WO2020100618A1 - Composition de résine cristal liquide et connecteur comprenant un article moulé de ladite composition de résine cristal liquide - Google Patents

Composition de résine cristal liquide et connecteur comprenant un article moulé de ladite composition de résine cristal liquide Download PDF

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WO2020100618A1
WO2020100618A1 PCT/JP2019/042849 JP2019042849W WO2020100618A1 WO 2020100618 A1 WO2020100618 A1 WO 2020100618A1 JP 2019042849 W JP2019042849 W JP 2019042849W WO 2020100618 A1 WO2020100618 A1 WO 2020100618A1
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liquid crystalline
crystalline resin
resin composition
connector
mica
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PCT/JP2019/042849
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English (en)
Japanese (ja)
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博樹 深津
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 JP2020526338A priority Critical patent/JP6841978B2/ja
Priority to CN201980074882.7A priority patent/CN113015765B/zh
Priority to KR1020217012860A priority patent/KR102397208B1/ko
Publication of WO2020100618A1 publication Critical patent/WO2020100618A1/fr
Priority to PH12021551106A priority patent/PH12021551106A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/46—Bases; Cases

Definitions

  • the present invention relates to a liquid crystal resin composition and a connector including a molded product of the liquid crystal resin composition.
  • the liquid crystalline resin is a thermoplastic resin with excellent dimensional accuracy and fluidity. Due to such characteristics, the liquid crystalline resin has been conventionally used as a material for various electronic components.
  • Patent Document 1 discloses a connector molded from a liquid crystalline resin composition reinforced with mica and glass fiber. Such a connector is for connecting a board-to-board connector or a flexible printed circuit board (FPC) and a flexible flat cable (FFC), which are required to have heat resistance, suppression of warp deformation, fluidity, and dimensional stability. It is used as a connector for flexible printed circuit boards used in.
  • FPC flexible printed circuit board
  • FFC flexible flat cable
  • the present invention has been made in view of such circumstances, is excellent in heat resistance and mechanical strength, it is possible to realize the production of a connector in which warp deformation is suppressed, liquid crystal resin composition having good fluidity, and
  • An object of the present invention is to provide a connector including a molded article of a liquid crystalline resin composition.
  • the present inventors have solved the above problems by combining a liquid crystalline resin, a fibrous wollastonite, and mica at a predetermined content, and setting the aspect ratio of the fibrous wollastonite within a predetermined range. I found that I could solve it. Specifically, the present invention provides the following.
  • a liquid crystalline resin composition comprising (A) a liquid crystalline resin, (B) fibrous wollastonite, and (C) mica,
  • the (B) fibrous wollastonite has an aspect ratio of 8 or more, With respect to the entire liquid crystalline resin composition, The content of the (A) liquid crystalline resin is 62.5 to 72.5% by mass, The content of the (B) fibrous wollastonite is 2.5 to 15% by mass, The content of the (C) mica is 17.5 to 30% by mass, The total content of the (B) fibrous wollastonite and the (C) mica is 27.5 to 37.5% by mass.
  • a connector including a molded product of the liquid crystalline resin composition according to (1) or (2), having a total product length of less than 30 mm and a product height of less than 5 mm.
  • the distance between pitches is 0.5 mm or less,
  • the total product length is 3.5 mm or more and less than 30 mm,
  • the product height is less than 1.5mm,
  • the connector according to (3) or (4) which is a low-profile narrow-pitch connector which is a board-to-board connector or a connector for a flexible printed board.
  • a liquid crystal resin composition having excellent heat resistance and mechanical strength, capable of producing a connector in which warp deformation is suppressed, and having good fluidity, and a molded article of the liquid crystal resin composition are provided.
  • a connector containing is provided.
  • the liquid crystalline resin composition according to the present invention contains a predetermined amount of a liquid crystalline resin, fibrous wollastonite, and mica, and the fibrous wollastonite has an aspect ratio of 8 or more.
  • the components constituting the liquid crystalline resin composition according to the present invention will be described below.
  • the liquid crystal resin (A) used in the present invention refers to a melt-processable polymer having a property capable of forming an optically anisotropic melt phase.
  • the properties of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using a crossed polarizer. More specifically, the confirmation of the anisotropic molten phase can be performed by using a Leitz polarization microscope and observing the molten sample placed on the Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times.
  • the liquid crystalline resin applicable to the present invention when inspected between orthogonal polarizers, normally transmits polarized light even if it is in a molten stationary state, and exhibits optical anisotropy.
  • the kind of the above-mentioned (A) liquid crystalline resin is not particularly limited, and is preferably an aromatic polyester and / or an aromatic polyesteramide. Further, a polyester partially containing an aromatic polyester and / or an aromatic polyesteramide in the same molecular chain is also in the range.
  • the (A) liquid crystalline resin is preferably at least about 2.0 dl / g, more preferably 2.0 to 10.0 dl / g when dissolved in pentafluorophenol at a concentration of 0.1% by mass at 60 ° C. Those having a logarithmic viscosity (IV) of 1 are preferably used.
  • the aromatic polyester or aromatic polyesteramide as the liquid crystalline resin (A) applicable to the present invention is particularly preferably an aromatic polyester or aromatic polyesteramide having a repeating unit derived from an aromatic hydroxycarboxylic acid as a constituent component. Is.
  • a polyester comprising a repeating unit derived from two or more kinds, and (c) a repeating unit derived from at least one kind or two or more kinds of an aromatic diol, an alicyclic diol, an aliphatic diol, and a derivative thereof; (4) Repeating units mainly derived from (a) one or more aromatic hydroxycarboxylic acids and their derivatives, and (b) one or two aromatic hydroxyamines, aromatic diamines and their derivatives.
  • a polyester amide comprising a repeating unit derived from one or more species, and (c) a repeating unit derived from one or more species of an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and derivatives thereof; (5) A repeating unit mainly derived from (a) one or more aromatic hydroxycarboxylic acids and their derivatives, and (b) one or two aromatic hydroxyamines, aromatic diamines and their derivatives.
  • a repeating unit derived from one or more species (c) a repeating unit derived from one or more of an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, and derivatives thereof, and (d) an aromatic diol, an alicyclic ring
  • the polyester amide include a group diol, an aliphatic diol, and a repeating unit derived from at least one or two or more of their derivatives.
  • a molecular weight modifier may be used in combination with the above constituent components.
  • Preferred examples of specific compounds constituting the liquid crystalline resin (A) applicable to the present invention include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; 2,6-dihydroxy.
  • Aromatic diols such as naphthalene, 1,4-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl, hydroquinone, resorcin, compounds represented by the following general formula (I), and compounds represented by the following general formula (II)
  • Aromatic carboxylic acids such as terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and compounds represented by the following general formula (III); p-aminophenol, p- Aromatic amines such as phenylenediamine may be mentioned.
  • the most preferable liquid crystal resin (A) applicable to the present invention comprises the following structural units (I) to (VI) as essential constituent components,
  • the content of the structural unit (I) is 50 to 70 mol% based on all the structural units,
  • the content of the structural unit (II) is 0.5 mol% or more and less than 4.5 mol% with respect to all the structural units,
  • the content of the structural unit (III) is 10.25 to 22.25 mol% with respect to all the structural units,
  • the content of the structural unit (IV) is 0.5 mol% or more and less than 4.5 mol% with respect to all the structural units,
  • the content of the structural unit (V) is 5.75 to 23.75 mol% with respect to all the structural units,
  • the content of the structural unit (VI) is 1 to 7 mol% with respect to all the structural units,
  • the total content of the structural unit (II) and the structural unit (IV) is 1 mol% or more and less than 5 mol% with respect to all the structural units
  • the liquid crystalline resin (A) used in the present invention can be prepared from the above-mentioned monomer compound (or a mixture of monomers) by a known method using a direct polymerization method or a transesterification method, usually a melt polymerization method.
  • a solution polymerization method, a slurry polymerization method, a solid phase polymerization method or the like, or a combination of two or more thereof is preferably used, and a melt polymerization method or a combination of the melt polymerization method and the solid phase polymerization method is preferably used.
  • the above-mentioned compounds having an ester-forming ability may be used as they are in the polymerization, or they may be modified from a precursor to a derivative having an ester-forming ability in the preceding stage of the polymerization.
  • Various catalysts can be used in these polymerizations, and representative ones are potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, tris (2). , 4-pentanedionato) cobalt (III) and the like, and organic compound-based catalysts such as N-methylimidazole and 4-dimethylaminopyridine.
  • the catalyst is generally used in an amount of about 0.001 to 1% by mass, preferably about 0.01 to 0.2% by mass, based on the total mass of the monomers. If necessary, the polymers produced by these polymerization methods can be increased in molecular weight by a solid-state polymerization method of heating under reduced pressure or in an inert gas.
  • the melt viscosity of the liquid crystalline resin (A) obtained by the above method is not particularly limited. Generally, those having a melt viscosity at a molding temperature of 3 Pa ⁇ s or more and 500 Pa ⁇ s or less at a shear rate of 1000 sec ⁇ 1 can be used. However, if the viscosity itself is too high, the fluidity is extremely deteriorated, which is not preferable.
  • the liquid crystal resin (A) may be a mixture of two or more kinds of liquid crystal resins.
  • the liquid crystalline resin composition according to the present invention contains (A) a liquid crystalline resin in the liquid crystalline resin composition in an amount of 62.5 to 72.5% by mass based on the entire liquid crystalline resin composition.
  • A a liquid crystalline resin in the liquid crystalline resin composition in an amount of 62.5 to 72.5% by mass based on the entire liquid crystalline resin composition.
  • the liquid crystalline resin composition according to the present invention preferably contains (A) a liquid crystalline resin in the liquid crystalline resin composition in an amount of 63.5 to 71.5 mass% with respect to the entire liquid crystalline resin composition, It is more preferable that the content is 65 to 70% by mass.
  • the aspect ratio of the fibrous wollastonite that is, the value of average fiber length / average fiber diameter is 8 or more.
  • the aspect ratio is preferably 10 to 25, and more preferably 15 to 20 from the viewpoint of the bending elastic modulus and warp deformation suppressing effect of a molded article such as a connector obtained from the liquid crystalline resin composition according to the present invention. Is.
  • the (B) fibrous wollastonite is not particularly limited, and known fibrous wollastonite can be used, for example.
  • the (B) 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 (B) fibrous wollastonite is preferably 3.0 to 50 ⁇ m, and more preferably 4.5 to 40 ⁇ m.
  • the average fiber diameter is 3.0 ⁇ m or more, a molded product such as a connector obtained from the liquid crystalline resin composition according to the present invention can easily secure sufficient mechanical strength and deflection temperature under load.
  • the average fiber diameter is 50 ⁇ m or less, the effect of suppressing napping on the surface of the molded body tends to be high.
  • the average fiber diameter is the average of the values obtained by observing fibrous wollastonite with a scanning electron microscope and measuring the fiber diameters of 100 fibrous wollastonite.
  • the average fiber length of the fibrous wollastonite is preferably 30 to 800 ⁇ m, and more preferably the average fiber length is 50 to 600 ⁇ m.
  • a molded product such as a connector obtained from the liquid crystalline resin composition according to the present invention can easily secure sufficient mechanical strength and deflection temperature under load.
  • the average fiber length is 800 ⁇ m or less, the effect of suppressing napping on the surface of the molded body tends to be high.
  • 10 stereoscopic microscope images of fibrous wollastonite are taken into a PC from a CCD camera, and 100 images are obtained for each stereoscopic microscope image by an image processing method using an image measuring machine.
  • the fibrous wollastonite of, that is, the average of the values obtained by measuring the fiber length of a total of 1000 fibrous wollastonites is adopted.
  • the liquid crystalline resin composition according to the present invention contains (B) fibrous wollastonite in the liquid crystalline resin composition in an amount of 2.5 to 15% by mass based on the entire liquid crystalline resin composition.
  • fibrous wollastonite (B) is less than 2.5% by mass relative to the entire liquid crystalline resin composition, warpage deformation of a molded article such as a connector obtained from the liquid crystalline resin composition, particularly It is not preferable because warpage deformation after reflow may increase.
  • the fibrous wollastonite (B) in the present invention is preferably contained in the liquid crystalline resin composition in an amount of 3 to 13% by mass, and preferably 5 to 10% by mass, based on the entire liquid crystalline resin composition. More preferable.
  • the liquid crystalline resin composition according to the present invention contains mica. By including mica in the liquid crystalline resin composition according to the present invention, it is possible to obtain a molded article having a sufficient flexural modulus and suppressed warpage deformation. Mica can be used alone or in combination of two or more.
  • Mica is contained in an amount of 17.5 to 30 mass% with respect to the entire liquid crystalline resin composition.
  • the content of mica is less than 17.5% by mass with respect to the entire liquid crystalline resin composition, improvement in bending elastic modulus and suppression of warpage deformation of a molded article obtained from the liquid crystalline resin composition are not sufficient, which is preferable. Absent.
  • the content of mica is more than 30% by mass with respect to the entire liquid crystalline resin composition, the fluidity of the liquid crystalline resin composition may be deteriorated and molding of the liquid crystalline resin composition may be difficult. Therefore, it is not preferable.
  • Mica is preferably contained in the liquid crystalline resin composition in an amount of 18.5 to 27.5% by mass, and more preferably 20 to 25% by mass, based on the entire liquid crystalline resin composition.
  • Mica is a pulverized silicate mineral containing aluminum, potassium, magnesium, sodium, iron and the like.
  • the mica that can be used in the present invention include muscovite, phlogopite, biotite, artificial mica, and the like. Among them, muscovite is preferable because of its good hue and low cost.
  • the wet pulverization method is a method in which rough mica is roughly pulverized by a dry pulverizer, water is added to the mixture, and the slurry is wet pulverized to be main pulverized, followed by dehydration and drying.
  • the dry pulverization method is a low-cost and general method, but when the wet pulverization method is used, it is easier to pulverize a mineral thinly and finely.
  • it is preferable to use a thin and fine pulverized product 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 grinding method.
  • a step of dispersing the material to be pulverized in water is required. Therefore, in order to enhance the dispersion efficiency of the material to be pulverized, it is necessary to add an aggregating sedimentation agent and / or a sedimentation aid to the material to be pulverized. Is common.
  • Examples of the flocculating settling agent and the settling aid that can be used in the present invention include polyaluminum chloride, aluminum sulfate, ferrous sulfate, ferric sulfate, copper sulfide, polyferric sulfate, polyferric chloride, iron-silica inorganic high Examples include molecular flocculants, ferric chloride-silica inorganic polymer flocculants, slaked lime (Ca (OH) 2 ), caustic soda (NaOH), soda ash (Na 2 CO 3 ), and the like. These coagulating sedimentation agents and sedimentation aids have an alkaline or acidic pH.
  • the mica used in the present invention is preferably one that does not use a flocculating sedimentation agent and / or a sedimentation aid during wet pulverization.
  • the use of mica that has not been treated with a flocculating sedimentation agent and / or a sedimentation aid is obtained because the polymer in the liquid crystalline resin composition is less likely to decompose, and a large amount of gas is not generated or the molecular weight of the polymer is less likely to occur. It is easy to maintain the performance of the molded product such as the connector better.
  • the mica that can be used in the present invention preferably has an average particle size of 10 to 100 ⁇ m, particularly preferably 20 to 80 ⁇ m, as measured by the Microtrack laser diffraction method.
  • the average particle diameter of mica is 10 ⁇ m or more, the effect of improving the rigidity of the molded body tends to be sufficient, which is preferable.
  • the average particle size of mica is 100 ⁇ m or less, the rigidity of the molded body 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 connector and the like of the present invention.
  • the thickness of mica that can be used in the present invention is preferably 0.01 to 1 ⁇ m, and 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 break during melt processing of the liquid crystalline resin composition, and thus the rigidity of the molded body may be easily improved, which is preferable.
  • the thickness of the mica is 1 ⁇ m or less, the effect of improving the rigidity of the molded body 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 give a granular form.
  • the total content of (B) fibrous wollastonite and (C) mica is 27.5 to 37.5 mass% with respect to the entire liquid crystalline resin composition. is there.
  • the content is less than 27.5 mass% with respect to the entire liquid crystalline resin composition, the bending elastic modulus and warp deformation suppressing effect of a molded article such as a connector obtained from the liquid crystalline resin composition deteriorates. Not preferable.
  • the content is more than 37.5 mass% with respect to the entire liquid crystalline resin composition, the liquidity of the liquid crystalline resin composition is apt to deteriorate, and the connector etc. obtained from the liquid crystalline resin composition are likely to deteriorate. It is not preferable because the bending strain of the molded body may be reduced.
  • the content is preferably 28.0 to 36.5% by mass, and more preferably 28.5 to 35% by mass, based on the entire liquid crystalline resin composition.
  • liquid crystalline resin composition according to the present invention, other polymers, other fillers, known substances generally added to synthetic resins, that is, antioxidants and ultraviolet rays, within a range that does not impair the effects of the present invention.
  • Other components such as stabilizers such as absorbents, antistatic agents, flame retardants, colorants such as dyes and pigments, lubricants, release agents, crystallization accelerators, crystal nucleating agents, etc. are also added appropriately according to the required performance. be able to.
  • the other components may be used alone or in combination of two or more.
  • the other filler refers to a filler other than fibrous wollastonite having an aspect ratio of 8 or more, mica, and carbon black, for example, a fibrous filler other than the fibrous wollastonite having an aspect ratio of 8 or more (for example, , Fibrous wollastonite with an aspect ratio of less than 8, milled fiber), and plate-like fillers other than mica (for example, talc).
  • the liquid crystalline resin composition according to the present invention may not contain fibrous wollastonite having an aspect ratio of less than 8, milled fiber, and talc from the viewpoint of improving the mechanical strength of the molded body, suppressing warpage deformation, and the like. preferable.
  • the method for producing the liquid crystalline resin composition according to the present invention is not particularly limited as long as the components in the liquid crystalline resin composition can be uniformly mixed, and can be appropriately selected from conventionally known resin composition producing methods. For example, after melt-kneading and extruding each component using a melt-kneading device such as a single-screw or twin-screw extruder, the obtained liquid crystalline resin composition is processed into a desired form such as powder, flakes and pellets. There is a method of doing.
  • the minimum filling pressure during molding is unlikely to be excessive, and connectors, particularly parts having a small and complicated shape such as a low narrow pitch connector, etc. Can be preferably molded.
  • the degree of fluidity is judged by the minimum filling pressure of the connector. That is, the minimum injection filling pressure with which a good molded product can be obtained when the FPC connector shown in FIG. 1 is injection-molded is specified as the minimum filling pressure. The lower the minimum filling pressure, the better the flowability.
  • the melt viscosity of the liquid crystalline resin composition measured according to ISO11443 at a temperature 10 to 30 ° C. higher than the melting point of the liquid crystalline resin at a shear rate of 1000 / sec is preferably 1 ⁇ 10 5 Pa ⁇ s or less, It is preferably 5 Pa ⁇ s or more and 1 ⁇ 10 2 Pa ⁇ s or less.
  • the melt viscosity is 1 ⁇ 10 5 Pa ⁇ s or less, it is easy to secure the fluidity of the liquid crystalline resin composition during molding of a connector, particularly a low narrow pitch connector, and the filling pressure is unlikely to become excessive. ..
  • the connector of the present invention can be obtained by molding the liquid crystalline resin composition of the present invention.
  • the connector of the present invention is not particularly limited, and examples thereof include a connector having a total product length of less than 30 mm and a product height of less than 5 mm.
  • the connector having a product total length of less than 30 mm and a product height of less than 5 mm is not particularly limited, and examples thereof include a low narrow pitch connector, a coaxial connector, a micro SIM connector, and a micro SD connector. Above all, a low-profile narrow-pitch connector is preferable.
  • the low-profile narrow-pitch connector is not particularly limited, and includes, for example, a board-to-board connector (also known as "BtoB connector”), a connector for flexible printed circuit board (flexible printed circuit board (FPC) and flexible flat cable (FFC)). And also known as "FPC connector”) and the like.
  • a board-to-board connector also known as "BtoB connector”
  • FPC flexible printed circuit board
  • FFC flexible flat cable
  • FPC connector flexible flat cable
  • the distance between pitches is 0.5 mm or less
  • the total product length is 3.5 mm or more and less than 30 mm
  • the product height is 1.5 mm or less
  • a low-profile narrow-pitch connector that is a board-to-board connector or a connector for a flexible printed circuit board is available. It is suitable.
  • the molding method for obtaining the connector of the present invention is not particularly limited, and it is preferable to select molding conditions without residual internal stress in order to prevent deformation of the obtained connector.
  • the cylinder temperature of the molding machine is preferably a temperature above the melting point of the liquid crystalline resin.
  • the mold temperature is preferably 70 to 100 ° C.
  • the liquid crystalline resin composition filled in the mold may cause flow failure, which is not preferable. If the mold temperature is high, problems such as burrs may occur, which is not preferable.
  • the injection speed is preferably 150 mm / sec or more. If the injection speed is low, only unfilled compacts may be obtained. Even if a completely filled compact is obtained, it will be a compact with high filling pressure and large residual internal stress, resulting in poor flatness. There is a possibility that you can only get it.
  • the warp deformation of the connector of the present invention is suppressed.
  • Determine the degree of warpage of the connector as follows. That is, with the FPC connector shown in FIG. 1, the height is measured at a plurality of positions indicated by black circles in FIG. 2, and the difference between the maximum height and the minimum height from the least-squares plane is taken as the warp.
  • the change in warpage is suppressed before and after performing IR reflow.
  • the connector of the present invention is excellent in heat resistance, for example, heat resistance evaluated by high temperature rigidity.
  • the high temperature rigidity is evaluated by measuring the deflection temperature under load according to ISO75-1.
  • the connector of the present invention has excellent mechanical strength. Mechanical strength is evaluated by measuring bending strength, bending strain, and bending elastic modulus by a bending test based on ASTM D790.
  • liquid crystalline resins LCP1 and 2 were manufactured as follows. At that time, the melting point and 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. After that, 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 out acetic acid, excess acetic anhydride, and other low boiling components. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to change the pressure from a reduced pressure state to a normal pressure state to a pressure state, the polymer was discharged from the lower portion 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.
  • Fibrous filler Wollastonite 1 NYGLOS 8 (manufactured by NYCO Materials, aspect ratio 17, average fiber length 136 ⁇ m, average fiber diameter 8 ⁇ m)
  • Wollastonite 2 NYAD 325 (manufactured by NYCO Materials, aspect ratio 5, average fiber length 50 ⁇ m, average fiber diameter 5 ⁇ m)
  • Milled fiber Nitto Boseki PF70E001, fiber diameter 10 ⁇ m, average fiber length 70 ⁇ m (nominal manufacturer value) ⁇ Plate filler mica; 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 ⁇ m
  • Each liquid crystalline resin obtained above was mixed with components other than the above-mentioned liquid crystalline resin using a twin-screw extruder to obtain a liquid crystalline resin composition.
  • the blending amount of each component is as shown in Tables 1 and 2. In the following, "%" relating to the blending amount in the table indicates mass%.
  • the extrusion conditions for obtaining the liquid crystalline resin composition are as follows. [Extrusion conditions] [Examples 1 to 4, Comparative Examples 1 to 7] The temperature of the cylinder provided at the main feed port was 250 ° C, and the temperature of all other cylinders was 360 ° C. All of the liquid crystalline resin was supplied from the main feed port. The filler was supplied from the side feed port.
  • Example 5 The temperature of the cylinder provided at the main feed port was 250 ° C, and the temperature of all other cylinders was 370 ° C. All of the liquid crystalline resin was supplied from the main feed port. The filler was supplied from the side feed port.
  • the physical properties of the connector including the molded product of the liquid crystalline resin composition were measured based on the following methods. The evaluation results are shown in Tables 1 and 2.
  • the liquid crystalline resin composition was injection-molded under the following molding conditions to obtain a molded body, and the deflection temperature under load was measured according to ISO75-1 and 2.
  • Molding machine Sumitomo Heavy Industries, SE100DU Cylinder temperature: 360 ° C (Examples 1 to 4, Comparative Examples 1 to 7) 370 ° C (Example 5) Mold temperature: 80 °C Injection speed: 33 mm / sec
  • the liquid crystalline resin composition was injection-molded under the following molding conditions to obtain a molded body having a thickness of 0.8 mm, and the bending strength, bending strain, and bending elastic modulus were measured according to ASTM D790.
  • Molding machine Sumitomo Heavy Industries, SE100DU Cylinder temperature: 360 ° C (Examples 1 to 4, Comparative Examples 1 to 7) 370 ° C (Example 5) Mold temperature: 80 °C Injection speed: 33 mm / sec
  • Example 5 Mold temperature: 80 °C Injection speed: 200 mm / sec Holding pressure: 50 MPa Pressure holding time: 0.5 seconds Cooling time: 10 seconds Screw rotation speed: 120 rpm Screw back pressure: 1.2 MPa
  • the obtained connector was left standing on a horizontal desk, and the height of the connector was measured by a Mitutoyo Quick Vision 404 PROCNC image measuring machine. At that time, the height was measured at a plurality of positions indicated by black circles in FIG. 2, and the difference between the maximum height and the minimum height from the least square plane was used as the warp of the FPC connector. The warpage was measured before and after the IR reflow performed under the following conditions.
  • the minimum injection filling pressure at which a good molded product was obtained when the FPC connector of FIG. 1 was injection-molded was measured as the minimum filling pressure.
  • the deflection temperature under load is 245 ° C. or more
  • the bending strain is 2.0% or more
  • the bending elastic modulus is 14000 MPa or more
  • the FPC connector warpage before reflow is less than 0.030 mm
  • the FPC connector warp after reflow was less than 0.090 mm
  • the FPC connector minimum filling pressure was less than 75 MPa. Therefore, the liquid crystalline resin composition according to the present invention is excellent in fluidity, and a connector including a molded article of the liquid crystalline resin composition is excellent in heat resistance and mechanical strength, and warpage deformation is suppressed. confirmed.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Connector Housings Or Holding Contact Members (AREA)
  • Manufacturing Of Electrical Connectors (AREA)

Abstract

L'invention concerne : une composition de résine cristal liquide ayant une bonne fluidité, de sorte qu'il est possible de fabriquer un connecteur qui a une excellente résistance à la chaleur et une excellente résistance mécanique, et dans lequel un gauchissement est supprimé; et un connecteur comprenant un article moulé de la composition de résine cristal liquide.　La composition de résine cristal liquide de la présente invention comprend une résine cristal liquide (A), de la wollastonite fibreuse (B) et du mica (C), le rapport d'aspect de la wollastonite fibreuse (B) étant d'au moins 8, la teneur en résine cristal liquide (A) étant de 62,5 à 72,5 % en masse, la teneur en wollastonite fibreuse (B) étant de 2,5 à 15 % en masse, la teneur en mica (C) étant de 17,5 à 30 % en masse, et la teneur totale en wollastonite fibreuse (B) et en mica (C) étant de 27,5 à 37,5 % en masse par rapport à la composition de résine cristal liquide dans son ensemble.
PCT/JP2019/042849 2018-11-15 2019-10-31 Composition de résine cristal liquide et connecteur comprenant un article moulé de ladite composition de résine cristal liquide WO2020100618A1 (fr)

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JP2020526338A JP6841978B2 (ja) 2018-11-15 2019-10-31 液晶性樹脂組成物、及び当該液晶性樹脂組成物の成形品を含むコネクター
CN201980074882.7A CN113015765B (zh) 2018-11-15 2019-10-31 液晶性树脂组合物、及包含该液晶性树脂组合物的成形品的连接器
KR1020217012860A KR102397208B1 (ko) 2018-11-15 2019-10-31 액정성 수지 조성물 및 상기 액정성 수지 조성물의 성형품을 포함하는 커넥터
PH12021551106A PH12021551106A1 (en) 2018-11-15 2021-05-14 Liquid crystalline resin composition and connector including molded article of said liquid crystalline resin composition

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JP2018-214698 2018-11-15

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WO2021229931A1 (fr) * 2020-05-13 2021-11-18 ポリプラスチックス株式会社 Composition de résine cristalline liquide pour des relais montés en surface, et relais monté en surface l'utilisant
WO2023054314A1 (fr) * 2021-09-28 2023-04-06 ポリプラスチックス株式会社 Composition de résine

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CN115651368B (zh) * 2022-11-08 2023-12-19 珠海万通特种工程塑料有限公司 一种抗静电液晶聚酯组合物及其制备方法和应用

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KR102397208B1 (ko) 2022-05-12
JP6841978B2 (ja) 2021-03-10
KR20210055782A (ko) 2021-05-17
CN113015765B (zh) 2022-04-26
TW202028365A (zh) 2020-08-01
PH12021551106A1 (en) 2021-11-22
CN113015765A (zh) 2021-06-22
JPWO2020100618A1 (ja) 2021-02-15

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