WO2017110867A1 - Composition de résine composite et connecteur fabriqué à partir de ladite composition de résine composite - Google Patents

Composition de résine composite et connecteur fabriqué à partir de ladite composition de résine composite Download PDF

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WO2017110867A1
WO2017110867A1 PCT/JP2016/088081 JP2016088081W WO2017110867A1 WO 2017110867 A1 WO2017110867 A1 WO 2017110867A1 JP 2016088081 W JP2016088081 W JP 2016088081W WO 2017110867 A1 WO2017110867 A1 WO 2017110867A1
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resin composition
composite resin
connector
mol
respect
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PCT/JP2016/088081
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English (en)
Japanese (ja)
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智弘 瀧
博樹 深津
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ポリプラスチックス株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy 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
    • 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
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a composite resin composition and a connector molded from the composite resin composition.
  • 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.
  • Patent Document 1 discloses a connector formed from a liquid crystalline polymer composition reinforced with mica and glass fiber. Such connectors are used to connect board-to-board connectors, flexible printed boards (FPCs) and flexible flat cables (FFCs) that require heat resistance, warpage deformation suppression, fluidity, dimensional stability, etc. It is adopted as a connector for flexible printed circuit boards used in the industry.
  • FPCs flexible printed boards
  • FFCs flexible flat cables
  • the liquid crystalline polymer composition may have a problem of blistering. That is, liquid crystalline polyester, which is a liquid crystalline polymer, is often used as a material that requires heat treatment at a high temperature because of high thermal stability at high temperatures.
  • liquid crystalline polyester which is a liquid crystalline polymer
  • the molded product is left in high temperature air and liquid for a long time, there arises a problem that fine blisters called blisters are generated on the surface. This phenomenon is caused by the decomposition gas generated when the liquid crystalline polyester is in a molten state, and then the gas expands when the high-temperature heat treatment is performed. This is because the pushed up part appears as a blister.
  • the generation of blisters can be reduced by sufficiently degassing the vent hole during melt extrusion of the material, or by not allowing the material to stay in the molding machine for a long time during molding.
  • the range of conditions is very narrow, and it is not sufficient to obtain a molded product in which generation of blisters is suppressed, that is, a molded product having blister resistance.
  • the present invention has been made in view of such circumstances, a composite resin composition having excellent fluidity, excellent in heat resistance, capable of producing a connector in which warpage deformation and blister generation are suppressed, and the composite resin It is an object to provide a connector molded from the 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, a fibrous filler, and a plate-like filler. Specifically, the present invention provides the following.
  • a composite resin composition comprising (A) a liquid crystalline polymer, (B) a fibrous filler, and (C) a plate-like filler,
  • the (A) liquid crystalline polymer comprises the following structural units (I) to (IV) as essential structural components,
  • the content of the structural unit (I) is 61 to 68 mol% with respect to all the structural units,
  • the content of the structural unit (II) is 7 to 14 mol% with respect to all the structural units
  • the content of the structural unit (III) with respect to all the structural units is 5.5 to 9 mol%,
  • the content of the structural unit (IV) is 16 to 19.5 mol% with respect to all the structural units
  • the ratio of the structural unit (III) to the total of the structural unit (II) and the structural unit (III) is 0.30 to 0.48
  • the total content of the structural units (I) to (IV) is 100 mol% with respect to all the structural units, It has an ester bond or a combination of an ester bond and
  • the (A) liquid crystalline polymer is 60 to 82.5% by mass with respect to the entire composite resin composition
  • the (B) fibrous filler is 1.5 to 20% by mass with respect to the entire composite resin composition
  • the (C) plate-like filler is 12.5 to 32% by mass relative to the entire composite resin composition
  • the total amount of the (B) fibrous filler and the (C) plate filler is 17.5 to 35% by mass with respect to the entire composite resin composition
  • the (C) plate-like filler is mica.
  • the pitch distance is 0.5 mm or less
  • Product total length is 3.5mm or more
  • the product height is 4.0 mm or less
  • the connector according to (3) which is a low-profile narrow-pitch connector that is a board-to-board connector or a connector for a flexible printed board.
  • molded from the said composite resin composition are provided. Is done.
  • the unit of the numerical value in a figure is mm. It is a figure which shows the measurement location in the measurement of the curvature of the 0.6 mm pitch connector performed in the Example. It is a figure which shows the FPC connector shape
  • the composite resin composition in the present invention contains a predetermined amount of a specific liquid crystalline polymer, a fibrous filler, and a plate-like filler.
  • a specific liquid crystalline polymer e.g., polyethylene glycol dimethacrylate copolymer
  • fibrous filler e.g., polypropylene glycol dimethacrylate copolymer
  • plate-like filler e.g., polymethyl methacrylate-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrenethacrylate-styrenethacrylate-styrenethacrylate-styrenethacrylate-styrenethacrylate-styrenethacrylate-styrenethacrylate-styrenethacrylate-styrene-
  • the composite resin composition in the present invention includes a liquid crystalline polymer that is the above-mentioned wholly aromatic polyester. Since the wholly aromatic polyester has a low melting point, the processing temperature can be lowered, and generation of decomposition gas during melting is suppressed. As a result, in the molded product obtained by molding the composite resin composition containing the wholly aromatic polyester, blister generation is suppressed and blister resistance is improved.
  • a liquid crystalline polymer can be used individually by 1 type or in combination of 2 or more types.
  • the wholly aromatic polyester in the present invention comprises the following structural unit (I), the following structural unit (II), the following structural unit (III), and the following structural unit (IV).
  • the structural unit (I) is derived from 4-hydroxybenzoic acid (hereinafter also referred to as “HBA”).
  • HBA 4-hydroxybenzoic acid
  • the wholly aromatic polyester in the present invention contains 61 to 68 mol% of the structural unit (I) with respect to all the structural units. When the content of the structural unit (I) is less than 61 mol% or exceeds 68 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient.
  • the structural unit (II) is derived from 1,4-phenylenedicarboxylic acid (hereinafter also referred to as “TA”).
  • the wholly aromatic polyester in the present invention contains 7 to 14 mol%, preferably 9.5 to 11.5 mol%, of the structural unit (II) with respect to all the structural units. If the content of the structural unit (II) is less than 7 mol% or exceeds 14 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient.
  • the structural unit (III) is derived from 1,3-phenylenedicarboxylic acid (hereinafter also referred to as “IA”).
  • the wholly aromatic polyester in the present invention contains 5.5 to 9 mol%, preferably 6.5 to 8 mol% of the structural unit (III) with respect to all the structural units.
  • the content of the structural unit (III) is less than 5.5 mol% or exceeds 9 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient.
  • the structural unit (IV) is derived from 4,4′-dihydroxybiphenyl (hereinafter also referred to as “BP”).
  • BP 4,4′-dihydroxybiphenyl
  • the wholly aromatic polyester in the present invention contains 16 to 19.5 mol% of the structural unit (IV) with respect to the total structural unit. When the content of the structural unit (IV) is less than 16 mol% or exceeds 19.5 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient.
  • the ratio of the structural unit (III) to the total of the structural unit (II) and the structural unit (III) is 0.30 to 0.48 mol%.
  • the ratio is less than 0.30 mol% or exceeds 0.48 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient.
  • the total number of moles of the structural unit (II) and the structural unit (III) is 1 to 1.06 times the number of moles of the structural unit (IV), or the structural unit (IV ) Is preferably 1 to 1.06 times the total number of moles of the structural unit (II) and the structural unit (III).
  • One of the factors affecting all physical properties of wholly aromatic polyesters is a ketone bond formed by a side reaction during polymerization.
  • the amount of the ketone bond relative to the total of the ester bond and the ketone bond is 0 to 0.18 mol%.
  • the hue tends to be lowered.
  • the wholly aromatic polyester in the present invention contains a specific amount of each of the specific structural units (I) to (IV) with respect to all the structural units, and the structural unit (II) and the structural units. Since the ratio of the structural unit (III) to the total of (III) is adjusted to a specific range, and the amount of ketone bond is adjusted to a specific range, both low melting point and heat resistance are compatible. Is sufficient and has excellent hue.
  • the wholly aromatic polyester of the present invention contains 100 mol% of the structural units (I) to (IV) in total with respect to the total structural units.
  • DTUL a difference between a melting point and a deflection temperature under load
  • this difference is 85 ° C. or less, the heat resistance tends to increase, which is preferable.
  • DTUL is a polyester resin obtained by melt-kneading 60% by mass of the wholly aromatic polyester and 40% by mass of milled fiber having an average fiber diameter of 11 ⁇ m and an average fiber length of 75 ⁇ m at the melting point of the wholly aromatic polyester + 20 ° C. It is a value measured in the state of the composition, and can be measured in accordance with ISO75-1,2.
  • the wholly aromatic polyester in the present invention is polymerized using a direct polymerization method or a transesterification method.
  • a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, or the like is used.
  • an acylating agent for the polymerization monomer or a monomer having an activated terminal as an acid chloride derivative can be used.
  • the acylating agent include fatty acid anhydrides such as acetic anhydride.
  • various catalysts can be used. Typical examples include dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, fatty acid metal salts, BF 3 Lewis acid salts such as are mentioned, and fatty acid metal salts are preferred.
  • the amount of the catalyst used is generally about 0.001 to 1% by weight, particularly about 0.003 to 0.2% by weight, based on the total weight of the monomers.
  • liquid paraffin high heat resistant synthetic oil, inert mineral oil, or the like is used as a solvent.
  • the reaction conditions are, for example, a reaction temperature of 200 to 380 ° C. and a final ultimate pressure of 0.1 to 760 Torr (that is, 13 to 101,080 Pa).
  • the reaction temperature is 260 to 380 ° C., preferably 300 to 360 ° C.
  • the final ultimate pressure is 1 to 100 Torr (ie, 133 to 13,300 Pa), preferably 1 to 50 Torr (ie, 133 to 6,670 Pa). ).
  • the reaction can be started by charging all the raw material monomers (HBA, TA, IA, and BP), the acylating agent, and the catalyst in the same reaction vessel (one-stage system), or the hydroxyl groups of the raw material monomers HBA and BP. Can be acylated with an acylating agent and then reacted with carboxyl groups of TA and IA (two-stage system).
  • the melt polymerization is performed after the inside of the reaction system has reached a predetermined temperature, and the pressure reduction is started to a predetermined degree of pressure reduction. After the torque of the stirrer reaches a predetermined value, an inert gas is introduced, and the total aromatic polyester is discharged from the reaction system by changing from a reduced pressure state to a normal pressure to a predetermined pressure state.
  • the molecular weight of the wholly aromatic polyester produced by the above polymerization method can be further increased by solid-phase polymerization which is heated at normal pressure or reduced pressure in an inert gas.
  • Preferred conditions for the solid phase polymerization reaction are a reaction temperature of 230 to 330 ° C., preferably 250 to 320 ° C., and a final ultimate pressure of 10 to 760 Torr (ie 1,330 to 101,080 Pa).
  • 1,4-phenylenedicarboxylic acid and 1-hydroxydibenzoic acid are obtained by acylating 4-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl with a fatty acid anhydride in the presence of a fatty acid metal salt.
  • Preferably comprising a step of transesterification with 3,3-phenylenedicarboxylic acid For all monomers consisting of 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, 1,3-phenylenedicarboxylic acid, and 4,4′-dihydroxybiphenyl,
  • the amount of 4-hydroxybenzoic acid used is 61 to 68 mol%
  • the amount of 1,4-phenylene dicarboxylic acid used is 7 to 14 mol%
  • the amount of 1,3-phenylenedicarboxylic acid used is 5.5-9 mol%
  • the amount of 4,4′-dihydroxybiphenyl used is 16 to 19.5 mol%
  • the ratio of the amount of 1,3-phenylene dicarboxylic acid used relative to the total amount of 1,4-phenylene dicarboxylic acid and 1,3-phenylene dicarboxylic acid is preferably 0.30 to 0.48
  • the amount of the fatty acid anhydride used is preferably 1.
  • the fatty acid metal salt is an acetic acid metal salt and the fatty acid anhydride is acetic anhydride.
  • the total number of moles of 1,4-phenylene dicarboxylic acid and 1,3-phenylene dicarboxylic acid is 1 to 1.06 times the number of moles of 4,4′-dihydroxybiphenyl, or 4,4
  • the number of moles of '-dihydroxybiphenyl is preferably 1 to 1.06 times the total number of moles of 1,4-phenylenedicarboxylic acid and 1,3-phenylenedicarboxylic acid.
  • the wholly aromatic polyester in the present invention exhibits optical anisotropy when melted.
  • the optical anisotropy when melted means that the wholly aromatic polyester in the present invention is a liquid crystalline polymer.
  • the fact that the wholly aromatic polyester is a liquid crystalline polymer is an indispensable element when the wholly aromatic polyester has both thermal stability and easy processability.
  • the wholly aromatic polyester composed of the structural units (I) to (IV) may not form an anisotropic melt phase depending on the constituent components and the sequence distribution in the polymer. Limited to wholly aromatic polyesters that exhibit optical anisotropy when melted.
  • melt anisotropy can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the melting anisotropy can be confirmed by melting a sample placed on a hot stage manufactured by Linkham Co., Ltd. using a polarizing microscope manufactured by Olympus and observing it at a magnification of 150 times in a nitrogen atmosphere.
  • the liquid crystalline polymer is optically anisotropic and transmits light when inserted between crossed polarizers. If the sample is optically anisotropic, for example, polarized light is transmitted even in a molten stationary liquid state.
  • a nematic liquid crystalline polymer causes a significant decrease in viscosity at a melting point or higher, generally exhibiting liquid crystallinity at a melting point or higher is an index of workability.
  • the melting point is preferably as high as possible from the viewpoint of heat resistance, but considering the thermal deterioration during the melt processing of the polymer, the heating ability of the molding machine, etc., a preferable standard is 320 to 340 ° C. More preferably, the temperature is 325 to 335 ° C.
  • the composite resin composition in the present invention contains 60 to 82.5% by mass of the above liquid crystalline polymer in the composite resin composition with respect to the entire composite resin composition.
  • the content of the liquid crystalline polymer is less than 60% by mass with respect to the entire composite resin composition, the fluidity of the composite resin composition tends to deteriorate, and a molded article such as a connector obtained from the composite resin composition This is not preferable because there is a risk that the warp deformation of the substrate becomes large.
  • the content of the liquid crystalline polymer is more than 82.5% by mass with respect to the entire composite resin composition, the bending elastic modulus and crack resistance of a molded article such as a connector obtained from the composite resin composition are lowered. It is not preferable.
  • the composite resin composition in the present invention preferably contains 65 to 77.5% by mass of the above-mentioned liquid crystalline polymer in the composite resin composition with respect to the entire composite resin composition.
  • Fibrous filler Since the composite resin composition in the present invention contains the above-mentioned liquid crystalline polymer and a fibrous filler, a molded product obtained by molding the composite resin composition is excellent in high-temperature rigidity.
  • a fibrous filler can be used individually by 1 type or in combination of 2 or more types.
  • the fibrous filler in the present invention is not particularly limited, and is glass fiber, milled fiber, carbon fiber, asbestos fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, titanium.
  • a potassium acid fiber etc. are mentioned.
  • the fibrous filler in the present invention is preferably at least one selected from the group consisting of glass fibers and milled fibers, and more preferably milled fibers. .
  • the weight average fiber length of the fibrous filler is preferably 50 to 300 ⁇ m. It is preferable for the weight average fiber length to be 50 ⁇ m or more because the molded article obtained from the composite resin composition has sufficient high-temperature rigidity.
  • the weight average fiber length is 300 ⁇ m or less, the fluidity of the composite resin composition is good, the composite resin composition is hardly difficult to mold, and warpage deformation of the molded product is difficult to increase.
  • the weight average fiber length of the fibrous filler means that the composite resin composition is heated and ashed at 600 ° C. for 2 hours to obtain an ash residue, and the ash residue is 5% by mass.
  • a dispersion is obtained by dispersing in an aqueous polyethylene glycol solution, and the weight average fiber length measured with an image measuring device is used for this dispersion.
  • the fiber diameter of the fibrous filler in the present invention is not particularly limited, and generally about 5 to 15 ⁇ m is used.
  • the composite resin composition in the present invention contains a fibrous filler in the composite resin composition in an amount of 1.5 to 20% by mass with respect to the entire composite resin composition.
  • the content of the fibrous filler is less than 1.5% by mass with respect to the entire composite resin composition, the deflection temperature under load of a molded product such as a connector obtained from the composite resin composition is low, and the high-temperature rigidity is sufficient. It is not preferable because it is not.
  • the content of the fibrous filler is more than 20% by mass with respect to the entire composite resin composition, the fluidity of the composition is deteriorated and the warpage deformation of the molded product may be increased.
  • the fibrous filler in the present invention is preferably contained in the composite resin composition in an amount of 3 to 15% by mass with respect to the entire composite resin composition.
  • the composite resin composition in the present invention further contains a plate-like filler.
  • a plate-like filler By including a plate-like filler in the composite resin composition in the present invention, a molded product in which warpage deformation is suppressed can be obtained.
  • a plate-shaped filler can be used individually by 1 type or in combination of 2 or more types.
  • the plate-like filler is contained in an amount of 12.5 to 32% by mass with respect to the entire composite resin composition. If the content of the plate-like filler is less than 12.5% 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 filler is more than 32% 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. Therefore, it is not preferable.
  • the plate-like filler in the present invention is preferably contained in the composite resin composition in an amount of 17.5 to 32% by mass with respect to the entire composite resin composition.
  • Examples of the plate-like filler in the present invention include talc, mica, glass flakes, various metal foils, etc., and warpage of a molded product obtained from the composite resin composition without deteriorating the fluidity of the composite resin composition. Mica is preferable in terms of suppressing deformation. Further, the average particle size of the plate-like filler is not particularly limited, and a smaller one is desirable in consideration of fluidity in the thin portion. On the other hand, in order to reduce warping deformation of a molded article such as a connector obtained from the composite resin composition, it is necessary to maintain a certain size. Specifically, it is preferably 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ 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.
  • the wet pulverization method requires a step of dispersing the material to be pulverized in water, a coagulating sedimentation agent and / or settling aid is added to the material to be pulverized in order to increase the dispersion efficiency of the material to be pulverized. Is common.
  • 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.
  • a coagulating sedimentation agent and / or sedimentation aid when used, the polymer in the composite resin composition is unlikely to decompose, and a large amount of gas generation or molecular weight reduction is unlikely to occur. It is easy to maintain the performance of a molded product such as the above better.
  • 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 diameter of mica is 100 ⁇ m or less, it is easy to ensure sufficient fluidity for molding the 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.
  • the total amount of the fibrous filler and the plate-like filler is 17.5 to 35% by mass with respect to the entire composite resin composition.
  • the total amount is less than 17.5% by mass with respect to the entire composite resin composition, a molded article such as a connector obtained from the composite resin composition has a low deflection temperature under load and does not have sufficient high-temperature rigidity. This is not preferable because warpage may increase.
  • the total amount is more than 35% by mass with respect to the entire composite resin composition, the fluidity of the composite resin composition is deteriorated and warpage deformation of the molded product may be increased.
  • the total amount is preferably 22.5 to 35% by mass with respect to the entire composite resin composition.
  • 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 minimum filling pressure at the time of molding is hardly excessive, and preferably a connector, particularly a component having a small and complicated shape such as a low profile narrow pitch connector. Can be molded.
  • the degree of fluidity is determined by the minimum filling pressure of the connector. That is, the minimum injection pressure at which a good molded product can be obtained when the FPC connector shown in FIG. 3 is injection-molded is specified as the minimum filling pressure. The lower the minimum filling pressure, the better the fluidity.
  • the melt viscosity of the composite resin composition measured in accordance with ISO 11443 at a temperature 10 to 20 ° C. higher than the melting point of the liquid crystalline polymer at a shear rate of 1000 / second is 1 ⁇ 10 5 Pa ⁇ s or less (more preferably 5 Pa S to 1 ⁇ 10 2 Pa ⁇ s) in order to ensure fluidity of the composite resin composition and to prevent excessive filling pressure when molding a connector, particularly a low profile narrow pitch connector. preferable.
  • the connector of the present invention can be obtained by molding the composite 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 total product 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 profile narrow pitch connector, a coaxial connector, a micro SIM connector, and a micro SD connector. Among these, a low profile narrow pitch connector is preferable.
  • the low-profile narrow-pitch connector is not particularly limited.
  • a board-to-board connector also known as a “BtoB connector”
  • a connector for a flexible printed circuit board a flexible printed circuit board (FPC) and a flexible flat cable (FFC)
  • FPC connector a low-profile narrow pitch connector that is a board-to-board connector or a connector for a flexible printed board having a pitch distance of 0.5 mm or less, a total product length of 3.5 mm or more, and a product height of 4.0 mm or less is suitable. is there.
  • the molding method for obtaining the connector of the present invention is not particularly limited, and it is preferable to select molding conditions having no residual internal stress in order to prevent deformation of the obtained connector.
  • the cylinder temperature of the molding machine is preferably a temperature equal to or higher than the melting point of the liquid crystalline polymer.
  • the mold temperature is preferably 70 to 100 ° C. If the mold temperature is low, the composite resin composition filled in the mold may cause flow failure, which is not preferable. If the mold temperature is high, problems such as the occurrence of burrs may occur, which is not preferable.
  • the injection speed is preferably 150 mm / second or more. If the injection speed is low, there is a possibility that only an unfilled molded product can be obtained. Even if a completely filled molded product is obtained, it becomes a molded product with a high filling pressure and a large residual internal stress, resulting in a poor flatness. May only be obtained.
  • the warp deformation of the connector of the present invention is suppressed.
  • the degree of connector warping is determined as follows. That is, with the FPC connector shown in FIG. 3, the height is measured at a plurality of positions indicated by black circles in FIG. 4, and the difference between the maximum height and the minimum height from the least square plane is warped. In the connector of the present invention, the change in warpage is suppressed before and after performing the IR reflow.
  • the generation of blisters is suppressed.
  • the degree of blistering is determined by the blister temperature. That is, the presence or absence of blisters on the surface of a molded product sandwiched between hot presses at a predetermined temperature for 5 minutes is visually observed, and the highest temperature at which the number of blisters generated becomes zero is defined as the blister temperature. It is evaluated that the higher the blister temperature, the more blister generation is suppressed.
  • the connector obtained from the composite resin composition in the present invention is excellent in heat resistance, for example, heat resistance as evaluated by 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.
  • the L value of the polymer was measured using a spectral color difference meter (“SE6000” manufactured by Nippon Denshoku Industries Co., Ltd.).
  • the ketone bond amount of the polymer was calculated by a pyrolysis gas chromatography method described in Polymer Degradation and Stability 76 (2002) 85-94. Specifically, the polymer is heated in the presence of tetramethylammonium hydroxide (TMAH) using a pyrolysis device ("PY2020iD” manufactured by Frontier Laboratories) to generate gas by pyrolysis / methylation. It was. This gas is analyzed using gas chromatography (“GC-6890N” manufactured by Agilent Technologies), and the amount of ketone bond is calculated from the ratio of the peak area derived from the ketone bond to the peak area derived from the ester bond. did.
  • TMAH tetramethylammonium hydroxide
  • liquid crystalline polymer 1 is the liquid crystalline polymer obtained in Synthesis Example 1.
  • Liquid crystalline polymers 2 and 3 were produced as follows.
  • the melting point 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, 1330 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 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 (ie, 1330 Pa) over 20 minutes, while acetic acid, excess acetic anhydride, and other low-boiling components 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. and a melt viscosity of 9 Pa ⁇ s.
  • the extrusion conditions for obtaining the composite resin composition are as follows. [Extrusion conditions] [Examples 1 to 5, Comparative 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 360 ° C. All liquid crystalline polymers were supplied from the main feed port. The filler was supplied from the side feed port. [Comparative Example 5] The temperature of the cylinder provided at the main feed port was 250 ° C., and the temperatures of the other cylinders were all 380 ° C. All liquid crystalline polymers were supplied from the main feed port. The filler was supplied from the side feed port.
  • melt viscosity of composite resin composition Uses Capillograph Type 1B manufactured by Toyo Seiki Seisakusho Co., Ltd. at a temperature 10 to 20 ° C. higher than the melting point of the liquid crystalline polymer and uses an orifice with an inner diameter of 1 mm and a length of 20 mm at a shear rate of 1000 / sec. In conformity, the melt viscosity of the composite resin composition was measured. The measurement temperature is 360 ° C. for the composite resin composition using the liquid crystalline polymer 1, 350 ° C. for the composite resin composition using the liquid crystalline polymer 2, and the composite resin composition using the liquid crystalline polymer 3. Was 380 ° C. The results are shown in Tables 3 and 4.
  • the composite resin composition was injection molded under the following molding conditions to obtain a 12.5 mm ⁇ 120 mm ⁇ 0.8 mm molded product having a weld portion. A fragment obtained by dividing the molded product into two parts at the weld part was used as one specimen, and was sandwiched in a hot press at a predetermined temperature for 5 minutes. Thereafter, it was visually examined whether blisters were generated on the surface of the specimen. The blister temperature was the maximum temperature at which the number of blisters generated was zero. The predetermined temperature was set in increments of 10 ° C. in the range of 250 to 300 ° C. [Molding condition] Molding machine: Sumitomo Heavy Industries, SE100DU Cylinder temperature: 360 ° C. (Examples 1 to 5, Comparative Examples 1 to 4) 380 ° C. (Comparative Example 5) Mold temperature: 90 °C Injection speed: 33mm / sec
  • FIG. 1A is a top view
  • FIG. 1B is a side view
  • FIG. 1C is a cross-sectional view along AA.
  • Molded product (0.6mm pitch connector) size is 0.6mm in basic wall thickness, 57.2mm in total length, 0.3mm in pitch between terminals, 0.3mm in terminal pitch, 90 pins x 2 rows ( 180 pins in total).
  • Molding machine Sumitomo Heavy Industries, SE30DUZ Cylinder temperature: 360 ° C. (Examples 1 to 5, Comparative Examples 1 to 4) 380 ° C. (Comparative Example 5) Mold temperature: 80 °C Injection speed: 200mm / sec
  • 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. 4, and the difference between the maximum height and the minimum height from the least squares plane was taken as the warp of the FPC connector.
  • the warpage was measured before and after IR reflow performed under the following conditions, and evaluated according to the following criteria. Before IR reflow ⁇ (good): The warp was 0.03 mm or less. X (defect): The warp was more than 0.03 mm. -After IR reflow O (good): The warp was 0.15 mm or less.
  • FPC connector deformation The difference in warpage before and after reflow measured by the above method was determined as the FPC connector deformation amount and evaluated according to the following criteria. ⁇ (Good): The amount of deformation was 0.12 mm or less. X (defect): The amount of deformation was more than 0.12 mm.
  • the composite resin composition in the present invention was excellent in fluidity, and the connector molded from this composite resin composition was excellent in heat resistance, and warpage deformation and blister generation were suppressed. .

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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)

Abstract

L'invention concerne une composition de résine composite qui présente une remarquable résistance à la chaleur et une fluidité avantageuse et qui permet de produire un connecteur ne présentant ni déformations par gauchissement, ni cloquage. L'invention concerne également un connecteur qui est fabriqué à partir de ladite composition de résine composite. Cette composition de résine composite comprend : (A) un polymère à cristaux liquides, (B) une charge fibreuse et (C) une charge lamellaire. Le polymère à cristaux liquides (A) comprend des quantités prédéterminées de motifs structuraux (I) à (IV) en tant que composants structurels essentiels et possède des liaisons ester ou une combinaison de liaisons ester et de liaisons cétone au niveau moléculaire. La proportion de liaisons cétone par rapport à la totalité des liaisons ester et des liaisons cétone varie de 0 à 0,18 % en moles. La charge lamellaire (C) est constituée de mica. Cette composition de résine composite correspond à un polyester entièrement aromatique qui présente une anisotropie optique à l'état fondu.
PCT/JP2016/088081 2015-12-25 2016-12-21 Composition de résine composite et connecteur fabriqué à partir de ladite composition de résine composite WO2017110867A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019203157A1 (fr) * 2018-04-16 2019-10-24 ポリプラスチックス株式会社 Composition de résine cristalline liquide
US10829634B2 (en) 2017-12-05 2020-11-10 Ticona Llc Aromatic polymer composition for use in a camera module
US11086200B2 (en) 2019-03-20 2021-08-10 Ticona Llc Polymer composition for use in a camera module
US11722759B2 (en) 2019-03-20 2023-08-08 Ticona Llc Actuator assembly for a camera module
US12032272B2 (en) 2021-07-14 2024-07-09 Ticona Llc Polymer composition for use in a camera module

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11084925B2 (en) 2018-02-20 2021-08-10 Ticona Llc Thermally conductive polymer composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02240134A (ja) * 1989-03-15 1990-09-25 Tosoh Corp サーモトロピック液晶性コポリエステル
JP2010138228A (ja) * 2008-12-09 2010-06-24 Nippon Oil Corp 液晶ポリエステル樹脂組成物
WO2014050371A1 (fr) * 2012-09-26 2014-04-03 ポリプラスチックス株式会社 Composition de résine composite pour composant électronique, et composant électronique moulé à partir de celle-ci
CN103804666A (zh) * 2013-12-19 2014-05-21 金发科技股份有限公司 一种液晶聚合物的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02240134A (ja) * 1989-03-15 1990-09-25 Tosoh Corp サーモトロピック液晶性コポリエステル
JP2010138228A (ja) * 2008-12-09 2010-06-24 Nippon Oil Corp 液晶ポリエステル樹脂組成物
WO2014050371A1 (fr) * 2012-09-26 2014-04-03 ポリプラスチックス株式会社 Composition de résine composite pour composant électronique, et composant électronique moulé à partir de celle-ci
CN103804666A (zh) * 2013-12-19 2014-05-21 金发科技股份有限公司 一种液晶聚合物的制备方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10829634B2 (en) 2017-12-05 2020-11-10 Ticona Llc Aromatic polymer composition for use in a camera module
US11725106B2 (en) 2017-12-05 2023-08-15 Ticona Llc Aromatic polymer composition for use in a camera module
WO2019203157A1 (fr) * 2018-04-16 2019-10-24 ポリプラスチックス株式会社 Composition de résine cristalline liquide
JPWO2019203157A1 (ja) * 2018-04-16 2020-06-18 ポリプラスチックス株式会社 液晶性樹脂組成物
CN111971346A (zh) * 2018-04-16 2020-11-20 宝理塑料株式会社 液晶性树脂组合物
CN111971346B (zh) * 2018-04-16 2022-09-06 宝理塑料株式会社 液晶性树脂组合物
US11086200B2 (en) 2019-03-20 2021-08-10 Ticona Llc Polymer composition for use in a camera module
US11722759B2 (en) 2019-03-20 2023-08-08 Ticona Llc Actuator assembly for a camera module
US12032272B2 (en) 2021-07-14 2024-07-09 Ticona Llc Polymer composition for use in a camera module

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