WO2014050370A1 - 複合樹脂組成物及び該複合樹脂組成物から成形される平面状コネクター - Google Patents
複合樹脂組成物及び該複合樹脂組成物から成形される平面状コネクター Download PDFInfo
- Publication number
- WO2014050370A1 WO2014050370A1 PCT/JP2013/072224 JP2013072224W WO2014050370A1 WO 2014050370 A1 WO2014050370 A1 WO 2014050370A1 JP 2013072224 W JP2013072224 W JP 2013072224W WO 2014050370 A1 WO2014050370 A1 WO 2014050370A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- composite resin
- mol
- respect
- structural units
- Prior art date
Links
Images
Classifications
-
- 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
- H01R43/18—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors for manufacturing bases or cases for contact members
Definitions
- the present invention relates to a composite resin composition and a planar 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 planar connector molded from a liquid crystalline polymer composition reinforced with glass fibers.
- Patent Document 2 discloses a planar connector molded from a liquid crystalline polymer composition reinforced with glass fiber and talc.
- Such a connector is employed as a planar connector (such as a CPU socket) having a lattice structure inside the outer frame, which requires high heat resistance and the like.
- planar connectors In recent years, the shape required for planar connectors has changed as the integration rate of planar connectors has increased. For example, as the shape of the planar connector, an increase in the number of connector pins, a shape in which the width of the lattice portion is thinner, and the like are required.
- the present invention has been made in view of such circumstances, a composite resin composition capable of obtaining a planar connector having excellent flatness and fluidity, suppressing warpage deformation, and excellent crack resistance, And it aims at providing the planar connector shape
- 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 fiber, and a predetermined inorganic filler. Specifically, the present invention provides the following.
- a composite resin composition comprising (A) a liquid crystalline polymer, (B) glass fiber, and (C) one or more inorganic fillers selected from the group consisting of talc and milled fiber,
- the (A) liquid crystalline polymer has the following constituent units as essential constituents: (I) 4-hydroxybenzoic acid, (II) 2-hydroxy-6-naphthoic acid, (III) terephthalic acid, (IV) Including isophthalic acid and (V) 4,4′-dihydroxybiphenyl,
- the structural unit of (I) is 35 to 75 mol% with respect to all the structural units,
- the structural unit of (II) is 2 to 8 mol% with respect to all the structural units,
- the structural unit of (III) is 4.5 to 30.5 mol% with respect to all the structural units,
- the structural unit of (IV) is 2 to 8 mol% with respect to all the structural units,
- the structural unit of (V) is 12.5 to 32.5 mol% with
- the flatness and fluidity are good, warpage deformation is suppressed, and a planar connector having excellent crack resistance is obtained, and the composite resin composition is molded from the composite resin composition.
- a flat connector is provided.
- the composite resin composition of the present invention contains a predetermined amount of a specific liquid crystalline polymer, glass fiber, and inorganic filler.
- a specific liquid crystalline polymer glass fiber, and inorganic filler.
- the liquid crystalline polymer according to the present invention has the following constituent units as essential constituents: (I) 4-hydroxybenzoic acid (also referred to as “HBA”), (II) 2-hydroxy-6-naphthoic acid (“HNA”) (III) terephthalic acid (also referred to as “TA”), (IV) isophthalic acid (also referred to as “IA”) and (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
- BP 4,4′-dihydroxybiphenyl
- the liquid crystalline polymer in the present invention contains the above structural units at a specific ratio. That is, the structural unit of (I) is 35 to 75 mol% (preferably 40 to 65 mol%) with respect to all the structural units.
- the structural unit (II) is 2 to 8 mol% (preferably 3 to 7 mol%) with respect to the total structural units.
- the structural unit of (III) is 4.5 to 30.5 mol% (preferably 13 to 26 mol%) with respect to the total structural units.
- the structural unit (IV) is 2 to 8 mol% (preferably 3 to 7 mol%) with respect to the total structural units.
- the structural unit (V) is 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) 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 becomes remarkably high, and liquid crystallinity is produced in the production of molded products such as planar connectors. This is not preferable because the polymer may solidify in the reactor and a liquid crystalline polymer having a desired molecular weight may not be produced.
- the constituent unit of (III) is less than 4.5 mol% or more than 30.5 mol% with respect to all the constituent units, the melting point of the liquid crystalline polymer becomes remarkably high, and a molded product such as a planar connector is produced. At this time, 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 crystallization heat amount of the liquid crystalline polymer can be 2.5 J / g or more.
- 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 having an activated terminal 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-step system) in which all the raw material monomers, the acylating agent and the catalyst are charged in the same reaction vessel and the reaction is started, and the hydroxyl groups of the raw material monomers (I), (II) and (V) are acylated.
- a method of reacting with the carboxyl groups of (III) and (IV) (two-stage system) after acylation with an agent may be used.
- liquid crystalline polymers obtained from 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 one that forms an anisotropic molten phase, that is, a liquid crystalline polymer that exhibits optical anisotropy when melted.
- 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 is 1 ⁇ 10 5 Pa ⁇ s or less (more preferably 5 Pa ⁇ s or more and 1 ⁇ 10 2 Pa ⁇ s) at a temperature 10 to 40 ° C. higher than the melting point and a shear rate of 1000 / sec. s or less) is preferable in that the fluidity of the composite resin composition is ensured and the filling pressure does not become excessive at the time of forming the lattice portion of the planar connector.
- the composite resin composition of the present invention contains 45 to 60% by mass of the liquid crystalline polymer in the composite resin composition with respect to the total composite resin composition. If the content of the liquid crystalline polymer is less than 45% by mass relative to the entire composite resin composition, the fluidity deteriorates, which is not preferable. If the content of the liquid crystalline polymer is more than 60% by mass with respect to the entire composite resin composition, the bending elastic modulus and crack resistance of a molded product such as a planar connector obtained from the composite resin composition are reduced. It is not preferable.
- the composite resin composition of the present invention preferably contains the liquid crystalline polymer in the composite resin composition in an amount of 50 to 60% by mass based on the total composite resin composition.
- the composite resin composition of the present invention contains the above liquid crystalline polymer and glass fiber, a molded product obtained by molding the composite resin composition has high crack resistance.
- the composite resin composition of the present invention contains 35 to 50% by mass of glass fiber in the composite resin composition with respect to the total composite resin composition.
- the glass fiber content is less than 35% by mass with respect to the entire composite resin composition, the flexural modulus of the molded product obtained from the composite resin composition is low, and the molded product is a planar connector or the like. Is not preferable because cracks may occur in the lattice portion. If the glass fiber content is more than 50% by mass relative to the entire composite resin composition, the fluidity of the composition deteriorates, which is not preferable.
- the glass fiber in the present invention is preferably contained in the composite resin composition in an amount of 40 to 50% by mass with respect to the entire composite resin composition.
- the composite resin composition of the present invention further includes one or more inorganic fillers selected from the group consisting of talc and milled fiber.
- inorganic fillers selected from the group consisting of talc and milled fiber.
- the average glass fiber length calculated from the fiber length of the glass fiber and the fiber length of the milled fiber among the inorganic fillers is preferably 200 to 500 ⁇ m.
- An average fiber length of less than 200 ⁇ m is not preferable because cracks may occur in a lattice portion of a molded product such as a planar connector obtained from the composite resin composition. If the average fiber length is more than 500 ⁇ m, the fluidity is deteriorated and it may be difficult to mold the composite resin composition.
- the fiber diameter of the glass fiber and milled fiber in the present invention is not particularly limited, but generally about 5 to 15 ⁇ m is used.
- 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 of the present invention is not particularly limited as long as the above liquid crystalline polymer and glass fiber can be mixed uniformly, 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 a portion having a complicated shape such as a lattice portion of a planar connector can be preferably molded.
- 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 planar connector of the present invention By molding the composite resin composition of the present invention, the planar connector of the present invention can be obtained.
- the shape of the planar connector is not particularly limited, but has a lattice structure inside the outer frame portion, an opening inside the lattice structure, and a pitch interval of the lattice portion in the lattice structure is 1.5 mm. It may be the following, and the planar connector whose thickness ratio of the said outer frame part and the said grating
- Examples of the shape of the planar connector of the present invention include those shown in FIG.
- This flat connector has an overall size of 43.88 mm ⁇ 43.88 mm ⁇ 3 mmt, an outer frame portion having a thickness of 3 mm or less, a lattice portion having a thickness of 1.5 mm or less, and 13.88 mm in the center portion.
- X 13.88 mm opening Further, the pin insertion hole of the planar connector may be partially narrowed in order to prevent the pin inserted into the planar connector from coming off.
- the shape of the pin insertion hole in the lattice portion of the planar connector of the present invention is not particularly limited, and may be a square shape, a round shape, or the like.
- Examples of the shape of the pin insertion hole that is preferable in the present invention include shapes other than square and round (referred to as “variant” in the present invention), such as the shape shown in FIG. 5 and the shape of a star. It is done.
- a pin insertion hole having such a shape (referred to as “an irregularly shaped hole” in the present invention) is not only very difficult to mold, but also easily cracks, and the crack resistance of the molded product tends to decrease.
- the planar connector of the present invention has excellent crack resistance even if the pin insertion hole is an irregular hole.
- the planar connector of the present invention includes not only one having an opening in the lattice part but also one having no opening in the lattice part.
- the molding method for obtaining the planar connector of the present invention is not particularly limited, but there is no residual internal stress in order to prevent deformation of the obtained planar connector and to obtain a planar connector having good flatness (described later). It is preferable to select the molding conditions.
- 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 planar connector of the present invention has a good flexural modulus and excellent crack resistance.
- the bending elastic modulus of the planar connector of the present invention may be 17 GPa or more.
- a planar connector having an elastic modulus of 17 GPa or more is hardly cracked even if it has a thin lattice portion, and has excellent crack resistance.
- a bending elastic modulus is measured based on ISO178.
- planar connector of the present invention is suppressed from being deformed.
- the degree of deformation of the planar connector is determined using the flatness of the planar connector as an index. Specifically, the flat connector is placed on a horizontal desk, the height of the flat connector is measured with an image measuring device, and the position of 0.5 mm is measured at 10 mm intervals from the connector end surface. The difference between the height and the minimum height is defined as flatness.
- the change in flatness is suppressed before and after performing IR reflow.
- 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 reduced to 5 Torr (ie, 667 Pa) over 30 minutes to melt while distilling acetic acid, excess acetic anhydride, and other low-boiling components. 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 pellets were heat-treated at 300 ° C. for 8 hours under a nitrogen stream. The melting point of the pellet was 349 ° C., the heat of crystallization was 5.6 J / g, and the melt viscosity was 23 Pa ⁇ s.
- 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 to melt while distilling acetic acid, excess acetic anhydride, and other low-boiling components. 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 heat of crystallization 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 reduced to 10 Torr (ie, 1330 Pa) over 20 minutes to melt while distilling acetic acid, excess acetic anhydride, and other low-boiling components. 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 heat of crystallization of 1.6 J / g, and a melt viscosity of 9 Pa ⁇ s.
- the composite resin composition was injection molded under the following molding conditions, and the flexural modulus was measured according to ISO178.
- 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. (Examples 1 to 6, Comparative Examples 3 to 7) 370 ° C.-370 ° C.-370 ° C.-370 ° C.-370 ° C.-380 ° C.
- the composite resin composition has an overall size of 43.88 mm ⁇ 43.88 mm ⁇ 3 mmt, an opening of 13.88 mm ⁇ 13.88 mm in the center, and a lattice pitch of 1.0 mm.
- the flat connector (number of pin holes: 1248) was injection molded.
- As the gate a special gate (overflow) shown in FIG. 2 was used.
- 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 device. At that time, as shown in FIG. 3, 0.5 mm positions were measured at 10 mm intervals from the connector end face, and the difference between the maximum height and the minimum height from the least square plane was defined as flatness.
- IR reflow was performed under the following conditions, the flatness was measured by the method described above, and the difference in flatness of the flat connector before and after reflow was determined as the amount of connector deformation.
- Measureasuring instrument RF-300 (using far infrared heater) Sample feed rate: 140 mm / sec Reflow furnace passage time: 5 minutes Preheating zone temperature condition: 150 ° C. Reflow zone temperature condition; 225 ° C Peak temperature: 287 ° C [Molding condition] Molding machine; Sumitomo Heavy Industries SE30DUZ Cylinder temperature (indicates temperature from nozzle side); 360 ° C.-365 ° C.-340 ° C.-330 ° C.
- the evaluation injection-molded product shown in FIG. 4 has an outer diameter of 23.6 mm, 31 holes of ⁇ 3.2 mm inside, and a minimum wall thickness of 0.16 mm.
- a three-point gate indicated by an arrow in FIG. Use a stereomicroscope to observe the cracking of the molded product at a magnification of 5 times, and observe the occurrence of cracks around the hole. If there was a crack in the molded product, “X”; if not, “ ⁇ ” It was judged.
- Molding machine Sumitomo Heavy Industries SE30DUZ Cylinder temperature (indicates temperature from nozzle side); 370 ° C.-375 ° C.-360 ° C.-350 ° C.
- the planar connector of the present invention was excellent in flatness, warp deformation, fluidity and crack resistance, and had a flexural modulus of 17 GPa or more. Further, when a similar test was performed on a planar connector obtained from the composite resin composition of the present invention, in which the pin insertion hole is a deformed hole (a deformed hole having the shape of FIG. 5), the same preferable results were obtained. Obtained.
Landscapes
- 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)
- Polyesters Or Polycarbonates (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Connector Housings Or Holding Contact Members (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
Abstract
Description
上記(A)液晶性ポリマーは、必須の構成成分として、下記の構成単位;(I)4-ヒドロキシ安息香酸、(II)2-ヒドロキシ-6-ナフトエ酸、(III)テレフタル酸、(IV)イソフタル酸及び(V)4,4’-ジヒドロキシビフェニルを含み、
全構成単位に対して(I)の構成単位は35~75モル%であり、
全構成単位に対して(II)の構成単位は2~8モル%であり、
全構成単位に対して(III)の構成単位は4.5~30.5モル%であり、
全構成単位に対して(IV)の構成単位は2~8モル%であり、
全構成単位に対して(V)の構成単位は12.5~32.5モル%であり、
全構成単位に対して(II)及び(IV)の構成単位の総量は4~10モル%であり、
上記(A)液晶性ポリマーは、複合樹脂組成物全体に対して45~60質量%であり、
上記(B)ガラス繊維は、複合樹脂組成物全体に対して35~50質量%であり、
上記(C)タルク及びミルドファイバーからなる群より選択される1以上の無機充填材は、複合樹脂組成物全体に対して0~15質量%である複合樹脂組成物。
外枠部の内部に格子構造を有し、上記格子構造の内部に開口部を有し、
上記格子構造における格子部のピッチ間隔が1.5mm以下であり、
上記外枠部と上記格子部の厚み比率が1.0以下であり、
ピン挿入穴が異形穴である、平面状コネクター。
本発明の複合樹脂組成物は、特定の液晶性ポリマーとガラス繊維と無機充填材とを所定量ずつ含む。以下、本発明の複合樹脂組成物を構成する成分について説明する。
本発明における液晶性ポリマーは、必須の構成成分として、下記の構成単位;(I)4-ヒドロキシ安息香酸(「HBA」とも呼ばれる)、(II)2-ヒドロキシ-6-ナフトエ酸(「HNA」とも呼ばれる)、(III)テレフタル酸(「TA」とも呼ばれる)、(IV)イソフタル酸(「IA」とも呼ばれる)及び(V)4,4’-ジヒドロキシビフェニル(「BP」とも呼ばれる)を含む。
本発明の複合樹脂組成物は、上記の液晶性ポリマーとガラス繊維とを含むため、当該複合樹脂組成物を成形して得られた成形品は高い耐クラック性を有する。
本発明の複合樹脂組成物には、タルク及びミルドファイバーからなる群より選択される1以上の無機充填材がさらに含まれる。これらの成分がガラス繊維とともに複合樹脂組成物に含まれることにより、複合樹脂組成物の流動性を悪化させることなく、そり変形が抑制された成形体を得ることができる。これらの成分は、その総量が複合樹脂組成物全体に対して0~15質量%含まれる。
本発明の複合樹脂組成物には、上記の成分の他に、核剤、カーボンブラック、無機焼成顔料等の顔料、酸化防止剤、安定剤、可塑剤、滑剤、離型剤、難燃剤、及び公知の無機充填剤のうちの1種以上を配合してもよい。
本発明の複合樹脂組成物を成形することにより、本発明の平面状コネクターを得ることができる。平面状コネクターの形状としては、特に限定されないが、外枠部の内部に格子構造を有し、前記格子構造の内部に開口部を有し、上記格子構造における格子部のピッチ間隔が1.5mm以下であり、上記外枠部と前記格子部の厚み比率が1.0以下である平面状コネクターであってもよい。また、平面状コネクターにおける端子を保持する格子部の樹脂部分の幅が0.5mm以下、製品全体の高さが5.0mm以下という非常に薄肉の平面状コネクターであってもよい。
撹拌機、還流カラム、モノマー投入口、窒素導入口、減圧/流出ラインを備えた重合容器に、以下の原料モノマー、金属触媒、アシル化剤を仕込み、窒素置換を開始した。
(I)2-ヒドロキシ-6-ナフトエ酸;166g(48モル%)(HNA)
(II)テレフタル酸;76g(25モル%)(TA)
(III)4,4’-ジヒドロキシビフェニル;86g(25モル%)(BP)
(IV)4-ヒドロキシ安息香酸;5g(2モル%)(HBA)
酢酸カリウム触媒;22.5mg
無水酢酸;191g
L=20mm、d=1mmの(株)東洋精機製キャピログラフ1B型を使用し、液晶性ポリマーの融点よりも10~20℃高い温度で、剪断速度1000/秒で、ISO11443に準拠して、液晶性ポリマーの溶融粘度を測定した。
撹拌機、還流カラム、モノマー投入口、窒素導入口、減圧/流出ラインを備えた重合容器に、以下の原料モノマー、金属触媒、アシル化剤を仕込み、窒素置換を開始した。
(I)4-ヒドロキシ安息香酸;188.4g(60モル%)(HBA)
(II)6-ヒドロキシ-2-ナフトエ酸;21.4g(5モル%)(HNA)
(III)テレフタル酸;66.8g(17.7モル%)(TA)
(IV)4,4’-ジヒドロキシビフェニル;52.2g(12.3モル%)(BP)
(V)4-アセトキシアミノフェノール;17.2g(5モル%)(APAP)
酢酸カリウム触媒;15mg
無水酢酸;226.2g
撹拌機、還流カラム、モノマー投入口、窒素導入口、減圧/流出ラインを備えた重合容器に、以下の原料モノマー、金属触媒、アシル化剤を仕込み、窒素置換を開始した。
(I)4-ヒドロキシ安息香酸;1041g(48モル%)(HBA)
(II)6-ヒドロキシ-2-ナフトエ酸;89g(3モル%)(HNA)
(III)テレフタル酸;565g(21.7モル%)(TA)
(IV)イソフタル酸;78g(3モル%)(IA)
(V)4,4’-ジヒドロキシビフェニル;711g(24.3モル%)(BP)
酢酸カリウム触媒;110mg
無水酢酸;1645g
上記で得られた各液晶性ポリマーと、下記の成分とを二軸押出機を使用して混合し、複合樹脂組成物を得た。各成分の配合量は表1及び2に示した通りである。なお、以下、表中の「%」は質量%を示す。
ガラス繊維;日本電気硝子(株)製ECS03T-786H、繊維径10μm、長さ3mmのチョプドストランド
タルク;松村産業(株)製クラウンタルクPP、平均粒径10μm
ミルドファイバー;日東紡(株)製PF70E001、繊維径10μm、繊維長70μm
複合樹脂組成物ペレット5gを600℃で2時間加熱し灰化した。灰化残渣を5%ポリエチレングリコール水溶液に十分分散させた後、スポイトでシャーレに移し、顕微鏡でガラス繊維を観察した。同時に画像測定器((株)ニレコ製LUZEXFS)を用いてガラス繊維の重量平均繊維長を測定した。なお、ミルドファイバーを含む組成物については、平均ガラス繊維長とは、ガラス繊維及びミルドファイバーの繊維長の平均を指す。
下記成形条件で、複合樹脂組成物を射出成形し、ISO178に準拠して曲げ弾性率を測定した。
[成形条件]
成形機;住友重機械工業SE100DU
シリンダー温度(ノズル側からの温度を示す);
360℃-370℃-370℃-360℃-340℃-330℃(実施例1~6、比較例3~7)
370℃-370℃-370℃-370℃-370℃-380℃(比較例1)
350℃-350℃-350℃-350℃-340℃-330℃(比較例2)
金型温度;80℃
射出速度;2m/min
保圧力;50MPa
保圧時間;2sec
冷却時間;10sec
スクリュー回転数;120rpm
スクリュー背圧;1.2MPa
複合樹脂組成物を図1に示すような、全体の大きさ43.88mm×43.88mm×3mmt、中央部に13.88mm×13.88mmの開口部を有し、格子部ピッチ間隔1.0mmの平面状コネクター(ピン孔数1248ピン)に射出成形した。なお、ゲートは、図2に示す特殊なゲート(オーバーフロー)を使用した。
下記条件のIRリフローを行い、上述の方法で平面度を測定し、リフロー前後における平面状コネクターの平面度の差をコネクター変形量として求めた。
[IRリフロー条件]
測定器;日本パルス技術研究所製大型卓上リフローハンダ付け装置RF-300(遠赤外線ヒーター使用)
試料送り速度;140mm/秒
リフロー炉通過時間;5分
プレヒートゾーンの温度条件;150℃
リフローゾーンの温度条件;225℃
ピーク温度;287℃
[成形条件]
成形機;住友重機械工業SE30DUZ
シリンダー温度(ノズル側からの温度を示す);
360℃-365℃-340℃-330℃(実施例1~6、比較例3~7)
370℃-370℃-370℃-380℃(比較例1)
350℃-350℃-340℃-330℃(比較例2)
金型温度;80℃
射出速度;300mm/sec
保圧力;50MPa
保圧時間;2sec
冷却時間;10sec
スクリュー回転数;120rpm
スクリュー背圧;1.2MPa
図1の平面状コネクターを射出成形する際に良好な成形品を得られる最小の射出充填圧力を最小充填圧力として測定した。
図4に示す評価用射出成形品は、外周が直径:23.6mmで内部に31個のφ3.2mmの孔が開いており、孔間距離の最小肉厚が0.16mmである。ゲートは図4の矢印部の3点ゲートを採用した。成形品割れ観察は実体顕微鏡を使用し、倍率5倍で孔周りの割れ発生状況を観察し、成形品に割れが発生していた場合は“×”、発生していなかった場合は“○”と判断した。
[成形条件]
成形機;住友重機械工業SE30DUZ
シリンダー温度(ノズル側からの温度を示す);
370℃-375℃-360℃-350℃(実施例1~6、比較例3~7)
360℃-360℃-360℃-370℃(比較例1)
350℃-350℃-340℃-330℃(比較例2)
金型温度;140℃
射出速度;150mm/sec
保圧力;100MPa
保圧時間;2sec
冷却時間;10sec
スクリュー回転数;120rpm
スクリュー背圧;1.2MPa
Claims (4)
- (A)液晶性ポリマーと、(B)ガラス繊維と、(C)タルク及びミルドファイバーからなる群より選択される1以上の無機充填材と、を含む複合樹脂組成物であって、
前記(A)液晶性ポリマーは、必須の構成成分として、下記の構成単位;(I)4-ヒドロキシ安息香酸、(II)2-ヒドロキシ-6-ナフトエ酸、(III)テレフタル酸、(IV)イソフタル酸及び(V)4,4’-ジヒドロキシビフェニルを含み、
全構成単位に対して(I)の構成単位は35~75モル%であり、
全構成単位に対して(II)の構成単位は2~8モル%であり、
全構成単位に対して(III)の構成単位は4.5~30.5モル%であり、
全構成単位に対して(IV)の構成単位は2~8モル%であり、
全構成単位に対して(V)の構成単位は12.5~32.5モル%であり、
全構成単位に対して(II)及び(IV)の構成単位の総量は4~10モル%であり、
前記(A)液晶性ポリマーは、複合樹脂組成物全体に対して45~60質量%であり、
前記(B)ガラス繊維は、複合樹脂組成物全体に対して35~50質量%であり、
前記(C)タルク及びミルドファイバーからなる群より選択される1以上の無機充填材は、複合樹脂組成物全体に対して0~15質量%である複合樹脂組成物。 - 前記(B)ガラス繊維の繊維長及び前記(C)ミルドファイバーの繊維長の平均ガラス繊維長は200~500μmである請求項1に記載の複合樹脂組成物。
- 請求項1又は2に記載の複合樹脂組成物から成形され、
外枠部の内部に格子構造を有し、前記格子構造の内部に開口部を有し、
前記格子構造における格子部のピッチ間隔が1.5mm以下であり、
前記外枠部と前記格子部の厚み比率が1.0以下であり、
ピン挿入穴が異形穴である、平面状コネクター。 - ISO178に準拠して測定された曲げ弾性率が17GPa以上である請求項3に記載の平面状コネクター。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020157009524A KR101627243B1 (ko) | 2012-09-27 | 2013-08-20 | 복합 수지 조성물 및 당해 복합 수지 조성물로 성형되는 평면상 커넥터 |
CN201380050126.3A CN104662087B (zh) | 2012-09-27 | 2013-08-20 | 复合树脂组合物以及由该复合树脂组合物成型而成的平面状连接器 |
JP2014538281A JP5826404B2 (ja) | 2012-09-27 | 2013-08-20 | 複合樹脂組成物及び該複合樹脂組成物から成形される平面状コネクター |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012-213668 | 2012-09-27 | ||
JP2012213668 | 2012-09-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014050370A1 true WO2014050370A1 (ja) | 2014-04-03 |
Family
ID=50387780
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/072224 WO2014050370A1 (ja) | 2012-09-27 | 2013-08-20 | 複合樹脂組成物及び該複合樹脂組成物から成形される平面状コネクター |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP5826404B2 (ja) |
KR (1) | KR101627243B1 (ja) |
CN (1) | CN104662087B (ja) |
TW (1) | TWI502018B (ja) |
WO (1) | WO2014050370A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6022127B1 (ja) * | 2014-12-05 | 2016-11-09 | ポリプラスチックス株式会社 | 複合樹脂組成物及び平面状コネクター |
JP6473796B1 (ja) * | 2017-11-27 | 2019-02-20 | 住友化学株式会社 | 液晶ポリエステル樹脂組成物および成形体 |
WO2021085224A1 (ja) * | 2019-10-31 | 2021-05-06 | ポリプラスチックス株式会社 | 樹脂組成物及び平面状コネクター |
US11584850B2 (en) | 2017-11-27 | 2023-02-21 | Sumitomo Chemical Company, Limited | Liquid crystal polyester resin composition and molded body |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105837803B (zh) * | 2016-02-01 | 2017-05-31 | 金发科技股份有限公司 | 一种液晶聚酯以及由其组成的模塑组合物和其应用 |
JP6944615B1 (ja) * | 2019-10-31 | 2021-10-06 | ポリプラスチックス株式会社 | 樹脂組成物及びコネクター |
CN111303410A (zh) * | 2020-03-18 | 2020-06-19 | 南京清研高分子新材料有限公司 | 一种液晶聚合物及其制备方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61243826A (ja) * | 1985-04-19 | 1986-10-30 | Asahi Chem Ind Co Ltd | ポリエステルフイルム及びその製造方法 |
JPH0216120A (ja) * | 1988-07-05 | 1990-01-19 | Polyplastics Co | 溶融時に光学的異方性を示すポリエステル樹脂及び樹脂組成物 |
JP2001200034A (ja) * | 2000-01-14 | 2001-07-24 | Ticona Llc | 伸縮自在なポリマーを製造するための組成物および方法ならびにそれらによって製造される造形物品 |
JP2009127024A (ja) * | 2007-11-28 | 2009-06-11 | Polyplastics Co | 全芳香族ポリエステル及びポリエステル樹脂組成物 |
JP2011122148A (ja) * | 2009-11-16 | 2011-06-23 | Sumitomo Chemical Co Ltd | コネクタ用液晶ポリエステル組成物およびこれを用いたコネクタ |
JP2012107221A (ja) * | 2010-10-29 | 2012-06-07 | Sumitomo Chemical Co Ltd | 液晶ポリエステル組成物 |
WO2012137636A1 (ja) * | 2011-04-01 | 2012-10-11 | 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ポリエステル樹脂組成物 |
JP2012214652A (ja) * | 2011-04-01 | 2012-11-08 | Polyplastics Co | 平面状コネクター |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5804634A (en) * | 1995-12-15 | 1998-09-08 | Toray Industries, Inc. | Liquid crystalline resin compound and moldings thereof |
JP4717366B2 (ja) | 2004-03-26 | 2011-07-06 | ポリプラスチックス株式会社 | 平面状コネクター |
JP5165492B2 (ja) | 2008-05-23 | 2013-03-21 | ポリプラスチックス株式会社 | 平面状コネクター |
JP2010037364A (ja) * | 2008-07-31 | 2010-02-18 | Polyplastics Co | コネクター |
-
2013
- 2013-08-20 CN CN201380050126.3A patent/CN104662087B/zh active Active
- 2013-08-20 WO PCT/JP2013/072224 patent/WO2014050370A1/ja active Application Filing
- 2013-08-20 JP JP2014538281A patent/JP5826404B2/ja active Active
- 2013-08-20 KR KR1020157009524A patent/KR101627243B1/ko active IP Right Grant
- 2013-08-26 TW TW102130410A patent/TWI502018B/zh active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61243826A (ja) * | 1985-04-19 | 1986-10-30 | Asahi Chem Ind Co Ltd | ポリエステルフイルム及びその製造方法 |
JPH0216120A (ja) * | 1988-07-05 | 1990-01-19 | Polyplastics Co | 溶融時に光学的異方性を示すポリエステル樹脂及び樹脂組成物 |
JP2001200034A (ja) * | 2000-01-14 | 2001-07-24 | Ticona Llc | 伸縮自在なポリマーを製造するための組成物および方法ならびにそれらによって製造される造形物品 |
JP2009127024A (ja) * | 2007-11-28 | 2009-06-11 | Polyplastics Co | 全芳香族ポリエステル及びポリエステル樹脂組成物 |
JP2011122148A (ja) * | 2009-11-16 | 2011-06-23 | Sumitomo Chemical Co Ltd | コネクタ用液晶ポリエステル組成物およびこれを用いたコネクタ |
JP2012107221A (ja) * | 2010-10-29 | 2012-06-07 | Sumitomo Chemical Co Ltd | 液晶ポリエステル組成物 |
WO2012137636A1 (ja) * | 2011-04-01 | 2012-10-11 | 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ポリエステル樹脂組成物 |
JP2012214652A (ja) * | 2011-04-01 | 2012-11-08 | Polyplastics Co | 平面状コネクター |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6022127B1 (ja) * | 2014-12-05 | 2016-11-09 | ポリプラスチックス株式会社 | 複合樹脂組成物及び平面状コネクター |
JP6473796B1 (ja) * | 2017-11-27 | 2019-02-20 | 住友化学株式会社 | 液晶ポリエステル樹脂組成物および成形体 |
US11485851B2 (en) | 2017-11-27 | 2022-11-01 | Sumitomo Chemical Company, Limited | Liquid crystal polyester resin composition and molded body |
US11584850B2 (en) | 2017-11-27 | 2023-02-21 | Sumitomo Chemical Company, Limited | Liquid crystal polyester resin composition and molded body |
WO2021085224A1 (ja) * | 2019-10-31 | 2021-05-06 | ポリプラスチックス株式会社 | 樹脂組成物及び平面状コネクター |
JP6944616B1 (ja) * | 2019-10-31 | 2021-10-06 | ポリプラスチックス株式会社 | 樹脂組成物及び平面状コネクター |
Also Published As
Publication number | Publication date |
---|---|
JPWO2014050370A1 (ja) | 2016-08-22 |
KR101627243B1 (ko) | 2016-06-03 |
TW201422714A (zh) | 2014-06-16 |
KR20150060765A (ko) | 2015-06-03 |
CN104662087A (zh) | 2015-05-27 |
TWI502018B (zh) | 2015-10-01 |
CN104662087B (zh) | 2016-08-17 |
JP5826404B2 (ja) | 2015-12-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5826404B2 (ja) | 複合樹脂組成物及び該複合樹脂組成物から成形される平面状コネクター | |
KR101399743B1 (ko) | 평면상 커넥터 | |
JP5753144B2 (ja) | 全芳香族ポリエステル及びポリエステル樹脂組成物、並びにポリエステル成形品 | |
JP6356938B1 (ja) | 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 | |
CN109790379B (zh) | 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 | |
JP5769888B2 (ja) | 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 | |
JP6321899B1 (ja) | 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 | |
JP5753143B2 (ja) | 全芳香族ポリエステル及びポリエステル樹脂組成物、並びにポリエステル成形品 | |
WO2017110867A1 (ja) | 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 | |
JP6109651B2 (ja) | 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平面状コネクター | |
JP2016124947A (ja) | 成形品の製造方法及び複合樹脂組成物 | |
WO2017110866A1 (ja) | 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 | |
CN109790380B (zh) | 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 | |
JP2018095684A (ja) | 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 | |
JP6944615B1 (ja) | 樹脂組成物及びコネクター | |
JP6189750B2 (ja) | 全芳香族ポリエステル、ポリエステル樹脂組成物、及びポリエステル成形品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13842681 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014538281 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20157009524 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13842681 Country of ref document: EP Kind code of ref document: A1 |