[go: up one dir, main page]

WO2009110514A1 - Poudre de particules inorganiques creuses, son procédé de fabrication et composition la contenant - Google Patents

Poudre de particules inorganiques creuses, son procédé de fabrication et composition la contenant Download PDF

Info

Publication number
WO2009110514A1
WO2009110514A1 PCT/JP2009/054086 JP2009054086W WO2009110514A1 WO 2009110514 A1 WO2009110514 A1 WO 2009110514A1 JP 2009054086 W JP2009054086 W JP 2009054086W WO 2009110514 A1 WO2009110514 A1 WO 2009110514A1
Authority
WO
WIPO (PCT)
Prior art keywords
powder
hollow
inorganic
inorganic hollow
mass
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2009/054086
Other languages
English (en)
Japanese (ja)
Inventor
亮治 稲葉
亨 梅崎
浩明 吉開
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Denka Co Ltd
Original Assignee
Denki Kagaku Kogyo KK
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 Denki Kagaku Kogyo KK filed Critical Denki Kagaku Kogyo KK
Priority to JP2010501935A priority Critical patent/JP5519489B2/ja
Publication of WO2009110514A1 publication Critical patent/WO2009110514A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof

Definitions

  • the present invention relates to an inorganic hollow powder, a method for producing the same, and a resin composition using the same.
  • micro hollow glass sphere As a typical inorganic hollow powder.
  • these micro hollow glass spheres are called glass micro balloons and have a lighter specific gravity than non-hollow inorganic powders, making use of various characteristics such as heat resistance, heat insulation, impact resistance, and pressure resistance.
  • it is used for weight reduction, heat insulation performance and dimensional stability.
  • resin molded parts such as molding compounds for portable electronic devices and automobiles, paint for moving bodies, members, various building materials, and the like.
  • the hollow glass spherical body has a wide range of uses, in recent years, further refinement of the hollow glass spherical powder, the appearance of high-purity inorganic oxide hollow powder, and the like have been strongly demanded.
  • a fine powder having a glass forming component and a foaming agent component supported on silica gel is fired in a furnace to obtain a fine hollow glass sphere (see Patent Document 1). .
  • the particle density is about 0.3 g / cm 3 and the average particle size is about 70 ⁇ m.
  • a foaming agent component is essential as a production method, Purity does not increase, such as foaming agent components remaining.
  • the average particle diameter is around 70 ⁇ m, and it cannot be used for applications in which the thickness of the composite material is regulated including applications for reducing the dielectric constant.
  • a fine silica hollow powder having a high specific surface area is fired in a furnace to obtain a fine inorganic hollow powder (see Patent Document 2 and Patent Document 3).
  • the physical properties of the fine inorganic hollow powder obtained by this method are shown to have an average hollowness of about 20 to 85% by volume, but the hollowness distribution of the hollow particles is not described.
  • An object of the present invention is to provide an inorganic hollow powder that is further refined than conventional hollow glass spheres, particularly an inorganic hollow powder that is refined and has a high purity and a low segregation of hollow ratio, a method for producing the same, and a method for producing the same. It is to provide a contained resin composition.
  • the present invention has the following gist.
  • a resin composition comprising the inorganic hollow powder according to any one of (1) to (5).
  • a slit of 0.1 to 2.0 mm with an inorganic raw material powder having a pore volume of 0.1 to 1.0 ml / g and a maximum particle size of 10 ⁇ m or less at a powder concentration of 50 to 500 g / Nm 3 The method for producing an inorganic hollow powder according to any one of (1) to (3), wherein the inorganic hollow powder is supplied from a raw material supply pipe having a doughnut-like structure having a width and hollowed by a flame.
  • the flame is a high temperature flame of 1700 to 2200 ° C. and a low temperature flame of 1000 to 1400 ° C.
  • a method for producing an inorganic hollow powder which is supplied from a raw material supply pipe having a donut-like structure having a width and hollowed by a high temperature flame of 1700 to 2200 ° C. and a low temperature flame of 1000 to 1400 ° C.
  • an inorganic hollow powder that is further refined than conventional hollow glass spheres, particularly an inorganic hollow powder that is refined and has high purity and low segregation of hollow ratio.
  • the obtained inorganic hollow powder is useful for the production of electronic parts, wire coating materials, semiconductor encapsulants, varnishes and the like.
  • the inorganic hollow powder of the present invention contains 60 to 100% by mass of a hollow particle powder having a particle hollow ratio of 60 to 80% by volume, and 5% of a hollow particle powder having a particle hollow ratio of 0 to 20% by volume. It is contained by mass% or less (including 0 mass%). If the hollowness exceeds 80% by volume, the shell thickness of the particles becomes thin and the particle strength becomes weak, and the particles may be broken during handling of the powder or kneading with rubber or resin. In addition, in the impedance characteristics, when the hollow particle having a particle hollow ratio of 60 to 80% by volume is less than 60% by mass, a uniform resin molded body can be produced when segregation of the hollow particle for each hollow ratio occurs. Becomes difficult.
  • the inorganic hollow powder of the present invention preferably contains 70 to 90% by mass of a hollow particle powder having a particle hollow ratio of 60 to 80% by volume, and is a hollow particle having a particle hollow ratio of 0 to 20% by volume. It is preferable to contain 3% by mass or less (including 0% by mass) of the powder.
  • the hollow particles in the inorganic hollow powder of the present invention have shells on the surface layer of the particles, and the inside of the particles has a hollow structure. Basically, it is single-pored and has a different structure from porous hollow particles. Porous hollow particles do not sufficiently exhibit the effect of low dielectric properties, which is a feature of the hollow particles of the present invention.
  • the hollow ratio can be defined as the content of closed cells in the particle, and can be calculated from the ratio of the measured value of the particle density to the theoretical density of the particle.
  • the degree of hollowness of the hollow particles can also be measured from the relationship between the particles and the film thickness by a scanning electron microscope.
  • the portion corresponding to closed cells is 70% by volume, and thus the volume of the bubble part is 187.56 ⁇ m 3 and the radius is 3.55 ⁇ m. It becomes. Therefore, the thickness of the shell containing closed cells is calculated as 0.45 ⁇ m from the difference between the radius of the hollow particles and the radius of the closed cells.
  • the relationship between such particles and shell thickness is that the resin hollow product obtained by mixing and curing the inorganic hollow powder of the present invention with resin is cut and polished, and the inorganic hollow particles exposed on the polished surface are cut.
  • the surface can be imaged with a scanning electron microscope, and can be determined by measuring the shell thickness of any 500 particles.
  • Hollow ratio distribution is measured by stirring and dispersing / sedimentation of inorganic hollow powder in an aqueous sucrose solution with a specific gravity of 1.3.
  • the suspended matter and sediment are collected, washed, dried and weighed, and less than 40% by volume.
  • the distribution of is calculated.
  • the cross section of the sediment is observed with a scanning electron microscope, the hollow ratio is obtained from the particle diameter and film thickness, and the mass frequency of 20% by volume or less is calculated.
  • the suspended matter is further stirred and dispersed and settled in an alcohol aqueous solution having a liquid specific gravity of 0.9, and the suspended matter and sediment are collected, washed, dried and weighed to calculate a distribution of 60% by volume or more and less.
  • the cross section of the suspended matter is observed with a scanning electron microscope, the hollow ratio is obtained from the particle diameter and film thickness, and the mass frequency of 80% by volume or less is calculated.
  • the maximum particle size of the inorganic hollow powder of the present invention is 25 ⁇ m or less, preferably 20 ⁇ m or less.
  • the maximum particle size exceeds 25 ⁇ m, for example, when a resin molded body is used, the smoothness of the surface is impaired, which causes deterioration of the appearance and deterioration starting from the uneven portion.
  • the maximum particle diameter exceeds 25 ⁇ m, when used as an interlayer insulating material for a multilayer substrate or a filler for a resist material, it cannot be accommodated in a predetermined layer thickness, and various problems such as short-circuiting and disconnection of a conductive part are caused. There is a risk of inviting.
  • the maximum particle size can be measured, for example, using a laser diffraction scattering method particle size distribution analyzer (trade name “LS-230”) manufactured by Beckman Coulter.
  • the average particle size is not particularly limited, but is preferably about 1/5 times the maximum particle size.
  • the specific surface area of the inorganic hollow powder of the present invention is 30 m 2 / g or less, preferably 20 m 2 / g or less.
  • the specific surface area exceeds 30 m 2 / g or more, for example, when the varnish is formed, the viscosity increases, and it may be difficult to perform high filling, and the moldability may be deteriorated.
  • the specific surface area increases, the water absorption also increases, and the moisture resistance reliability may decrease when resin molding is performed.
  • the average sphericity of the inorganic hollow powder of the present invention is 0.85 or more. If the average sphericity is less than 0.85, the mixing with the resin and the fluidity of the resin composition are problematic. Particularly preferably, the average sphericity is 0.90 or more.
  • the average sphericity is measured by measuring the projected area (A) and perimeter (PM) of a particle from a scanning electron micrograph, and assuming that the area of a perfect circle with respect to the perimeter (PM) is (B), the sphericity of the particle Is represented as A / B.
  • the material of the inorganic hollow powder is not particularly limited, and examples thereof include silica, alumina, zirconia, titania, and the like, and a composite oxide containing at least one of these components as a constituent component.
  • amorphous silica is preferable because it is excellent in strength, low thermal expansion, and low dielectric properties.
  • the purity of the amorphous silica is preferably such that the content of silicon dioxide (SiO 2 ) is 99.0% by mass or more. In the case of a complex oxide having two or more components, the component constituting the complex oxide is not an impurity.
  • the SiO 2 content is measured by, for example, an energy dispersive X-ray fluorescence analyzer (EDX), an atomic absorption photometer (AAS), a plasma emission spectrometer (ICP), a fluorescent X-ray analyzer (XRF), or the like.
  • EDX energy dispersive X-ray fluorescence analyzer
  • AS atomic absorption photometer
  • ICP plasma emission spectrometer
  • XRF fluorescent X-ray analyzer
  • the inorganic hollow powder is heated and dissolved in a mixed solution of hydrogen fluoride and perchloric acid (20: 1 volume ratio), diluted with pure water, and then an atomic absorption photometer (for example, Shimadzu Corporation). ).
  • the amorphous ratio is preferably 100 to 99.0%.
  • the amorphous ratio of amorphous silica is determined by X-ray diffraction analysis using a powder X-ray diffractometer (for example, RIGAKU (“Model Mini Flex”)) with CuK ⁇ ray 2 ⁇ in the range of 26 ° to 27.5 °.
  • RIGAKU Powder X-ray diffractometer
  • CuK ⁇ ray 2 ⁇ in the range of 26 ° to 27.5 °.
  • crystalline silica has a main peak at 26.7 °, but there is no peak in amorphous silica.
  • amorphous ratio (%) (1-crystalline silica mixing ratio) ⁇ 100.
  • the inorganic hollow powder of the present invention is preferably treated with a surface treatment agent such as a silane coupling agent.
  • a surface treatment agent such as a silane coupling agent.
  • the surface of the inorganic powder is hydrophilic, the dispersibility in a hydrophobic dispersion medium such as a resin or an organic solvent is not good. Therefore, when the surface is treated with a surface treatment agent, the dispersibility is improved. In addition, when treated with a surface treatment agent, adhesion to rubber or resin, peel strength, and the like are also improved.
  • the amount of the surface treatment agent used is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the inorganic hollow powder.
  • a silane coupling agent As the surface treatment agent, a silane coupling agent, an aluminum coupling agent, a titanate coupling agent, a Zr chelate, or the like can be used.
  • the silane coupling agent include epoxy silanes such as ⁇ -glycidoxypropyltrimethoxysilane and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane; aminopropyltriethoxysilane, ureidopropyltriethoxy Aminosilanes such as silane and N-phenylaminopropyltrimethoxysilane; hydrophobic silane compounds such as phenyltrimethoxysilane, methyltrimethoxysilane and octadecyltrimethoxysilane; vinylsilanes such as vinyltriethoxysilane and vinyltrimethoxysilane; mercaptosilane Etc.
  • an inorganic raw material powder having a pore volume of 0.1 to 1.0 ml / g is mixed with a powder concentration of 50 to 500 g in a high temperature flame and a low temperature flame formed by a burner. This is a method of collecting after spheroidizing and hollowing by supplying at / Nm 3 .
  • the pore volume of the inorganic raw material powder exceeds 1.0 ml / g, spheroidization and / or hollowing cannot be achieved, resulting in porosity, and the pore volume is less than 0.1 ml / g. Then, hollowing cannot be achieved, and it becomes solid.
  • the preferred pore volume is 0.2 to 0.8 ml / g.
  • the maximum particle size of the inorganic raw material powder is 10 ⁇ m or less. If it exceeds 10 ⁇ m, the particle size when hollowed out exceeds 25 ⁇ m, and the inorganic hollow powder of the present invention cannot be produced.
  • a preferred maximum particle size is 1.0 to 8.0 ⁇ m.
  • the powder concentration when supplying the inorganic raw material powder is less than 50 g / Nm 3 , the powder is partially overheated, so that hollowing is insufficient and hollow particles are hardly formed. If it is 500 g / Nm 3 or more, dispersion is insufficient and uniform heating cannot be achieved, and spheroidization and hollowing are insufficient, so that the inorganic hollow powder of the present invention cannot be produced.
  • the powder concentration of the supply of the inorganic raw material powder is preferably 100 to 300 g / Nm 3 .
  • the inorganic raw material powder is supplied from a raw material supply pipe separate from the burner.
  • a method for supporting the inorganic raw material powder on the supporting gas for example, a known method such as supplying the inorganic raw material powder cut from the table feeder together with the supporting gas from the raw material supply pipe may be used.
  • the inorganic raw material powder can be supported on one or both of a combustible gas and a combustion-supporting gas.
  • the method of supporting on any one of the gases is preferably the method of supporting on a combustion-supporting gas, and it is easy to achieve the object of the present invention.
  • the raw material supply pipe of the present invention has a donut-like structure having a slit width of 0.1 to 2.0 mm. If the doughnut-shaped structure is not used, the distribution of the ejection speed becomes large at the wall surface portion and the center portion of the supply pipe. Although the velocity distribution can be suppressed by reducing the supply pipe diameter, the pressure loss is large and it is difficult to eject the inorganic raw material powder. Even if the slit width is less than 0.1 mm, the pressure loss is similarly large, and it is difficult to eject the inorganic raw material powder.
  • the raw material supply pipe preferably has a donut-like structure having a slit width of 0.5 to 1.5 mm.
  • the high temperature flame and the low temperature flame are formed by supplying a combustible gas and a combustion supporting gas to each burner.
  • Each burner is arranged in order from the inside to surround the raw material supply pipe, high temperature flame burner group, low temperature flame burner group with an angle to the raw material supply pipe side, and adjusting the angle of each burner group, the inorganic raw material
  • the residence time of the powder in the flame can be controlled.
  • Each burner group consists of 2-8. One burner group cannot uniformly heat all of the inorganic raw material powders. If the number of burner groups is nine or more, flame temperature control becomes difficult. Preferably, there are 3 to 6 burner groups.
  • the combustible gas for example, one or more mixed gases selected from the group consisting of hydrocarbon gases such as methane, ethane, acetylene, propane, butane, and propylene, and hydrogen gas are used.
  • the combustion-supporting gas any gas having any component composition can be used as long as it contains oxygen.
  • the adjustment control of the flame temperature can be controlled by adjusting the ratio of the amount of combustible gas and the amount of combustible gas. It is also possible by adjusting and controlling the oxygen concentration in the combustion-supporting gas.
  • the temperature of the high temperature flame is 1700-2200 ° C. If it is less than 1700 ° C., it is difficult to make it spherical.
  • the temperature of the high temperature flame is preferably 1800 to 2000 ° C.
  • the temperature of the low temperature flame is 1000-1400 ° C. If it is less than 1000 degreeC, the bubble expansion effect is not acquired and the inorganic hollow powder of this invention cannot be manufactured. If it exceeds 1400 ° C., the temperature close to the softening temperature of the inorganic raw material powder will continue, and bubbles will be degassed and it will be difficult to make them hollow.
  • the temperature of the low temperature flame is preferably 1100 to 1300 ° C.
  • the furnace for forming the flame may be either a vertical furnace or a horizontal furnace, but the above burner is placed at the top of the furnace from the viewpoints of suppressing adhesion of inorganic hollow powder to the furnace body, flame stability, operational stability, etc.
  • a vertical furnace with a lower part connected to the collection system is preferred.
  • a dust collector is installed in the collection system, and the produced inorganic hollow powder is sucked, transported and collected in the collection system by a blower provided on the exhaust side, and classified as necessary. Examples of the dust collector include a cyclone, an electric dust collector, and a bag filter.
  • the burner structure which can be used.
  • the average sphericity of the inorganic hollow powder can be adjusted and controlled mainly by controlling the temperature of the high-temperature flame. Further, the maximum particle size and specific surface area of the inorganic hollow powder can be adjusted and controlled mainly by the maximum particle size of the inorganic raw material powder and the powder concentration at the time of supplying the inorganic raw material powder.
  • the hollow ratio of the inorganic hollow powder can be adjusted and controlled by controlling the temperature of the low-temperature flame and the powder concentration at the time of supplying the inorganic raw material powder.
  • the flame temperature is increased and the inorganic raw material powder is sufficiently heated, so that an inorganic hollow powder having a high average sphericity can be obtained.
  • the flame temperature of the low-temperature flame burner is increased, the expansion effect of the inorganic raw material powder is increased, and an inorganic hollow powder having a large hollow ratio can be obtained. Distribution occurs in the state, and an inorganic hollow powder having a small hollow ratio is generated.
  • the resin composition of the present invention is one in which the inorganic hollow powder of the present invention is contained in rubber and / or resin.
  • the content of the inorganic hollow powder varies depending on the purpose and is, for example, 1 to 97% by mass, preferably 5 to 95% by mass.
  • Examples of the rubber in the resin composition of the present invention include natural rubber, polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), polyisoprene rubber (IR), butyl rubber (IIR), and nitrile-butadiene copolymer. Examples thereof include polymer rubber (NBR).
  • BR polybutadiene rubber
  • SBR styrene-butadiene copolymer rubber
  • IR polyisoprene rubber
  • IIR butyl rubber
  • NBR polymer rubber
  • Examples of the resin in the resin composition of the present invention include epoxy resin, phenol resin, furan resin, unsaturated ester resin, xylene resin, silicone resin, melamine resin, urea resin, unsaturated polyester, fluororesin, BT resin (bismaleimide). ⁇ Triazine resin), polyamide such as polyimide, polyamideimide, polyetherimide, polyester such as polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, wholly aromatic polyester, polysulfone, liquid crystal polymer, polyethersulfone, polycarbonate, maleimide modified resin, Examples include ABS resin, AAS (acrylonitrile-acrylic rubber / styrene) resin, AES (acrylonitrile / ethylene / propylene / diene rubber / styrene) resin, and the like.
  • AAS acrylonitrile-acrylic rubber / styrene
  • AES acrylonitrile /
  • Examples of the resin for multilayer substrates in the resin composition of the present invention include polyimide resins such as modified polyimide resins; fluorine resins; low dielectric constant resins such as polyphenylene oxide, polyphenylene ether, and BT resin; polyimide, polyester, polyamide In particular, resins having good heat resistance and mechanical strength such as aromatic polyamide, polyamideimide, polyetherimide, etc. can be used.
  • polyimide resins such as modified polyimide resins
  • fluorine resins such as polyphenylene oxide, polyphenylene ether, and BT resin
  • polyimide polyester, polyamide
  • resins having good heat resistance and mechanical strength such as aromatic polyamide, polyamideimide, polyetherimide, etc. can be used.
  • an epoxy resin having two or more epoxy groups in one molecule is preferable.
  • Specific examples include phenol novolac epoxy resins, orthocresol novolac epoxy resins, epoxidized phenol and aldehyde novolac resins, glycidyl ethers such as bisphenol A, bisphenol F and bisphenol S, phthalic acid, Glycidyl ester acid epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, alkyl-modified polyfunctional epoxy resin obtained by reaction of polybasic acid such as dimer acid and epochlorohydrin, ⁇ -naphthol novolac-type epoxy resin, 1,6-dihydroxynaphthalene-type epoxy resin, 2,7-dihydroxynaphthalene-type epoxy resin, bishydroxybiphenyl-type epoxy resin, and bromine to impart flame retardancy Androgenic is introduced epoxy resin or the like.
  • orthocresol novolac type epoxy resins from the viewpoint of moisture resistance and solder reflow resistance, orthocresol novolac type epoxy resins, bishydroxybiphenyl type epoxy resins, epoxy resins having a naphthalene skeleton, and the like are preferable.
  • a curing agent is used, but the curing agent is not particularly limited as long as it is cured by reacting with the epoxy resin.
  • the curing agent is not particularly limited as long as it is cured by reacting with the epoxy resin.
  • the curing agent is not particularly limited as long as it is cured by reacting with the epoxy resin.
  • the curing agent is not particularly limited as long as it is cured by reacting with the epoxy resin.
  • the curing agent is not particularly limited as long as it is cured by reacting with the epoxy resin.
  • the curing agent is not particularly limited as long as it is cured by reacting with the epoxy resin.
  • the curing agent is not particularly limited as long as it is cured by reacting with the epoxy resin.
  • the curing agent is not particularly limited as long as it is cured by reacting with the epoxy resin.
  • a curing accelerator can be blended to promote the reaction between the epoxy resin and the curing agent.
  • the curing accelerator include 1,8-diazabicyclo (5,4, 0) undecene-7, triphenylphosphine, benzyldimethylamine, 2-methylimidazole and the like.
  • the resin composition of the present invention may contain the following components as necessary. That is, as a stress reducing agent, silicone rubber, polysulfide rubber, acrylic rubber, butadiene rubber, rubbery substances such as styrene block copolymers and saturated elastomers, various thermoplastic resins, resinous substances such as silicone resins, Examples thereof include resins obtained by modifying part or all of epoxy resins and phenol resins with amino silicone, epoxy silicone, alkoxy silicone, and the like.
  • silane coupling agents include epoxy silanes such as ⁇ -glycidoxypropyltrimethoxysilane and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane; aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N— And aminosilanes such as phenylaminopropyltrimethoxysilane; hydrophobic silane compounds such as phenyltrimethoxysilane, methyltrimethoxysilane, and octadecyltrimethoxysilane; mercaptosilane;
  • the surface treatment agent include Zr chelates, titanate coupling agents, and aluminum coupling agents.
  • Examples of the flame retardant aid include Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 and the like.
  • Examples of the flame retardant include halogenated epoxy resins and phosphorus compounds.
  • Examples of the colorant include carbon black, iron oxide, dye, and pigment.
  • a release agent such as wax can be added. Specific examples include natural waxes, synthetic waxes, metal salts of linear fatty acid salts, acid amides, esters, paraffins and the like.
  • ion trapping agents additive of various ion trapping agents is effective when moisture resistance reliability and high temperature storage stability are required.
  • Specific examples of ion trapping agents include Kyowa Chemical Co., Ltd. (trade names; “DHF-4A”, “KW-2000”, “KW-2100”, etc.) and Toa Gosei Chemical Industries Co., Ltd. (trade name; “IXE-”). 600 "etc.).
  • the resin composition of the present invention is obtained by, for example, blending a predetermined amount of each of the above materials with a blender, a Henschel mixer or the like, then kneading with a heating roll, kneader, uniaxial or biaxial extruder, etc. Can be manufactured.
  • the above materials and organic solvents are mixed to make a varnish, but these materials can be mixed by mixing machines such as a raking machine, bead mill, three rolls, stirring mixer, etc. Is used.
  • After forming the varnish it is preferable to remove bubbles in the varnish by vacuum degassing.
  • an antifoaming agent such as silicone, acrylic, or fluorine
  • the apparatus used for producing the inorganic hollow powder of the present invention is composed of three high-temperature flame burners inclined at 20 degrees with respect to the raw material supply pipe and three low-temperature flame burners inclined at 10 degrees with respect to the raw material supply pipe. It is installed at the top of the mold furnace and the lower part of the furnace is connected to a collection system (cyclone, bag filter). The inorganic hollow powder was sucked and transported with a combustion exhaust gas by a blower and collected by a cyclone and a bag filter.
  • Examples 1 to 10 and Comparative Examples 1 to 8 A raw material supply pipe having a slit width of 0.1 to 1.5 mm was used. Hot flame burner group, a 1 ⁇ 4Nm 3 / Hr of LPG per one burner to form a high temperature flame oxygen is supplied to the 3 ⁇ 15Nm 3 / Hr to. Further, the low temperature flame burner group formed a low temperature flame by supplying LPG of 0.5 to 3 Nm 3 / Hr and oxygen enriched air of 1 to 10 Nm 3 / Hr per burner.
  • the inorganic raw material powder (silica) shown in Table 1 was supplied from a raw material supply pipe at a powder concentration of 50 to 500 g / Nm 3 and sprayed into a high temperature flame and a low temperature flame.
  • a hollow particles mean hollow particles having a hollow ratio of 60 to 80% by volume
  • B hollow particles mean hollow particles having a hollow ratio of 0 to 20% by volume.
  • the measuring method of various physical properties is as follows. (1) Pore volume The pore volume was determined by creating an adsorption isotherm of nitrogen at 7 8 K using an automatic specific surface area / pore distribution measuring device (manufactured by Micromeritics, TriStar 3000). The pore distribution curve was prepared by the BJH method.
  • Specific surface area The specific surface area measured the multipoint method specific surface area by BET method using the automatic specific surface area / pore distribution measuring apparatus (The product made by Micromeritics, TriStar3000). (7) Average sphericity The average sphericity of the hollow particles was measured by the method described above.
  • the glass cloth was impregnated with varnish, heated in an electric furnace at 150 ° C. for 5 minutes, and then cut to obtain a prepreg.
  • This prepreg is piled up to the required thickness, and a laminate is manufactured by heating molding press for 200 minutes at a pressure (gauge pressure) of 5.0 MPa and a temperature of 180 ° C., and the coefficient of thermal expansion and flame retardancy are compared.
  • the dielectric constant was measured.
  • a microstrip line wiring board was prepared so that the characteristic impedance was 50 ⁇ , and the variation in the characteristic impedance was measured.
  • Table 1 In addition, when using a varnish for a laminated board, it is preferable from a point which shape
  • Varnish viscosity Measured using an E-type viscometer manufactured by Tokimec Co., Ltd. under conditions of a cone rotor of 3 ° R14, a temperature of 30 ° C., and a rotor rotational speed of 2.5 rpm.
  • Thermal expansion coefficient of laminated plate A test piece having a diameter of 5 mm and a height of 10 mm was prepared from the laminated plate, and measured according to JIS K7197 standard using a thermomechanical analyzer (TMA) manufactured by Shimadzu Corporation.
  • TMA thermomechanical analyzer
  • Flame retardancy of laminate A test piece of 12.7 mm ⁇ 127 mm ⁇ 1 mm was prepared from the laminate and measured according to UL-94 standards.
  • Relative dielectric constant of the laminate A test piece having a diameter of 100 mm and a thickness of 2 mm was prepared from the laminate, and measured according to the JIS K6911 standard using a dielectric constant measuring device manufactured by Hewlett-Packard Company.
  • Characteristic impedance The substrate thickness (h) was 0.1 ⁇ 0.02 mm and the conductor thickness (t) was 0.016 ⁇ 0.002 mm so that the characteristic impedance would be 50 ⁇ , and measured in (4).
  • the thermal expansion coefficient is 30 ppm or less
  • the flame retardancy is V-0
  • the relative dielectric constant is 3.3 or less (25 ° C., 1 GHz).
  • the inorganic hollow powder of the present invention is used as a filler for resin molded parts such as molding compounds for automobiles, portable electronic devices, home appliances, etc., as well as putty, sealing materials, lightweight outer wall materials and the like.
  • the resin composition of the present invention is impregnated into a glass woven fabric, glass nonwoven fabric, or other organic base material and cured.
  • a prepreg for a printed circuit board or one or a plurality of prepregs is thermoformed together with a copper foil or the like.
  • it is used for manufacturing electronic parts, electric wire coating materials, semiconductor encapsulants, varnishes and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Compounds (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Abstract

L'invention porte sur une poudre de particules inorganiques creuses, qui présente une dimension de particules réduite et une pureté élevée et qui est réduite dans le caractère homogène du pourcentage de creux. L'invention porte également sur un procédé de fabrication de la poudre ; et sur une composition de résine contenant la poudre de particules inorganiques creuses. La poudre de particules inorganiques creuses inclut de 60 à 100 % en masse de particules creuses présentant un pourcentage de creux de 60 à 80 % en volume et jusqu'à 5 % en masse (y compris 0 % en masse) de particules creuses présentant un pourcentage de creux de 0 à 20 % en volume. Dans la poudre, les particules creuses présentent un diamètre de particule maximal de 25 µm ou moins, une aire de surface spécifique telle que déterminée par la méthode BET de 30 m2/g ou moins, et une sphéricité moyenne de 0,85 ou plus. Dans le procédé de fabrication de la poudre de particules inorganiques creuses, une poudre de particules inorganiques creuses présentant un volume de pores de 0,1 à 1,0 mL/g et un diamètre de particule maximal de 10 µm ou moins, est introduite à une concentration de poudre de 50 à 500 g/Nm3 via un conduit d'alimentation en matière brute d'une structure en beignet présentant une largeur de fente de 0,1 à 2,0 mm, et est rendue creuse par une flamme.
PCT/JP2009/054086 2008-03-05 2009-03-04 Poudre de particules inorganiques creuses, son procédé de fabrication et composition la contenant Ceased WO2009110514A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2010501935A JP5519489B2 (ja) 2008-03-05 2009-03-04 無機質中空粉体の製造方法及びそれ用いた樹脂組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-054370 2008-03-05
JP2008054370 2008-03-05

Publications (1)

Publication Number Publication Date
WO2009110514A1 true WO2009110514A1 (fr) 2009-09-11

Family

ID=41056067

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/054086 Ceased WO2009110514A1 (fr) 2008-03-05 2009-03-04 Poudre de particules inorganiques creuses, son procédé de fabrication et composition la contenant

Country Status (2)

Country Link
JP (1) JP5519489B2 (fr)
WO (1) WO2009110514A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010285307A (ja) * 2009-06-10 2010-12-24 Denki Kagaku Kogyo Kk 非晶質シリカ質粉末およびその製造方法、用途
JP2011021068A (ja) * 2009-07-14 2011-02-03 Kao Corp 低誘電樹脂組成物
WO2011093079A1 (fr) * 2010-01-28 2011-08-04 三井化学株式会社 Composite métal-résine
JP2011225756A (ja) * 2010-04-21 2011-11-10 Kao Corp 低誘電樹脂組成物
US8785522B2 (en) 2009-07-14 2014-07-22 Kao Corporation Low-permittivity resin composition
JP2019182715A (ja) * 2018-04-13 2019-10-24 デンカ株式会社 非晶質シリカ粉末、樹脂組成物、及び半導体封止材

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005206436A (ja) * 2004-01-26 2005-08-04 Denki Kagaku Kogyo Kk 球状無機質中空粉体およびその製造方法、樹脂組成物
JP2006062902A (ja) * 2004-08-26 2006-03-09 Denki Kagaku Kogyo Kk 球状無機質中空粉体およびその製造方法、樹脂組成物
WO2007125891A1 (fr) * 2006-04-24 2007-11-08 Denki Kagaku Kogyo Kabushiki Kaisha Particule creuse inorganique, son procede de production et composition la contenant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005206436A (ja) * 2004-01-26 2005-08-04 Denki Kagaku Kogyo Kk 球状無機質中空粉体およびその製造方法、樹脂組成物
JP2006062902A (ja) * 2004-08-26 2006-03-09 Denki Kagaku Kogyo Kk 球状無機質中空粉体およびその製造方法、樹脂組成物
WO2007125891A1 (fr) * 2006-04-24 2007-11-08 Denki Kagaku Kogyo Kabushiki Kaisha Particule creuse inorganique, son procede de production et composition la contenant

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010285307A (ja) * 2009-06-10 2010-12-24 Denki Kagaku Kogyo Kk 非晶質シリカ質粉末およびその製造方法、用途
JP2011021068A (ja) * 2009-07-14 2011-02-03 Kao Corp 低誘電樹脂組成物
US8785522B2 (en) 2009-07-14 2014-07-22 Kao Corporation Low-permittivity resin composition
WO2011093079A1 (fr) * 2010-01-28 2011-08-04 三井化学株式会社 Composite métal-résine
JPWO2011093079A1 (ja) * 2010-01-28 2013-05-30 三井化学株式会社 金属樹脂複合体
JP2011225756A (ja) * 2010-04-21 2011-11-10 Kao Corp 低誘電樹脂組成物
JP2019182715A (ja) * 2018-04-13 2019-10-24 デンカ株式会社 非晶質シリカ粉末、樹脂組成物、及び半導体封止材

Also Published As

Publication number Publication date
JP5519489B2 (ja) 2014-06-11
JPWO2009110514A1 (ja) 2011-07-14

Similar Documents

Publication Publication Date Title
JP5414027B2 (ja) 無機質中空粉体、その製造方法及びそれを用いた組成物
JP5411497B2 (ja) 無機質中空粉体、その製造方法及び該無機質中空粉体を含有する組成物
JP5358273B2 (ja) 無機質中空粉体、その製造方法及びその用途
JP4112540B2 (ja) 球状無機質中空粉体の製造方法。
JP4244323B2 (ja) 球状無機質中空粉体およびその製造方法、樹脂組成物
JP5294015B2 (ja) セラミックス粉末及びその用途
JP5864299B2 (ja) 樹脂組成物
JP5519489B2 (ja) 無機質中空粉体の製造方法及びそれ用いた樹脂組成物
US20240308858A1 (en) Hollow silica particles and method for producing same
JP5584692B2 (ja) プリプレグ
JP5606740B2 (ja) シリカ質粉末、その製造方法及び用途
Sethuraman et al. Surface free energy and dielectric properties of vinyltriethoxysilane functionalized SBA‐15‐reinforced unsaturated polyester nanocomposites
Zhang et al. Polyhedral oligosilsesquioxane-modified boron nitride enhances the mechanical properties of polyimide nanocomposites
JP2006273969A (ja) 硬化可能な組成物およびその用途
JP2019182715A (ja) 非晶質シリカ粉末、樹脂組成物、及び半導体封止材
TW202407016A (zh) 液狀組成物、預浸體、附樹脂之金屬基材、配線板及氧化矽粒子
JP5345787B2 (ja) 半導体封止材用シリカ・アルミナ複合酸化物超微粉末の製造方法
JP2006273948A (ja) 熱伝導性樹脂組成物およびその用途
WO2024237111A1 (fr) Poudre de silice sphérique et procédé de production de poudre de silice sphérique
US20250100890A1 (en) Method for producing spherical silica powder
KR20250008054A (ko) 실리카 입자 분산액
TW202335000A (zh) 電磁干擾抑制材料
TW202402962A (zh) 液狀組成物、預浸體、附樹脂之金屬基材、及配線板
JP2021143089A (ja) 無機酸化物中空粒子
CN117730054A (zh) 球状二氧化硅粉末及球状二氧化硅粉末的制造方法

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: 09718277

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2010501935

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09718277

Country of ref document: EP

Kind code of ref document: A1