WO2016088714A1 - Composition de résine composite et connecteur plan - Google Patents

Composition de résine composite et connecteur plan Download PDF

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Publication number
WO2016088714A1
WO2016088714A1 PCT/JP2015/083602 JP2015083602W WO2016088714A1 WO 2016088714 A1 WO2016088714 A1 WO 2016088714A1 JP 2015083602 W JP2015083602 W JP 2015083602W WO 2016088714 A1 WO2016088714 A1 WO 2016088714A1
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Prior art keywords
resin composition
composite resin
glass fiber
mass
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PCT/JP2015/083602
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English (en)
Japanese (ja)
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信彰 佐々木
博樹 深津
麻美 西山
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ポリプラスチックス株式会社
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Priority to JP2016527480A priority Critical patent/JP6022127B1/ja
Priority to CN201580057975.0A priority patent/CN107148448B/zh
Publication of WO2016088714A1 publication Critical patent/WO2016088714A1/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
    • 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 planar connector.
  • liquid crystalline polymers are excellent in fluidity and the like, they have been conventionally used as materials for various electronic components.
  • molded products such as planar connectors
  • a molded resin composition composed of a predetermined liquid crystalline polymer, an inorganic filler, and glass fiber is molded, and the moldability, flatness, warpage deformation, and heat resistance.
  • a planar connector that is excellent in performance such as, and that is less prone to cracks (also referred to as “cracks”) in the lattice portion.
  • the present invention has been made in view of such circumstances, and an object thereof is to provide a composite resin composition capable of forming a molded article having excellent crack resistance, and a planar connector formed from the composite resin composition.
  • the present inventors have found that the above-mentioned problems can be solved by a composite resin composition containing a predetermined amount of glass fibers having a predetermined weight average fiber length and fiber length distribution together with a liquid crystalline polymer and talc. It came to complete. Specifically, the present invention provides the following.
  • a composite resin composition comprising a liquid crystalline polymer, glass fiber, and one or more plate-like inorganic fillers selected from the group consisting of mica and talc,
  • the liquid crystalline polymer has a melt viscosity measured according to ISO 11443 at a shear rate of 1000 / sec at a temperature 10 to 20 ° C. higher than the melting point of the liquid crystalline polymer.
  • the content of the glass fiber is 25.0 mass% or more and 27.5 mass% or less with respect to the entire composite resin composition
  • the glass fiber has a weight average fiber length of 350 ⁇ m or more and 500 ⁇ m or less
  • the content of the glass fiber having a fiber length of 800 ⁇ m or more is 6.00% by mass or more based on the whole glass fiber
  • the composite resin composition whose total amount of the said plate-shaped inorganic filler is 20.0 mass% or more and 25.0 mass% or less with respect to the whole composite resin composition.
  • a composite resin composition capable of forming a molded article having excellent crack resistance, and a planar connector formed from the composite resin composition.
  • the composite resin composition of the present invention includes a liquid crystalline polymer, glass fibers having a predetermined weight average fiber length and fiber length distribution, and talc.
  • a liquid crystalline polymer glass fibers having a predetermined weight average fiber length and fiber length distribution
  • talc talc
  • the liquid crystalline polymer in the present invention is a melt-processable polyester and exhibits optical anisotropy when melted.
  • the property of 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.
  • the liquid crystalline polymer in the present invention is not particularly limited, but is obtained from condensation polymerization of aromatic hydroxycarboxylic acid or condensation polymerization of aromatic diol and aromatic dicarboxylic acid. Or you may consist of a structural component containing the structural unit derived from the compound which has a hydroxyl group.
  • the aromatic carboxylic acid include aromatic dicarboxylic acids and aromatic hydroxycarboxylic acids.
  • the compound having a hydroxyl group include aromatic diols, alicyclic diols, aliphatic diols, and aromatic hydroxyamines. .
  • Preferred examples of the monomer from which the constituent component (structural unit) of the liquid crystalline polymer is derived include (I) naphthalene compounds such as 2,6-naphthalenedicarboxylic acid, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene and 6-hydroxy-2-naphthoic acid, (Ii) biphenyl compounds such as 4,4′-biphenyldicarboxylic acid, 4,4′-dihydroxybiphenyl, 4-hydroxy-4′-biphenylcarboxylic acid, (Iii) A compound represented by the following general formula (I), (II) or (III):
  • (X represents a group selected from alkylene or alkylidene having 1 to 4 carbon atoms, —O—, —SO—, —SO 2 —, —S—, —CO—, and Y: — (CH 2 ) n.
  • benzene compounds such as p-hydroxybenzoic acid (4-hydroxybenzoic acid), terephthalic acid, hydroquinone, p-aminophenol, 4-acetoxyaminophenol and p-phenylenediamine, and their nuclear substitution
  • Benzene compounds substituted for nuclear substitution are selected from halogens such as fluorine, chlorine, bromine and iodine, alkyls having 1 to 4 carbon atoms, phenyl and 1-phenylethyl), and (v) isophthalic acid, resorcin, etc.
  • Meta-substituted benzene compounds, and their nuclear-substituted benzene compounds are selected from chlorine, bromine, alkyl having 1 to 4 carbon atoms, phenyl, and 1-phenylethyl).
  • para-substituted benzene compounds p-hydroxybenzoic acid, methylhydroquinone and 1-phenylethylhydroquinone are particularly preferred.
  • the liquid crystalline polymer in the present invention is preferably an aromatic polyester and / or an aromatic polyester amide, and may partially contain the aromatic polyester and / or the aromatic polyester amide in the same molecular chain.
  • a liquid crystalline aromatic polyester and / or liquid crystal having a structural unit derived from at least one compound selected from the group consisting of an aromatic hydroxycarboxylic acid, an aromatic hydroxyamine, and an aromatic diamine as a constituent component.
  • Aromatic polyester amide Aromatic polyester amide.
  • the liquid crystalline polymer in the present invention is: (1) A polyester composed mainly of structural units derived from one or more aromatic hydroxycarboxylic acids and derivatives thereof (2) A composition derived mainly from one or more aromatic hydroxycarboxylic acids and derivatives thereof A unit, a structural unit derived from one or more of aromatic dicarboxylic acid, alicyclic dicarboxylic acid, and derivatives thereof, and aromatic diol, alicyclic diol, aliphatic diol, and derivatives thereof.
  • Polyester composed of structural units derived from at least one or more kinds (3) Constituent units derived mainly from one or more types of aromatic hydroxycarboxylic acids and derivatives thereof, aromatic hydroxyamines, aromatic diamines And structural units derived from one or more of these derivatives, aromatic dicarboxylic acid, and alicyclic dica A polyesteramide comprising a structural unit derived from one or more of each of boric acid and derivatives thereof (4) a structural unit derived mainly from one or more of aromatic hydroxycarboxylic acid and derivatives thereof; , A structural unit derived from one or more of aromatic hydroxyamine, aromatic diamine, and derivatives thereof, and one or more of aromatic dicarboxylic acid, alicyclic dicarboxylic acid, and derivatives thereof And polyester amides composed of structural units derived from one or more of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof.
  • a molecular weight regulator such as a monofunctional monomer such as benzoic acid or a trifunctional monomer such as aromatic hydroxydicarboxylic acid or aromatic tricarboxylic acid may be used in combination with the monomer that is the origin of the above-described constituent components. Good.
  • the liquid crystalline polymer in the present invention may contain a structural unit derived from polyalkylene terephthalate that does not partially exhibit an anisotropic molten phase in the same molecular chain, in addition to the above-described structural components.
  • the alkyl group has 2 to 4 carbon atoms.
  • the liquid crystalline polymer of the present invention has a melt viscosity of 5.00 Pa ⁇ s or higher and 13.30 Pa ⁇ s or higher measured at a shear rate of 1000 / sec at a temperature 10 to 20 ° C. higher than the melting point of the liquid crystalline polymer according to ISO11443. 0 Pa ⁇ s or less.
  • the melt viscosity of the liquid crystalline polymer is in the above range, the melt viscosity of the composite resin composition does not become excessive, and the inclination and position of the weld part of the molded product molded from the composite resin composition vary. The following action can be promoted.
  • the melt viscosity of the liquid crystalline polymer ensures the fluidity of the composite resin composition when molding the lattice portion of the planar connector, and the filling pressure does not become excessive. It is preferably 12.0 Pa ⁇ s or less.
  • the melt viscosity of the liquid crystalline polymer is preferably 7.00 Pa ⁇ s or more from the viewpoint of easily obtaining a composite resin composition capable of forming a molded article having excellent crack resistance.
  • Preferred liquid crystal polymers capable of realizing the melt viscosity defined in the present invention include, as constituent components, the following constituent units: (I) constituent units derived from 4-hydroxybenzoic acid (also referred to as “HBA”), (II ) A structural unit derived from 2-hydroxy-6-naphthoic acid (also referred to as “HNA”), (III) a structural unit derived from terephthalic acid (also referred to as “TA”), and (IV) isophthalic acid (also referred to as “IA”). And a structural unit derived from (V) 4,4′-dihydroxybiphenyl (also referred to as “BP”).
  • HBA 4-hydroxybenzoic acid
  • HNA 2-hydroxy-6-naphthoic acid
  • TA terephthalic acid
  • IA isophthalic acid
  • V 4,4′-dihydroxybiphenyl
  • the above-mentioned structural units may be contained in a specific ratio. That is, the structural unit (I) may be 35 to 75 mol% (preferably 40 to 65 mol%) with respect to the total structural units.
  • the structural unit (II) may be 2 to 8 mol% (preferably 3 to 7 mol%) with respect to the total structural units.
  • the structural unit (III) may be 4.5 to 30.5 mol% (preferably 13 to 26 mol%) with respect to the total structural units.
  • the structural unit of (IV) may be 2 to 8 mol% (preferably 3 to 7 mol%) with respect to the total structural units.
  • the structural unit (V) may be 12.5 to 32.5 mol% (preferably 15.5 to 29 mol%) with respect to the total structural units.
  • the total amount of the structural units (II) and (IV) may be 4 to 10 mol% (preferably 5 to 10 mol%) with respect to all the structural units.
  • the composite resin composition of the present invention may contain 45% by mass or more and 55% by mass or less of the above liquid crystalline polymer with respect to the entire composite resin composition.
  • the amount of the liquid crystalline polymer is 45% by mass or more based on the entire composite resin composition, the fluidity of the composite resin composition is unlikely to deteriorate.
  • the amount of the liquid crystalline polymer is 55% by mass or less based on the entire composite resin composition, the crack resistance of a molded product (planar connector or the like) obtained from the composite resin composition is unlikely to decrease.
  • the composite resin composition of the present invention contains the liquid crystalline polymer in an amount of 50% by mass or more based on the entire composite resin composition. More preferably, the content is 55% by mass or less.
  • the composite resin composition of this invention contains 25.0 mass% or more and 27.5 mass% or less of glass fiber with respect to the whole composite resin composition.
  • the weight average fiber length of the glass fiber is 350 ⁇ m or more and 500 ⁇ m or less, and the content of the glass fiber having a fiber length of 800 ⁇ m or more is 6.00% by mass with respect to the entire glass fiber in the composite resin composition. That's it.
  • the composite resin composition not only the weld strength but also the glass fiber having the weight average fiber length and the fiber length distribution is blended with the liquid crystalline polymer and talc in the above amounts. Further, it has been found that a composite resin composition capable of molding a molded article (such as a planar connector) having excellent crack resistance can be obtained.
  • the amount of glass fiber is less than 25.0% by mass with respect to the entire composite resin composition, the weld strength of the molded product obtained from the composite resin composition is low, and the molded product is a planar connector or the like. Are prone to cracks in the lattice portion.
  • the amount of the glass fiber is more than 27.5% by mass with respect to the entire composite resin composition, the fluidity of the composite resin composition is deteriorated, and a molded product obtained from the composite resin composition is a flat connector or the like. In such a case, cracks are likely to occur in the lattice portion or the like.
  • a glass fiber having a weight average fiber length of 350 ⁇ m or more and 500 ⁇ m or less and a fiber length of 800 ⁇ m or more (hereinafter, a glass fiber having a fiber length of 800 ⁇ m or more is also referred to as “long fiber”).
  • a resin composition is obtained.
  • the weight average fiber length of the glass fiber is preferably 380 ⁇ m or more and 450 ⁇ m or less.
  • the weight average fiber length of the glass fiber is specified by the method described in the examples.
  • the weight average fiber length of glass fiber can be adjusted to a desired value by adjusting the conditions of the manufacturing method of a resin composition.
  • the proportion of long fibers is preferably 6.50% by mass or more based on the whole glass fibers.
  • the upper limit of the proportion of long fibers is not particularly limited, but is preferably 15% by mass or less, more preferably, based on the entire glass fiber, from the viewpoint of easily obtaining a composite resin composition capable of forming a molded article having excellent crack resistance. It is 10 mass% or less.
  • the ratio of long fibers to the entire glass fibers (that is, fiber length distribution) is specified by the method described in the examples.
  • the ratio of the long fiber is in the above range, and the glass fiber having a fiber length of less than 200 ⁇ m (hereinafter referred to as a glass fiber having a fiber length of less than 200 ⁇ m).
  • the ratio of “short fiber” is preferably 10.0% by mass or more based on the entire glass fiber.
  • the upper limit of the proportion of short fibers is not particularly limited, but is preferably 40% by mass or less, more preferably based on the whole glass fiber, from the viewpoint of easily obtaining a composite resin composition capable of molding a molded article having excellent crack resistance. 35% by mass or less.
  • the method for specifying the ratio of short fibers to the entire glass fibers is the same as the method for long fibers.
  • the reason why the weight average fiber length and the ratio of long fibers of the glass fiber in the composite resin composition affect the crack resistance of the molded product obtained from the composite resin composition is taken as an example of a planar connector as a molded product.
  • I will give you a description. That is, when the composite resin composition containing glass fibers whose weight average fiber length and long fiber ratio are within the scope of the present invention is poured into a mold, the long fibers contained in the composite resin composition are locally and minute. Since the flow inhibition is caused, the composite resin composition has a flow variation and hardly flows uniformly. Therefore, the shape of the flow front of the composite resin composition poured into the mold (the front end portion of the composite resin composition poured into the mold) is not a linear shape but an indefinite shape.
  • the molded product is a planar connector having a lattice structure inside the outer frame portion, variations in the inclination and position of the weld portion occur in the lattice structure. As a result, the distance between the welds is not uniform, the strength of the planar connector is increased, and cracks are less likely to occur even when reflowing is performed during mounting (see FIG. 1A).
  • the weight average fiber length of the glass fiber in the composite resin composition and the ratio of the long fibers do not satisfy the conditions of the present invention, when the composite resin composition is poured into the mold, it flows uniformly and into the mold. The shape of the flow front of the poured composite resin composition is linear.
  • the molded product is a planar connector having the above-described lattice structure, there is no variation in the inclination and position of the weld in the lattice structure, the distance between the welds is uniform, and cracks are likely to occur when reflowing is performed. (See FIG. 1B).
  • the fiber diameter of the glass fiber in the present invention is not particularly limited, but generally a fiber diameter of about 5 ⁇ m to 15 ⁇ m is used.
  • the composite resin composition of the present invention includes one or more plate-like inorganic fillers selected from the group consisting of mica and talc.
  • the plate-like inorganic filler is improved in dimensional stability without deteriorating the fluidity of the composite resin composition, and a molded article having excellent crack resistance is formed. A composite resin composition is obtained.
  • the total amount of the plate-like inorganic filler contained in the composite resin composition of the present invention is 20.0% by mass or more and 25.0% by mass or less with respect to the entire composite resin composition.
  • the plate-like inorganic filler is contained in such a range in the composite resin composition, the effect of improving the weld strength and the effect of reducing the number of cracks of the molded body produced by the glass fiber are reinforced.
  • mica and talc may be combined, but using mica or talc alone is preferable from the viewpoint that the effect of the present invention is easily achieved. .
  • Mica is a pulverized product of silicate mineral containing aluminum, potassium, magnesium, sodium, iron and the like.
  • examples of mica 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 low-cost and general method, but it is difficult to pulverize the mineral thinly and finely.
  • 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 crushed. Is common.
  • polyaluminum chloride aluminum sulfate, ferrous sulfate, ferric sulfate, copper chloride, polyiron sulfate, polyferric chloride, iron-silica inorganic polymer flocculant, chloride
  • ferric-silica inorganic polymer flocculant examples thereof include ferric-silica inorganic polymer flocculant, slaked lime (Ca (OH) 2 ), caustic soda (NaOH), soda ash (Na 2 CO 3 ) and the like.
  • 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 pulverizing.
  • the mica in the present invention preferably has an average particle size of 10 to 100 ⁇ m as measured by a microtrack laser diffraction method, and particularly preferably has an average particle size of 20 to 80 ⁇ m. It is preferable that the average particle diameter of mica is 10 ⁇ m or more because the rigidity of the molded product tends to be sufficient. It is preferable that the average particle diameter of mica is 100 ⁇ m or less because the rigidity and weld strength of the molded product are likely to be sufficient. Moreover, the fluidity
  • the thickness of the mica in the present invention is preferably from 0.01 to 1 ⁇ m, particularly preferably from 0.03 to 0.3 ⁇ m, as measured by observation with an electron microscope. It is preferable that the mica thickness is 0.01 ⁇ m or more because the mica is difficult to break during the melt processing of the composite resin composition. If the mica thickness is 1 ⁇ m or less, the rigidity of the molded product tends to be sufficient.
  • the mica in the present invention may be surface-treated with a silane coupling agent or the like and / or granulated with a binder.
  • ⁇ talc ⁇ Talc in the present invention is not particularly limited with respect to the total solid content of the talc, the total content of Fe 2 O 3, Al 2 O 3 and CaO is not more than 2.5 mass%, Fe 2 O The total content of 3 and Al 2 O 3 is more than 1.0% by mass and 2.0% by mass or less, and the content of CaO is less than 0.5% by mass. That is, the talc 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 may be included in the above range. Good.
  • the total amount 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.
  • the cumulative average particle diameter (D 50 ) of talc measured by laser diffraction method in the present invention is 4.0 ⁇ m or more and 20.0 ⁇ m or less from the viewpoint of maintaining the fluidity of the composite resin composition. Preferably, it is 10 ⁇ m or more and 18 ⁇ m or less.
  • the composite resin composition of the present invention may contain a nucleating agent, carbon black, pigment, antioxidant, stabilizer, plasticizer, lubricant, mold release agent, flame retardant, and the like. .
  • a nucleating agent carbon black, pigment, antioxidant, stabilizer, plasticizer, lubricant, mold release agent, flame retardant, and the like.
  • the amounts and types of these components can be appropriately adjusted according to the effect to be obtained.
  • the method for producing a composite resin composition of the present invention is a method capable of realizing the weight average fiber length and the ratio of long fibers of glass fibers defined in the present invention, and optionally the ratio of short fibers defined in the present invention. If it is, it will not specifically limit, For example, the method shown to the following (1) thru
  • Resin is supplied from the main feed port of the extruder, and two or more types of glass fibers having different average fiber lengths and other inorganic fillers are supplied from the side feed port of the extruder.
  • the cylinder temperature, the screw rotation speed, and the extrusion amount are adjusted as appropriate.
  • a resin and a glass fiber-containing resin composition are supplied from the main feed port of the extruder, and glass fibers and other inorganic fillers are supplied from the side feed port of the extruder.
  • the cylinder temperature, the screw rotation speed, and the extrusion amount are adjusted as appropriate.
  • resin is supplied from the main feed port of the extruder
  • glass fibers and other inorganic fillers are supplied from the side feed port of the extruder.
  • the cylinder temperature, the screw rotation speed, and the extrusion amount are adjusted as appropriate.
  • the composite resin composition of the present invention can be preferably applied to the production of molded products that require crack resistance.
  • An example of such a molded product is a planar connector.
  • the shape of the planar connector is not particularly limited, but it may be a planar connector having a lattice structure inside the outer frame portion, which is known to easily cause cracks from the viewpoint of easily achieving the effects of the present invention. Good.
  • the planar connector having the lattice structure may be a planar connector in which the pitch interval between the lattice portions is 1.5 mm or less.
  • planar connector may be a very thin planar connector in which the width of the resin portion of the lattice portion holding the terminals in the planar connector is 0.5 mm or less and the total height of the product is 5.0 mm or less.
  • Specific examples of the planar connector of the present invention include those shown in FIG.
  • the molding method for obtaining the planar connector of the present invention is not particularly limited, but molding conditions with little residual internal stress are required in order to obtain a planar connector having good flatness to prevent deformation of the obtained planar connector. Is preferred.
  • the cylinder temperature of the molding machine is preferably higher than the melting point of the liquid crystalline polymer.
  • the mold temperature is preferably 70 ° C. or higher and 100 ° C. or lower. 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 planar connector molded from the composite resin composition of the present invention is excellent in crack resistance.
  • the crack resistance of the planar connector is evaluated by specifying the number of cracks after reflow by the method described in the examples. The smaller the number of cracks after reflow, the higher the crack resistance of the planar connector.
  • the interelectrode wall thickness of the planar connector of the present invention is not particularly limited, but is preferably 0.18 mm or more and 0.25 mm or less.
  • the interelectrode wall thickness is 0.25 mm or less, the flow variation caused by the long fibers contained in the composite resin composition is likely to be sufficient, and the effects of the present invention may be easily achieved.
  • the interelectrode wall thickness is 0.18 mm or more, the flow resistance of the composite resin composition does not increase too much, and it is difficult to fill the mold with the composite resin composition.
  • 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 obtained polymer had a melting point of 358 ° C. and a melt viscosity of 10.0 Pa ⁇ s.
  • 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. About the obtained pellet, heat processing was performed at 300 degreeC under nitrogen stream for 2 hours.
  • the obtained polymer had a melting point of 334 ° C. and a melt viscosity of 14.0 Pa ⁇ s.
  • 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 pellets were heat-treated at 300 ° C. for 4 hours under a nitrogen stream.
  • the obtained polymer had a melting point of 334 ° C. and a melt viscosity of 20.0 Pa ⁇ s.
  • the detailed configuration of the screw and feeder shown in FIG. 3 is as follows.
  • the detailed configuration of the screw and feeder shown in FIG. 5 is as follows.
  • Heavy weight type single screw feeder For glass fiber: Weight type twin screw feeder Feeder to side feed port For glass fiber: Japan Heavy steel single screw feeder manufactured by Steelworks Co., Ltd.
  • Example 4 the cylinder C0 provided in the main feed port 1 is 100 ° C, C8 to C11 are 320 ° C, and the other cylinder temperatures are all 370 ° C.
  • (4) Kneading and Extruding Method of Resin Composition liquid crystal polyester pellets were supplied from the main feed port 1 using the above twin screw extruder, and talc Was supplied from the side feed port 3. The glass fiber was supplied from the main feed port 1 for 1/5 of the filling amount, and from the side feed port 3 for 4/5.
  • Comparative Examples 1 to 6 liquid crystal polyester pellets were supplied from the main feed port 1 and fillers were supplied from the side feed port 3 using the above twin screw extruder.
  • Example 1 the screw rotation speed and the extrusion amount were set to 300 rpm and 20 kg / h, respectively, and the molten resin composition discharged in a strand form from the die was transferred by a mesh belt conveyor. While being transported and cooled by spray spray water, cutting was performed to obtain pellets.
  • Example 4 a biaxial screw extruder provided with a screw having a mixing element (not shown in FIG. 5) in the kneading section 4 is used to supply liquid crystalline polyester pellets from the main feed port 1 and to fill the filler. was supplied from the side feed port 3.
  • Example 4 the screw rotation speed and the extrusion amount were set to 485 rpm and 383 kg / h, respectively, and the molten resin composition discharged in a strand form from the die was cooled by spray spray water while being conveyed by a mesh belt conveyor. Then, cutting was performed to obtain a pellet.
  • Table 3 shows the effects of the screw rotation speed and the extrusion amount on the weight average fiber length of the glass fiber and the ratio of the long fiber and the short fiber.
  • the composite resin composition was injection molded under the following molding conditions on a test specimen for measurement (125 mm ⁇ 13 mm ⁇ 0.4 mm, two-point film gate). The weld strength of the obtained test piece was measured under the following measurement conditions.
  • Molding machine Sumitomo Heavy Industries SE100DU Cylinder temperature: 365 ° C-365 ° C-365 ° C-365 ° C-365 ° C-365 ° C-365 ° C Mold temperature: 90 ° C Injection speed: 200mm / sec Holding pressure: 70 MPa Holding pressure time: 5 sec Cooling time: 8 sec Screw rotation speed: 150rpm Screw back pressure: 1MPa [Measurement condition] Measuring instrument: RTM-100 manufactured by Orientec Tensilon Universal Tester Load cell: 100kg Mold temperature: 90 ° C Distance between chucks: 2.5mm Chuck force: 2.0 kgf / cm 2 Tensile speed: 0.5 mm / min
  • IR reflow was performed on the planar connector of FIG. 2 under the following conditions, the lattice portion was observed with an optical microscope, and the number of cracks was measured. A smaller number of cracks indicates higher crack resistance.
  • Measuring instrument RF-300 (using far infrared heater) Sample feed rate: 140 mm / sec Reflow furnace transit time: 5 min Temperature conditions; Preheat zone: 150 ° C Reflow zone: 240 ° C Peak temperature: 260 ° C
  • the planar connector molded from the composite resin composition of the present invention has no crack after reflow and is excellent in crack resistance. Moreover, the planar connector molded from the composite resin composition of the present invention tended to have high weld strength.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne une composition de résine composite capable de former un article moulé présentant une excellente résistance à la fissuration, et un connecteur plan formé à partir de ladite composition de résine composite. Cette composition de résine composite contient un polymère de cristaux liquides, des fibres de verre, et au moins une charge inorganique lamellaire sélectionnée dans le groupe constitué par le mica et le talc. Le polymère de cristal liquide présente une viscosité prescrite à l'état fondu, la teneur en fibres de verre est comprise entre 25,0 et 27,5 % en masse de la totalité de la composition de la résine composite, la longueur de fibre moyenne en poids des fibres de verre est comprise entre 350 et 500 µm, les fibres de verre de longueur de fibre de 800 µm ou plus représentent 6,00 % ou plus en masse de la totalité des fibres de verre, et la quantité totale de la charge inorganique lamellaire est comprise entre 20,0 et 25,0 % en masse de la totalité de la composition de résine composite.
PCT/JP2015/083602 2014-12-05 2015-11-30 Composition de résine composite et connecteur plan WO2016088714A1 (fr)

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JP2016527480A JP6022127B1 (ja) 2014-12-05 2015-11-30 複合樹脂組成物及び平面状コネクター
CN201580057975.0A CN107148448B (zh) 2014-12-05 2015-11-30 复合树脂组合物和平面状连接器

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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
CN110982297A (zh) * 2019-12-17 2020-04-10 东莞市德发塑胶科技有限公司 一种5g低介电强度lcp复合材料及其制备方法
WO2020153220A1 (fr) * 2019-01-25 2020-07-30 ポリプラスチックス株式会社 Article moulé composite
US11086200B2 (en) 2019-03-20 2021-08-10 Ticona Llc Polymer composition for use in a camera module
WO2023145517A1 (fr) * 2022-01-26 2023-08-03 ポリプラスチックス株式会社 Composition de résine cristalline liquide pour connecteur plan, et connecteur plan obtenu à l'aide de celle-ci
US11722759B2 (en) 2019-03-20 2023-08-08 Ticona Llc Actuator assembly for a camera module

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EP4035881A4 (fr) * 2019-09-25 2023-08-30 Mitsui Chemicals, Inc. Matériau de modelage tridimensionnel, objet modélisé tridimensionnel, et procédé de production d'un objet modélisé tridimensionnel

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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
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
KR102052662B1 (ko) * 2016-10-07 2019-12-05 포리프라스틱 가부시키가이샤 복합 수지 조성물, 및 당해 복합 수지 조성물로 성형된 커넥터
CN109790378A (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连接器
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
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
KR20190028556A (ko) * 2016-10-07 2019-03-18 포리프라스틱 가부시키가이샤 복합 수지 조성물, 및 당해 복합 수지 조성물로 성형된 커넥터
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
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
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
WO2020153220A1 (fr) * 2019-01-25 2020-07-30 ポリプラスチックス株式会社 Article moulé composite
JP2020116862A (ja) * 2019-01-25 2020-08-06 ポリプラスチックス株式会社 複合成形品
KR20210076164A (ko) * 2019-01-25 2021-06-23 포리프라스틱 가부시키가이샤 복합 성형품
KR102343382B1 (ko) 2019-01-25 2021-12-24 포리프라스틱 가부시키가이샤 복합 성형품
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
CN110982297A (zh) * 2019-12-17 2020-04-10 东莞市德发塑胶科技有限公司 一种5g低介电强度lcp复合材料及其制备方法
CN110982297B (zh) * 2019-12-17 2021-07-09 东莞市德发塑胶科技有限公司 一种5g低介电强度lcp复合材料及其制备方法
WO2023145517A1 (fr) * 2022-01-26 2023-08-03 ポリプラスチックス株式会社 Composition de résine cristalline liquide pour connecteur plan, et connecteur plan obtenu à l'aide de celle-ci

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TW201634572A (zh) 2016-10-01
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TWI648337B (zh) 2019-01-21
CN107148448B (zh) 2018-02-27
JPWO2016088714A1 (ja) 2017-04-27

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