WO2020230890A1 - Composition de résine cristalline liquide et corps moulé l'utilisant - Google Patents

Composition de résine cristalline liquide et corps moulé l'utilisant Download PDF

Info

Publication number
WO2020230890A1
WO2020230890A1 PCT/JP2020/019448 JP2020019448W WO2020230890A1 WO 2020230890 A1 WO2020230890 A1 WO 2020230890A1 JP 2020019448 W JP2020019448 W JP 2020019448W WO 2020230890 A1 WO2020230890 A1 WO 2020230890A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
crystal resin
resin composition
mass
content
Prior art date
Application number
PCT/JP2020/019448
Other languages
English (en)
Japanese (ja)
Inventor
真奈 中村
博樹 深津
Original Assignee
ポリプラスチックス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ポリプラスチックス株式会社 filed Critical ポリプラスチックス株式会社
Priority to CN202080034568.9A priority Critical patent/CN113874432B/zh
Priority to JP2021500763A priority patent/JP7026842B2/ja
Publication of WO2020230890A1 publication Critical patent/WO2020230890A1/fr

Links

Images

Classifications

    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity

Definitions

  • the present invention relates to a liquid crystal resin composition and a molded product using the same.
  • Liquid crystal resins represented by liquid crystal polyester resins have a good balance of excellent mechanical strength, heat resistance, chemical resistance, electrical properties, etc., and also have excellent dimensional stability, so they are widely used as high-performance engineering plastics. It's being used. Recently, liquid crystal resins have come to be used for precision equipment parts by taking advantage of these features.
  • Examples of precision equipment parts in which liquid crystal resin is used include connectors; relay cases and the like. In these parts, if a large warp deformation occurs, the quality may be adversely affected.
  • a liquid crystal resin composition has been developed using the flatness of a flat plate as an index (for example, Patent Document 1).
  • the above-mentioned parts are not formed only from a flat plate, but are formed from a liquid crystal resin molded body having a bent portion.
  • a liquid crystal resin molded body for example, a liquid crystal resin molded body having an L-shaped corner portion, particularly a U-shaped liquid crystal resin molded body, may undergo so-called inward tilt deformation.
  • the inward tilting deformation since the wide-angle side is rapidly cooled at the bent portion, the liquid crystal resin composition is solidified before crystallization proceeds and the shrinkage rate is small, whereas the narrow-angle side is slowly cooled. Therefore, the liquid crystal resin composition is solidified in a more crystallized state, and the shrinkage rate is large.
  • the present invention has been made in view of such circumstances, and the molding is performed while suppressing inward tilt deformation of a liquid crystal resin molded body having an L-shaped corner portion, particularly a U-shaped liquid crystal resin molded body. It is an object of the present invention to provide a liquid crystal resin composition capable of imparting sufficient mechanical strength to a body and having good fluidity at the time of melting, and a molded product made of the liquid crystal resin composition.
  • the present inventors have found that the above problems can be solved by combining a liquid crystal resin, a fibrous filler, and silica at a predetermined content and setting the total amount of the filler within a predetermined range. .. Specifically, the present invention provides the following.
  • a liquid crystal resin composition containing (A) a liquid crystal resin, (B) a fibrous filler, and (C) silica.
  • the content of the liquid crystal resin (A) is 55 to 65% by mass.
  • the content of the fibrous filler (B) is 5 to 15% by mass.
  • the content of the silica (C) is 10 to 32.5% by mass.
  • the content of the total filler contained in the liquid crystal resin composition is 35 to 45% by mass.
  • a liquid crystal resin molded product having an L-shaped corner portion, particularly a U-shaped liquid crystal resin molded product, is provided with sufficient mechanical strength while suppressing inward deformation. It is possible to provide a liquid crystal resin composition which can be used and has good fluidity when melted, and a molded product made of the liquid crystal resin composition.
  • FIG. 1A is a perspective view showing a U-shaped liquid crystal resin molded product used for the evaluation of inward tilt deformation performed in the examples
  • FIG. 1B is a U-shaped liquid crystal resin molded product. It is a side view which shows the molded body.
  • the liquid crystal resin composition of the present invention contains (A) a liquid crystal resin, (B) a fibrous filler, and (C) silica.
  • the liquid crystal resin (A) used in the present invention refers to a melt-processable polymer having a property of forming an optically anisotropic molten phase.
  • the properties of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizing element. More specifically, the confirmation of the anisotropic molten phase can be carried out by observing the molten sample placed on the Leitz hot stage at a magnification of 40 times under a nitrogen atmosphere using a Leitz polarizing microscope.
  • Liquid crystalline polymers applicable to the present invention normally transmit polarized light and are optically anisotropy when inspected between orthogonal polarizers, even in the molten and resting state.
  • the type of the liquid crystal resin (A) as described above is not particularly limited, and is preferably an aromatic polyester and / or an aromatic polyester amide.
  • the range also includes polyesters that partially contain aromatic polyesters and / or aromatic polyester amides in the same molecular chain.
  • the liquid crystal resin (A) preferably at least about 2.0 dl / g, more preferably 2.0 to 10.0 dl / g when dissolved in pentafluorophenol at 60 ° C. at a concentration of 0.1% by mass. Those having a logarithmic viscosity (IV) of are preferably used.
  • the aromatic polyester or aromatic polyesteramide as the (A) liquid crystal resin applicable to the present invention is particularly preferably at least one selected from the group consisting of aromatic hydroxycarboxylic acid, aromatic hydroxyamine, and aromatic diamine. It is an aromatic polyester or an aromatic polyester amide having a repeating unit derived from a species compound as a constituent.
  • Polyester consisting of repeating units mainly derived from one or more aromatic hydroxycarboxylic acids and their derivatives; (2) Repeating units mainly derived from (a) one or more aromatic hydroxycarboxylic acids and their derivatives, and (b) aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and one of their derivatives.
  • a polyester consisting of a repeating unit derived from two or more kinds and (c) a repeating unit derived from at least one kind or two or more kinds of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof; (3) Repetitive units mainly derived from (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, and (b) one or two aromatic hydroxyamines, aromatic diamines, and derivatives thereof.
  • a polyester amide consisting of a repeating unit derived from a species or more and (c) a repeating unit derived from one or more of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof; (4) Repeating units mainly derived from (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, and (b) aromatic hydroxyamines, aromatic diamines, and one or two derivatives thereof. Repetitive units derived from species or higher, (c) aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and repeating units derived from one or more of their derivatives, and (d) aromatic diols, alicyclics.
  • polyesteramides consisting of group diols, aliphatic diols, and repeating units derived from at least one or more of the derivatives thereof.
  • a molecular weight adjusting agent may be used in combination with the above-mentioned constituent components as needed.
  • Preferred examples of the specific compound constituting the (A) liquid crystal resin applicable to the present invention include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and 2,6-dihydroxy.
  • Aromatic diols such as naphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, hydroquinone, resorcin, a compound represented by the following general formula (I), and a compound represented by the following general formula (II).
  • Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and compounds represented by the following general formula (III); p-aminophenol, p- Examples include aromatic amines such as phenylenediamine.
  • X A group selected from alkylene (C 1 to C 4 ), alkylidene, -O-, -SO-, -SO 2- , -S-, and -CO-)
  • the liquid crystal resin (A) used in the present invention can be prepared by a known method from the above-mentioned monomer compound (or mixture of monomers) by a direct polymerization method or a transesterification method, and is usually a melt polymerization method.
  • a melt polymerization method Solution polymerization method, slurry polymerization method, solid phase polymerization method, etc., or a combination of two or more of these is used, and a melt polymerization method or a combination of a melt polymerization method and a solid phase polymerization method is preferably used.
  • the above compounds having an ester-forming ability may be used in the polymerization as they are, or may be modified from a precursor to a derivative having the ester-forming ability in the pre-polymerization step.
  • Various catalysts can be used for these polymerizations, and typical ones are potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and tris (2). , 4-Pentandionato) Metal salt-based catalysts such as cobalt (III), and organic compound-based catalysts such as N-methylimidazole and 4-dimethylaminopyridine.
  • the amount of the catalyst used is generally preferably about 0.001 to 1% by mass, particularly preferably about 0.01 to 0.2% by mass, based on the total mass of the monomer. If necessary, the polymer produced by these polymerization methods can be increased in molecular weight by a solid-phase polymerization method in which the polymer is heated under reduced pressure or in an inert gas.
  • the melt viscosity of the liquid crystal resin (A) obtained by the above method is not particularly limited. Generally, a melt viscosity at a molding temperature of 1000 sec -1 and a shear rate of 3 Pa ⁇ s or more and 500 Pa ⁇ s or less can be used. However, the one having a very high viscosity by itself is not preferable because the fluidity is very deteriorated.
  • the liquid crystal resin (A) may be a mixture of two or more kinds of liquid crystal resins.
  • the content of the liquid crystal resin (A) is 55 to 65% by mass.
  • the content of the component (A) is within the above range, the fluidity of the liquid crystal resin composition tends to be sufficient, and a molded product having excellent mechanical strength can be easily obtained.
  • the liquid crystal resin composition of the present invention can impart sufficient mechanical strength to the molded product made of the liquid crystal resin composition.
  • the fibrous filler can be used alone or in combination of two or more.
  • the weight average fiber length of the fibrous filler is not particularly limited, and may be, for example, 250 ⁇ m or more, preferably 350 to 600 ⁇ m, and more preferably 450 to 500 ⁇ m.
  • the weight average fiber length is 250 ⁇ m or more, the molded product obtained from the liquid crystal resin composition of the present invention tends to have improved mechanical strength and heat resistance.
  • the weight average fiber length is 600 ⁇ m or less, the fluidity of the liquid crystal resin composition tends to be sufficient.
  • the weight average fiber length of the (B) fibrous filler in the liquid crystal resin composition is the fibrous state remaining after the liquid crystal resin composition is incinerated by heating at 600 ° C. for 2 hours.
  • the stereomicroscopic image of the filler is captured from the CCD camera into the PC, and the average of the values obtained by measuring the fiber length of the fibrous filler by an image processing method with an image measuring machine is adopted.
  • the average fiber diameter of the fibrous filler is not particularly limited, and may be, for example, 20 ⁇ m or less, or 5 to 15 ⁇ m.
  • the average fiber diameter of the (B) fibrous filler in the liquid crystal resin composition is defined as the fibrous filling remaining after the liquid crystal resin composition is incinerated by heating at 600 ° C. for 2 hours. The agent is observed with a scanning electron microscope, and the average of the measured values of the fiber diameter of the fibrous filler is adopted.
  • any fiber can be used as long as it is a fibrous filler satisfying the above shape.
  • the (B) fibrous filler for example, glass fiber, milled fiber, carbon fiber, asbestos fiber, silica fiber , Silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, and inorganic fibrous material such as metal fibrous material such as stainless steel, aluminum, titanium, copper and brass. Be done.
  • glass fiber for example, glass fiber, milled fiber, carbon fiber, asbestos fiber, silica fiber , Silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, and inorganic fibrous material such as metal fibrous material such as stainless steel, aluminum, titanium, copper and brass. Be done.
  • glass fiber it is preferable to use glass fiber as the component (B) from the viewpoint of mechanical strength.
  • the content of the fibrous filler (B) is 5 to 15% by mass, preferably 6.5 to 15% by mass, and more preferably 8 to 15% by mass in the liquid crystal resin composition of the present invention.
  • the content of the fibrous filler (B) is within the above range, the fluidity of the liquid crystal resin composition is sufficiently ensured, and the mechanical strength of the molded product obtained from the liquid crystal resin composition is improved.
  • Cheap is 5 to 15% by mass, preferably 6.5 to 15% by mass, and more preferably 8 to 15% by mass in the liquid crystal resin composition of the present invention.
  • the liquid crystal resin composition of the present invention can provide a liquid crystal resin molded product in which inward tilt deformation is suppressed.
  • (C) Silica can be used alone or in combination of two or more.
  • the median diameter of (C) silica is not particularly limited, and may be, for example, 1.3 to 30.0 ⁇ m. When the median diameter is within this range, the effect of suppressing inward deformation of the liquid crystal resin molded product tends to be higher.
  • the median diameter is preferably 1.5 to 25.0 ⁇ m, more preferably 2.0 to 15.0 ⁇ m.
  • the median diameter means the median value of the volume standard measured by the laser diffraction / scattering type particle size distribution measurement method.
  • the content of (C) silica is 10 to 32.5% by mass in the liquid crystal resin composition of the present invention.
  • the content of silica (C) is within the above range, it is easy to sufficiently suppress the inward deformation of the liquid crystal resin molded product.
  • the preferable content of (C) silica is 10 to 30% by mass.
  • the liquid crystal resin composition according to the present invention may contain a plate-like filler. Since the liquid crystal resin composition according to the present invention contains a plate-like filler, it is easy to obtain a molded product in which warpage deformation is suppressed.
  • the plate-shaped filler can be used alone or in combination of two or more.
  • the preferable content of the (D) plate-like filler is 7.7 to 30% by mass.
  • the content of the plate-like filler (D) is more preferably 9 to 20% by mass, and even more preferably 10 to 15% by mass.
  • Examples of the plate-like filler in the present invention include talc, mica, glass flakes, and various metal foils.
  • talc and mica are preferable, and mica is more preferable in that the warp deformation of the molded product obtained from the liquid crystal resin composition is suppressed without deteriorating the fluidity of the liquid crystal resin composition.
  • the average particle size of the plate-shaped filler is not particularly limited, and a smaller one is desirable in consideration of the fluidity in the thin-walled portion.
  • the total content of Fe 2 O 3 , Al 2 O 3 and Ca O is 2.5% by mass or less with respect to the total solid content of the talc, and Fe 2 O 3 and Al It is preferable that the total content of 2O 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 that can be used in the present invention contains at least one of Fe 2 O 3 , Al 2 O 3, and CaO in addition to SiO 2 and MgO, which are the main components thereof, and each component has the above content range. It may be contained in.
  • the total content of Fe 2 O 3 , Al 2 O 3 and CaO in the above talc was 2.5% by mass or less, the liquid crystal resin composition was molded from the molding processability and the liquid crystal resin composition. The heat resistance of the molded product is unlikely to deteriorate. Therefore, the total content of Fe 2 O 3 , Al 2 O 3 and CaO is preferably 1.0% by mass or more and 2.0% by mass or less.
  • talc having a total content of Fe 2 O 3 and Al 2 O 3 of more than 1.0% by mass is easily available.
  • the total content of Fe 2 O 3 and Al 2 O 3 is 2.0% by mass or less, the liquid crystal resin composition is molded from the moldability and the liquid crystal resin composition. The heat resistance of the molded product is unlikely to deteriorate. Therefore, the total content of Fe 2 O 3 and Al 2 O 3 is preferably more than 1.0% by mass and 1.7% by mass or less.
  • the CaO content is preferably 0.01% by mass or more and 0.4% by mass or less.
  • the mass-based or volume-based cumulative average particle diameter (D 50 ) of talc in the present invention measured by a laser diffraction method is determined from the viewpoint of preventing warpage deformation of the molded product and maintaining the fluidity of the liquid crystal resin composition. It is preferably 4.0 to 20.0 ⁇ m, more preferably 10 to 18 ⁇ m.
  • Mica is a pulverized product of silicate minerals 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 because it has a good hue and is inexpensive.
  • a wet pulverization method and a dry pulverization method are known as methods for pulverizing minerals.
  • the wet pulverization method is a method in which rough mica is roughly pulverized by a dry pulverizer, water is added, and the pulverization is carried out by wet pulverization in a slurry state, followed by dehydration and drying.
  • the dry pulverization method is a low-cost and general method as compared with the wet pulverization method, it is easier to pulverize the mineral thinly and finely by using the wet pulverization method.
  • the present invention it is preferable to use a thin and fine pulverized product because mica having a preferable average particle size and thickness described later can be obtained. Therefore, in the present invention, it is preferable to use mica produced by the wet pulverization method.
  • a coagulation sedimentation agent and / or a sedimentation aid is added to the object to be pulverized in order to improve the dispersion efficiency of the object to be pulverized.
  • a coagulation sedimentation agent and sedimentation aid that can be used in the present invention include polyaluminum chloride, aluminum sulfate, ferrous sulfate, ferric sulfate, copper chloride, polyiron sulfate, ferric chloride, and iron-silica inorganic high.
  • ferric chloride-silica inorganic polymer flocculant examples thereof include ferric chloride-silica inorganic polymer flocculant, aluminum sulfate (Ca (OH) 2 ), caustic soda (NaOH), soda ash (Na 2 CO 3 ) and the like.
  • These coagulation sedimentation agents and sedimentation aids have an alkaline or acidic pH.
  • the mica used in the present invention preferably does not use a coagulation sedimentation agent and / or a sedimentation aid during wet pulverization.
  • the mica that can be used in the present invention preferably has an average particle size of 10 to 100 ⁇ m measured by a microtrack laser diffraction method, and particularly preferably an average particle size of 20 to 80 ⁇ m.
  • the average particle size of mica is 10 ⁇ m or more, the effect of improving the rigidity of the molded product is likely to be sufficient, which is preferable.
  • the average particle size of mica is 100 ⁇ m or less, the rigidity of the molded product is likely to be sufficiently improved, and the weld strength is also likely to be sufficient, which is preferable.
  • the average particle size of mica is 100 ⁇ m or less, it is easy to secure sufficient fluidity for molding the connector or the like of the present invention.
  • the thickness of mica that can be used in the present invention is preferably 0.01 to 1 ⁇ m, particularly preferably 0.03 to 0.3 ⁇ m, as measured by observation with an electron microscope.
  • the thickness of the mica is 0.01 ⁇ m or more, the mica is less likely to crack during the melt processing of the liquid crystal resin composition, and the rigidity of the molded product may be easily improved, which is preferable.
  • the thickness of mica is 1 ⁇ m or less, the effect of improving the rigidity of the molded product is likely to be sufficient, which is preferable.
  • the mica that can be used in the present invention may be surface-treated with a silane coupling agent or the like, and / or may be granulated with a binder to form granules.
  • the content of the total filler contained in the liquid crystal resin composition according to the present invention is 35 to 45% by mass with respect to the entire liquid crystal resin composition, and the content of (C) silica is x% by mass.
  • x and y satisfy the following formula (1).
  • the content of the total filler is within the above range and the following formula (1) is satisfied, the liquid crystal resin molded body is deformed inward while sufficiently ensuring the fluidity of the liquid crystal resin composition. Easy to suppress sufficiently.
  • the liquid crystal resin composition according to the present invention includes (A) a polymer other than the liquid crystal resin, (C) a granular filler other than silica, a nucleating agent, carbon black, an inorganic fired pigment, and the like.
  • a polymer other than the liquid crystal resin e.g., polyethylene glycol dimethacrylate copolymer
  • a granular filler other than silica e.g., silica
  • a nucleating agent e.g., carbon black, an inorganic fired pigment, and the like.
  • Granular fillers other than silica include, for example, silicates such as quartz powder, glass beads, glass powder, calcium carbonate, aluminum silicate, kaolin, clay, diatomaceous earth, and wollastonite; iron oxide, oxidation.
  • Metal oxides such as titanium, zinc oxide and alumina; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; diatomaceous earth; diatomaceous earth; boron nitride and the like.
  • the granular filler other than silica may be used alone or in combination of two or more.
  • the liquid crystal resin composition according to the present invention is other than (C) silica. It is preferably free of granular fillers, especially glass beads.
  • the method for producing the liquid crystal resin composition according to the present invention is not particularly limited as long as the components in the liquid crystal resin composition can be uniformly mixed, and can be appropriately selected from the conventionally known methods for producing the liquid crystal resin composition.
  • each component is melt-kneaded and extruded using a melt-kneading device such as a single-screw or twin-screw extruder, and then the obtained liquid crystal resin composition is processed into a desired form such as powder, flakes, and pellets. There is a way to do it.
  • the molded product of the present invention comprises the liquid crystal resin composition of the present invention.
  • the molded product of the present invention is suppressed from inwardly tilting deformation and has sufficient mechanical strength.
  • the molded product of the present invention can be used, for example, as a connector such as an IGBT connector; a relay case or the like.
  • Examples 1 to 8 Comparative Examples 1 to 6>
  • the liquid crystal resin was produced as follows. At that time, the melting point and the melt viscosity of the pellets were measured under the following conditions, respectively.
  • the stirring torque reached a predetermined value
  • nitrogen was introduced to bring the mixture from a reduced pressure state to a pressurized state through normal pressure
  • the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized to obtain pellets.
  • the obtained pellets were heat-treated at 300 ° C. for 2 hours under a nitrogen stream to obtain the desired polymer.
  • the melting point of the obtained polymer was 336 ° C., and the melt viscosity at 350 ° C. was 19.0 Pa ⁇ s.
  • the melt viscosity of the polymer was measured in the same manner as the method for measuring the melt viscosity described later.
  • HBA 4-Hydroxybenzoic acid
  • HNA 2-Hydroxy-6-naphthoic acid
  • TA Terephthalic acid
  • BP 4,4'-dihydroxybiphenyl
  • APAP 4-acetoxyaminophenol
  • APAP 126 g (5 mol%)
  • Metal catalyst potassium acetate catalyst
  • 110 mg Acylating agent acetic anhydride
  • the liquid crystal resin obtained above and components other than the liquid crystal resin described above were mixed using a twin-screw extruder to obtain a liquid crystal resin composition.
  • the blending amount of each component is as shown in Tables 1 and 2. In the following, "%" regarding the blending amount in the table indicates mass%.
  • the extrusion conditions for obtaining the liquid crystal resin composition are as follows. [Extrusion conditions] [Examples 1 to 8, Comparative Examples 1 to 6] The temperature of the cylinder provided at the main feed port was set to 250 ° C, and the temperature of all other cylinders was set to 350 ° C. All liquid crystal resin was supplied from the main feed port. The filler was supplied from the side feed port.
  • the physical properties of the molded product made of the liquid crystal resin composition were measured based on the following method.
  • the pellets were molded using a molding machine (“SE-100DU” manufactured by Sumitomo Heavy Industries, Ltd.) under the following molding conditions to prepare five flat test pieces of 80 mm ⁇ 80 mm ⁇ 1 mm.
  • the first plate-shaped test piece was allowed to stand on a horizontal surface, and using a CNC image measuring machine (model: QVBHU404-PRO1F) manufactured by Mitutoyo Co., Ltd., at nine locations on the flat plate-shaped test piece, from the horizontal surface. The height was measured, and the average height was calculated from the obtained measured values.
  • the position where the height was measured is when a square with a side of 74 mm is placed on the main plane of the flat plate-shaped test piece so that the distance from each side of this main plane is 3 mm, and each vertex of this square is placed. , The midpoint of each side of this square, and the position corresponding to the intersection of the two diagonal lines of this square.
  • the height from the horizontal plane is the same as the average height, and a plane parallel to the horizontal plane is used as a reference plane. From the heights measured at the above nine points, the maximum height and the minimum height from the reference plane were selected, and the difference between the two was calculated. Similarly, the above difference was calculated for the other four flat plate-shaped test pieces, and the five values obtained were averaged to obtain the flatness value.
  • the liquid crystal resin composition according to the present invention can be applied to a liquid crystal resin molded product having L-shaped corners, particularly a U-shaped liquid crystal resin molded product, while suppressing inward deformation. It was confirmed that sufficient mechanical strength could be given and that the fluidity at the time of melting was good. Further, it was confirmed that the molded product obtained from the liquid crystal resin composition containing the plate-like filler had a small flatness and suppressed warpage deformation.

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)

Abstract

La présente invention concerne : une composition de résine cristalline liquide qui est apte à impartir une résistance mécanique suffisante à un corps moulé en résine cristalline liquide ayant une partie d'angle en forme de L, en particulier à un corps moulé en résine cristalline liquide en forme de U carré, tout en supprimant la déformation d'affaissement vers l'intérieur du corps moulé, et qui présente une bonne fluidité lorsqu'elle est fondue ; et un corps moulé qui est formé de cette composition de résine cristalline liquide.　Une composition de résine cristalline liquide selon la présente invention contient (A) une résine cristalline liquide, (B) une charge fibreuse et (C) de la silice ; par rapport à la totalité de la composition de résine cristalline liquide, le contenu de la résine cristalline liquide (A) est de 55 à 65 % en masse, la teneur de la charge fibreuse (B) est de 5 à 15 % en masse et la teneur en silice (C) est de 10-32,5 % en masse ; la teneur totale de toutes les charges contenues dans la composition de résine cristalline liquide est de 35 à 45 % en masse ; et si x (% en masse) est la teneur en silice (C) et y (% en masse) est la teneur totale de toutes les charges, x et y satisfont à la formule y ≥ -0,5 x + 45.
PCT/JP2020/019448 2019-05-16 2020-05-15 Composition de résine cristalline liquide et corps moulé l'utilisant WO2020230890A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202080034568.9A CN113874432B (zh) 2019-05-16 2020-05-15 液晶性树脂组合物及使用其的成型体
JP2021500763A JP7026842B2 (ja) 2019-05-16 2020-05-15 液晶性樹脂組成物及びそれを用いた成形体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019093112 2019-05-16
JP2019-093112 2019-05-16

Publications (1)

Publication Number Publication Date
WO2020230890A1 true WO2020230890A1 (fr) 2020-11-19

Family

ID=73289827

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/019448 WO2020230890A1 (fr) 2019-05-16 2020-05-15 Composition de résine cristalline liquide et corps moulé l'utilisant

Country Status (4)

Country Link
JP (1) JP7026842B2 (fr)
CN (1) CN113874432B (fr)
TW (1) TW202104406A (fr)
WO (1) WO2020230890A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0192263A (ja) * 1987-10-02 1989-04-11 Kuraray Co Ltd 電子部品用封止剤
JP2003253097A (ja) * 2002-03-01 2003-09-10 Ngk Insulators Ltd 複合材料
JP2005060443A (ja) * 2003-08-18 2005-03-10 Toray Ind Inc ランプユニット部品用樹脂組成物、それから得られるランプユニット部品
JP2010150534A (ja) * 2008-11-27 2010-07-08 Toray Ind Inc 熱可塑性ポリエステル樹脂組成物
JP2013072070A (ja) * 2011-09-29 2013-04-22 Sumitomo Chemical Co Ltd 液晶ポリエステル組成物及びコネクタ
WO2017110424A1 (fr) * 2015-12-24 2017-06-29 ポリプラスチックス株式会社 Composition de résine à cristaux liquides pour module de caméra, son procédé de production, et module de caméra obtenu avec ladite composition
WO2018012371A1 (fr) * 2016-07-11 2018-01-18 ポリプラスチックス株式会社 Composition de résine cristalline liquide

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5727229B2 (ja) * 2008-12-11 2015-06-03 ポリプラスチックス株式会社 液晶性樹脂組成物
JP5407988B2 (ja) * 2010-03-30 2014-02-05 住友化学株式会社 液晶性樹脂組成物及びその成形体

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0192263A (ja) * 1987-10-02 1989-04-11 Kuraray Co Ltd 電子部品用封止剤
JP2003253097A (ja) * 2002-03-01 2003-09-10 Ngk Insulators Ltd 複合材料
JP2005060443A (ja) * 2003-08-18 2005-03-10 Toray Ind Inc ランプユニット部品用樹脂組成物、それから得られるランプユニット部品
JP2010150534A (ja) * 2008-11-27 2010-07-08 Toray Ind Inc 熱可塑性ポリエステル樹脂組成物
JP2013072070A (ja) * 2011-09-29 2013-04-22 Sumitomo Chemical Co Ltd 液晶ポリエステル組成物及びコネクタ
WO2017110424A1 (fr) * 2015-12-24 2017-06-29 ポリプラスチックス株式会社 Composition de résine à cristaux liquides pour module de caméra, son procédé de production, et module de caméra obtenu avec ladite composition
WO2018012371A1 (fr) * 2016-07-11 2018-01-18 ポリプラスチックス株式会社 Composition de résine cristalline liquide

Also Published As

Publication number Publication date
JPWO2020230890A1 (ja) 2021-05-20
CN113874432A (zh) 2021-12-31
JP7026842B2 (ja) 2022-02-28
TW202104406A (zh) 2021-02-01
CN113874432B (zh) 2023-08-22

Similar Documents

Publication Publication Date Title
TWI648337B (zh) Composite resin composition and planar connector
JP2001207054A (ja) 液晶性ポリマー成形品
KR102058121B1 (ko) 복합 수지 조성물, 및 당해 복합 수지 조성물로 성형된 전자 부품
JP6841978B2 (ja) 液晶性樹脂組成物、及び当該液晶性樹脂組成物の成形品を含むコネクター
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
WO2018074156A1 (fr) Composition de résine composite et connecteur moulé formé à partir de cette dernière
JP6906123B1 (ja) 耐ボールベアリング摺動摩耗部材用液晶性樹脂組成物及びそれを用いた耐ボールベアリング摺動摩耗部材
WO2017110867A1 (fr) Composition de résine composite et connecteur fabriqué à partir de ladite composition de résine composite
JP6837184B2 (ja) 液晶性樹脂組成物
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
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
WO2020230890A1 (fr) Composition de résine cristalline liquide et corps moulé l'utilisant
JP6895032B1 (ja) 液晶性樹脂組成物、及び当該液晶性樹脂組成物の成形品を含むコネクター
WO2020070903A1 (fr) Résine de polyester à cristaux liquides
JP7393590B1 (ja) 平面状コネクター用液晶性樹脂組成物及びそれを用いた平面状コネクター
JP7373080B2 (ja) 導電性液晶性樹脂組成物
WO2024143334A1 (fr) Composition de résine cristalline liquide et connecteur utilisant celle-ci

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: 20806088

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021500763

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20806088

Country of ref document: EP

Kind code of ref document: A1