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 PDF

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Publication number
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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liquid crystal
mol
crystal resin
resin composition
relay
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PCT/JP2021/012893
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French (fr)
Japanese (ja)
Inventor
昭宏 長永
卓馬 松村
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ポリプラスチックス株式会社
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Application filed by ポリプラスチックス株式会社 filed Critical ポリプラスチックス株式会社
Priority to JP2021547691A priority Critical patent/JP7019110B1/en
Priority to CN202180034532.5A priority patent/CN115551948B/en
Priority to MYPI2022006321A priority patent/MY197276A/en
Priority to KR1020227040467A priority patent/KR102501091B1/en
Publication of WO2021229931A1 publication Critical patent/WO2021229931A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44Polyester-amides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/10Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12Polyester-amides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01HELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H45/00Details of relays
    • H01H45/02Bases; Casings; Covers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/016Additives 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

Provided are: a liquid-crystalline resin composition for surface-mounted relays, which has excellent heat resistance and air-tightness, can provide a molded article free from the deformation thereof and the detachment of a filler therefrom, and has satisfactory fluidability; and a surface-mounted relay component and a surface-mounted relay, each using the liquid-crystalline resin composition for surface-mounted relays. The liquid-crystalline resin composition for surface-mounted relays according to the present invention comprises (A) a liquid-crystalline resin, (B) fibrous wollastonite and (C) mica, in which the liquid-crystalline resin (A) is a wholly aromatic polyester amide that contains specified amounts of structural units (I) to (VI) as essential constituent components and shows optical anisotropy when being melted, and the fibrous wollastonite (B) has an aspect ratio of 8 or more; and the surface-mounted relay is provided with a base and a terminal that protrudes from the base, and is configured such that the terminal is soldered to a printed substrate.

Description

表面実装リレー用液晶性樹脂組成物及びそれを用いた表面実装リレーLiquid crystal resin composition for surface mount relay and surface mount relay using it
 本発明は、表面実装リレー用液晶性樹脂組成物及びそれを用いた表面実装リレーに関する。 The present invention relates to a liquid crystal resin composition for a surface mount relay and a surface mount relay using the same.
 リレーは、エレクトロニクス産業の発展とともに、その生産量も順調に伸びており、通信機器、OA機器、家電機器、自販機等使用される分野も多岐にわたっている。従来、プリント基板に実装して使用するリレーとして、挿入実装型(スルーホールタイプ)のリレーが知られている。挿入実装リレーは、リレー本体より垂直に突き出した端子を備え、まず、プリント基板の孔にこの端子を挿入することでプリント基板の一方の面に載置される。その後、上記プリント基板の他方の面において上記端子を半田付けすることにより、挿入実装リレーは、電気的に導通可能にプリント基板に固定される。 With the development of the electronics industry, the production volume of relays is steadily increasing, and there are a wide range of fields in which they are used, such as communication equipment, OA equipment, home appliances, and vending machines. Conventionally, as a relay mounted on a printed circuit board and used, an insertion mounting type (through hole type) relay is known. 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.
 近年、プリント基板に実装して使用する新たなリレーとして、表面実装型(サーフェースアマウントタイプ)のリレーが開発されている(例えば、特許文献1)。表面実装リレーでは、半田付け面がリレー本体と平行になるように、リレー本体より垂直に突き出した端子が直角に曲げられている。そのため、表面実装リレーは、プリント基板に孔を設けることなく、プリント基板表面の導体パターン上に設けられた半田パッドに上記端子を載置し、半田リフロー処理を行うことにより、電気的に導通可能にプリント基板に固定される。 In recent years, 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). In 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.
特許第3463310号公報Japanese Patent No. 3436310
 上述の通り、表面実装リレーは、半田リフロー処理によりプリント基板に固定されるため、表面実装リレーを構成する成形体、例えば、ベース、ケース、ボビン等は、半田リフロー処理に耐えられるよう、優れた耐熱性が求められる。また、表面実装リレーは、半田リフロー処理後でも気密性及び形状を保持できることも求められる。 As described above, since 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.
 ところで、耐熱性、寸法精度、流動性等に優れる点で、液晶性樹脂組成物が注目されている。しかし、液晶性樹脂組成物には、当該組成物の成形体表面からフィラーが突出し、更に脱離して、製品の導通不良等の機能障害を発生させる問題が生じ得る。また、液晶性樹脂組成物を成形して、表面実装リレーを構成する成形体を得る場合、該液晶性樹脂組成物には、良好な流動性が求められる。 By the way, liquid crystal resin compositions are attracting attention because of their excellent heat resistance, dimensional accuracy, fluidity, and the like. However, in the liquid crystal resin composition, there may be a problem that 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. Further, when a liquid crystal resin composition is molded to obtain a molded body constituting a surface mount relay, the liquid crystal resin composition is required to have good fluidity.
 本発明は、かかる事情に鑑みてなされたものであり、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た成形体を与える、流動性が良好な表面実装リレー用液晶性樹脂組成物、前記組成物からなる表面実装リレー用部品、及び前記部品を備える表面実装リレーを提供することを目的とする。 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.
 本発明者らは、所定の含有量で、特定の構成単位を所定量含む液晶性樹脂と、繊維状ウォラストナイトと、マイカと、を組み合わせ、繊維状ウォラストナイトのアスペクト比を所定の範囲とすることで上記の課題を解決できることを見出した。具体的には、本発明は、以下のようなものを提供する。 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.
 (1) (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。
Figure JPOXMLDOC01-appb-C000002
(1) 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.
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.
Figure JPOXMLDOC01-appb-C000002
 (2) 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(1)に記載の液晶性樹脂組成物。 (2) 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.
 (3) (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。 (3) A surface mount relay component made of the composition according to (1) or (2).
 (4) (3)に記載の部品を備える表面実装リレー。 (4) A surface mount relay equipped with the parts described in (3).
 本発明によれば、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た成形体を与える、流動性が良好な表面実装リレー用液晶性樹脂組成物、前記組成物からなる表面実装リレー用部品、及び前記部品を備える表面実装リレーを提供することができる。 According to the present invention, 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.
図1(a)は、本発明に係る表面実装リレーの実施形態を模式的に示す斜視図であり、図1(b)は、図1(a)のAA断面を示す部分断面図である。1 (a) is a perspective view schematically showing an embodiment of a surface mount relay according to the present invention, and FIG. 1 (b) is a partial cross-sectional view showing an AA cross section of FIG. 1 (a). 図2(a)及び図2(b)は、本発明に係る表面実装リレーの実施形態をプリント基板に実装した状態を模式的に示す側面図である。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. 図3(a)は、実施例で成形したリレーケースを示す平面図であり、図3(b)は、図3(a)のBB断面を示す部分縦断面図である。なお、特に記載がない限り図中の数値の単位はmmである(以下、図4(a)~図5(b)でも同じ)。3A is a plan view showing a relay case molded in an embodiment, and FIG. 3B is a partial vertical sectional view showing a BB cross section of FIG. 3A. Unless otherwise specified, the unit of the numerical value in the figure is mm (hereinafter, the same applies to FIGS. 4 (a) to 5 (b)). 図4(a)は、図3(a)及び図3(b)に示すリレーケースの底面側から装着される台座を示す平面図であり、図4(b)は、図4(a)のCC断面を示す部分縦断面図である。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). It is a partial vertical sectional view which shows the CC cross section. 図5(a)は、実施例においてリレーケースリフロー時膨れ及びリレーケース気密性を評価するために、図4(a)及び図4(b)に示す台座を装着して内部を密閉したリレーケースを示す部分縦断面図である。図5(b)は、実施例で行ったリレーケースのリフロー時膨れの評価における測定箇所を示す図である。具体的にいうと、図5(b)は、図3(a)と同様に、リレーケースを示す平面図であり、黒丸で示す複数の位置が測定箇所である。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. It is a partial vertical sectional view showing. FIG. 5B is a diagram showing measurement points in the evaluation of swelling during reflow of the relay case performed in the embodiment. Specifically, 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.
 以下、本発明の実施形態について具体的に説明する。 Hereinafter, embodiments of the present invention will be specifically described.
<表面実装リレー用液晶性樹脂組成物>
 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.
[液晶性樹脂]
 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.
 本発明における全芳香族ポリエステルアミドは、下記構成単位(I)、下記構成単位(II)、下記構成単位(III)、下記構成単位(IV)、下記構成単位(V)、及び下記構成単位(VI)からなる。 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).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
 構成単位(I)は、4-ヒドロキシ安息香酸(以下、「HBA」ともいう。)から誘導される。本発明における全芳香族ポリエステルアミドは、全構成単位に対して構成単位(I)を50~70モル%含む。構成単位(I)の含有量が50モル%未満、又は70モル%を超えると、低融点化及び耐熱性の少なくとも一方が不十分となりやすい。低融点化と耐熱性との両立の観点から、構成単位(I)の含有量は、好ましくは54~67モル%、より好ましくは58~64モル%である。 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. When 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. From the viewpoint of achieving both a low melting point and heat resistance, the content of the structural unit (I) is preferably 54 to 67 mol%, more preferably 58 to 64 mol%.
 構成単位(II)は、6-ヒドロキシ-2-ナフトエ酸(以下、「HNA」ともいう。)から誘導される。本発明における全芳香族ポリエステルアミドは、全構成単位に対して構成単位(II)を0.5モル%以上4.5モル%未満含む。構成単位(II)の含有量が0.5モル%未満、又は4.5モル%以上であると、低融点化及び耐熱性の少なくとも一方が不十分となりやすい。低融点化と耐熱性との両立の観点から、構成単位(II)の含有量は、好ましくは0.75~3.75モル%、より好ましくは1~3モル%である。 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. When 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. From the viewpoint of achieving both a low melting point and heat resistance, the content of the structural unit (II) is preferably 0.75 to 3.75 mol%, more preferably 1 to 3 mol%.
 構成単位(III)は、1,4-フェニレンジカルボン酸(以下、「TA」ともいう。)から誘導される。本発明における全芳香族ポリエステルアミドは、全構成単位に対して構成単位(III)を10.25~22.25モル%含む。構成単位(III)の含有量が10.25モル%未満、又は22.25モル%を超えると、低融点化及び耐熱性の少なくとも一方が不十分となりやすい。低融点化と耐熱性との両立の観点から、構成単位(III)の含有量は、好ましくは12.963~20.75モル%、より好ましくは15.675~19.25モル%である。 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. When 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. From the viewpoint of achieving both a low melting point and heat resistance, the content of the structural unit (III) is preferably 12.963 to 20.75 mol%, more preferably 15.675 to 19.25 mol%.
 構成単位(IV)は、1,3-フェニレンジカルボン酸(以下、「IA」ともいう。)から誘導される。本発明における全芳香族ポリエステルアミドは、全構成単位に対して構成単位(IV)を0.5モル%以上4.5モル%未満含む。構成単位(IV)の含有量が0.5モル%未満、又は4.5モル%以上であると、低融点化及び耐熱性の少なくとも一方が不十分となりやすい。低融点化と耐熱性との両立の観点から、構成単位(IV)の含有量は、好ましくは0.5~3.75モル%、より好ましくは0.5~3モル%である。 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. When 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. From the viewpoint of achieving both a low melting point and heat resistance, the content of the structural unit (IV) is preferably 0.5 to 3.75 mol%, more preferably 0.5 to 3 mol%.
 構成単位(V)は、4,4’-ジヒドロキシビフェニル(以下、「BP」ともいう。)から誘導される。本発明における全芳香族ポリエステルアミドには、全構成単位に対して構成単位(V)を5.75~23.75モル%含む。構成単位(V)の含有量が5.75モル%未満、又は23.75モル%を超えると、低融点化及び耐熱性の少なくとも一方が不十分となりやすい。低融点化と耐熱性との両立の観点から、構成単位(V)の含有量は、好ましくは8.5~20.375モル%、より好ましくは11.25~17モル%(例えば、11.675~17モル%)である。 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. When 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. From the viewpoint of achieving both a low melting point and heat resistance, 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%).
 構成単位(VI)は、N-アセチル-p-アミノフェノール(以下、「APAP」ともいう。)から誘導される。本発明における全芳香族ポリエステルアミドには、全構成単位に対して構成単位(VI)を1~7モル%含む。構成単位(VI)の含有量が1モル%未満、又は7モル%を超えると、低融点化及び耐熱性の少なくとも一方が不十分となりやすい。低融点化と耐熱性との両立の観点から、構成単位(VI)の含有量は、好ましくは1.5~7モル%、より好ましくは2~7モル%である。 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. When 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%.
 本発明における全芳香族ポリエステルアミドは、全構成単位に対して構成単位(II)と構成単位(IV)との合計を1モル%以上5モル%未満含む。上記全芳香族ポリエステルアミドにおいては、ナフタレン骨格を有する屈曲性の構成単位(II)とベンゼン骨格を有する屈曲性の構成単位(IV)とが上記範囲の合計量で並存することで低融点化と耐熱性との両立が十分となりやすい。上記合計の含有量が1モル%未満であると、屈曲性の構成単位の割合が少なくなり過ぎるため、低融点化は不十分となりやすい。上記合計の含有量が5モル%以上であると、屈曲性の構成単位の割合が多くなり過ぎるため、耐熱性は不十分となりやすい。低融点化と耐熱性との両立の観点から、上記合計の含有量は、好ましくは1.75~4.75モル%、より好ましくは2.5~4.5モル%である。 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. In the above-mentioned total aromatic polyester amide, 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. When 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. From the viewpoint of achieving both a low melting point and heat resistance, the total content is preferably 1.75 to 4.75 mol%, more preferably 2.5 to 4.5 mol%.
 本発明における全芳香族ポリエステルアミドにおいては、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。上記モル比が0.04未満であると、ビフェニル骨格を有する構成単位の割合が多くなるため、全芳香族ポリエステルアミドの結晶性が低くなり、低融点化と耐熱性との両立が不十分となりやすい。また、上記モル比が0.37を超えると、エステル結合以外の異種結合が増加するため、全芳香族ポリエステルアミドの結晶性が低くなり、低融点化と耐熱性との両立が不十分となりやすい。低融点化と耐熱性との両立の観点から、上記モル比は、好ましくは0.07~0.36、より好ましくは0.11~0.35である。 In the total aromatic polyester amide in the present invention, 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. When 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. Further, 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. .. From the viewpoint of achieving both a low melting point and heat resistance, the molar ratio is preferably 0.07 to 0.36, more preferably 0.11 to 0.35.
 低融点化と耐熱性との両立の観点から、構成単位(III)と構成単位(IV)との合計のモル数(以下、「モル数1A」ともいう。)は、構成単位(V)と構成単位(VI)との合計のモル数(以下、「モル数2A」ともいう。)の1~1.1倍であり、又は、モル数2Aは、モル数1Aの1~1.1倍であることが好ましい。モル数1Aは、モル数2Aの1.02~1.06倍であり、又は、モル数2Aは、モル数1Aの1.02~1.06倍であることがより好ましい。モル数1Aは、モル数2Aの1.024~1.056倍であり、又は、モル数2Aは、モル数1Aの1.024~1.056倍であることが更により好ましい。 From the viewpoint of achieving both low melting point and heat resistance, 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.
 以上の通り、本発明における全芳香族ポリエステルアミドは、特定の構成単位である(I)~(VI)及び構成単位(II)と構成単位(IV)との合計のそれぞれを、全構成単位に対して特定の量含有し、かつ、構成単位(V)と構成単位(VI)との合計に対する構成単位(VI)のモル比が特定の範囲であるため、低融点化と耐熱性との両立が十分である。なお、本発明の全芳香族ポリエステルアミドは、全構成単位に対して構成単位(I)~(VI)を合計で100モル%含む。 As described above, in the total aromatic polyesteramide in the present invention, 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. On the other hand, since 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.
 次いで、本発明における全芳香族ポリエステルアミドの製造方法について説明する。本発明における全芳香族ポリエステルアミドは、直接重合法やエステル交換法等を用いて重合される。重合に際しては、溶融重合法、溶液重合法、スラリー重合法、固相重合法等、又はこれらの2種以上の組み合わせが用いられ、溶融重合法、又は溶融重合法と固相重合法との組み合わせが好ましく用いられる。 Next, the method for producing the total aromatic polyester amide in the present invention will be described. The total aromatic polyester amide in the present invention is polymerized by using a direct polymerization method, a transesterification method, or the like. In the polymerization, 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.
 本発明では、重合に際し、重合モノマーに対するアシル化剤や、酸塩化物誘導体として末端を活性化したモノマーを使用できる。アシル化剤としては、無水酢酸等の脂肪酸無水物等が挙げられる。 In the present invention, an acylating agent for a polymerization monomer or a monomer having an activated terminal can be used as an acid chloride derivative during polymerization. Examples of the acylating agent include fatty acid anhydrides such as acetic anhydride.
 これらの重合に際しては種々の触媒の使用が可能であり、代表的なものとしては、酢酸カリウム、酢酸マグネシウム、酢酸第一錫、テトラブチルチタネート、酢酸鉛、酢酸ナトリウム、三酸化アンチモン、トリス(2,4-ペンタンジオナト)コバルト(III)等の金属塩系触媒、1-メチルイミダゾール、4-ジメチルアミノピリジン等の有機化合物系触媒を挙げることができる。 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.
 反応条件としては、例えば、反応温度200~380℃、最終到達圧力0.1~760Torr(即ち、13~101,080Pa)である。特に溶融反応では、例えば、反応温度260~380℃、好ましくは300~360℃、最終到達圧力1~100Torr(即ち、133~13,300Pa)、好ましくは1~50Torr(即ち、133~6,670Pa)である。 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). Particularly in the melting reaction, for example, the reaction temperature is 260 to 380 ° C., preferably 300 to 360 ° C., and 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). ).
 反応は、全原料モノマー(HBA、HNA、TA、IA、BP、及びAPAP)、アシル化剤、及び触媒を同一反応容器に仕込んで反応を開始させることもできるし(一段方式)、原料モノマーHBA、HNA、BP、及びAPAPの水酸基をアシル化剤によりアシル化させた後、TA及びIAのカルボキシル基と反応させることもできる(二段方式)。 In the reaction, all raw material monomers (HBA, HNA, TA, IA, BP, and APAP), an acylating agent, and 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).
 溶融重合は、反応系内が所定温度に達した後、減圧を開始して所定の減圧度にして行う。撹拌機のトルクが所定値に達した後、不活性ガスを導入し、減圧状態から常圧を経て、所定の加圧状態にして反応系から全芳香族ポリエステルアミドを排出する。 After the inside of the reaction system reaches a predetermined temperature, melt polymerization is carried out by starting depressurization to a predetermined decompression degree. After the torque of the stirrer reaches a predetermined value, 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.
 上記重合方法により製造された全芳香族ポリエステルアミドは、更に常圧又は減圧、不活性ガス中で加熱する固相重合により分子量の増加を図ることができる。固相重合反応の好ましい条件は、反応温度230~350℃、好ましくは260~330℃、最終到達圧力10~760Torr(即ち、1,330~101,080Pa)である。 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).
 次いで、全芳香族ポリエステルアミドの性質について説明する。本発明における全芳香族ポリエステルアミドは、溶融時に光学的異方性を示す。溶融時に光学的異方性を示すことは、本発明における全芳香族ポリエステルアミドが液晶性樹脂であることを意味する。 Next, the properties of the total aromatic polyester amide will be described. 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.
 本発明において、全芳香族ポリエステルアミドが液晶性樹脂であることは、全芳香族ポリエステルアミドが熱安定性と易加工性を併せ持つ上で不可欠な要素である。上記構成単位(I)~(VI)から構成される全芳香族ポリエステルアミドは、構成成分及びポリマー中のシーケンス分布によっては、異方性溶融相を形成しないものも存在するが、本発明における液晶性樹脂は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に限られる。 In the present invention, 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.
 溶融異方性の性質は直交偏光子を利用した慣用の偏光検査方法により確認することができる。より具体的には溶融異方性の確認は、オリンパス社製偏光顕微鏡を使用しリンカム社製ホットステージにのせた試料を溶融し、窒素雰囲気下で150倍の倍率で観察することにより実施できる。液晶性樹脂は光学的に異方性であり、直交偏光子間に挿入したとき光を透過させる。試料が光学的に異方性であると、例えば溶融静止液状態であっても偏光は透過する。 The nature of 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.
 ネマチックな液晶性樹脂は融点以上で著しく粘性低下を生じるので、一般的に融点又はそれ以上の温度で液晶性を示すことが加工性の指標となる。融点は、でき得る限り高い方が耐熱性の観点からは好ましいが、液晶性樹脂の溶融加工時の熱劣化や成形機の加熱能力等を考慮すると、360℃以下であることが好ましい目安となる。なお、より好ましくは300~360℃であり、更により好ましくは340~358℃である。 Since 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.
 本発明における全芳香族ポリエステルアミドの融点より10~30℃高い温度、かつ、剪断速度1000/秒における前記全芳香族ポリエステルアミドの溶融粘度は、好ましくは500Pa・s以下であり、より好ましくは0.5~300Pa・sであり、更により好ましくは1~100Pa・sである。上記溶融粘度が上記範囲内であると、前記全芳香族ポリエステルアミドそのもの、又は、前記全芳香族ポリエステルアミドを含有する組成物は、その成形時において、流動性が確保されやすく、充填圧力が過度になりにくい。なお、本明細書において、溶融粘度とは、ISO11443に準拠して測定した溶融粘度をいう。 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. When the melt viscosity is within the above range, the total aromatic polyester amide itself or the composition containing the total aromatic polyester amide tends to secure fluidity at the time of molding, and the filling pressure is excessive. It is hard to become. In addition, in this specification, the melt viscosity means the melt viscosity measured in accordance with ISO11443.
 本発明に係る液晶性樹脂組成物は、上記の液晶性樹脂を、液晶性樹脂組成物全体に対して55~75質量%含む。液晶性樹脂の含有量が、液晶性樹脂組成物全体に対し55質量%未満であると、液晶性樹脂組成物の流動性が悪化しやすく、また、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気密性が低下する恐れがあるため好ましくない。液晶性樹脂の含有量が、液晶性樹脂組成物全体に対して75質量%超であると、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、気密性等の少なくともいずれかが低下する恐れがあるため好ましくない。本発明に係る液晶性樹脂組成物は、上記の液晶性樹脂を、液晶性樹脂組成物全体に対して57.5~72.5質量%含むことが好ましく、60~70質量%含むことがより好ましい。 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. When 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. When 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. It is not preferable because at least one of the above may decrease. 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.
[(B)繊維状ウォラストナイト]
 (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.
 (B)繊維状ウォラストナイトとしては、特に限定されず、例えば、公知の繊維状ウォラストナイトを用いることができる。(B)繊維状ウォラストナイトは、1種単独で使用してもよく、アスペクト比、平均繊維長、平均繊維径等が異なる2種以上を組み合わせて使用してもよい。 (B) The fibrous wollastonite is not particularly limited, and for example, a known fibrous wollastonite can be used. (B) 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.
 (B)繊維状ウォラストナイトの平均繊維径は好ましくは3.0~50μmであり、より好ましい平均繊維径は4.5~40μmである。上記平均繊維径が3.0μm以上であると、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は、十分な機械的強度及び荷重たわみ温度が確保されやすい。上記平均繊維径が50μm以下であると、上記成形体表面の起毛抑制効果が高くなりやすい。なお、本明細書において、液晶性樹脂組成物中の(B)繊維状ウォラストナイトの平均繊維径としては、液晶性樹脂組成物を600℃で2時間の加熱により灰化して残存した繊維状ウォラストナイトを走査型電子顕微鏡で観察し、100本の繊維状ウォラストナイトについて繊維径を測定した値の平均を採用する。 (B) The average fiber diameter of the fibrous wollastonite is preferably 3.0 to 50 μm, and the more preferable average fiber diameter is 4.5 to 40 μm. When the average fiber diameter is 3.0 μm or more, 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. When the average fiber diameter is 50 μm or less, the effect of suppressing raising of the surface of the molded product tends to be high. In the present specification, 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.
 (B)繊維状ウォラストナイトの平均繊維長は好ましくは30~800μmであり、より好ましい平均繊維長は50~600μmである。上記平均繊維長が30μm以上であると、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は、十分な機械的強度及び荷重たわみ温度が確保されやすい。上記平均繊維長が800μm以下であると、上記成形体表面の起毛抑制効果が高くなりやすい。なお、本明細書において、液晶性樹脂組成物中の(B)繊維状ウォラストナイトの平均繊維長としては、液晶性樹脂組成物を600℃で2時間の加熱により灰化して残存した繊維状ウォラストナイトの実体顕微鏡画像10枚をCCDカメラからPCに取り込み、画像測定機によって画像処理手法により、実体顕微鏡画像1枚ごとに100本の繊維状ウォラストナイト、即ち、合計1000本の繊維状ウォラストナイトについて繊維長を測定した値の平均を採用する。 (B) The average fiber length of the fibrous wollastonite is preferably 30 to 800 μm, and the more preferable average fiber length is 50 to 600 μm. When the average fiber length is 30 μm or more, 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. When the average fiber length is 800 μm or less, the effect of suppressing raising of the surface of the molded product tends to be high. In the present specification, 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. 10 fibrous wollastonite images were taken from a CCD camera to a PC, and 100 fibrous wollastonites were taken for each stereoscopic microscopic image by an image processing method using an image measuring machine, that is, a total of 1000 fibrous images. The average of the measured fiber lengths for wollastonite is used.
 本発明に係る液晶性樹脂組成物は、(B)繊維状ウォラストナイトを、液晶性樹脂組成物全体に対して2.5~17.5質量%含む。(B)繊維状ウォラストナイトの含有量が、液晶性樹脂組成物全体に対して2.5質量%未満であると、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気密性が低下する恐れがあるため好ましくない。(B)繊維状ウォラストナイトの含有量が、液晶性樹脂組成物全体に対して17.5質量%超であると、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が低下する、恐れがあるため好ましくない。本発明における(B)繊維状ウォラストナイトは、液晶性樹脂組成物中に、液晶性樹脂組成物全体に対して3.5~14質量%含まれることが好ましく、5~10質量%含まれることがより好ましい。 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. (B) When the content of the fibrous wollastonite is less than 2.5% by mass with respect to 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. (B) When the content of the fibrous wollastonite is more than 17.5% by mass with respect to 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 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.
[(C)マイカ]
 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.
 マイカは、液晶性樹脂組成物全体に対して15~32.5質量%含まれる。マイカの含有量が、液晶性樹脂組成物全体に対して15質量%未満であると、液晶性樹脂組成物から得られる成形体の変形抑制が十分ではないため好ましくない。マイカの含有量が、液晶性樹脂組成物全体に対して32.5質量%超であると、液晶性樹脂組成物の流動性が悪化しやすく、液晶性樹脂組成物の成形が困難になる可能性があり、また、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気密性が低下する恐れがあるため好ましくない。マイカは、液晶性樹脂組成物中に、液晶性樹脂組成物全体に対して17~31.5質量%含まれることが好ましく、20~30質量%含まれることがより好ましい。 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.
 〔マイカ〕
 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.
 また、マイカの製造において、鉱物を粉砕する方法としては、湿式粉砕法及び乾式粉砕法が知られている。湿式粉砕法とは、マイカ原石を乾式粉砕機にて粗粉砕した後、水を加えてスラリー状態にて湿式粉砕で本粉砕し、その後、脱水、乾燥を行う方法である。湿式粉砕法と比較して、乾式粉砕法は低コストで一般的な方法であるが、湿式粉砕法を用いると、鉱物を薄く細かく粉砕することがより容易である。後述する好ましい平均粒子径及び厚みを有するマイカが得られるという理由で、本発明においては薄く細かい粉砕物を使用することが好ましい。したがって、本発明においては、湿式粉砕法により製造されたマイカを使用するのが好ましい。 Further, in the production of mica, 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. Although 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.
 また、湿式粉砕法においては、被粉砕物を水に分散させる工程が必要であるため、被粉砕物の分散効率を高めるために、被粉砕物に凝集沈降剤及び/又は沈降助剤を加えることが一般的である。本発明において使用できる凝集沈降剤及び沈降助剤としては、ポリ塩化アルミニウム、硫酸アルミニウム、硫酸第一鉄、硫酸第二鉄、塩化コッパラス、ポリ硫酸鉄、ポリ塩化第二鉄、鉄-シリカ無機高分子凝集剤、塩化第二鉄-シリカ無機高分子凝集剤、消石灰(Ca(OH))、苛性ソーダ(NaOH)、ソーダ灰(NaCO)等が挙げられる。これらの凝集沈降剤及び沈降助剤は、pHがアルカリ性又は酸性である。本発明で使用するマイカは、湿式粉砕する際に凝集沈降剤及び/又は沈降助剤を使用していないものが好ましい。凝集沈降剤及び/又は沈降助剤で処理されていないマイカを使用すると、液晶性樹脂組成物中の液晶性樹脂の分解が生じにくく、多量のガス発生や液晶性樹脂の分子量低下等が起きにくいため、得られる表面実装リレー用部品等の成形体の性能をより良好に維持するのが容易である。 Further, since the wet pulverization method requires a step of dispersing the object to be crushed in water, 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. Is common. Examples of the 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. Examples thereof include ferric chloride-silica inorganic polymer flocculants, slaked lime (Ca (OH) 2 ), caustic soda (NaOH), soda ash (Na 2 CO 3 ) and the like. These 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. When mica that has not been treated with the coagulation sedimentation agent and / or the sedimentation aid is used, 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.
 本発明において使用できるマイカは、マイクロトラックレーザー回折法により測定した平均粒子径が10~100μmであるものが好ましく、平均粒子径が20~80μmであるものが特に好ましい。マイカの平均粒子径が10μm以上であると、成形体の剛性に対する改良効果が十分となりやすいため好ましい。マイカの平均粒子径が100μm以下であると、成形体の剛性の向上が十分となりやすく、ウェルド強度も十分となりやすいため好ましい。更に、マイカの平均粒子径が100μm以下であると、本発明の表面実装リレー用部品等を成形するのに十分な流動性を確保しやすい。 The mica that can be used in the present invention preferably has an average particle size of 10 to 100 μm measured by a microtrack laser diffraction method, and particularly preferably an average particle size of 20 to 80 μm. When the average particle size of mica is 10 μm or more, the effect of improving the rigidity of the molded product is likely to be sufficient, which is preferable. When the average particle size of mica is 100 μm 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. Further, when the average particle size of mica is 100 μm or less, it is easy to secure sufficient fluidity for molding the surface mount relay component of the present invention.
 本発明において使用できるマイカの厚みは、電子顕微鏡の観察により実測した厚みが0.01~1μmであることが好ましく、0.03~0.3μmであることが特に好ましい。マイカの厚みが0.01μm以上であると、液晶性樹脂組成物の溶融加工の際にマイカが割れにくくなるため、成形体の剛性が向上しやすい可能性があるため好ましい。マイカの厚みが1μm以下であると、成形体の剛性に対する改良効果が十分となりやすいため好ましい。 The thickness of mica that can be used in the present invention is preferably 0.01 to 1 μm, particularly preferably 0.03 to 0.3 μm, as measured by observation with an electron microscope. When the thickness of the mica is 0.01 μm 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. When the thickness of mica is 1 μm or less, the effect of improving the rigidity of the molded product is likely to be sufficient, which is preferable.
 本発明において使用できるマイカは、シランカップリング剤等で表面処理されていてもよく、かつ/又は、結合剤で造粒し顆粒状とされていてもよい。 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.
 本発明に係る液晶性樹脂組成物において、(B)繊維状ウォラストナイト及び(C)マイカの合計の含有量は、液晶性樹脂組成物全体に対して25~45質量%である。上記含有量が、液晶性樹脂組成物全体に対して25質量%未満であると、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、気密性等の少なくともいずれかが低下する恐れがあるため好ましくない。上記含有量が、液晶性樹脂組成物全体に対して45質量%超であると、液晶性樹脂組成物の流動性が悪化しやすく、また、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気密性が低下する恐れがあるため好ましくない。上記含有量は、液晶性樹脂組成物全体に対して27.5~37.5質量%であることが好ましく、30~40質量%であることがより好ましい。 In the liquid crystal resin composition according to the present invention, 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. When 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. When the content is more than 45% 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 component obtained from the liquid crystal resin composition This is not preferable because the airtightness of the molded product may decrease. 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.
[その他の成分]
 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.
 その他の重合体としては、例えば、(A)液晶性樹脂以外の液晶性樹脂が挙げられる。但し、成形体の変形抑制効果、気密性等の少なくともいずれかの観点から、本発明に係る液晶性樹脂組成物は、(A)液晶性樹脂以外の液晶性樹脂を含まないことが好ましい。その他の重合体としては、例えば、エポキシ基含有共重合体も挙げられる。但し、エポキシ基含有共重合体の加熱分解によりガスが発生することも、それに起因して表面実装リレー用部品等の成形体が膨れることも起きにくいことから、本発明に係る液晶性樹脂組成物は、エポキシ基含有共重合体を含まないことが好ましい。 Examples of other polymers include liquid crystal resins other than (A) liquid crystal resin. However, it is preferable that 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. Examples of other polymers include epoxy group-containing copolymers. However, 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.
 その他の充填剤とは、アスペクト比8以上の繊維状ウォラストナイト、マイカ、及びカーボンブラック以外の充填剤をいい、例えば、アスペクト比8以上の繊維状ウォラストナイト以外の繊維状充填剤(例えば、アスペクト比8未満の繊維状ウォラストナイト、ミルドファイバー)、マイカ以外の板状充填剤(例えば、タルク)が挙げられる。但し、液晶性樹脂組成物の流動性、成形体の変形抑制効果、フィラー脱離抑制効果等の観点から、本発明に係る液晶性樹脂組成物は、アスペクト比8未満の繊維状ウォラストナイト、ミルドファイバー、及びタルクを含有しないことが好ましい。 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). However, from the viewpoints of the fluidity of the liquid crystal resin composition, the effect of suppressing deformation of the molded product, the effect of suppressing filler detachment, etc., 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.
 本発明に係る液晶性樹脂組成物の製造方法は、液晶性樹脂組成物中の成分を均一に混合できれば特に限定されず、従来知られる樹脂組成物の製造方法から適宜選択することができる。例えば、1軸又は2軸押出機等の溶融混練装置を用いて、各成分を溶融混練して押出した後、得られた液晶性樹脂組成物を粉末、フレーク、ペレット等の所望の形態に加工する方法が挙げられる。 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. For example, 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.
 本発明に係る液晶性樹脂組成物は流動性に優れるため、成形時の最小充填圧力が過度になりにくく、表面実装リレー用部品等を好ましく成形できる。 Since the 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.
 液晶性樹脂の融点より10~30℃高い温度で、剪断速度1000/秒で、ISO11443に準拠して測定した液晶性樹脂組成物の溶融粘度が500Pa・s以下(より好ましくは、5Pa・s以上100Pa・s以下)であることが、表面実装リレー用部品の成形時において、液晶性樹脂組成物の流動性を確保しやすく、充填圧力が過度になりにくい点で好ましい。 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.
<表面実装リレー用部品及び表面実装リレー>
 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.
 本発明に係る表面実装リレー用部品及び本発明に係る表面実装リレーについて説明する。図1(a)は、本発明に係る表面実装リレーの実施形態を模式的に示す斜視図であり、図1(b)は、図1(a)のAA断面を示す部分断面図である。表面実装リレー1は、ベース2と、ケース3と、コイルブロック4と、接極子ブロック5と、端子6とを備える。 The surface mount relay component according to the present invention and the surface mount relay according to the present invention will be described. 1 (a) is a perspective view schematically showing an embodiment of a surface mount relay according to 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, a polaron block 5, and a terminal 6.
 ベース2は、ベース2から突出する端子6を備える。ベース2の上面の外周部には、ケース3が配置される。ベース2の上面の中央部には、コイルブロック4及び接極子ブロック5がこの順に配置される。 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.
 ケース3は、ベース2の上面の外周部と、コイルブロック4及び接極子ブロック5とを覆うように配置される。ベース2とケース3とで形成される中空容器状の空間内部にコイルブロック4及び接極子ブロック5が収容される。 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.
 コイルブロック4は、ボビン41と、コイル42と、鉄心43とを備え、ベース2の上面の中央部に配置される。ボビン41は、長軸方向に貫通した円筒部を有し、ボビン41の外周には、端子6の一部の一端と電気的に接続されているコイル42が巻かれ、ボビン41の上記円筒部には、鉄心43が挿入されている。 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.
 接極子ブロック5は、接極子連結部51と、接極子連結部51からボビン41の長軸方向に沿って互いに逆向きに延びる接極子52とを備え、コイルブロック4上に配置される。接極子52は、端子6の別の一部の一端と電気的に接続されている。コイル42への導通により電磁石が形成されると、磁力により、接極子52の先端は、コイルブロック4側に移動する。その結果、コイル42を含む入力側からの信号が、接極子52を含む出力側へと伝達される。 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. When an electromagnet is formed by conduction to the coil 42, the tip of the quadrupole 52 moves toward the coil block 4 due to the magnetic force. As a result, the signal from the input side including the coil 42 is transmitted to the output side including the polaron 52.
 端子6は、一端がコイル42又は接極子52と電気的に接続されており、他端が後述のプリント基板7に電気的に導通可能に接続されている。端子6は、ベース2から突出しており、後述の通り、プリント基板7に半田付けするようになっている。 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.
 上述の部品のうち、ベース2、ケース3、ボビン41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た成形体として形成できる点等を考慮し、本発明に係る液晶性樹脂組成物からなることが好ましい。即ち、本発明に係る表面実装リレー用部品としては、例えば、ベース、ケース、ボビン等が挙げられる。 Among the above-mentioned parts, 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.
 表面実装リレー1は、例えば、ベース2の上面の中央部にコイルブロック4及び接極子ブロック5をこの順に配置し、その後、ベース2の上面の外周部にケース3を配置し、ベース2とケース3とを接着剤により接着することにより、製造することができる。 In the surface mount relay 1, for example, 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.
 表面実装リレー1をプリント基板7に実装する方法について説明する。図2(a)に示す通り、表面実装リレー1では、半田付け面が表面実装リレー1と平行になるように、表面実装リレー1より垂直に突き出した端子6が直角に曲げられている。そのため、表面実装リレー1は、プリント基板7に孔を設けることなく、プリント基板7表面の導体パターン8上に設けられた半田パッド(図示せず)に端子6を載置し、半田リフロー処理を行うことにより、電気的に導通可能にプリント基板7に固定される。 The method of mounting the surface mount relay 1 on the printed circuit board 7 will be described. As shown in FIG. 2A, in the surface mount relay 1, 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.
 なお、上述の説明では、図2(a)に示す通り、表面実装リレー1より垂直に突き出した端子6の先端が表面実装リレー1の外側へ直角に曲げられている場合を示した。一方、図2(b)に示す通り、表面実装リレー1より垂直に突き出した端子6の先端が表面実装リレー1の内側へ直角に曲げられていてもよい。 In the above description, as shown in 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. On the other hand, as shown in 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.
 以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.
<実施例1~3、比較例1~11>
 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.
 [融点の測定]
 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.
 [溶融粘度の測定]
 (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.
 (LCP1の製造方法)
 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.
 (LCP2の製造方法)
 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.
 (LCP3の製造方法)
 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
 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。得られたペレットの融点は355℃、溶融粘度は10Pa・sであった。 After charging the raw materials in 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 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.
 (LCP4の製造方法)
 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.
 (液晶性樹脂以外の成分)
・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, average fiber diameter 8 μm)
Fibrous wollastonite 2: NYAD 325 (manufactured by NYCO Materials, aspect ratio 5, average fiber length 50 μm, average fiber diameter 5 μm)
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 length 3 mm; AB-25S manufactured by Yamaguchi Mica Industry Co., Ltd., average particle diameter 25 μm
Talc; Crown Talc PP manufactured by Matsumura Sangyo Co., Ltd., average particle size 10 μm
 上記で得られた各液晶性樹脂と、上述した液晶性樹脂以外の成分とを二軸押出機を使用して混合し、液晶性樹脂組成物を得た。各成分の配合量は表1及び表2に示した通りである。なお、以下、表中の配合量に関する「%」は質量%を示す。また、液晶性樹脂組成物を得る際の押出条件は下記の通りである。
 [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)
 (液晶性樹脂組成物の溶融粘度の測定)
 (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.
 下記の方法に基づき、液晶性樹脂組成物から成形した成形体の物性を測定した。各評価結果を表1及び表2に示す。 Based on the following method, the physical characteristics of the molded product molded from the liquid crystal resin composition were measured. The evaluation results are shown in Tables 1 and 2.
 (荷重たわみ温度)
 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
 (曲げ試験)
 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
 (リレーケース最小充填圧力)
 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
 上記のリレーケースを射出成形する際に良好な成形体を得られる最小の射出充填圧力を最小充填圧力として測定した。 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.
 (リレーケース変形)
 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
 (リレーケースリフロー時膨れ)
 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.
 (フィラー脱離性)
 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.
 (リレーケース気密性)
 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.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
 表1及び表2に示される通り、実施例において、溶融粘度、荷重たわみ温度、曲げ強度、曲げ歪、曲げ弾性率は良好な値を示し、リレーケース最小充填圧力は80MPa以下であり、リレーケース変形、リレーケースリフロー時膨れ、リレーケースフィラー脱離、リレーケース気密性の評価はいずれも良好であった。よって、本発明に係る液晶性樹脂組成物は、流動性に優れ、この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ことが確認された。したがって、上記液晶性樹脂組成物は、表面実装リレー用部品及び表面実装リレーの製造に好適に用いることができる。 As shown in Tables 1 and 2, in the examples, 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, and 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.
 1 表面実装リレー
 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 Surface mount relay 2 Base 3 Case 4 Coil block 41 Bobbin 42 Coil 43 Iron core 5 Polaron block 51 Polaron connection 52 Polaron 6 Terminal 7 Printed circuit board 8 Conductor pattern

Claims (4)

  1.  (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。
    Figure JPOXMLDOC01-appb-C000001
    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.
    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.
    Figure JPOXMLDOC01-appb-C000001
  2.  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.
  3.  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.
  4.  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.
PCT/JP2021/012893 2020-05-13 2021-03-26 Liquid-crystalline resin composition for surface-mounted relays, and surface-mounted relay using same WO2021229931A1 (en)

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