dimensions of the bottom surface of the relay case shown in FIGS. 3 (a) and 3 (b) obtained as described above were measured by a Mitutoyo Quick Vision 404PROCNC image measuring machine. The measurement was performed before and after the reflow performed under the following conditions, and evaluated according to the following criteria.
◯ (Good): The absolute value of the dimensional change before and after the reflow was less than 0.6% of the dimension before the reflow.
X (defective): The absolute value of the dimensional change before and after the reflow was 0.6% or more of the dimension before the reflow.
[Reflow condition]
Measuring machine: Futaba Kagaku Co., Ltd. Conveyor type hot air circulation dryer DFC-27-022S
Sample feed rate: 0.45 mm / min
Reflow furnace transit time: 5 minutes Preheat zone temperature condition: 185 ° C
Reflow zone temperature conditions: 295 ° C
Peak temperature: 257 ° C
上述の通りにして得た図3(a)及び図3(b)に示すリレーケースの底面側から、図4(a)及び図4(b)に示す台座(材質はリレーケースと同一)を装着し、図5(a)に示す通り、リレーケース内部を密閉した。このリレーケースを、前述の条件で行ったリフローに供した後、水平な机の上に静置し、リレーケース天面の高さをミツトヨ製クイックビジョン404PROCNC画像測定機により測定した。その際、図5(b)において黒丸で示す複数の位置で高さを測定し、最小二乗平面からの最大高さと最小高さとの差をリレーケース天面の平面度として、以下の
基準に従って評価した。
○(良好):平面度が0.45mm未満であり、リレーケースにリフロー時膨れが生じなかった。
×(不良):平面度が0.45mm以上であり、リレーケースにリフロー時膨れが生じた。 (Swelling during relay case reflow)
From the bottom surface side of the relay case shown in FIGS. 3 (a) and 3 (b) obtained as described above, the pedestal (material is the same as that of the relay case) shown in FIGS. 4 (a) and 4 (b). It was attached and the inside of the relay case was sealed as shown in FIG. 5 (a). After the relay case was subjected to the reflow performed under the above-mentioned conditions, it was allowed to stand on a horizontal desk, and the height of the top surface of the relay case was measured by a Mitutoyo Quick Vision 404PROCNC image measuring machine. At that time, the height is measured at a plurality of positions indicated by black circles in FIG. 5 (b), and the difference between the maximum height and the minimum height from the least squares plane is evaluated as the flatness of the top surface of the relay case according to the following criteria. bottom.
◯ (Good): The flatness was less than 0.45 mm, and the relay case did not swell during reflow.
X (defective): The flatness was 0.45 mm or more, and the relay case swelled during reflow.
上述の通りにして得た図3(a)及び図3(b)に示すリレーケースを、前述の条件で行ったリフローに供した後、充填剤の脱離状況を観察し、以下の基準に従って評価した。
○(良好):変化がなく、充填剤の脱離が抑制されていた。
×(不良):充填剤が脱離していた。 (Filler desorption)
After the relay cases shown in FIGS. 3 (a) and 3 (b) obtained as described above were subjected to the reflow performed under the above-mentioned conditions, the desorption state of the filler was observed, and the following criteria were followed. evaluated.
◯ (Good): There was no change, and the desorption of the filler was suppressed.
X (defective): The filler was detached.
上述と同様にして、図5(a)に示す通り、リレーケース内部を密閉した。このリレーケースを、前述の条件で行ったリフローに供した後、70℃の温水に1分間浸漬した。その際の気泡の有無を観察し、以下の基準に従って評価した。
○(良好):気泡が観察されなかった。
×(不良):気泡が観察された。 (Relay case airtightness)
In the same manner as described above, the inside of the relay case was sealed as shown in FIG. 5 (a). This relay case was subjected to the reflow performed under the above-mentioned conditions, and then immersed in warm water at 70 ° C. for 1 minute. The presence or absence of air bubbles at that time was observed and evaluated according to the following criteria.
○ (Good): No bubbles were observed.
× (defective): Bubbles were observed.
2 ベース
3 ケース
4 コイルブロック
41 ボビン
42 コイル
43 鉄心
5 接極子ブロック
51 接極子連結部
52 接極子
6 端子
7 プリント基板
8 導体パターン 1
Claims (4)
- (A)液晶性樹脂と、(B)繊維状ウォラストナイトと、(C)マイカと、を含む表面実装リレー用液晶性樹脂組成物であって、
前記(A)液晶性樹脂は、必須の構成成分として、下記構成単位(I)~(VI)からなり、
全構成単位に対して構成単位(I)の含有量は50~70モル%であり、
全構成単位に対して構成単位(II)の含有量は0.5モル%以上4.5モル%未満であり、
全構成単位に対して構成単位(III)の含有量は10.25~22.25モル%であり、
全構成単位に対して構成単位(IV)の含有量は0.5モル%以上4.5モル%未満であり、
全構成単位に対して構成単位(V)の含有量は5.75~23.75モル%であり、
全構成単位に対して構成単位(VI)の含有量は1~7モル%であり、
全構成単位に対して構成単位(II)と構成単位(IV)との合計の含有量は1モル%以上5モル%未満であり、
全構成単位に対して構成単位(I)~(VI)の合計の含有量は100モル%であり、
構成単位(V)と構成単位(VI)との合計に対する構成単位(VI)のモル比が0.04~0.37である、溶融時に光学的異方性を示す全芳香族ポリエステルアミドであり、
前記(B)繊維状ウォラストナイトのアスペクト比は、8以上であり、
前記液晶性樹脂組成物全体に対して、
前記(A)液晶性樹脂の含有量は、55~75質量%、
前記(B)繊維状ウォラストナイトの含有量は、2.5~17.5質量%、
前記(C)マイカの含有量は、15~32.5質量%、
前記(B)繊維状ウォラストナイト及び前記(C)マイカの合計の含有量は、25~45質量%
であり、
前記表面実装リレーは、ベースと、前記ベースから突出する端子とを備え、前記端子をプリント基板に半田付けするようにした表面実装リレーである液晶性樹脂組成物。
The liquid crystal resin (A) is composed of the following structural units (I) to (VI) as essential constituents.
The content of the constituent unit (I) is 50 to 70 mol% with respect to all the constituent units.
The content of the constituent unit (II) is 0.5 mol% or more and less than 4.5 mol% with respect to all the constituent units.
The content of the constituent unit (III) is 10.25 to 22.25 mol% with respect to all the constituent units.
The content of the constituent unit (IV) is 0.5 mol% or more and less than 4.5 mol% with respect to all the constituent units.
The content of the constituent unit (V) is 5.75 to 23.75 mol% with respect to all the constituent units.
The content of the constituent unit (VI) is 1 to 7 mol% with respect to all the constituent units.
The total content of the constituent unit (II) and the constituent unit (IV) with respect to all the constituent units is 1 mol% or more and less than 5 mol%.
The total content of the constituent units (I) to (VI) is 100 mol% with respect to all the constituent units.
A total aromatic polyesteramide exhibiting optical anisotropy when melted, wherein the molar ratio of the structural unit (VI) to the total of the structural unit (V) and the structural unit (VI) is 0.04 to 0.37. ,
The aspect ratio of the fibrous wollastonite (B) is 8 or more.
For the entire liquid crystal resin composition,
The content of the liquid crystal resin (A) is 55 to 75% by mass.
The content of the fibrous wollastonite (B) is 2.5 to 17.5% by mass.
The content of (C) mica is 15 to 32.5% by mass,
The total content of the (B) fibrous wollastonite and the (C) mica is 25 to 45% by mass.
And
The surface mount relay is a liquid crystal resin composition which is a surface mount relay having a base and terminals protruding from the base, and the terminals are soldered to a printed circuit board.
- 構成単位(III)と構成単位(IV)との合計のモル数が構成単位(V)と構成単位(VI)との合計のモル数の1~1.1倍であり、又は、構成単位(V)と構成単位(VI)との合計のモル数が構成単位(III)と構成単位(IV)との合計のモル数の1~1.1倍である請求項1に記載の液晶性樹脂組成物。 The total number of moles of the constituent unit (III) and the constituent unit (IV) is 1 to 1.1 times the total number of moles of the constituent unit (V) and the constituent unit (VI), or the constituent unit ( The liquid crystal resin according to claim 1, wherein the total number of moles of V) and the constituent unit (VI) is 1 to 1.1 times the total number of moles of the constituent unit (III) and the constituent unit (IV). Composition.
- 請求項1又は2に記載の組成物からなる表面実装リレー用部品。 A surface mount relay component comprising the composition according to claim 1 or 2.
- 請求項3に記載の部品を備える表面実装リレー。 A surface mount relay including the component according to claim 3.
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JP2021547691A JP7019110B1 (en) | 2020-05-13 | 2021-03-26 | Liquid crystal resin composition for surface mount relay and surface mount relay using it |
CN202180034532.5A CN115551948B (en) | 2020-05-13 | 2021-03-26 | Liquid crystalline resin composition for surface mount relay and surface mount relay using same |
MYPI2022006321A MY197276A (en) | 2020-05-13 | 2021-03-26 | Liquid-crystalline resin composition for surface-mounted relays and surface-mounted relay using same |
KR1020227040467A KR102501091B1 (en) | 2020-05-13 | 2021-03-26 | Liquid crystalline resin composition for surface mount relay and surface mount relay using the same |
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PCT/JP2021/012893 WO2021229931A1 (en) | 2020-05-13 | 2021-03-26 | Liquid-crystalline resin composition for surface-mounted relays, and surface-mounted relay using same |
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JP (1) | JP7019110B1 (en) |
KR (1) | KR102501091B1 (en) |
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WO2018116888A1 (en) * | 2016-12-21 | 2018-06-28 | ポリプラスチックス株式会社 | Liquid crystalline resin composition for surface-mounted relays and surface-mounted relay using same |
JP2018106005A (en) * | 2016-12-26 | 2018-07-05 | ポリプラスチックス株式会社 | Liquid crystalline resin composition for camera module and camera module using the same |
WO2019203157A1 (en) * | 2018-04-16 | 2019-10-24 | ポリプラスチックス株式会社 | Liquid-crystalline resin composition |
WO2020100618A1 (en) * | 2018-11-15 | 2020-05-22 | ポリプラスチックス株式会社 | Liquid crystalline resin composition and connector including molded article of said liquid crystalline resin composition |
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JP3463310B2 (en) | 1993-03-12 | 2003-11-05 | オムロン株式会社 | Surface mount relay |
JP2015021063A (en) * | 2013-07-19 | 2015-02-02 | 東レ株式会社 | Liquid crystal polyester resin composition |
JP6206174B2 (en) * | 2013-12-26 | 2017-10-04 | 東レ株式会社 | Liquid crystalline polyester resin composition and molded product thereof |
CN108368329B (en) * | 2015-12-09 | 2021-11-12 | 住友化学株式会社 | Liquid crystal polyester composition and molded article |
JP6851979B2 (en) * | 2015-12-09 | 2021-03-31 | 住友化学株式会社 | Liquid crystal polyester composition and molded article |
JP6345376B1 (en) * | 2016-10-07 | 2018-06-20 | ポリプラスチックス株式会社 | Composite resin composition and electronic component molded from the composite resin composition |
CN109790378B (en) * | 2016-10-07 | 2020-09-11 | 宝理塑料株式会社 | Composite resin composition and connector molded from the same |
WO2018074156A1 (en) * | 2016-10-21 | 2018-04-26 | ポリプラスチックス株式会社 | Composite resin composition and connector molded from same |
CN109844027B (en) * | 2016-12-22 | 2020-08-04 | 宝理塑料株式会社 | Liquid crystalline resin composition for surface mount relay and surface mount relay using same |
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- 2021-03-26 WO PCT/JP2021/012893 patent/WO2021229931A1/en active Application Filing
- 2021-03-26 JP JP2021547691A patent/JP7019110B1/en active Active
- 2021-03-26 CN CN202180034532.5A patent/CN115551948B/en active Active
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WO2017038421A1 (en) * | 2015-09-01 | 2017-03-09 | ポリプラスチックス株式会社 | Liquid crystalline resin composition for camera module and camera module using same |
WO2018116888A1 (en) * | 2016-12-21 | 2018-06-28 | ポリプラスチックス株式会社 | Liquid crystalline resin composition for surface-mounted relays and surface-mounted relay using same |
JP2018106005A (en) * | 2016-12-26 | 2018-07-05 | ポリプラスチックス株式会社 | Liquid crystalline resin composition for camera module and camera module using the same |
WO2019203157A1 (en) * | 2018-04-16 | 2019-10-24 | ポリプラスチックス株式会社 | Liquid-crystalline resin composition |
WO2020100618A1 (en) * | 2018-11-15 | 2020-05-22 | ポリプラスチックス株式会社 | Liquid crystalline resin composition and connector including molded article of said liquid crystalline resin composition |
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CN115551948A (en) | 2022-12-30 |
KR20220158871A (en) | 2022-12-01 |
JP7019110B1 (en) | 2022-02-14 |
JPWO2021229931A1 (en) | 2021-11-18 |
KR102501091B1 (en) | 2023-02-17 |
MY197276A (en) | 2023-06-09 |
CN115551948B (en) | 2023-04-11 |
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