WO2023153007A1 - Composition de résine contenant une charge inorganique fibreuse et corps moulé - Google Patents

Composition de résine contenant une charge inorganique fibreuse et corps moulé Download PDF

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WO2023153007A1
WO2023153007A1 PCT/JP2022/033758 JP2022033758W WO2023153007A1 WO 2023153007 A1 WO2023153007 A1 WO 2023153007A1 JP 2022033758 W JP2022033758 W JP 2022033758W WO 2023153007 A1 WO2023153007 A1 WO 2023153007A1
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resin composition
fibrous
inorganic filler
resin
average
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PCT/JP2022/033758
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English (en)
Japanese (ja)
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兵 劉
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Jnc株式会社
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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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • 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

Definitions

  • the present invention relates to a resin composition containing a fibrous inorganic filler having a flat shape and a molded article using the same.
  • Patent Document 1 70% by weight of spherical silica having an average particle size of 0.5 ⁇ m is filled with respect to 100% by weight of the total solid content of a thermosetting resin composition to reduce the coefficient of linear thermal expansion. is disclosed.
  • a large amount of spherical inorganic filler is added to the insulating resin, a certain effect is obtained in reducing the coefficient of linear thermal expansion.
  • Non-Patent Document 1 discloses that the use of fibrous potassium titanate with an aspect ratio of 5 as a filler is effective in reducing the linear thermal expansion coefficient of the composite.
  • the linear thermal expansion coefficient of the fibrous inorganic filler can be reduced more than the spherical inorganic filler of the same particle size even if the content is low.
  • no composite has been known that has both high flexibility (flexibility and good bending properties) and low coefficient of linear thermal expansion.
  • An object of the present invention is to provide a resin composition that achieves both a reduced coefficient of linear thermal expansion and high flexibility, and a molded article using the same.
  • the inventors have conducted extensive research to solve the above problems. As a result, by using a fibrous inorganic filler having a specific oblateness, a resin composition that achieves both a low linear thermal expansion coefficient and high flexibility and a molded article using the same were found, and the present invention was completed. Arrived.
  • the present invention has the following configurations.
  • a resin composition comprising a fibrous inorganic filler having an average length-to-breadth ratio of 2.0 or more in the cross section of the fiber, and a resin.
  • the fibrous inorganic filler contains at least one selected from the group consisting of alumina, aluminum titanate, silica, zirconium tungstate, and barium titanate.
  • the described resin composition Any one of [1] to [5], wherein the resin contains at least one selected from the group consisting of polyimide resins, epoxy resins, silicone resins, polyamide resins, acrylic resins, or fluororesins. of the resin composition.
  • [7] A molded article using the resin composition according to any one of [1] to [6].
  • the molded article according to [7] which has a coefficient of linear thermal expansion of 40 ppm/K or less.
  • FIG. 1 is a scanning electron micrograph of fibrous alumina filler (1) according to Example 1 of the present invention.
  • 4 is a scanning electron micrograph of fibrous aluminum titanate filler (1) according to Example 4 of the present invention.
  • 1 is a scanning electron micrograph of fibrous alumina filler (2) according to Comparative Example 1 of the present invention.
  • FIG. 4 is a scanning electron micrograph of fibrous aluminum titanate filler (3) according to Comparative Example 8 of the present invention.
  • the resin composition of the present invention is characterized by containing a resin and a fibrous inorganic filler having an average value (average oblateness) of the ratio of the major axis to the minor axis in the fiber cross section of 2.0 or more.
  • the term "fibrous” means elongated, that is, having an aspect ratio of 10 or more.
  • the aspect ratio in the present invention is defined as the ratio of the fiber length to the short diameter in the cross section of the fiber.
  • the aspect ratio is preferably 10 or more from the viewpoint of reducing the coefficient of linear thermal expansion of the molded article obtained from the resin composition of the present invention.
  • the average value (average oblateness) of the ratio of the major axis to the minor axis in the fiber cross section of the fibrous inorganic filler used in the present invention is 2.0 or more, preferably 2.2 to 10.02 0.5 to 9.0, more preferably 3.0 to 8.0. If the average oblateness is 2.0 or more, it is possible to reduce the linear thermal expansion coefficient, and if it is 10.0 or less, it is possible to obtain a fibrous inorganic filler having excellent mechanical strength. Become.
  • the CV value (standard deviation/average value) of the long diameter in the fiber cross section of the fibrous inorganic filler used in the present invention is not particularly limited, but from the viewpoint of more effectively reducing the linear thermal expansion coefficient, it is 0.5 or less. It is preferably 0.25 or less, more preferably 0.15 or less, and ideally 0. The smaller the CV value of the long diameter, the more uniform the long diameter of the inorganic fiber. It becomes possible to reduce it effectively.
  • the average length (average length) of the fiber cross section of the fibrous inorganic filler used in the present invention is not particularly limited, but from the viewpoint of suppressing the aggregation of the fibrous inorganic filler, it is 0.1 to 10 ⁇ m. is preferred, 0.2 to 5.0 ⁇ m is more preferred, and 0.5 to 2.0 ⁇ m is even more preferred. If the average major axis of the fibrous inorganic filler is 0.1 ⁇ m or more, the cohesiveness is suppressed and the fibrous inorganic filler is well dispersed in the matrix component, so that a composite having uniform physical properties can be formed. Therefore, if the thickness is 10 ⁇ m or less, the contact area with the resin is sufficient, and the coefficient of linear thermal expansion of the molded article obtained from the resin composition of the present invention can be effectively reduced.
  • the average short diameter (average short diameter) in the fiber cross section of the fibrous inorganic filler is not particularly limited, but from the viewpoint of suppressing the aggregation of the fibrous inorganic filler, it is 0.05 to 5.0 ⁇ m. is preferred, 0.1 to 2.0 ⁇ m is more preferred, and 0.15 to 1.0 ⁇ m is even more preferred. If the average minor axis is 0.05 ⁇ m or more, the cohesiveness is suppressed, and it is possible to form a composite having uniform physical properties. It becomes possible to reduce the linear thermal expansion coefficient of the composite.
  • the material constituting the fibrous inorganic filler used in the present invention is not particularly limited, and lithium, beryllium, boron, sodium, magnesium, aluminum, silicon, phosphorus, sulfur, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, cadmium, indium, tin, antimony, tellurium, cesium, barium, lanthanum, hafnium, Oxides, nitrides containing elements such as tantalum, tungsten, mercury, thallium, lead, bismuth, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium,
  • the fibrous inorganic filler may be composed of one component oxide, nitride or carbide, or may be a mixture or solid solution of two or more components oxide, nitride or carbide.
  • the fibrous inorganic filler is at least one selected from the group consisting of alumina, aluminum titanate, silica, zirconium tungstate and barium titanate. is preferred, and alumina or aluminum titanate is more preferred.
  • the resin used in the present invention is not particularly limited, and may be a thermoplastic resin, a thermosetting resin, or a photocurable resin.
  • examples include polyolefin resins, polyamide resins, and polyester resins. , polycarbonate resin, polyacetal resin, aramid resin, polyurethane resin, vinyl chloride resin, polysulfone resin, cellulose resin, fluorine resin, epoxy resin, silicone resin, acrylic resin, polyimide resin, and maleimide resin.
  • polyimide resins From the viewpoint of resistance, heat resistance, etc., it is preferably at least one selected from the group consisting of polyimide resins, epoxy resins, silicone resins, polyamide resins, acrylic resins, and fluororesins, more preferably epoxy resins and polyimide resins.
  • Polyimide resin is most preferable from the viewpoint of mechanical properties, thermal properties, dimensional stability when heated, and chemical resistance.
  • polyimide resins examples include polyimide resins and polyetherimide resins obtained by reacting acid dianhydrides and diamines. These polyimide resins may be used singly or in combination of two or more.
  • silicone resins examples include dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, and modified silicones obtained by reacting these various silicones with organic groups. These silicone resins may be used singly or in combination of two or more.
  • polyamide resins examples include aliphatic polyamides such as polyamide 6, polyamide 46, polyamide 66 and polyamide 12, and semi-aromatic polyamides such as polyamide 6T and polyamide 9T. These polyamide resins may be used singly or in combination of two or more.
  • Epoxy resins include dicyclopentadiene type epoxy resin, phosphorus-containing epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin.
  • Epoxy resins, biphenyl-type epoxy resins, alicyclic epoxy resins, diglycidyl ether compounds of polyfunctional phenols, and diglycidyl ether compounds of polyfunctional alcohols can be exemplified. These may be used individually by 1 type, and may be used in combination of 2 or more type. Of these, bisphenol A type epoxy resins are preferred from the viewpoint of heat resistance and versatility.
  • acrylic resins include compounds obtained by blending at least one monomer component selected from (meth)acrylic acid and its esters with a polymer that can dissolve or swell in this monomer component. These acrylic resins may be used singly or in combination of two or more.
  • fluororesins examples include polytetrafluoroethylene [PTFE], tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer [PFA], tetrafluoroethylene/hexafluoropropylene copolymer [FEP], ethylene/tetrafluoroethylene copolymer Polymer [ETFE], ethylene/tetrafluoroethylene/hexafluoropropylene copolymer, polychlorotrifluoroethylene [PCTFE], chlorotrifluoroethylene/tetrafluoroethylene copolymer, ethylene/chlorotrifluoroethylene copolymer, Examples include polyvinylidene fluoride [PVDF], vinylidene fluoride/hexafluoropropylene copolymer, and the like. These fluororesins may be used singly or in combination of two or more.
  • the resin composition of the present invention is characterized by containing a resin and a fibrous inorganic filler having an average value (average oblateness) of the ratio of the major axis to the minor axis in the cross section of the fiber is 2.0 or more. .
  • a fibrous inorganic filler having a specific oblateness it is possible to reduce the coefficient of linear thermal expansion even with a low content.
  • the content of the fibrous inorganic filler in the present invention is preferably 5 to 60% by weight of the solid content in the resin composition, more preferably 15 to 60% by weight, and 25 to 60% by weight. is more preferred. If the content of the fibrous inorganic filler is 5% by weight or more of the solid content in the resin composition, it is possible to reduce the coefficient of linear thermal expansion of the resulting molded product. It becomes possible to obtain a highly flexible molding.
  • the resin composition contains, as components other than the resin and the fibrous inorganic filler, a solvent, a curing agent, a dispersant, a polymer compound, inorganic particles, metal particles, a surfactant, and an antistatic agent, as long as the effects of the present invention are not impaired. agents, leveling agents, viscosity modifiers, thixotropy modifiers, adhesion improvers, epoxy curing agents, rust inhibitors, preservatives, antifungal agents, antioxidants, reduction inhibitors, evaporation accelerators, chelating agents, Additives such as pigments, titanium black, carbon black, or dyes may be included.
  • the solvent contained in the resin composition is not particularly limited, and water, methanol, ethanol, propanol, 1-butanol, isobutanol, ethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, acetone, N,N-dimethyl.
  • the curing agent contained in the resin composition is not particularly limited, and includes polyfunctional acid anhydrides, styrene maleic anhydride resin (SMA), amine curing agents, thiol curing agents, cyanate curing agents, active ester curing agents.
  • SMA styrene maleic anhydride resin
  • a curing agent, or a phenol-based curing agent or the like can be used. These may be appropriately selected according to the reactivity and the properties of the resulting molded article, and may be used singly or in combination of two or more.
  • the resin composition may be in the form of powder (for example, a powder mixture obtained by mixing a fibrous inorganic filler and a resin) or in the form of pellets (for example, a mixture obtained by kneading a fibrous inorganic filler and a resin). pellets) or liquid (for example, liquid compositions such as paints, inks, and varnishes containing resins, fibrous inorganic fillers, and solvents).
  • the resin composition of the present invention can be used to produce a molded article (a cured resin composition), and can be used as a paint, an adhesive, a filler, or the like in an uncured or semi-cured state. It can also be used as
  • the molded article of the present invention is obtained by molding the above resin composition into a shape according to the application and curing it, and has a low linear thermal expansion coefficient and excellent flexibility. It can be suitably used for devices, optical instruments, measuring instruments, electronic devices, and the like.
  • the shape of the molded body is not particularly limited, and includes films, sheets, plates, particles, porous materials, and the like. From the viewpoint, it is preferably a film or a sheet, and more preferably a film.
  • the molded article of the present invention contains fibrous inorganic fillers having a flat shape, the micro-Brownian motion of polymer chains existing between the inorganic fibers can be restrained more than the fibrous fillers having a circular cross section, resulting in low linear thermal expansion. coefficients can be realized.
  • the coefficient of linear thermal expansion of the molded product is not particularly limited, it is preferably 40 ppm/K or less, more preferably 23 ppm/K or less.
  • the method for producing the resin composition of the present invention is not particularly limited, but includes a step of preparing a spinning solution containing an inorganic component (hereinafter referred to as a spinning solution preparation step) and spinning the spinning solution to prepare a precursor fiber.
  • a process hereinafter referred to as a spinning process
  • a process of baking the precursor fibers to produce inorganic fibers hereinafter referred to as a baking process
  • a process of pulverizing the inorganic fibers to produce fibrous inorganic fillers hereinafter referred to as pulverization step
  • a mixing step a step of mixing the fibrous inorganic filler and the resin
  • the spinning solution in the present invention is not particularly limited as long as it has spinnability and contains a solvent and an inorganic component, and may be a spinning solution in which the inorganic component is dispersed or dissolved in the solvent. From the viewpoint of reducing the average major diameter of the inorganic filler and improving the uniformity of the major diameter and composition, it is preferable to use a spinning solution in which the inorganic component is dissolved in a solvent.
  • a method for obtaining such a spinning solution is not particularly limited, and it can be obtained using known equipment such as a magnetic stirrer, a shaker, a planetary stirrer, or an ultrasonic device.
  • the inorganic component is not particularly limited as long as the fibrous inorganic filler described above is obtained, and includes silicon, aluminum, lithium, sodium, potassium, magnesium, calcium, strontium, barium, yttrium, lanthanum, titanium, zirconium, hafnium, and vanadium.
  • the inorganic component preferably contains an alkoxide.
  • alkoxides include tetraethoxysilane, triethoxysilane, aluminum sec-butoxide, aluminum triisopropoxide, titanium tetrabutoxide, titanium tetraisopropoxide, magnesium alkoxide and zirconium tetraisopropoxide.
  • the solvent used in the spinning solution preparation step is not particularly limited, and water, methanol, ethanol, propanol, 1-butanol, isobutanol, ethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, acetone, N,N-dimethyl.
  • the organic acid is preferably formic acid, acetic acid or propionic acid, more preferably acetic acid.
  • the spinning solution in the present invention is not particularly limited, but may further contain a fiber-forming polymer for the purpose of improving spinnability.
  • the fiber-forming polymer is selected from those capable of dissolving in the solvent and decomposed by baking, as long as it has the effect of promoting fibrilization of the spinning solution.
  • fiber-forming polymers include polyvinyl alcohol, polyethyleneimine, polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, polyethylene, polypropylene, polyethylene terephthalate, polylactic acid, polyamide, polyurethane, polystyrene, polyvinylidene fluoride, polyacrylonitrile, and polymethyl methacrylate.
  • the fiber-forming polymer is preferably polyvinyl alcohol, polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, or polyacrylic acid, and is polyvinylpyrrolidone, from the viewpoints of solubility in a solvent and degradability in the baking process. is more preferable.
  • Components other than those described above may be included as components of the spinning solution as long as they do not significantly impair the effects of the present invention. good.
  • Electrospinning is a method of ejecting a spinning solution and applying an electric field to turn the ejected spinning solution into fibers and obtain fibers on a collector. Electrospinning includes, for example, a method of extruding a spinning solution from a nozzle and applying an electric field for spinning, a method of making a spinning solution foam and applying an electric field for spinning, and a method of introducing a spinning solution onto the surface of a cylindrical electrode and A method of spinning by applying an electric field can be mentioned. Uniform fibers with a diameter of 10 nm to 10 ⁇ m can be obtained by these methods.
  • the amount of spinning solution discharged is not particularly limited, and is preferably 0.1 to 10 mL/hr.
  • a discharge rate of 0.1 mL/hr or more is preferable because sufficient productivity can be obtained, and a discharge rate of 10 mL/hr or less is preferable because uniform and fine fibers can be easily obtained.
  • the polarity of the applied voltage may be positive or negative.
  • the magnitude of the voltage is not particularly limited as long as the fibers are formed, and in the case of a positive voltage, the range of 5 to 100 kV can be exemplified.
  • the distance between the nozzle and the collector is not particularly limited as long as the fibers are formed, and a range of 5 to 50 cm can be exemplified.
  • the collector is not particularly limited as long as it can collect the spun precursor fibers, and its material and shape are not particularly limited.
  • a conductive material such as metal is preferably used as the material of the collector.
  • the shape of the collector is not particularly limited, and examples thereof include a plate shape, a shaft shape, and a conveyor shape.
  • a conveyor-like collector is preferable because the precursor fibers can be continuously produced.
  • inorganic fibers are obtained by firing the precursor fibers obtained in the spinning step.
  • the elements in the inorganic component are oxidized, nitrided, or carbonized, and the inorganic fiber can be obtained. Further, when a fiber-forming polymer is used, the fiber-forming polymer contained in the precursor fiber is thermally decomposed and disappears.
  • a general electric furnace can be used for firing.
  • the firing atmosphere is not particularly limited, but even if it is performed in an air atmosphere or an inert gas atmosphere such as nitrogen gas or argon gas, it is performed in an air atmosphere for a certain period of time and then in an inert gas atmosphere.
  • the firing method may be one-step firing or multi-step firing.
  • the firing temperature in the present invention is not particularly limited, it is preferably 600°C or higher, more preferably 800 to 1700°C, and even more preferably 1100 to 1500°C.
  • the firing temperature is 600°C or higher, the firing is sufficient, the crystallization of the inorganic fibers proceeds, and components other than the inorganic fibers are less likely to remain, making it possible to obtain high-purity inorganic fibers. If it is below, energy consumption can be kept low, and manufacturing costs can be kept low.
  • the firing temperature is in the range of 1100 to 1500° C., the crystallinity of the inorganic fibers can be enhanced and the manufacturing cost can be sufficiently reduced.
  • the firing time is not particularly limited, but may be, for example, 1 to 24 hours.
  • the rate of temperature increase is not particularly limited, but can be appropriately changed within the range of 5 to 50° C./min for firing.
  • the crystallinity and composition of inorganic fibers can be determined, for example, from diffraction images obtained by X-ray diffraction.
  • the inorganic fibers obtained in the firing step are further pulverized to obtain a fibrous inorganic filler.
  • the method of pulverization is not particularly limited as long as the fibrous inorganic filler can maintain the shape described above, and can be ball mill, bead mill, jet mill, high-pressure homogenizer, planetary mill, rotary crusher, hammer crusher, cutter mill, stone mill, mortar, or screen.
  • Mesh pulverization can be exemplified, and it may be dry or wet, but screen mesh pulverization is preferably used because it is easy to control to a specific shape and size.
  • Screen mesh pulverization is performed by placing inorganic fibers on a mesh having a predetermined opening and filtering with a brush or spatula, or by placing beads such as alumina, zirconia, glass, PTFE, nylon, or polyethylene and inorganic fibers on a mesh.
  • a method of applying vertical and/or horizontal vibrations can be exemplified.
  • the opening of the mesh to be used is not particularly limited, it is preferably 20 to 1000 ⁇ m, more preferably 50 to 500 ⁇ m.
  • a mesh size of 20 ⁇ m or more is preferable because the pulverization time can be shortened, and a mesh size of 1000 ⁇ m or less is preferable because coarse substances and agglomerates of the fibrous inorganic filler can be removed.
  • the pulverization method and conditions may be appropriately changed according to the required properties.
  • the resin composition is obtained by mixing the fibrous inorganic filler obtained in the pulverizing step with the resin.
  • the mixing method is not particularly limited, and may be a dry method or a wet method.
  • the dry method is preferable in that a resin composition can be obtained without requiring a solvent.
  • a solution method (wet method) is preferable because it yields a resin composition or a molded article with little variation in physical properties.
  • a method for producing a resin composition by a dry method for example, a method of blending a fibrous inorganic filler and a resin and mixing using a mortar at room temperature, or a method of melt-kneading using a pelletizer or the like can be mentioned. can.
  • a fibrous inorganic filler, a resin, and a solvent are blended, and a magnetic stirrer, a shaker, a ball mill, a jet mill, a planetary stirrer, an ultrasonic device, or the like is used. and the solvent may be evaporated after mixing.
  • the mixing conditions are not particularly limited, and for example, the mixing can be performed at 10 to 120° C. for 1 to 24 hours.
  • a molded article can be obtained by molding the resin composition obtained as described above into a shape according to the application and curing the molded article.
  • a method for producing a film-like molded article will be described below, but the present invention is not limited to this.
  • the resin composition When using a powdery or pelletized resin composition, for example, the resin composition is sandwiched between stainless steel plates or placed in a mold of any shape, and then hot-pressed with a compression molding machine at a predetermined temperature, pressure, and time for curing. a method of curing by cooling and solidifying after melt-molding; and a method of irradiating with ultraviolet rays.
  • the compression molding conditions may be appropriately changed depending on the fluidity of the resin composition and the desired physical properties.
  • the temperature during compression molding is 60 to 400° C.
  • the pressure is 1 to 30 MPa
  • the time is 1 to 60. Minutes can be exemplified.
  • ease of handling can be further improved. For example, it is possible to form the composition in a semi-cured state into a film shape, cut it into a desired shape, place it between suitable members and bond them together.
  • a method of coating the resin composition on a support and drying the solvent to cure the resin composition for example, a method of heat curing or photocuring can be used.
  • the coating method is not particularly limited, and known methods such as spin coating, spray coating, roll coating, gravure coating, or cast coating can be used.
  • patterning it can be carried out using a known method such as an inkjet method, a screen printing method, or a flexographic printing method.
  • the support on which the liquid resin composition is applied is not particularly limited, and a glass substrate, an aluminum substrate, a copper substrate, a polymer film, or the like can be used.
  • the molded product may be left as a film on the support, or a support whose surface has been subjected to release treatment may be used in order to form a self-supporting film.
  • a method for drying the solvent is not particularly limited, and induction heating, hot air circulation heating, vacuum drying, infrared rays, or microwave heating can be exemplified.
  • drying conditions for example, drying may be performed at 40 to 150° C. for 1 to 180 minutes, and further heat treatment may be performed at 200 to 400° C. for 20 to 90 minutes for the purpose of curing by heat.
  • the heat radiating member after drying can be further subjected to hot press or heat treatment for the purpose of suppressing voids.
  • the hot press conditions are not particularly limited, and examples include a press temperature of 60 to 400° C., a press pressure of 1 to 30 MPa, and a press time of 1 to 60 minutes.
  • the heat treatment conditions for example, the heat treatment may be performed in an oven at 60 to 200° C. for 1 to 24 hours.
  • ⁇ Average major axis of fibrous inorganic filler, CV value of major axis, average minor axis and average oblateness> Observe the obtained fibrous inorganic filler using a scanning electron microscope (SN-3400N) manufactured by Hitachi, Ltd., and use the image analysis function to cross 50 or more fibrous inorganic fillers obtained. Measure the major axis and minor axis on the surface, average major axis, standard deviation of major axis / average major axis CV value of major axis, average minor axis, average minor axis / average minor axis flattened.
  • thermomechanical measuring device TMA-7100 of Hitachi High-Tech Science Co., Ltd. a test piece of 3 ⁇ 20 mm, under a tensile load of 50 mN, at a heating rate of 10 ° C / min, linear heating in the plane direction (XY direction) of the molded body The coefficient of expansion was measured.
  • the unit is ppm/K.
  • Example 1 ⁇ Preparation of spinning solution> While stirring 12.80 parts by weight of propylene glycol monomethyl ether and 3.20 parts by weight of acetic acid, 0.55 parts by weight of polyvinylpyrrolidone was added and stirred for 1 hour. Then, 6 parts by weight of aluminum sec-butoxide was added to prepare a spinning solution.
  • the spinning solution prepared by the above method was supplied by a syringe pump to a nozzle with an inner diameter of 0.30 mm at 6 mL/hr, and a voltage of 22 kV was applied to the nozzle to collect the precursor fibers in a grounded collector. The distance between the nozzle and the collector was 210 mm.
  • the electrostatically spun precursor fiber was heated to 1150° C. at a heating rate of 10° C./min in the air, held at the sintering temperature of 1150° C. for 2 hours, cooled to room temperature, and alumina fiber (1) was obtained.
  • the fibrous alumina filler (1) was obtained by placing the powder on a screen mesh with an opening of 500 ⁇ m together with a nylon ball of 9.5 mm in diameter and pulverizing it by vibrating it in the longitudinal direction.
  • the obtained fibrous alumina filler (1) had an average major axis of 1.06 ⁇ m, a CV value of the major axis of 0.09, an average minor axis of 0.21 ⁇ m, and an average oblateness of 5.0.
  • a scanning electron micrograph of the obtained fibrous alumina filler (1) is shown in FIG.
  • the obtained fibrous alumina filler (1) was flat with different major and minor diameters in the cross section.
  • ⁇ Preparation of resin composition > 0.7 parts by weight of a polyimide resin synthesized by the method described in Japanese Patent No. 5617235 as a resin, and 3-methoxy-N,N-dimethylpropanamide (KJ Chemicals Co., Ltd., KJCMPA (registered trademark)-100) as a solvent.
  • fibrous alumina filler (1) as an inorganic filler were blended and mixed with an Awatori Mixer (ARE-310, THINKY Co., Ltd.) to prepare a liquid resin composition. did.
  • the content of the fibrous alumina filler (1) was 32.7% by weight (15% by volume) of the solid content in the resin composition.
  • Preparation of compact> Then, using an applicator, the liquid resin composition was cast on an aluminum substrate having a thickness of 25 ⁇ m, dried on a hot plate at 80° C. for 30 minutes, and then dried in an oven at 150° C. for 15 minutes and at 350° C. It was heated in an oven for 30 minutes to produce a compact.
  • the linear thermal expansion coefficient from 100° C. to 360° C. in the resulting molded product was 22.4 ppm/K.
  • Example 2 ⁇ Preparation of Resin Composition and Molded Body> 0.48 parts by weight of fibrous alumina filler (1) and 1.05 parts by weight of 3-methoxy-N,N-dimethylpropanamide (KJ Chemicals Co., Ltd., KJCMPA (registered trademark)-100) , a resin composition and a molded article were prepared in the same manner as in Example 1.
  • the content of the fibrous alumina filler (1) was 40.7% by weight (20% by volume) of the solid content in the resin composition.
  • the coefficient of linear thermal expansion of the molded product obtained from 100 to 360° C. was 16.2 ppm/K.
  • the fibrous alumina filler (2) was obtained by firing and pulverizing under the same conditions as in Example 1.
  • the obtained fibrous alumina filler (2) had an average major axis of 0.82 ⁇ m, a CV value of the major axis of 0.10, an average minor axis of 0.82 ⁇ m, and an average oblateness of 1.0.
  • a scanning electron micrograph of the obtained fibrous alumina filler (2) is shown in FIG. As shown in the upper right cross-sectional view of FIG. 3, the obtained fibrous alumina filler (2) had a circular cross section with the same length and width.
  • Example 1 ⁇ Preparation of Resin Composition and Molded Body> Example 1 except that instead of the fibrous alumina filler (1), 0.82 parts by weight of the fibrous alumina filler (2) and 1.05 parts by weight of 3-methoxy-N,N-dimethylpropanamide were used.
  • a resin composition and a molded article were prepared in the same manner as in the above.
  • the content of the fibrous alumina filler (2) was 53.9% by weight (30% by volume) of the solid content in the resin composition.
  • the coefficient of linear thermal expansion of the molded product obtained from 100 to 360° C. was 23.3 ppm/K.
  • Table 1 summarizes the physical properties of the inorganic fillers, the physical properties of the resins, and the linear thermal expansion coefficients of the moldings used in Examples 1-2 and Comparative Examples 1-5.
  • the molded body using a fibrous inorganic filler having an average oblateness of 2.0 or more has a lower coefficient of linear thermal expansion than the polyimide film molded body (Comparative Example 5) that does not contain an inorganic filler.
  • the results showed that the modulus was the same or higher, and the flexibility was excellent.
  • Example 3 ⁇ Preparation of resin composition> 1.04 parts by weight of fibrous alumina filler (1) as an inorganic filler, 0.3 parts by weight of an epoxy resin (DIC Corporation, EXA-850CRP) as a resin, and a phenol-based curing agent (Gunei Chemical Industry ( Co., Ltd., ELP83H) 0.40 parts by weight, curing accelerator (Shikoku Kasei Kogyo Co., Ltd., 2PHZ-PW) 0.006 parts by weight, cyclopentanone as a solvent (Tokyo Chemical Industry Co., Ltd.) 0.55 parts by weight were blended and mixed with a Thinky Mixer (ARE-310, THINKY Co., Ltd.) to prepare a liquid resin composition.
  • an epoxy resin DIPEXA-850CRP
  • a phenol-based curing agent Gunei Chemical Industry ( Co., Ltd., ELP83H) 0.40 parts by weight
  • curing accelerator Shikoku Kasei Kogyo Co., Ltd
  • the content of the fibrous alumina filler (1) was 59.8% by weight (30% by volume) of the solid content in the resin composition.
  • ⁇ Preparation of compact> Next, using an applicator, the liquid resin composition is cast on an aluminum substrate having a thickness of 25 ⁇ m, dried on a hot plate at 80° C. for 30 minutes, heated in an oven at 150° C. for 30 minutes, and molded. made the body.
  • the coefficient of linear thermal expansion of the molded product obtained from 60 to 120° C. was 32.8 ppm/K.
  • Table 2 summarizes the physical properties of the inorganic fillers, the physical properties of the resins, and the linear thermal expansion coefficients of the moldings used in Example 3 and Comparative Examples 6-7.
  • the molded body using the fibrous inorganic filler having an average flatness of 2.0 or more has a linear thermal expansion coefficient relative to the epoxy film molded body (Comparative Example 7) that does not contain the inorganic filler. This resulted in a higher reduction rate.
  • Example 4 ⁇ Preparation of spinning solution> While stirring 14.60 parts by weight of propylene glycol monomethyl ether and 2.40 parts by weight of acetic acid, 0.56 parts by weight of polyvinylpyrrolidone was added and stirred for 1 hour. Then, 4.8 parts by weight of aluminum sec-butoxide and 2.76 parts by weight of titanium tetraisopropoxide were added to prepare a spinning solution.
  • ⁇ Production of fiber> The spinning solution prepared by the above method was supplied to a nozzle with an inner diameter of 0.30 mm at 5 mL/hr by a syringe pump, and a voltage of 23 kV was applied to the nozzle to collect the precursor fibers on a grounded collector.
  • the distance between the nozzle and the collector was 200 mm.
  • the electrostatically spun precursor fiber was heated to 1150° C. at a heating rate of 10° C./min in air, held at the sintering temperature of 1150° C. for 2 hours, cooled to room temperature, and aluminum titanate fiber ( 1) was obtained. Then, it was placed on a screen mesh with an opening of 500 ⁇ m together with a nylon ball of 9.5 mm in diameter, and pulverized by vibrating in the longitudinal direction to obtain a fibrous aluminum titanate filler (1).
  • the obtained fibrous aluminum titanate filler (1) had an average major axis of 1.00 ⁇ m, a CV value of the major axis of 0.12, an average minor axis of 0.19 ⁇ m, and an average oblateness of 5.3.
  • a scanning electron micrograph of the obtained fibrous aluminum titanate filler (1) is shown in FIG.
  • the obtained fibrous aluminum titanate filler (1) had a flat shape with different major and minor diameters in the cross section.
  • Example 5 ⁇ Preparation of spinning solution> While stirring 2.00 parts by weight of ethanol and 4.40 parts by weight of diethyl ether, 4.0 parts by weight of polyvinylpyrrolidone was added and stirred for 1 hour. Then, 1.8 parts by weight of aluminum acetylacetonate and 0.73 parts by weight of titanyl acetylacetonate were added to prepare a spinning solution.
  • the spinning solution prepared by the above method was supplied by a syringe pump to a nozzle with an inner diameter of 0.30 mm at 2 mL/hr, and a voltage of 30 kV was applied to the nozzle to collect precursor fibers on a grounded collector.
  • the fibrous aluminum titanate filler (2) was obtained by firing and pulverizing under the same conditions as in Example 4.
  • the obtained fibrous aluminum titanate filler (2) had an average major axis of 1.05 ⁇ m, a CV value of the major axis of 0.84, an average minor axis of 0.15 ⁇ m, and an average oblateness of 7.0.
  • the obtained fibrous aluminum titanate filler (3) had an average major axis of 1.10 ⁇ m, a CV value of the major axis of 0.13, an average minor axis of 1.10 ⁇ m, and an average oblateness of 1.0.
  • a scanning electron micrograph of the obtained fibrous aluminum titanate filler (3) is shown in FIG. As shown in the upper right cross-sectional view of FIG. 4, the obtained fibrous aluminum titanate filler (3) had the same major and minor diameters in cross section and was circular.
  • ⁇ Preparation of resin composition> Instead of the fibrous alumina filler (1), 0.77 parts by weight of the fibrous aluminum titanate filler (3), 3-methoxy-N,N-dimethylpronamide (KJ Chemicals Co., Ltd., KJCMPA (registered trademark) -100) was used in the same manner as in Example 1 to obtain a liquid resin composition.
  • the content of the fibrous aluminum titanate filler (3) was 52.4% by weight (30% by volume) of the solid content in the resin composition.
  • ⁇ Preparation of compact> A compact was produced in the same manner as in Example 1.
  • the coefficient of linear thermal expansion of the molded product obtained from 100 to 360° C. was 24.9 ppm/K.
  • Table 3 summarizes the physical properties of the inorganic fillers, the physical properties of the resins, and the linear thermal expansion coefficients of the moldings used in Examples 4 and 5 and Comparative Example 8.
  • the resin composition of the present invention can effectively suppress thermal expansion by adding a small amount, and can suppress thermal expansion while maintaining the excellent handleability of the insulating resin. It can be suitably used for applications such as equipment, measuring equipment, electronic devices, and aerospace.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine qui permet d'obtenir un corps moulé permettant d'atteindre à la fois un faible coefficient de dilatation thermique linéaire et une flexibilité élevée.　La présente invention concerne une composition de résine contenant une résine et une charge inorganique fibreuse dans laquelle une valeur moyenne du rapport de l'axe majeur à l'axe mineur dans la section transversale de fibre (planéité moyenne) est de 2,0 ou plus, la charge inorganique fibreuse présentant de préférence une valeur CV d'axe majeur (écart-type/valeur moyenne) de 0,5 ou moins, et présentant de préférence une valeur moyenne d'axe majeur (axe majeur moyen) comprise entre 0,1 et 10 µm.
PCT/JP2022/033758 2022-02-10 2022-09-08 Composition de résine contenant une charge inorganique fibreuse et corps moulé WO2023153007A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011142305A1 (fr) * 2010-05-10 2011-11-17 日東紡績株式会社 Procédé de moulage de mousse de résine à renfort de fibres de verre plates
JP2015044905A (ja) * 2013-08-27 2015-03-12 昭和電工株式会社 樹脂組成物、透明フィルム、その製造方法及び用途
WO2020137004A1 (fr) * 2018-12-27 2020-07-02 日東紡績株式会社 Article moulé en résine renforcée de fibres de verre
WO2021039201A1 (fr) * 2019-08-26 2021-03-04 イビデン株式会社 Résine thermoconductrice, structure de dissipation de chaleur et procédé de production de résine thermoconductrice
CN112708268A (zh) * 2020-12-08 2021-04-27 金发科技股份有限公司 一种耐磨且尺寸稳定的聚酰胺组合物及其制备方法和应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011142305A1 (fr) * 2010-05-10 2011-11-17 日東紡績株式会社 Procédé de moulage de mousse de résine à renfort de fibres de verre plates
JP2015044905A (ja) * 2013-08-27 2015-03-12 昭和電工株式会社 樹脂組成物、透明フィルム、その製造方法及び用途
WO2020137004A1 (fr) * 2018-12-27 2020-07-02 日東紡績株式会社 Article moulé en résine renforcée de fibres de verre
WO2021039201A1 (fr) * 2019-08-26 2021-03-04 イビデン株式会社 Résine thermoconductrice, structure de dissipation de chaleur et procédé de production de résine thermoconductrice
CN112708268A (zh) * 2020-12-08 2021-04-27 金发科技股份有限公司 一种耐磨且尺寸稳定的聚酰胺组合物及其制备方法和应用

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