WO2014050371A1 - Composition de résine composite pour composant électronique, et composant électronique moulé à partir de celle-ci - Google Patents

Composition de résine composite pour composant électronique, et composant électronique moulé à partir de celle-ci Download PDF

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Publication number
WO2014050371A1
WO2014050371A1 PCT/JP2013/072226 JP2013072226W WO2014050371A1 WO 2014050371 A1 WO2014050371 A1 WO 2014050371A1 JP 2013072226 W JP2013072226 W JP 2013072226W WO 2014050371 A1 WO2014050371 A1 WO 2014050371A1
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resin composition
composite resin
electronic component
respect
content
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PCT/JP2013/072226
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English (en)
Japanese (ja)
Inventor
博樹 深津
峰生 大竹
和博 龍
淳一郎 杉浦
吉昭 田口
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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 SG11201502394YA priority Critical patent/SG11201502394YA/en
Priority to KR1020157010325A priority patent/KR20150060829A/ko
Priority to CN201380050474.0A priority patent/CN104704049B/zh
Priority to JP2014538282A priority patent/JP5769888B2/ja
Publication of WO2014050371A1 publication Critical patent/WO2014050371A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
    • C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K2019/521—Inorganic solid particles

Definitions

  • the present invention relates to a composite resin composition for electronic parts and an electronic part molded from the composite resin composition.
  • the present invention relates to a composite resin composition for an asymmetric electronic component, an asymmetric electronic component molded from the composite resin composition, a composite resin composition for a low profile narrow pitch connector, and a low molding molded from the composite resin composition.
  • narrow pitch connectors relate to narrow pitch connectors.
  • the liquid crystalline polymer is a thermoplastic resin excellent in dimensional accuracy, fluidity and the like. Due to these characteristics, liquid crystalline polymers have been conventionally employed as materials for various electronic components. In manufacturing such an electronic component, the liquid crystal polymer composition is required to have good fluidity. Examples of the electronic component include an asymmetric electronic component, a low profile narrow pitch connector, and a coaxial connector.
  • the molding technique has been devised, and a specific plate-like filler has been proposed in terms of material.
  • a specific plate-like filler has been proposed in terms of material.
  • a typical example of such an asymmetric electronic component is a memory module connector having a latch structure (having fixing claws at both ends) such as a DDR-DIMM connector.
  • a memory module connector for a notebook personal computer has a latch structure for mounting and a notch for alignment, and thus has a very complicated shape.
  • Patent Document 1 is formed from a liquid crystalline polymer composition obtained by blending a specific amount of a specific fibrous filler and a specific plate-like filler.
  • An asymmetric electronic component having no symmetry with respect to any of the XY axis plane, the YZ axis plane, and the XZ axis plane of the product is disclosed.
  • Patent Document 2 discloses a connector formed from a liquid crystalline polymer composition reinforced with mica and glass fiber. Such connectors are for board-to-board connectors and flexible printed boards used to connect flexible printed boards (FPCs) and flexible flat cables (FFCs) that require fluidity and dimensional stability. Used as a connector.
  • conventional liquid crystalline polymer compositions are not sufficiently fluid.
  • the asymmetric electronic component is disclosed in the above-mentioned Patent Document 1 due to a shape change accompanying an increase in the integration rate in the recent asymmetric electronic component, particularly a decrease in pitch distance, a product height, and an increase in the number of poles. It has been found that conventional liquid crystal polymer compositions such as the prepared liquid crystal polymer composition may not be able to cope with them. That is, the conventional liquid crystalline polymer composition has insufficient fluidity, and it has been difficult to obtain an asymmetric electronic component in which warpage deformation is suppressed from such a liquid crystalline polymer composition.
  • the present inventors have found that the above problem can be solved by combining a liquid crystalline polymer containing a predetermined amount of a specific structural unit, glass fibers and / or milled fibers, and a plate-like inorganic filler. Specifically, the present invention provides the following.
  • a composite resin composition for electronic parts comprising (A) a liquid crystalline polymer, (B) a milled fiber, and (C) a plate-like inorganic filler,
  • the (A) liquid crystalline polymer has, as essential constituents, the following constituent units: (I) constituent units derived from 4-hydroxybenzoic acid, (II) constituent units derived from 2-hydroxy-6-naphthoic acid, III) a structural unit derived from terephthalic acid, (IV) a structural unit derived from isophthalic acid, and (V) a structural unit derived from 4,4′-dihydroxybiphenyl,
  • the content of the structural unit (I) with respect to all the structural units is 35 to 75 mol%
  • the content of the structural unit (II) with respect to the total structural unit is 2 to 8 mol%
  • the content of the structural unit (III) with respect to all the structural units is 4.5 to 30.5 mol%
  • the electronic component is a low profile narrow pitch connector,
  • the above (A) liquid crystalline polymer has a [melting point-crystallization temperature] value of 50 to 60 ° C. and conforms to ISO 11443 at a shear rate of 1000 / sec at a temperature 10 to 20 ° C. higher than the melting point.
  • the composite resin composition for electronic parts according to (4), wherein the melt viscosity measured in this way is 5 to 15 Pa ⁇ s.
  • the average fiber length of the (B) milled fiber is 50 to 100 ⁇ m
  • (C) The plate-like inorganic filler is a composite resin composition for electronic parts according to (4) or (5), which is at least one selected from the group consisting of talc and mica.
  • the content of the liquid crystal polymer (A) is 47.5 to 65% by mass with respect to the entire composite resin composition
  • the content of the (B) milled fiber is 15 to 30% by mass with respect to the entire composite resin composition
  • the content of the (C) plate-like inorganic filler is 20 to 35% by mass with respect to the entire composite resin composition
  • the electronic component according to (7) which is an asymmetric electronic component having no symmetry with respect to any of the XY axis plane, the YZ axis plane, and the XZ axis plane of the molded product.
  • a connector for a memory module having a pitch distance of 0.8 mm or less, a total product length of 60.0 mm or more, a product height of 6.0 mm or less, and a pole number of 150 or more.
  • the content of the (C) plate-like inorganic filler is 10 to 30% by mass with respect to the entire composite resin composition,
  • the distance between pitches is 0.5 mm or less,
  • the total product length is 4.0mm or more,
  • the product height is 4.0 mm or less,
  • the electronic component according to (7) which is a low-profile narrow-pitch connector that is a board-to-board connector or a connector for a flexible printed board.
  • the above (A) liquid crystalline polymer has a [melting point-crystallization temperature] value of 50 to 60 ° C. and conforms to ISO 11443 at a shear rate of 1000 / sec at a temperature 10 to 20 ° C. higher than the melting point.
  • the average fiber length of the (B) glass fiber and milled fiber is 50 to 100 ⁇ m
  • the (C) plate-like inorganic filler is an electronic component according to (12) or (13), which is at least one selected from the group consisting of talc and mica.
  • a composite resin composition for electronic parts having good fluidity and an electronic part molded from the composite resin composition.
  • a composite resin composition for an asymmetric electronic component capable of obtaining an asymmetric electronic component having good fluidity and suppressing warpage deformation, and an asymmetric electronic component molded from the composite resin composition Is provided.
  • the composite resin composition in the present invention contains a predetermined amount of a specific liquid crystalline polymer, glass fibers and / or milled fibers, and a plate-like inorganic filler.
  • a specific liquid crystalline polymer glass fibers and / or milled fibers
  • a plate-like inorganic filler a plate-like inorganic filler
  • the liquid crystalline polymer in the present invention contains, as essential constituents, the following constituent units: (I) constituent units derived from 4-hydroxybenzoic acid (also referred to as “HBA”), (II) 2-hydroxy-6-naphthoic acid A structural unit derived from (also referred to as “HNA”), (III) a structural unit derived from terephthalic acid (also referred to as “TA”), (IV) a structural unit derived from isophthalic acid (also referred to as “IA”), and (V) Contains structural units derived from 4,4′-dihydroxybiphenyl (also referred to as “BP”).
  • HBA 4-hydroxybenzoic acid
  • HNA 2-hydroxy-6-naphthoic acid
  • HNA terephthalic acid
  • IA isophthalic acid
  • V Contains structural units derived from 4,4′-dihydroxybiphenyl (also referred to as “BP”).
  • the liquid crystalline polymer in the present invention contains the above structural units at a specific ratio. That is, the content of the structural unit (I) is 35 to 75 mol% (preferably 40 to 65 mol%) with respect to all the structural units.
  • the content of the structural unit (II) is 2 to 8 mol% (preferably 3 to 7 mol%) with respect to all the structural units.
  • the content of the structural unit (III) is 4.5 to 30.5 mol% (preferably 13 to 26 mol%) based on all the structural units.
  • the content of the structural unit (IV) is 2 to 8 mol% (preferably 3 to 7 mol%) with respect to all the structural units.
  • the content of the structural unit (V) is 12.5 to 32.5 mol% (preferably 15.5 to 29 mol%) with respect to all the structural units.
  • the total amount of the structural units (II) and (IV) is 4 to 10 mol% (preferably 5 to 10 mol%) with respect to the total structural units.
  • the melting point of the liquid crystalline polymer is remarkably increased, and asymmetric electronic components, low-profile narrow pitch connectors, and
  • the liquid crystalline polymer is solidified in the reactor, and it may not be possible to manufacture a liquid crystalline polymer having a desired molecular weight.
  • the content of the constituent unit (II) is less than 2 mol% with respect to all constituent units, when manufacturing molded articles such as electronic parts including asymmetric electronic parts, low profile narrow pitch connectors, and coaxial connectors This is not preferable because cracks may occur in the molded product. Further, if the content of the structural unit (II) is more than 8 mol% with respect to all the structural units, the heat resistance of the liquid crystalline polymer is lowered, which is not preferable.
  • the melting point of the liquid crystalline polymer becomes remarkably high, and the asymmetric electronic component, low profile
  • the liquid crystalline polymer is solidified in the reactor, and it may not be possible to produce a liquid crystalline polymer having a desired molecular weight.
  • the content of the constituent unit of (IV) is less than 2 mol% with respect to all constituent units, when manufacturing molded articles such as electronic parts including asymmetric electronic parts, low profile narrow pitch connectors, and coaxial connectors This is not preferable because cracks may occur in the molded product.
  • the melting point of the liquid crystalline polymer becomes extremely high, and the liquid crystalline polymer is solidified in the reactor when a molded product such as an asymmetric electronic component, a low-profile narrow pitch connector, and an electronic component including a coaxial connector is manufactured. Since it may become impossible to manufacture the liquid crystalline polymer of molecular weight, it is not preferable.
  • the content of the structural unit (IV) is more than 8 mol% with respect to all the structural units, the heat resistance of the liquid crystalline polymer is lowered, which is not preferable.
  • the melting point of the liquid crystalline polymer is remarkably increased, and the asymmetric electronic component liquid crystalline polymer is Solidifying in a reactor to produce a liquid crystalline polymer having a desired molecular weight is not preferable because it becomes impossible to produce a molded product such as a low-profile narrow pitch connector and an electronic component including a coaxial connector.
  • the crystallization heat amount of the liquid crystalline polymer can be 2.5 J / g or more.
  • a molded product such as an asymmetric electronic component, a low-profile narrow-pitch connector, and an electronic component including a coaxial connector
  • a preferable value for the heat of crystallization of the liquid crystalline polymer is 2.3 J / g or less, and more preferably 2.0 J / g or less.
  • the crystallization heat quantity indicates the crystallization state of the liquid crystalline polymer, and is a value obtained by differential calorimetry.
  • Tm1 endothermic peak temperature
  • Tm1 + 40 ° C. for 2 minutes the calorific value of the exothermic peak obtained from the peak of the exothermic peak temperature observed when measured under the temperature lowering condition per minute.
  • the heat resistance of the liquid crystalline polymer is lowered, which is not preferable.
  • the well-known other structural unit can also be introduce
  • the liquid crystalline polymer in the present invention can be obtained by polymerizing the above structural units by a direct polymerization method, a transesterification method, a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method or the like.
  • an acylating agent for the above structural unit or a monomer whose terminal is activated as an acid chloride derivative can be used in combination.
  • the acylating agent include acid anhydrides such as acetic anhydride.
  • various catalysts can be used, for example, dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, alkali metal salts of carboxylic acids, alkaline earths. Metal salts, Lewis acid salts (BF 3 and the like) and the like.
  • the amount of the catalyst used may be about 0.001 to 1% by mass, preferably about 0.003 to 0.2% by mass, based on the total amount of the above structural units.
  • the conditions for the polymerization reaction are not particularly limited as long as the polymerization of the above structural units proceeds.
  • the reaction temperature is 200 to 380 ° C.
  • the final ultimate pressure is 0.1 to 760 Torr (that is, 13 to 101,080 Pa). ).
  • the polymerization reaction may be a method (one-stage system) in which all the raw material monomers, acylating agent and catalyst are charged in the same reaction vessel to start the reaction, and corresponds to each structural unit of (I), (II) and (V).
  • acylating the raw material monomers that is, the structural unit derived from 4-hydroxybenzoic acid, the structural unit derived from 2-hydroxy-6-naphthoic acid, and the hydroxyl group of 4,4′-dihydroxybiphenyl with an acylating agent
  • a raw material monomer corresponding to each structural unit of (III) and (IV) that is, a method of reacting with carboxyl groups of terephthalic acid and isophthalic acid (two-stage method) may be used.
  • liquid crystalline polymers containing the structural units (I) to (V) do not form an anisotropic molten phase depending on the constituent components and the sequence distribution in the liquid crystalline polymer.
  • the liquid crystalline polymer in the present invention is preferably a liquid crystalline polymer that forms an anisotropic molten phase, that is, a liquid crystalline polymer that exhibits optical anisotropy when melted, in that it has processability.
  • melt anisotropy can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. Specifically, for melting anisotropy, a polarizing microscope (manufactured by Olympus Co., Ltd.) is used, a sample placed on a hot stage (manufactured by Linkham Co., Ltd.) is melted, and the magnification is 150 times under a nitrogen atmosphere. This can be confirmed by observation. Liquid crystalline polymers that exhibit optical anisotropy when melted are optically anisotropic and transmit light when inserted between crossed polarizers. When the sample is optically anisotropic, for example, polarized light is transmitted even in a molten stationary liquid state.
  • the melt viscosity of the liquid crystalline polymer measured in accordance with ISO 11443 at a temperature 10 to 20 ° C. higher than the melting point and at a shear rate of 1000 / second is more preferably 1 ⁇ 10 5 Pa ⁇ s or less (more preferably 5 Pa ⁇ s or more). And 1 ⁇ 10 2 Pa ⁇ s or less) at the time of molding an electronic component, particularly at the time of molding a portion having a complicated shape such as a latch structure or a notch in an asymmetric electronic component. This is preferable in that the fluidity of the resin is ensured and the filling pressure does not become excessive.
  • the liquid crystalline polymer in the present invention has a value of [melting point ⁇ crystallization temperature], which is a value obtained by subtracting the crystallization temperature from the melting point, and a temperature of 10 to 20 ° C. higher than the melting point.
  • the melt viscosity measured according to ISO 11443 at a shear rate of 1000 / sec is preferably 5 to 15 Pa ⁇ s. According to such a liquid crystalline polymer, the fluidity of the composite resin composition can be secured at the time of molding an electronic component, particularly at the time of molding a low profile narrow pitch connector, etc., and therefore the filling pressure becomes an excessive value. This can be suppressed.
  • the composite resin composition in the present invention contains the liquid crystalline polymer in the composite resin composition in an amount of 40 to 80% by mass with respect to the total composite resin composition. If the content of the liquid crystalline polymer is less than 40% by mass with respect to the entire composite resin composition, the fluidity is deteriorated, which is not preferable. When the content of the liquid crystalline polymer is more than 80% by mass with respect to the entire composite resin composition, an asymmetric electronic component obtained from the composite resin composition, a low-profile narrow pitch connector, an electronic component including a coaxial connector, etc. This is not preferable because the flexural modulus and crack resistance of the molded product are lowered.
  • the composite resin composition in the present invention preferably contains the liquid crystalline polymer in the composite resin composition in an amount of 50 to 70% by mass based on the entire composite resin composition.
  • the liquid crystal polymer is contained in the composite resin composition in an amount of 47.5 to 65% by mass with respect to the entire composite resin composition. Is preferred.
  • the content of the liquid crystalline polymer is 47.5% by mass or more based on the entire composite resin composition, the fluidity of the composite resin composition tends to be good, and the asymmetric electronic component obtained from the composite resin composition It is preferable because warpage deformation of a molded product such as the above is difficult to increase.
  • the content of the liquid crystalline polymer is 65% by mass or less with respect to the entire composite resin composition, the bending elastic modulus and crack resistance of molded products such as asymmetric electronic parts obtained from the composite resin composition are unlikely to decrease.
  • the composite resin composition of the present invention is for an asymmetric electronic component
  • the liquid crystalline polymer is contained in the composite resin composition in an amount of 50 to 55% by mass with respect to the total composite resin composition. preferable.
  • the composite resin composition in the present invention contains the above-mentioned liquid crystalline polymer and milled fiber, a molded product obtained by molding the composite resin composition is excellent in high-temperature rigidity.
  • the average fiber length of the milled fiber calculated from the fiber length of the milled fiber is preferably 50 to 150 ⁇ m.
  • An average fiber length of 50 ⁇ m or more is preferable because the high-temperature rigidity of a molded product obtained from the composite resin composition is sufficient.
  • An average fiber length of 150 ⁇ m or less is preferable because the fluidity of the composite resin composition becomes good and warpage deformation of the molded product does not easily increase.
  • the average fiber length of the milled fiber calculated from the fiber length of the milled fiber in the composite resin composition of the present invention is 50 to 100 ⁇ m.
  • the average fiber length of 50 ⁇ m or more is preferable because the high-temperature rigidity of a molded product obtained from the composite resin composition is sufficient.
  • the average fiber length is 100 ⁇ m or less, the fluidity of the composite resin composition becomes good and it is difficult to mold the composite resin composition, which is preferable.
  • the fiber diameter of the milled fiber in the present invention is not particularly limited, but generally about 5 to 15 ⁇ m is used.
  • the composite resin composition in the present invention contains 10 to 30% by mass of milled fiber with respect to the entire composite resin composition.
  • the content of the milled fiber is less than 10% by mass relative to the entire composite resin composition, molding of electronic components including asymmetric electronic components, low profile narrow pitch connectors, and coaxial connectors obtained from the composite resin composition This is not preferable because the weight deflection temperature of the product is low and the high-temperature rigidity is not sufficient. If the content of the milled fiber is more than 30% by mass with respect to the entire composite resin composition, the fluidity of the composition deteriorates, which is not preferable.
  • the composite resin composition in the present invention preferably contains 15 to 30% by mass of milled fiber with respect to the entire composite resin composition, particularly when used for asymmetric electronic components.
  • a molded article such as an asymmetric electronic component obtained from the composite resin composition is less likely to have a low deflection temperature, and has high-temperature rigidity. This is preferable because it is sufficient.
  • the content of the milled fiber is 30% by mass or less with respect to the entire composite resin composition because the fluidity of the composite resin composition becomes good and warpage deformation of the molded article is difficult to increase.
  • the composite resin composition in the present invention further includes a plate-like inorganic filler.
  • a plate-like inorganic filler By including a plate-like inorganic filler in the composite resin composition in the present invention, a molded product in which warpage deformation is suppressed can be obtained.
  • the plate-like inorganic filler is contained in an amount of 10 to 35% by mass with respect to the entire composite resin composition. If the content of the plate-like inorganic filler is less than 10% by mass with respect to the entire composite resin composition, it is not preferable because warpage deformation of a molded product obtained from the composite resin composition is not sufficient. If the content of the plate-like inorganic filler is more than 35% by mass with respect to the entire composite resin composition, the fluidity of the composite resin composition may be deteriorated and it may be difficult to mold the composite resin composition. This is not preferable.
  • the plate-like inorganic filler is preferably contained in an amount of 20 to 35% by mass with respect to the entire composite resin composition, particularly when the composite resin composition is for an asymmetric electronic component. It is preferable that the content of the plate-like inorganic filler is 20% by mass or more based on the entire composite resin composition because warpage deformation of a molded product such as an asymmetric electronic component obtained from the composite resin composition is difficult to increase. It is preferable that the content of the plate-like inorganic filler is 35% by mass or less with respect to the entire composite resin composition because the fluidity of the composite resin composition tends to be good.
  • the plate-like inorganic filler is preferably contained in an amount of 10 to 30% by mass based on the entire composite resin composition, particularly when the composite resin composition is for a low profile narrow pitch connector.
  • the content of the plate-like inorganic filler is 10% by mass or more based on the entire composite resin composition, it is possible to sufficiently suppress warpage deformation of a molded product such as a low profile narrow pitch connector obtained from the composite resin composition. It is preferable because it is easy.
  • the content of the plate-like inorganic filler is 30% by mass or less with respect to the entire composite resin composition, the fluidity of the composite resin composition tends to be good, and it is difficult to form the composite resin composition. preferable.
  • Examples of the plate-like inorganic filler in the present invention include talc, mica, glass flakes, various metal foils and the like, but a molded product obtained from the composite resin composition without deteriorating the fluidity of the composite resin composition. It is preferable that it is 1 or more types chosen from the group which consists of a talc and a mica at the point of suppressing warp deformation
  • a certain size must be maintained.
  • it is preferably 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m.
  • the total content of Fe 2 O 3 , Al 2 O 3 , and CaO is 2.5 mass% or less with respect to the total solid content of the talc, and Fe 2 O 3 and The total content of Al 2 O 3 is more than 1.0% by mass and 2.0% by mass or less, and the content of CaO is preferably less than 0.5% by mass. That is, the talc that can be used in the present invention contains at least one of Fe 2 O 3 , Al 2 O 3 , and CaO in addition to the main components SiO 2 and MgO, and each component has the above content. It may be contained in a range.
  • the molding processability of the composite resin composition and the asymmetric electron molded from the composite resin composition is unlikely to deteriorate.
  • the total content of Fe 2 O 3 , Al 2 O 3 , and CaO is preferably 1.0% by mass or more and 2.0% by mass or less.
  • talc having a total content of Fe 2 O 3 and Al 2 O 3 of more than 1.0% by mass is easily available. Further, in the talc, when the total content of Fe 2 O 3 and Al 2 O 3 is 2.0% by mass or less, the molding processability of the composite resin composition and the asymmetric electronic component molded from the composite resin composition In addition, the heat resistance of molded products such as electronic parts including low-profile narrow-pitch connectors and coaxial connectors is unlikely to deteriorate.
  • the total content of Fe 2 O 3 and Al 2 O 3 is preferably more than 1.0 mass% and not more than 1.7 mass%.
  • the CaO content is less than 0.5% by mass, the molding processability of the composite resin composition, the asymmetric electronic component molded from the composite resin composition, the low profile narrow pitch connector, and the coaxial The heat resistance of molded products such as electronic parts including connectors is unlikely to deteriorate.
  • the content of CaO is preferably 0.01% by mass or more and 0.4% by mass or less.
  • the mass average or volume-based cumulative average particle diameter (D 50 ) of talc in the present invention measured by laser diffraction method is 4 from the viewpoint of preventing warpage deformation of the molded product and maintaining fluidity of the composite resin composition. It is preferably from 0 to 20.0 ⁇ m, more preferably from 10 to 18 ⁇ m.
  • Mica is a pulverized product of 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, and artificial mica. Of these, muscovite is preferable in terms of good hue and low price.
  • wet pulverization and dry pulverization are known as methods for pulverizing minerals.
  • the wet pulverization method is a method in which raw mica is roughly pulverized with a dry pulverizer, then water is added and main pulverization is performed by wet pulverization in a slurry state, followed by dehydration and drying.
  • the dry pulverization method is a general method at a low cost.
  • the wet pulverization method it is easier to pulverize the mineral thinly and finely.
  • the present invention it is preferable to use a thin and fine pulverized product because mica having a preferable average particle diameter and thickness described later can be obtained. Therefore, in the present invention, it is preferable to use mica produced by a wet pulverization method.
  • Examples of the coagulating settling agent and settling aid that can be used in the present invention include polyaluminum chloride, aluminum sulfate, ferrous sulfate, ferric sulfate, copper chloride, polyiron sulfate, polyferric chloride, iron-silica inorganic high Examples thereof include molecular flocculants, ferric chloride-silica inorganic polymer flocculants, slaked lime (Ca (OH) 2 ), caustic soda (NaOH), and soda ash (Na 2 CO 3 ). These coagulating sedimentation agents and sedimentation aids are alkaline or acidic in pH.
  • the mica used in the present invention is preferably one that does not use a coagulating sedimentation agent and / or a sedimentation aid when wet milling.
  • the use of mica not treated with a coagulating sedimentation agent and / or a sedimentation aid makes it difficult for the polymer in the composite resin composition to decompose, resulting in a large amount of gas generation and a decrease in the molecular weight of the polymer. It is easy to better maintain the performance of molded parts such as electronic parts, electronic parts including low-profile narrow-pitch connectors, and coaxial connectors.
  • the mica that can be used in the present invention preferably has an average particle diameter of 10 to 100 ⁇ m as measured by a microtrack laser diffraction method, and particularly preferably has an average particle diameter of 20 to 80 ⁇ m. It is preferable that the average particle diameter of mica is 10 ⁇ m or more because the effect of improving the rigidity of the molded product is likely to be sufficient. It is preferable that the average particle diameter of mica is 100 ⁇ m or less because the rigidity of the molded product is likely to be sufficiently improved and the weld strength is likely to be sufficient. Furthermore, when the average particle size of mica is 100 ⁇ m or less, it is easy to ensure sufficient fluidity for molding electronic components including the asymmetric electronic component, low profile narrow pitch connector, and coaxial connector of the present invention.
  • the thickness of the 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 mica thickness is 0.01 ⁇ m or more, the mica is difficult to break during the melt processing of the composite resin composition, and therefore, the rigidity of the molded product may be easily improved. It is preferable that the mica thickness is 1 ⁇ m or less because the effect of improving the rigidity of the molded product tends to be sufficient.
  • the mica that can be used in the present invention may be surface-treated with a silane coupling agent or the like and / or granulated with a binder.
  • pigments such as nucleating agent, carbon black, inorganic calcined pigment, antioxidant, stabilizer, plasticizer, lubricant, mold release agent, flame retardant, and You may mix
  • the method for producing the composite resin composition in the present invention is not particularly limited as long as the components in the composite resin composition can be uniformly mixed, and can be appropriately selected from conventionally known methods for producing resin compositions.
  • each component is melt-kneaded and extruded using a melt-kneader such as a single-screw or twin-screw extruder, and then the resulting composite resin composition is processed into a desired form such as powder, flakes, pellets, etc.
  • a melt-kneader such as a single-screw or twin-screw extruder
  • the composite resin composition according to the present invention is excellent in fluidity, so that the minimum filling pressure at the time of molding is not excessively excessive, and the component having a complicated shape such as an asymmetric electronic component having a latch structure or a notch, a low profile A small and complex part such as a pitch connector, a coaxial connector, or the like can be preferably formed.
  • the minimum filling pressure is specified as the minimum injection filling pressure at which a good molded product can be obtained at 365 ° C. when molding the composite resin composition.
  • the electronic component of the present invention can be obtained by molding the composite resin composition of the present invention. Although it does not specifically limit as an electronic component, Asymmetrical electronic components, a low profile narrow pitch connector, a coaxial connector, etc. are mentioned.
  • the asymmetric electronic component of the present invention refers to a component that has no symmetry with respect to any of the XY axis plane, the YZ axis plane, and the XZ axis plane of the molded product.
  • the XY axis plane, the YZ axis plane, and the XZ axis plane have symmetry, so that the symmetry should be maintained during molding.
  • the asymmetric electronic component of the present invention has a complicated shape, and it is difficult to suppress warpage deformation by a molding method.
  • warpage deformation is suppressed by using a specific composite resin composition.
  • a typical example of such an asymmetric electronic component is a certain type of connector or socket.
  • Connector for memory module such as DIMM connector, DDR-DIMM connector, DDR2-DIMM connector, DDR-SO-DIMM connector, DDR2-SO-DIMM connector, DDR-Micro-DIMM connector, DDR2-Micro-DIMM connector Is mentioned.
  • DIMM connector DDR-DIMM connectors and DDR2-DIMM connectors are preferred, especially for thin-walled and complex memory module connectors for laptop computers, with a pitch-to-pitch distance of 0.8 mm or less and a total product length of 60.0 mm.
  • the product height is 6.0 mm or less and the number of poles is 150 or more.
  • Such a memory module connector is subjected to an IR reflow process for surface mounting at a peak temperature of 230 to 280 ° C, the warp before the IR reflow process is 0.1 mm or less, and the warp before and after the reflow.
  • such a requirement can be satisfied.
  • the socket examples include a memory card socket such as a card bus, CF card, memory stick, PC card, SD card, SDMo, smart card, smart media card, microSD card, miniSD card, xD picture card, TransFlash, etc.
  • a memory card socket having a rail structure and a product height of 3.0 mm or less is suitable.
  • the low profile narrow pitch connector of the present invention By molding the composite resin composition in the present invention, the low profile narrow pitch connector of the present invention can be obtained.
  • the shape of the low-profile narrow-pitch connector of the present invention is not particularly limited, but the low-profile narrow-pitch connector has a pitch distance of 0.5 mm or less, a total product length of 4.0 mm or more, and a product height of 4.0 mm or less. It may be.
  • the type of the low-profile narrow-pitch connector of the present invention is not particularly limited, but a board-to-board connector (also known as “BtoB connector”), a flexible printed circuit board (FPC), and a flexible flat cable (FFC) are connected. It may be a flexible printed circuit board connector (also known as an “FPC connector”) or the like.
  • the coaxial connector of the present invention can be obtained by molding the composite resin composition of the present invention.
  • the resin composition is excellent in fluidity.
  • this composite resin composition is The coaxial connector can be manufactured smoothly by using.
  • the coaxial connector with a thickness of 100 micrometers or less is mentioned.
  • the molding method for obtaining the electronic component of the present invention such as the asymmetric electronic component of the present invention, low-profile narrow pitch connector, coaxial connector, etc. is not particularly limited, but in order to prevent deformation of the obtained electronic component, warpage deformation is particularly suppressed.
  • the cylinder temperature of the molding machine should be higher than the melting point of the liquid crystalline polymer. preferable.
  • the mold temperature is preferably 70 to 100 ° C. If the mold temperature is not too low, it is particularly preferable that the mold temperature is 70 ° C. or higher because the composite resin composition filled in the mold hardly causes poor flow. If the mold temperature is not too high, it is particularly preferable that the mold temperature is 100 ° C. or lower because problems such as burrs are unlikely to occur.
  • the injection speed is preferably 150 mm / second or more. If the injection speed is not too low, particularly when the injection speed is 150 mm / sec or more, it is unlikely that only an unfilled molded product will be obtained. A completely filled molded product has a high filling pressure and a residual internal stress. It is difficult to obtain a large molded product, and it is unlikely that only an electronic component having a problem in terms of shape such as an asymmetric electronic component having a large warp deformation and a connector having poor flatness may be obtained.
  • warpage deformation is suppressed in the asymmetric electronic component of the present invention.
  • the degree of warping of the asymmetric electronic component is determined as follows. That is, the asymmetric electronic component is placed on a horizontal desk, the height of the asymmetric electronic component is measured by an image measuring machine, and the difference between the maximum height and the minimum height from the least squares plane is determined as the sled of the asymmetric electronic component. To do.
  • changes in warpage are suppressed before and after performing IR reflow.
  • the electronic parts of the present invention such as the asymmetric electronic parts of the present invention, low profile narrow pitch connectors, coaxial connectors, etc. are excellent in high temperature rigidity.
  • the high temperature stiffness is evaluated by measuring the deflection temperature under load in accordance with ISO 75-1 and 2 standard.
  • Method for producing liquid crystalline polymer 1 A polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a pressure reduction / outflow line was charged with the following raw material monomers, a metal catalyst, and an acylating agent, and nitrogen substitution was started.
  • the temperature of the reaction system was raised to 140 ° C. and reacted at 140 ° C. for 1 hour. Thereafter, the temperature is further increased to 360 ° C. over 5.5 hours, and then the pressure is reduced to 10 Torr (that is, 1330 Pa) over 20 minutes, while acetic acid, excess acetic anhydride, and other low boiling points are distilled off. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to change from a reduced pressure state to a normal pressure through a normal pressure, the polymer was discharged from the lower part of the polymerization vessel, and the strand was pelletized to pelletize. The obtained pellet had a melting point of 358 ° C., a crystallization temperature of 303 ° C., a crystallization heat amount of 1.6 J / g, and a melt viscosity of 9 Pa ⁇ s.
  • the melting point, crystallization temperature, crystallization heat quantity, and melt viscosity of the pellet were measured under the following conditions.
  • Method for producing liquid crystalline polymer 2 A polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a pressure reduction / outflow line was charged with the following raw material monomers, a metal catalyst, and an acylating agent, and nitrogen substitution was started.
  • the temperature of the reaction system was raised to 140 ° C. and reacted at 140 ° C. for 1 hour. Thereafter, the temperature is further raised to 340 ° C. over 4.5 hours, and then the pressure is reduced to 10 Torr (ie, 667 Pa) over 15 minutes while acetic acid, excess acetic anhydride, and other low boiling points are distilled off. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to change from a reduced pressure state to a normal pressure through a normal pressure, the polymer was discharged from the lower part of the polymerization vessel, and the strand was pelletized to pelletize. The obtained pellet had a melting point of 334 ° C., a crystallization temperature of 290 ° C., a crystallization heat amount of 2.7 J / g, and a melt viscosity of 18 Pa ⁇ s.
  • the extrusion conditions for obtaining the composite resin composition are as follows. [Extrusion conditions] [Examples 1 to 11, Comparative Examples 4, 5, 10, 11, Reference Examples 1 to 4] The temperature of the cylinder provided at the main feed port was 250 ° C., and the temperatures of the other cylinders were all 370 ° C. All liquid crystalline polymers were supplied from the main feed port. The filler was supplied from the side feed port. [Comparative Examples 1 to 3, 6 to 9] The temperature of the cylinder provided at the main feed port was 250 ° C., and the temperature of the other cylinders was all 350 ° C. All liquid crystalline polymers were supplied from the main feed port. The filler was supplied from the side feed port.
  • the average glass fiber length of the glass fiber and milled fiber in a composite resin composition was measured with the following method. [Measurement of average glass fiber length] 5 g of the composite resin composition pellets were heated and ashed at 600 ° C. for 2 hours. The incineration residue was sufficiently dispersed in a 5% by mass polyethylene glycol aqueous solution, then transferred to a petri dish with a dropper, and glass fibers or milled fibers were observed with a microscope. At the same time, the weight average fiber length of the glass fiber or milled fiber was measured using an image measuring instrument (LUZEXFS manufactured by Nireco Corporation).
  • the composite resin composition was injection-molded under the following molding conditions (gate: tunnel gate, gate size: ⁇ 0.75 mm), and the overall size as shown in FIG. 1 was 70.0 mm ⁇ 26.0 mm ⁇ 4.0 mmt, A DDR-DIMM connector having a pitch distance of 0.6 mm and a pin hole number of 100 ⁇ 2 was obtained.
  • Molding machine Sumitomo Heavy Industries SE30DUZ Cylinder temperature (indicates temperature from nozzle side): 360 ° C.-365 ° C.-340 ° C.-330 ° C.
  • Example 1 to 3 Comparative Examples 4 and 5, Reference Examples 1 and 2 350 ° C.-350 ° C.-340 ° C.-330 ° C. (Comparative Examples 1 to 3) Mold temperature: 80 °C Injection speed: 300 mm / sec Holding pressure: 50 MPa Holding time: 2 seconds Cooling time: 10 seconds Screw rotation speed: 120 rpm Screw back pressure: 1.2MPa
  • the obtained connector was placed on a horizontal desk, and the height of the connector was measured with 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 defined as the DDR connector warp. The warpage was measured before and after IR reflow performed under the following conditions.
  • IR reflow conditions Measuring machine: RF-300 (using far infrared heater) Sample feed rate: 140 mm / sec Reflow furnace passage time: 5 minutes
  • Preheat zone temperature condition 150 ° C.
  • Reflow zone temperature condition 190 ° C Peak temperature: 251 ° C
  • DDR connector deformation The difference in warpage before and after reflow measured by the above method was determined as the amount of deformation of the DDR connector.
  • DDR connector minimum filling pressure When the DDR-DIMM connector of FIG. 1 was injection molded, the minimum injection filling pressure at which a good molded product was obtained was measured as the minimum filling pressure.
  • Molding machine Sumitomo Heavy Industries, SE100DU Cylinder temperature (indicates temperature from nozzle side): 360 ° C.-370 ° C.-370 ° C.-360 ° C.-340 ° C.-330 ° C.
  • Example 1 to 3 Comparative Examples 4 and 5, Reference Examples 1 and 2 350 ° C-350 ° C-350 ° C-350 ° C-340 ° C-330 ° C (Comparative Examples 1 to 3) Mold temperature: 80 °C Injection speed: 2 m / min Holding pressure: 50 MPa Holding time: 2 seconds Cooling time: 10 seconds Screw rotation speed: 120 rpm Screw back pressure: 1.2MPa
  • the composite resin composition of the present invention has good fluidity, and the asymmetric electronic component molded from the composite resin composition is suppressed from warping deformation and has high-temperature rigidity. It was excellent.
  • the composite resin composition as shown in FIG. 3 has an overall size of 17.6 mm ⁇ 4.00 mm ⁇ 1.16 mm, a pitch distance of 0.5 mm, a pin hole number of 30 ⁇ 2 pins, and a minimum thickness.
  • a FPC connector having a thickness of 0.12 mm (gate: tunnel gate ( ⁇ 0.4 mm)) was injection molded, and the minimum injection filling pressure at which a good molded product was obtained was measured as the minimum filling pressure.
  • Molding machine Sumitomo Heavy Industries, SE30DUZ Cylinder temperature (indicates temperature from nozzle side): 365 ° C.-365 ° C.-355 ° C.-345 ° C.
  • Molding machine Sumitomo Heavy Industries, SE100DU Cylinder temperature (indicates temperature from nozzle side): 360 ° C.-370 ° C.-370 ° C.-360 ° C.-340 ° C.-330 ° C.
  • the composite resin composition of the present invention was excellent in fluidity, and the value of the minimum filling pressure of the low profile narrow pitch connector molded from the composite resin composition was reduced.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

L'invention fournit une composition de résine composite pour composant électronique dont la fluidité est satisfaisante, et un composant électronique moulé à partir de cette composition de résine composite. Plus précisément, l'invention concerne une composition de résine composite pour composant électronique qui contient un polymère cristallin liquide (A), des fibres broyées (B) et un matériau de remplissage inorganique en plaque (C). Ledit polymère cristallin liquide (A) contient, en tant que composants structuraux indispensables, les unités structurales suivantes : (I) une unité structurale dérivée d'un acide 4-hydroxybenzoïque ; (II) une unité structurale dérivée d'un acide 2-hydroxy-6-naphthoïque ; (III) une unité structurale dérivée d'un acide téréphtalique ; (IV) une unité structurale dérivée d'un acide isophtalique ; et (V) une unité structurale dérivée d'un 4,4'-hydroxybiphényle.
PCT/JP2013/072226 2012-09-26 2013-08-20 Composition de résine composite pour composant électronique, et composant électronique moulé à partir de celle-ci WO2014050371A1 (fr)

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SG11201502394YA SG11201502394YA (en) 2012-09-26 2013-08-20 Composite resin composition for electronic component and electronic component molded from composite resin composition
KR1020157010325A KR20150060829A (ko) 2012-09-26 2013-08-20 전자부품용 복합 수지 조성물, 및 당해 복합 수지 조성물로 성형된 전자부품
CN201380050474.0A CN104704049B (zh) 2012-09-26 2013-08-20 电子部件用复合树脂组合物、以及由该复合树脂组合物成型而成的电子部件
JP2014538282A JP5769888B2 (ja) 2012-09-26 2013-08-20 電子部品用複合樹脂組成物、及び当該複合樹脂組成物から成形された電子部品

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WO2017068867A1 (fr) * 2015-10-21 2017-04-27 ポリプラスチックス株式会社 Polyester entièrement aromatique et son procédé de production
WO2017110866A1 (fr) * 2015-12-25 2017-06-29 ポリプラスチックス株式会社 Composition de résine composite et composant électronique fabriqué à partir de ladite composition de résine composite
WO2017110867A1 (fr) * 2015-12-25 2017-06-29 ポリプラスチックス株式会社 Composition de résine composite et connecteur fabriqué à partir de ladite composition de résine composite
WO2018066417A1 (fr) * 2016-10-07 2018-04-12 ポリプラスチックス株式会社 Composition de résine composite, et raccord fabriqué à partir de ladite composition de résine composite
WO2018066416A1 (fr) * 2016-10-07 2018-04-12 ポリプラスチックス株式会社 Composition de résine composite, et composant électronique fabriqué à partir de ladite composition de résine composite
WO2018074155A1 (fr) * 2016-10-21 2018-04-26 ポリプラスチックス株式会社 Composition de résine composite et composant électronique fabriqué à partir de ladite composition de résine composite
WO2018074156A1 (fr) * 2016-10-21 2018-04-26 ポリプラスチックス株式会社 Composition de résine composite et connecteur moulé formé à partir de cette dernière
JPWO2022168706A1 (fr) * 2021-02-05 2022-08-11

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CN109844028B (zh) * 2016-12-21 2020-09-11 宝理塑料株式会社 表面安装继电器用液晶性树脂组合物及使用其的表面安装继电器

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WO2017068867A1 (fr) * 2015-10-21 2017-04-27 ポリプラスチックス株式会社 Polyester entièrement aromatique et son procédé de production
JP6157778B1 (ja) * 2015-10-21 2017-07-05 ポリプラスチックス株式会社 全芳香族ポリエステル及びその製造方法
WO2017110866A1 (fr) * 2015-12-25 2017-06-29 ポリプラスチックス株式会社 Composition de résine composite et composant électronique fabriqué à partir de ladite composition de résine composite
WO2017110867A1 (fr) * 2015-12-25 2017-06-29 ポリプラスチックス株式会社 Composition de résine composite et connecteur fabriqué à partir de ladite composition de résine composite
CN109790379A (zh) * 2016-10-07 2019-05-21 宝理塑料株式会社 复合树脂组合物、及由该复合树脂组合物成形而成的电子部件
WO2018066416A1 (fr) * 2016-10-07 2018-04-12 ポリプラスチックス株式会社 Composition de résine composite, et composant électronique fabriqué à partir de ladite composition de résine composite
JP6345376B1 (ja) * 2016-10-07 2018-06-20 ポリプラスチックス株式会社 複合樹脂組成物、及び当該複合樹脂組成物から成形された電子部品
JP6356938B1 (ja) * 2016-10-07 2018-07-11 ポリプラスチックス株式会社 複合樹脂組成物、及び当該複合樹脂組成物から成形されたコネクター
WO2018066417A1 (fr) * 2016-10-07 2018-04-12 ポリプラスチックス株式会社 Composition de résine composite, et raccord fabriqué à partir de ladite composition de résine composite
CN109790379B (zh) * 2016-10-07 2020-04-07 宝理塑料株式会社 复合树脂组合物、及由该复合树脂组合物成形而成的电子部件
WO2018074155A1 (fr) * 2016-10-21 2018-04-26 ポリプラスチックス株式会社 Composition de résine composite et composant électronique fabriqué à partir de ladite composition de résine composite
WO2018074156A1 (fr) * 2016-10-21 2018-04-26 ポリプラスチックス株式会社 Composition de résine composite et connecteur moulé formé à partir de cette dernière
JP6321898B1 (ja) * 2016-10-21 2018-05-09 ポリプラスチックス株式会社 複合樹脂組成物、及び当該複合樹脂組成物から成形された電子部品
JP6321899B1 (ja) * 2016-10-21 2018-05-09 ポリプラスチックス株式会社 複合樹脂組成物、及び当該複合樹脂組成物から成形されたコネクター
JPWO2022168706A1 (fr) * 2021-02-05 2022-08-11
JP7281023B2 (ja) 2021-02-05 2023-05-24 ポリプラスチックス株式会社 ファンインペラ用液晶性樹脂組成物及びそれを用いたファンインペラ

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SG11201502394YA (en) 2015-05-28
KR20150060829A (ko) 2015-06-03
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