WO2008044462A1 - Procédé de production de microparticule de silicone creuse, et microparticule de silicone creuse produite par le procédé - Google Patents

Procédé de production de microparticule de silicone creuse, et microparticule de silicone creuse produite par le procédé Download PDF

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Publication number
WO2008044462A1
WO2008044462A1 PCT/JP2007/068523 JP2007068523W WO2008044462A1 WO 2008044462 A1 WO2008044462 A1 WO 2008044462A1 JP 2007068523 W JP2007068523 W JP 2007068523W WO 2008044462 A1 WO2008044462 A1 WO 2008044462A1
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Prior art keywords
particles
group
hollow silicone
weight
organic polymer
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PCT/JP2007/068523
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English (en)
Japanese (ja)
Inventor
Akira Takaki
Takamitu Amano
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Kaneka Corporation
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Publication of WO2008044462A1 publication Critical patent/WO2008044462A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes

Definitions

  • the present invention relates to a method for producing hollow silicon fine particles having a volume average particle size of 0.001-1, 1 m with a small amount of residual metal, and hollow silicone fine particles obtained by the production method. It is.
  • Patent Document 3 silicates such as alkali metals and alkali-soluble inorganic compounds are made into colloidal particles with an alkaline aqueous solution of pHIO or higher, and after removing some of the elements other than silicon and oxygen in the particles, A method of coating these particles with a hydrolyzable organosilicon compound or the like is disclosed.
  • Patent Document 4 when tetraalkoxysilane solubilized in water is emulsified into an organic solvent with a surfactant, hydrolysis and condensation reactions occur, and micron-sized hollow silica particles are synthesized when the water content is high. It is disclosed that it can be done.
  • Patent Document 5 discloses a method for producing hollow silica by precipitating active silica from an alkali metal silicate on a core made of a material other than silica and removing the core.
  • the metal ion component remaining in the particles causes side effects such as a decrease in electrophotographic sensitivity and an increase in residual potential. Reduction of residual metal ions has been an issue (see Patent Document 6).
  • Patent Document 1 JP-A 63-258642
  • Patent Document 2 JP-A-6-330606
  • Patent Document 3 JP-A-7-133105
  • Patent Document 4 JP-A-11 29318
  • Patent Document 5 Special Table 2000-500113
  • Patent Document 6 Japanese Unexamined Patent Application Publication No. 2002-105122
  • the present invention relates to a method for producing hollow silicone fine particles having a volume average particle size of 1 am or less, which has a low residual metal content, good productivity, is hard to break and has a narrow particle size distribution, and It aims at providing the hollow silicone type microparticles
  • the present invention relates to 1) a step of coagulating a latex of core-shell particles (C) obtained by coating organic polymer particles (A) with a silicone compound (B) using an organic solvent (D). ! /, Relates to a method for producing hollow silicone fine particles, characterized in that the organic polymer (A) is removed.
  • 2) .Silicone compound (B) is composed of SiO units, RSiO units (wherein R is the number of carbon atoms)
  • R is at least one of an alkyl group having 1 to 4 carbon atoms, an aromatic group having 6 to 24 carbon atoms, a bur group, a ⁇ (meth) attaryloxypropyl group, or an SH group.
  • the present invention relates to the method for producing hollow silicone fine particles according to 1), which is characterized by the following.
  • the organic polymer particles (A) and the silicone compound (B) have a weight ratio of 2/98 to 95/5, according to any one of 1) to 3)
  • the present invention relates to a method for producing hollow silicone fine particles.
  • the present invention relates to hollow silicone fine particles obtained by the production method according to any one of 1) to 4), wherein the residual Na content is 50 ppm or less and the Ca content is 10 ppm or less.
  • a hollow silicone having a volume average particle size of 1 am or less with a small amount of residual metal and good productivity and a hard to break particle size distribution is narrow.
  • System fine particles can be obtained.
  • the present invention relates to a step of coagulating a latex of core-shell particles (C) obtained by coating organic polymer particles (A) with a silicone compound (B) using an organic solvent (D).
  • the present invention provides hollow silicone-based fine particles characterized by removing the organic polymer (A).
  • the shape of the organic polymer particles (A) used in the present invention is not particularly limited, and those having any shape such as a spherical shape, a continuous spherical shape, a rugby ball shape, a needle shape, a scale shape, a plate shape, and a polyhedral shape are used. it can. From the viewpoint that the hollow silicone fine particles to be obtained have a high porosity and are easy to produce by screening, a spherical shape is preferred.
  • the hollow silicone fine particles can be made into spherical hollow particles having a spherical cavity.
  • the composition of the organic polymer particles (A) of the present invention is not limited, and may be, for example, a soft polymer represented by polybutyl acrylate, polybutadiene, butyl acrylate-butadiene copolymer, and the like. Even hard polymers such as butyl acrylate styrene copolymer, butyl acrylate acrylonitrile copolymer, butyl acrylate styrene acrylonitrile copolymer, and styrene acrylonitrile copolymer can be used without any problem. Of these, polybutyl acrylate, which is preferred by a soft polymer, is more preferred because of its removability in the subsequent coagulation process.
  • the method for producing the organic polymer particles (A) of the present invention is not particularly limited, and a known method such as an emulsion polymerization method, a micro suspension polymerization method, a mini emulsion polymerization method, or an aqueous dispersion polymerization method can be used. .
  • the emulsion polymerization method is particularly preferred because it is easy to control the particle size and is suitable for industrial production.
  • a radical polymerization initiator can be used for the polymerization of the organic polymer particles (A).
  • radical polymerization initiators include, for example, tamenno, id-peroxide, tert-butylhydride peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, paramentane-hydride peroxide, etc.
  • Inorganic peroxides such as organic peroxides, potassium persulfate and ammonium persulfate, and azo compounds such as 2, 2'-azobisisobutyronitrile, 2, 2 'azobis 2,4 dimethylvaleronitrile, etc. Are listed.
  • the amount of the radical polymerization initiator used is 0.00 per 100 parts by weight of the raw material monomer. To 3 parts by weight, more preferably 0.01 to 0.5 parts by weight, and even more preferably 0.05 to 0.3 parts by weight.
  • ferrous sulfate, sodium formaldehydesulfoxylate ethylenediaminetetraacetic acid 2Na salt, ferrous sulfate monoglucose sodium pyrophosphate, ferrous sulfate monosodium pyrophosphate sodium monophosphate When the redox system is used, the polymerization can be completed efficiently even at a low polymerization temperature.
  • a chain transfer agent can be used for the polymerization of the organic polymer particles (A).
  • Chain movement Specific examples of the agent include t-dodecyl mercaptan and n-dodecyl mercaptan.
  • the amount of the chain transfer agent used is 0 to 50 parts by weight, more preferably 100 parts by weight of the raw material monomer. 5 to 45 parts by weight, more preferably 10 to 40 parts by weight are preferred.
  • the organic polymer particles (A) of the present invention are preferably non-crosslinked polymers in consideration of the case where removal of the organic polymer performed in a later stage is performed using an organic solvent.
  • the weight average molecular weight of the particles (A) is preferably low.
  • the force S is preferably a weight average molecular weight of less than 30000, and more preferably less than 10,000.
  • a suitable combination of various means such as the use of a chain transfer agent, a high polymerization temperature, and a large amount of initiator can be selected. can do.
  • the lower limit of the weight average molecular weight of the organic polymer particles (A) is not particularly limited, but is approximately 2000 from the viewpoint of the difficulty of synthesis.
  • the weight average molecular weight can be measured, for example, by analysis by gel permeation chromatography (GPC) (polystyrene conversion).
  • the organic polymer particles (A) may contain an organic solvent.
  • the organic solvent contained in the organic polymer particles (A) may be the same as or different from the organic solvent used as the component (D).
  • the organic solvent to be contained in the organic polymer particles (A) is not limited to force S that can preferably use a solvent that is not soluble in water, such as toluene, benzene, xylene, and n-hexane.
  • the amount of the organic solvent to be contained is preferably a ratio of organic polymer / organic solvent power to be contained in a weight ratio of 00/0 to 1/99.
  • a seed polymerization method can be used to narrow the particle size distribution of the organic polymer particles (A). From the viewpoint that the hollow silicone-based particles have a uniform refractive index, it is preferable that the particle size distribution of the organic polymer particles (A) is narrow.
  • the volume average particle diameter of the latex organic polymer particles (A) and core-shell particles (C) can be determined by light scattering or electron microscope observation. Volume average particle size and particle size distribution can be calculated, for example, by LEED & NORTHRUP INSTRUME It can be measured by using MICROTRAC UPA manufactured by NTS.
  • the silicone-based compound (B) serving as the coating in the core-shell particle (C) of the present invention is composed of 1 unit or 2 units selected from the group consisting of Si 2 O 3 units, RSiO units and R 2 SiO units.
  • Examples of the raw material of the SiO unit include silicon tetrachloride, tetraalkoxysilane,
  • Examples thereof include one or more selected from the group consisting of water glass and metal silicate.
  • Specific examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and condensates thereof.
  • R in the RSiO unit is an alkyl group having 1 to 4 carbon atoms or a fragrance having 6 to 24 carbon atoms.
  • R may be selected from a small amount of a bur group, an organic group having a ⁇ - (meth) atalyloxypropyl group or an SH group, and a large amount of an alkyl group or an aromatic group.
  • Examples of the raw material of the RSiO unit include methyltrimethoxysilane and methyltriethoxysilane.
  • R SiO unit of the present invention (R may be selected from the same group as R in the RSiO unit).
  • R SiO single particles are used.
  • the ratio of R SiO units in the silicone compound (B) in the core-shell particles (C) is preferably 20 mol% or less, and more preferably 10 mol%
  • the lower limit of the ratio of R 2 SiO units in the silicone compound (B) is 0 mol%.
  • the ratio of 3/2 is 10 to 100 mol from the viewpoint of the stability of the particle size distribution of the core-shell particles.
  • Power is preferably 0 , more preferably 20 to; more preferably 100 mol%.
  • the weight ratio of the organic polymer particles (A) to the silicone compound (B) is not necessarily limited, but is preferably 2/98 to 95/5. Furthermore, 10/90 to 50/50 force S is more preferable. If the ratio is less than 2/98, the void ratio of the final hollow silicone fine particles may be too low. On the other hand, if the ratio is greater than 95/5, the strength of the hollow silicone fine particles may be insufficient and may break during processing.
  • the volume average particle size of the core-shell particles (C) and the final hollow silicone fine particles of the present invention is not particularly limited, but the point that they can be synthesized stably is easy. , Preferably in the range of 0.001 to 1 ⁇ 111, and more preferably in the range of 0.002 to 0.5 ⁇ m.
  • the particle size distribution of the core-shell particles (C) of the present invention and the final hollow silicone fine particles is not particularly limited. However, if the hollow silicone particles have a uniform refractive index, V The particle size distribution is narrow! / Is better.
  • an emulsifier for example, an emulsifier, a raw material of SiO unit, a raw material of RSiO unit, and a R SiO unit for a mixture of water at 5 to 120 ° C containing organic polymer particles (A) and an acid catalyst.
  • the emulsion may be added all at once or continuously! Although it takes a long time, it is preferable to use continuous addition if importance is attached to the stability and particle size distribution of latex particles! If an acid catalyst is added before the emulsified liquid is added and the addition is continued under conditions where hydrolysis and condensation proceed immediately, the core-shell particles grow over time, and as in normal seed polymerization, What shows a particle size distribution can be obtained. 30 minutes! /, Relatively short of 1 hour! /, And continuous addition of time can achieve both relatively good productivity and narrow particle size distribution.
  • emulsifier that can be used in the present invention, a bay-type emulsifier or a no-one emulsifier can be suitably used.
  • the anionic emulsifier include, for example, sodium alkylbenzene sulfonate, sodium lauryl sulfonate, potassium oleate and the like, particularly sodium dodecylbenzene sulfonate.
  • Specific examples of the nonionic emulsifier include polyoxyethylene nouryl phenyl ether and polyoxyethylene lauryl ether.
  • Acid catalysts that can be used in the present invention include, for example, sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzene sulfonic acid, and aliphatic substituted naphthalene sulfonic acid, and minerals such as sulfuric acid, hydrochloric acid, and nitric acid.
  • sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzene sulfonic acid, and aliphatic substituted naphthalene sulfonic acid
  • minerals such as sulfuric acid, hydrochloric acid, and nitric acid.
  • acids include acids.
  • n-dodecylbenzenesulfonic acid is particularly preferred from the viewpoint of excellent emulsification stability of organosiloxane
  • aliphatic substituted benzenesulfonic acid is particularly preferred! /.
  • the heating for the reaction in producing the core-shell particles (C) is 5 to; 120 ° C is preferred in that an appropriate polymerization rate is obtained, and 20 to 80 ° C is more preferred.
  • the organic polymer (A) is removed in the process of coagulating the latex of the core-shell particles (C) using the organic solvent (D).
  • the step of coagulating the latex using the organic solvent (D) in the present invention is a step of adding an organic solvent to the latex of the core-shell particles to agglomerate the core-shell particles in the latex.
  • a part or substantially all of the organic polymer (A) in the L particle (C) is extracted into the supernatant, and the organic polymer (A) can also remove the core-shell particle (C) force. .
  • an organic solvent (D) is added to the latex of the core-shell particles (C).
  • the supernatant liquid containing the hollow silicone fine particles and the organic polymer is separated by a method such as filtration or centrifugation, and the obtained hollow silicone fine particles are washed as necessary.
  • the hollow silicone fine particles can be obtained.
  • the temperature at which the coagulation step is performed is not particularly limited, and may be performed at room temperature, may be performed while heating, or may be performed while refluxing.
  • the pressure at the time of performing the coagulation step is not particularly limited, and may be performed under atmospheric pressure or may be performed under high pressure.
  • the metal component remaining in the hollow silicone fine particles obtained by the present invention is preferably not more than lOOOppm, more preferably not more than 500ppm, particularly preferably not more than 250ppm as the total amount of contained metals.
  • the Na content is 30 ppm or less, the Ca content power S50 ppm, the Na content power Oppm or less, and the Ca content 10 ppm or less.
  • particles obtained by the method of coagulating with an organic solvent are superior in dispersibility in organic solvents and organic resins as compared with particles obtained by salt coagulation, so filling with various plastics, rubbers, paints, etc. When used as an agent, it can be dispersed well.
  • core-shell particles using organic polymer particles as the core are used. Therefore, when an organic solvent is used in the coagulation step, the core can be removed, and hollow structure particles can be obtained with a small number of steps. Touch with force S.
  • the organic solvent (D) used in the present invention must be capable of coagulating the core-shell particles (C) in the latex and dissolve the organic polymer that becomes the core.
  • preferred organic solvents (D) include water-soluble solvents, water-insoluble solvents, and mixtures thereof include water-soluble solvents such as acetone, methanol, ethanol, propanol, and butanol, methyl ethyl ketone, Non-water soluble solvents such as toluene, benzene, xylene, n-hexane, and mixtures thereof. Acetone and butanol are preferred from the viewpoint of easy availability, economy and operability.
  • the amount of the organic solvent (D) used is preferably (preferably 30 to 600 parts by weight ⁇ more preferably (50 to 300 parts by weight ⁇ special liters) with respect to 100 parts by weight of the core shell particle (C) latex. This amount is preferably 100 to 250 parts by weight. With such a use amount, it is possible to sufficiently coagulate latex and remove organic polymer (soot) while keeping the amount of waste liquid small.
  • the method of adding the organic solvent (D) to the latus status of (C) may be added continuously without any limitation, or may be added intermittently in a plurality of times.
  • the silicone fine particles can be washed with an organic solvent.
  • a known organic solvent can be used for washing without any particular limitation. From the viewpoint of easy availability and economy, a mixture of methanol and hexane is preferred.
  • hollow silicone-based fine particles having a volume average particle size of 111 m or less with a small amount of residual metal and a good productivity with a low productivity and a narrow particle size distribution are obtained. That power S.
  • the hollow silicone fine particles obtained by the production method of the present invention can be used for various applications. Specific examples include fillers for various plastics, rubber, paints, etc., liquid or gas inclusions, chromatographic fillers, abrasives, heat insulating materials, sound insulating materials, absorbents, insulating materials, spacers, etc. Can be mentioned.
  • the electrophotographic photoreceptor, transfer belt, and fixing belt have the property of having a small amount of residual metal. It can also be used as a material for electrical and electronic parts. In addition, it has the property of being hollow and is used as a material for a low refractive index layer of an antireflection film used for a display, etc., or used as a multilayer wiring for a semiconductor integrated circuit. It can also be used as a material for the edge film.
  • the volume average particle diameter of the organic polymer particles and the core-shell particles was measured in a latex state.
  • the volume average particle diameter ( ⁇ m) was measured by a light scattering method using a MICROTRAC UPA manufactured by LEED & NORTHHRUP INSTRUMENTS as a measuring device.
  • the weight average molecular weight of the organic polymer was converted from the GPC measurement data using a calibration curve prepared with a polystyrene standard sample.
  • the ethanol solution of the silicone microparticles that had been coagulated and washed was mixed with an acrylic resin, dissolved, dried, dyed with ruthenium, and observed by TEM.
  • the core-shell structure was judged as ⁇ , the core-shell structure was not! /, And the thing was judged as X.
  • the components of the supernatant after coagulation and washing were quantitatively analyzed.
  • a small amount of the supernatant was dried in a 70 ° C oven, and IR analysis was performed by KBr tablet method (equipment: Perkin Elmer FT—IR Spectrum One) to confirm that the non-volatile component was polybutyl acrylate. .
  • the solid content concentration of the supernatant was obtained, and the amount of polybutyl acrylate removed from this value and the total amount of the supernatant was calculated.
  • the fine particles were quantitatively analyzed in a helium atmosphere using a SPECTO energy dispersive X-ray fluorescence spectrometer XEPOS manufactured by Rigaku Corporation.
  • Isopropyl alcohol is added to 0.5 g of the isolated hollow silicone and 100 g of the dispersion is added. The dispersion state was determined visually. A transparent and uniformly dispersed product was judged as ⁇ , a part of which was agglomerated and clouded ⁇ , and a part of which was clouded and partly settled was judged as X.
  • racemic acid 2N salt 0.005 parts by weight
  • formaldehyde sulfoxylate 0.2 parts by weight
  • Table 1 shows the volume average particle diameter of the core-shell particles and the confirmation results of the core-shell particles.
  • the latex-like core-shell particles are mixed with the organic solvent shown in Table 1.
  • 50 parts by weight of the agent was added and stirred for 5 minutes, and then 150 parts by weight of the remaining organic solvent was added and stirred for 25 minutes. After standing for 3 hours, it separated into a coagulated particle layer and a transparent supernatant layer. A part of this supernatant was used to confirm the amount of organic polymer particles removed from the core-shell particles after solidification.
  • the coagulated particle layer was isolated using a filter paper and dispersed in 300 parts by weight of a mixed solvent of 70% by weight of methanol and 30% by weight of n-hexane. When this dispersion is allowed to stand for 3 hours, it separates into a coagulated particle layer and a transparent supernatant layer.
  • hollow silicone fine particles having a volume average particle diameter of 1 am or less with a small amount of residual metal can be produced. Furthermore, since the production method of the present invention can reduce the number of steps and particles having good productivity are not easily broken, hollow particles having the same particle diameter as the core-shell particles can be obtained. The resulting particles are excellent in dispersibility in organic solvents, and no aggregation or sedimentation is observed! /, So there is no formation of large coarse particles, so the particle size distribution is narrow! / I know that there is. Further, since it is excellent in dispersibility in organic solvents, it can be dispersed well when used as a filler for various plastics, rubbers, paints and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Silicon Polymers (AREA)

Abstract

L'objet de l'invention est un procédé de production d'une microparticule de silicone creuse dont la quantité de métaux résiduels est réduite, qui est facile à produire, qui est difficile à détruire, et qui présente une distribution étroite de diamètre particulaire et un diamètre particulaire à volume moyen de 1 µm ou moins, ainsi qu'une microparticule de silicone creuse produite par le procédé. Ledit procédé de production d'une microparticule de silicone creuse est caractérisé par l'élimination d'un polymère organique (A) dans l'étape de coagulation d'un latex d'une particule avec noyau en coquille (C) comprenant une particule du polymère organique (A) enduite avec un composé siliconé (B) en utilisant un solvant organique (D). L'invention fournit également une microparticule de silicone creuse produite par le procédé.
PCT/JP2007/068523 2006-10-05 2007-09-25 Procédé de production de microparticule de silicone creuse, et microparticule de silicone creuse produite par le procédé WO2008044462A1 (fr)

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JP2006-273775 2006-10-05
JP2006273775 2006-10-05

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008143162A1 (fr) * 2007-05-17 2008-11-27 Kaneka Corporation Base revêtue ayant un film de revêtement composé de particules creuses et de fines particules de silicone creuses enrobées d'un polymère organique
WO2010074063A1 (fr) * 2008-12-25 2010-07-01 電気化学工業株式会社 Particules composites, procédé de préparation de ces particules composites, particules creuses, procédé de préparation de ces particules creuses et utilisation de ces particules creuses
WO2014098107A1 (fr) * 2012-12-19 2014-06-26 国立大学法人東京大学 Structure de silice organique creuse et procédé pour produire celle-ci
CN103933903A (zh) * 2014-03-31 2014-07-23 清华大学 制备空心结构纳米有机硅微球的方法
CN113549218A (zh) * 2021-08-06 2021-10-26 江西新嘉懿新材料有限公司 一种空心球形硅树脂的制备方法

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Publication number Priority date Publication date Assignee Title
JPH04258636A (ja) * 1991-02-12 1992-09-14 Japan Synthetic Rubber Co Ltd ポリシロキサン複合重合体粒子の製造方法
JP2000191789A (ja) * 1998-12-28 2000-07-11 Takemoto Oil & Fat Co Ltd 有機シリコ―ン微粒子、その製造方法、有機シリコ―ン微粒子から成る高分子材料用改質剤及び化粧品原料
JP2000226453A (ja) * 1999-02-05 2000-08-15 Jsr Corp 中空粒子およびその製造方法
JP2003171465A (ja) * 2001-12-07 2003-06-20 Takemoto Oil & Fat Co Ltd 有機シリコーン微粒子、有機シリコーン微粒子の製造方法及び高分子材料用改質剤
WO2007099814A1 (fr) * 2006-03-02 2007-09-07 Kaneka Corporation Procede de production de fines particules creuses de silicone

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04258636A (ja) * 1991-02-12 1992-09-14 Japan Synthetic Rubber Co Ltd ポリシロキサン複合重合体粒子の製造方法
JP2000191789A (ja) * 1998-12-28 2000-07-11 Takemoto Oil & Fat Co Ltd 有機シリコ―ン微粒子、その製造方法、有機シリコ―ン微粒子から成る高分子材料用改質剤及び化粧品原料
JP2000226453A (ja) * 1999-02-05 2000-08-15 Jsr Corp 中空粒子およびその製造方法
JP2003171465A (ja) * 2001-12-07 2003-06-20 Takemoto Oil & Fat Co Ltd 有機シリコーン微粒子、有機シリコーン微粒子の製造方法及び高分子材料用改質剤
WO2007099814A1 (fr) * 2006-03-02 2007-09-07 Kaneka Corporation Procede de production de fines particules creuses de silicone

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008143162A1 (fr) * 2007-05-17 2008-11-27 Kaneka Corporation Base revêtue ayant un film de revêtement composé de particules creuses et de fines particules de silicone creuses enrobées d'un polymère organique
WO2010074063A1 (fr) * 2008-12-25 2010-07-01 電気化学工業株式会社 Particules composites, procédé de préparation de ces particules composites, particules creuses, procédé de préparation de ces particules creuses et utilisation de ces particules creuses
JP5576799B2 (ja) * 2008-12-25 2014-08-20 電気化学工業株式会社 複合粒子及びその製造方法、中空粒子、その製造方法及び用途
WO2014098107A1 (fr) * 2012-12-19 2014-06-26 国立大学法人東京大学 Structure de silice organique creuse et procédé pour produire celle-ci
CN103933903A (zh) * 2014-03-31 2014-07-23 清华大学 制备空心结构纳米有机硅微球的方法
CN113549218A (zh) * 2021-08-06 2021-10-26 江西新嘉懿新材料有限公司 一种空心球形硅树脂的制备方法

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