WO2019139092A1 - Particules fines hydrophobes et composition d'agent hydrofuge - Google Patents

Particules fines hydrophobes et composition d'agent hydrofuge Download PDF

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WO2019139092A1
WO2019139092A1 PCT/JP2019/000559 JP2019000559W WO2019139092A1 WO 2019139092 A1 WO2019139092 A1 WO 2019139092A1 JP 2019000559 W JP2019000559 W JP 2019000559W WO 2019139092 A1 WO2019139092 A1 WO 2019139092A1
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fine particles
hydrophobic fine
film
hydrophobic
inorganic compound
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PCT/JP2019/000559
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English (en)
Japanese (ja)
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大輔 松隈
藤田　浩之
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日東電工株式会社
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    • 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
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the present invention relates to hydrophobic microparticles and a water repellent composition containing the hydrophobic microparticles.
  • a water repellent coating has been applied to the surface of an object.
  • a water repellent film is formed, for example, by treating the surface of an object with a silicon-based or fluorine-based water repellent composition.
  • silica fine particles having an average primary particle diameter of 100 nm or less and containing 65% by mass or more of a hydrophobic solvent in all organic solvents are included.
  • a technique has been proposed for forming a film on the surface of an object using a coating liquid dispersed in an organic solvent. Since silica (SiO 2 ) is hydrophilic, hydrophobic silica is obtained by hydrophobizing the surface of silica.
  • Attapulgite which is one of silicate minerals, has a hollow needle-like shape and has excellent colloid properties, so that it can be used as a hydrophobic material by hydrophobizing the surface.
  • Patent Document 2 Chinese Patent Application Publication No. 104448950 (Patent Document 2) and Chinese Patent Application Publication No. 104559786 (Patent Document 3)
  • Patent Document 3 a technology for obtaining a hydrophobic attapulgite by hydrophobizing attapulgite is proposed. ing.
  • Attapulgite can impart transparency to a coating film
  • the conventional hydrophobic attapulgite has a problem that the transparency is impaired as it is imparted with water repellency.
  • the present invention is a hydrophobic fine particle for imparting water repellency to an object by treating the surface of the object, and a water repellent film having both water repellency and transparency can be obtained. It is an object of the present invention to provide hydrophobic microparticles and a water repellent composition containing the hydrophobic microparticles.
  • the present invention is characterized by the following (1) to (12).
  • Hydrophobic fine particles comprising an inorganic compound having a needle-like structure whose surface is coated with a hydrophobizing agent and having an average diameter of 100 nm or less in the direction orthogonal to the long axis direction.
  • the hydrophobic fine particles according to (1) or (2), wherein the inorganic compound is a silicate compound.
  • hydrophobic fine particles according to (3) wherein the silicate compound is at least one needle-like mineral selected from the group consisting of attapulgite, halloysite, imogolite, wollastonite, sepiolite and palygorskite .
  • the hydrophobizing agent is at least one coupling agent selected from the group consisting of a silane coupling agent, a phosphoric acid coupling agent and a thiol coupling agent.
  • the composition obtained by dispersing 60 mg of the hydrophobic fine particles in 3.5 g of toluene is applied to a transparent substrate having a thickness of 2 mm and dried to form a film having a thickness of 30 ⁇ m, the haze of the film
  • the hydrophobic fine particles of the present invention are made hydrophobic without impairing the shape and size of the inorganic compound before being hydrophobized, and therefore, have hydrophobicity without impairing the inherent properties of the inorganic compound.
  • a water repellent composition containing the hydrophobic fine particles of the present invention because the inorganic compound in the form of a hollow needle gives excellent antifogging properties to a film formed using a composition containing the inorganic compound.
  • the film formed by the above can have excellent water repellency and transparency.
  • FIG. 1 is a photograph by a scanning electron microscope of the hydrophobic fine particles obtained in Example 1.
  • FIG. 2 is a photograph by a scanning electron microscope of the hydrophobic fine particles obtained in Example 2.
  • FIG. 3 is a photograph by a scanning electron microscope of the hydrophobic fine particles obtained in Example 3.
  • FIG. 4 is a photograph by a scanning electron microscope of the hydrophobic fine particles obtained in Comparative Example 1.
  • hydrophobic fine particles are made of an inorganic compound having a needle-like structure whose surface is coated with a hydrophobic treatment.
  • hydrophobic refers to the property of exhibiting a contact angle of 90 ° or more when droplets of water (eg, pure water) are dropped on the material under an environment of 25 ° C.
  • silicate compounds represented by needle-like minerals such as attapulgite, halloysite, imogolite, wollastonite, sepiolite and palygorskite. One of these may be used alone, or two or more of these may be used in combination.
  • the inorganic compound is preferably hollow.
  • the film containing the hydrophobic fine particles of the present embodiment can have not only water repellency but also excellent transparency.
  • the inorganic compound has a hollow needle-like structure with a high aspect ratio, and it is preferable to use attapulgite because of the ease of surface hydrophobic modification.
  • the inorganic compound one having a diameter in a direction orthogonal to the long axis direction (hereinafter, also referred to as “diameter of cross section”) of 100 nm or less is used.
  • the diameter of the cross section of the inorganic compound is 100 nm or less
  • hydrophobic fine particles having an average value of the diameter of the cross section of 100 nm or less can be obtained. The dispersibility is improved, and the desired effects of the present invention can be easily obtained.
  • the diameter of the cross section of the inorganic compound is preferably 10 to 100 nm, the lower limit is more preferably 20 nm or more, further preferably 30 nm or more, and the upper limit is more preferably 85 nm or less, and 70 nm or less Is more preferred.
  • the inorganic compound preferably has a major axis of 0.2 to 20 ⁇ m.
  • the long axis length of the inorganic compound is in the above range, hydrophobic fine particles obtained by hydrophobizing the surface exhibit good dispersibility in a solvent, and the desired effect of the present invention can be easily obtained.
  • the lower limit is more preferably 1 ⁇ m or more
  • the upper limit is more preferably 15 ⁇ m or less
  • 10 ⁇ m or less is more preferable.
  • the attapulgite when the inorganic compound is attapulgite, the attapulgite preferably has a major axis of 1 to 2 ⁇ m and a cross-sectional diameter of 10 to 50 nm.
  • the ratio of the diameter of the cross section of the inorganic compound to the long axis length is preferably 10 or more, more preferably 10 to 100, still more preferably 30 to 80, with respect to the diameter 1 of the cross section. preferable.
  • the ratio of the diameter of the cross section to the major axis length is 10 or more, the uneven structure on the surface of the film formed of the water repellent composition containing the hydrophobic fine particles of the present embodiment is roughened. Water repellency is high.
  • the inorganic compound of the said needle-like structure can be obtained as a commercial item, for example, "Atagel” by Union Chemical Co., Ltd. (hollow needle-like attapulgite, long axis length: 1 to 2 ⁇ m, cross-sectional diameter: 10 to 50 nm ), Union Chemical Co., Ltd. "ASHAGEL SF” (hollow needle-like attapulgite, long axis length: 1 to 2 ⁇ m, cross-sectional diameter 10 to 50 nm), Hayashi Kasei Co., Ltd. "ATTAGEL 50” (hollow needle-like attapulgite, Long axis length: 1 to 2 ⁇ m, diameter of cross section 10 to 50 nm) and the like.
  • hydrophobizing agent for coating the inorganic compound examples include hydrophobic coupling agents such as silane coupling agents, phosphoric acid coupling agents, and thiol coupling agents, and one of these may be used alone or in combination. More than species can be used in combination.
  • silane coupling agent examples include alkoxysilanes, silazanes, chlorosilanes, special silylating agents, etc. Specifically, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltrimethoxysilane Ethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, hexadecyltrimethoxysilane (HDMS), methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltriethoxysilane Chlorosilane, diphenyldichlorosilane, N, O- (bistrimethylsilyl) acetamide, N,
  • Examples of the phosphoric acid coupling agent include 11-aminoundecylphosphonic acid, 10-carboxydecylphosphonic acid, 11-hydroxyundecylphosphonic acid, octadecylphosphonic acid, 11- [2- [2- (2-methoxy] Ethoxy) ethoxy] ethoxy] undecylphosphonic acid, 1H, 1H, 2H, 2H-perfluoro-n-hexylphosphonic acid, 1H, 1H, 2H, 2H-perfluoro-n-octylphosphonic acid, 1H, 1H, 2H , 2H-perfluoro-n-decylphosphonic acid, monooctyl ester phosphate, phenyl phosphate, 2- (1-methylguanidino) ethyl dihydrogenphosphate, and mono (2-methacryloxypropyl) ester phosphate It can be mentioned.
  • thiol coupling agent examples include alkyl thiols and derivatives thereof, triazine thiols and derivatives thereof and the like.
  • silane coupling agent from the viewpoint of achieving more stable and easy surface modification of the hydrophobization treatment agent, and hexadecyltrimethoxysilane (as a substance that can be easily subjected to highly hydrophobic surface treatment) It is preferred to use HDMS).
  • the surface of the inorganic compound may be coated with a hydrophilic silane coupling agent or a hydrophilic polymer material in combination to adjust water repellency.
  • hydrophilic silane coupling agents include tetramethoxysilane and tetraethoxysilane (TEOS).
  • the hydrophobic fine particles of the present embodiment have an average diameter of 100 nm or less in the direction (cross-sectional diameter) in the direction orthogonal to the long axis direction.
  • the hydrophobic fine particles of the present embodiment are characterized by having a shape substantially equal to the shape of the inorganic compound before the hydrophobization treatment. Therefore, it can be said that the fine particles after hydrophobization have hydrophobicity while having the property of the inorganic compound before hydrophobization. Therefore, a film formed of a water repellent composition containing hydrophobic fine particles can be provided with water repellency and also excellent transparency.
  • the dispersibility in a solvent is good, so that when the coating is formed, the hydrophobic fine particles are uniformly dispersed, and the repellence excellent on the film surface It can be water-based and transparent.
  • the lower limit is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more, and the upper limit is preferably 85 nm or less, and more preferably 70 nm or less. preferable.
  • the hydrophobic fine particles of the present embodiment preferably have a major axis length of 0.2 to 20 ⁇ m. If the length of the major axis is in the above range, it can be said that the shape of the inorganic compound before the hydrophobization treatment is also substantially the same, so the fine particles after hydrophobization have the hydrophobicity while having the properties of the inorganic compound before hydrophobization. It can be equipped. Moreover, since the dispersibility to a solvent is good and a uniform coating film can be formed, the desired effect of the present invention can be easily obtained.
  • the lower limit is more preferably 1 ⁇ m or more, and the upper limit is more preferably 15 ⁇ m or less, and further preferably 10 ⁇ m or less.
  • the hydrophobic fine particles preferably have a contact angle of 90 ° or more with respect to water on the surface of the film when the film is formed. If the contact angle of the film surface with water is 90 ° or more, it indicates that the film surface has low surface free energy, and it is possible to make the film difficult to be soiled.
  • the lower limit of the contact angle is more preferably 100 ° or more, further preferably 105 ° or more, and the upper limit is preferably 170 ° or less.
  • the contact angle was controlled by applying a composition in which 60 mg of hydrophobic fine particles were dispersed in 3.5 g of toluene on a transparent substrate with a thickness of 2 mm and forming a film with a thickness of 30 ⁇ m. It can measure by measuring the contact angle with respect to water (for example, pure water) of the said film
  • the hydrophobic fine particles preferably have a permeability of 80% or more when the film is formed.
  • the film has a transmittance of 80% or more, the transparency is high, so that when the coating is formed on a target to form a coating film, the target has good visibility without blocking the target.
  • the lower limit of the transmittance is more preferably 85% or more, further preferably 90% or more, and the upper limit is preferably 100% or less.
  • the transmittance is obtained by applying a composition in which 60 mg of hydrophobic fine particles are dispersed in 3.5 g of toluene on a transparent substrate having a thickness of 2 mm and drying to form a film having a thickness of 30 ⁇ m. It can be measured by measuring the transmittance at each wavelength of the total light beam of the film using a transmittance meter (for example, a haze meter “HR-100 type” manufactured by Murakami Color Research Laboratory, Inc.).
  • a transmittance meter for example, a haze meter “HR-100 type” manufactured by Murakami Color Research Laboratory, Inc.
  • the hydrophobic fine particles preferably have a haze of 50% or less when the film is formed.
  • the haze of the film is 50% or less, the transparency is high, and the visibility of the object is good.
  • the upper limit of the haze is more preferably 45% or less, still more preferably 30% or less, and the lower limit is preferably 0% or more.
  • the haze value is a haze meter when a composition in which 60 mg of hydrophobic fine particles are dispersed in 3.5 g of toluene is applied to a transparent substrate having a thickness of 2 mm and dried to form a film having a thickness of 30 ⁇ m. It can measure by measuring the haze value of the said film using.
  • the hydrophobic fine particles of the present embodiment can be produced using a known method.
  • a suspension polymerization method, an emulsion polymerization method, a dispersion polymerization method, a seed polymerization method, a kneading and pulverizing method, and the like are suitably used.
  • hydrophobic fine particles by suspension polymerization, first, an inorganic compound having a needle-like structure and a hydrophobizing agent (for example, a silane coupling agent containing hexadecyltrimethoxysilane (HDMS)) in a solvent
  • a hydrophobizing agent for example, a silane coupling agent containing hexadecyltrimethoxysilane (HDMS)
  • HDMS hexadecyltrimethoxysilane
  • Examples of the solvent for suspending the inorganic compound and the hydrophobization treatment agent include ethanol, methanol, isopropyl alcohol and the like.
  • the amount of the solvent used is 5 to 50 times, preferably 10 to 20 times, the amount (mass) of the solvent necessary for the hydrolysis of the hydrophobizing agent.
  • the hydrophobizing agent is preferably used in a weight ratio of 1: 1 to the inorganic compound.
  • a condition for subjecting a suspension in which an inorganic compound and a hydrophobizing agent are suspended in a solvent to ultrasonication it is preferable to carry out in a temperature range of 20 to 100 ° C. for about 3 to 72 hours.
  • the temperature is more preferably 50 to 80 ° C., further preferably 60 to 70 ° C., the time is more preferably 6 to 48 hours, and further preferably 18 to 24 hours.
  • water is mentioned, for example.
  • Water is preferably used in an amount of 50 to 100 times, and more preferably 60 to 80 times, the weight of the hydrophobizing agent.
  • aqueous ammonia As a catalyst solution to be added to accelerate the hydrolysis reaction, for example, aqueous ammonia can be mentioned.
  • Ammonia water is preferably used in an amount of 5 to 25 times, more preferably 10 to 20 times, the weight of the hydrophobizing agent.
  • the surface of the inorganic compound is modified with a hydrophobic group (HDMS) by ultrasonication again.
  • a temperature range of 20 to 100 ° C. for about 3 to 72 hours it is preferable to carry out at a temperature range of 20 to 100 ° C. for about 3 to 72 hours.
  • the temperature is more preferably 50 to 80 ° C., further preferably 60 to 80 ° C., the time is more preferably 6 to 48 hours, and further preferably 18 to 24 hours.
  • the pellet is separated from the solvent, washed with ethanol, and dried to obtain the hydrophobic fine particles of the present embodiment.
  • the drying conditions are preferably carried out, for example, in a temperature range of 60 to 100 ° C. for about 1 to 3 hours.
  • the surface of the inorganic compound is modified with a hydrophobic group, and since the modified portion is a linear alkyl group having a very short chain length, the thickness is in proportion to the size of the inorganic compound With little consideration, hydrophobic microparticles have a shape approximately equal to the shape of the inorganic compound. Thus, the hydrophobic fine particles can have water repellency while having the transparency of the inorganic compound.
  • the water repellent composition of the present embodiment contains a base component and the hydrophobic fine particles of the present embodiment.
  • the base component of the water repellent composition may be appropriately selected depending on the properties of the coating film to be formed, and examples thereof include toluene, acetic acid, methanol, ethanol, ethyl acetate, butyl acetate and the like.
  • additives which are usually used in the water repellent composition can be used as long as the effects of the present invention are not impaired.
  • the additive include an ultraviolet light inhibitor, a surfactant, a pigment, a filler, and a reinforcing material.
  • the water repellent composition can be obtained by adding the hydrophobic fine particles of the present embodiment and, if necessary, various additives to the base component, and mixing them using a polymer solution or the like according to a conventional method.
  • the water repellent composition may be in any form such as liquid, gel or cream depending on the method of application to the object.
  • the hydrophobic fine particles of the present embodiment are uniformly dispersed. Therefore, by forming a film on the surface of the object using the water repellent composition of the present embodiment, it is possible to impart water repellency to the surface of the object, and to suppress adhesion of ice, snow, etc. It does not interrupt the pattern or color.
  • the water repellent film preferably has a film thickness sufficient to exhibit sufficient water repellency.
  • the film thickness of the water repellent film is preferably 10 to 100 ⁇ m, the lower limit is more preferably 15 ⁇ m or more, further preferably 30 ⁇ m or more, and the upper limit is more preferably 50 ⁇ m or less, still more preferably 40 ⁇ m or less.
  • the film thickness is 10 ⁇ m or more, sufficient water repellency can be exhibited, and when the film thickness is 30 ⁇ m or more, a further sufficient strength can be provided.
  • the film thickness is 100 ⁇ m or less, good transparency can be obtained, and when the film thickness is 40 ⁇ m or less, problems such as cracking of the water repellent film are unlikely to occur.
  • the water repellent film preferably has a contact angle to water of 90 ° or more.
  • the contact angle to water of the water repellent film is 90 ° or more, it is possible to make the film surface difficult to be soiled.
  • the lower limit of the contact angle is more preferably 100 ° or more, further preferably 105 ° or more, and the upper limit is preferably 170 ° or less.
  • the contact angle can be measured by the method described above.
  • the water repellent film preferably has a transmittance of 80% or more at each wavelength of the total light. Since the transparency is high when the transmittance of the water repellent film is 80% or more, when the film is formed by applying to a target, the visibility of the target becomes good without blocking the target.
  • the lower limit of the transmittance is more preferably 85% or more, further preferably 90% or more, and the upper limit is preferably 100% or less.
  • permeability can be performed by the above-mentioned method.
  • the water repellent film preferably has a haze of 50% or less.
  • the haze of the water repellent film is 50% or less, the transparency is high, so that the visibility of the object becomes good.
  • the upper limit of the haze is more preferably 45% or less, still more preferably 30% or less, and the lower limit is preferably 0% or more.
  • the measuring method of haze can be performed by the above-mentioned method.
  • the physical properties of the hydrophobic fine particles in each example were measured by the following.
  • the ratio of hexadecyltrimethoxysilane (HDMS) to attapulgite of the hydrophobic fine particles was calculated using an infrared spectrum (IR spectrum, manufactured by Thermo Fisher Scientific, NICOLETIS 5). First, an IR spectrum of the obtained microparticles was obtained at room temperature.
  • the absorption intensity at 980 cm -1 derived from attapulgite was normalized between the samples, and the ratio of hexadecyltrimethoxysilane to attapulgite was calculated from the absorption intensity at 2917 cm -1 derived from hexadecyltrimethoxysilane.
  • required in this way (hexadecyl trimethoxysilane / attapulgite) is 30 or more.
  • Example 1 Preparation of hydrophobic fine particles>
  • the materials used are as follows. 1. Attapulgite (ATP, “Atagel” (trade name) manufactured by Union Kasei Co., Ltd., particle shape: hollow needle, particle length (average): 1 to 2 ⁇ m, diameter in a direction orthogonal to the axial direction (average): 10 to 50 nm 2. Tetraethoxysilane (TEOS, manufactured by Tokyo Chemical Industry Co., Ltd., specific gravity 0.933 to 0.9370, refractive index 1.3810 to 1.3850) 3. Hexadecyltrimethoxysilane (HDMS, manufactured by Sigma-Aldrich, specific gravity 0.8890 to 0.8930, refractive index 1.4340 to 1.4380)
  • TEOS Tetraethoxysilane
  • HDMS Hexadecyltrimethoxysilane
  • the particle length (average) of the obtained hydrophobic fine particles was 2 ⁇ m, and the average diameter in the direction orthogonal to the long axis direction was 62.4 ⁇ 16 nm. The value indicated by ⁇ is a standard deviation.
  • the ratio of hexadecyltrimethoxysilane to attapulgite (hexadecyltrimethoxysilane / attapulgite) was 32.8.
  • fine-particles with the scanning electron microscope is shown in FIG.
  • US Cleaner (trade name) manufactured by As One Corporation, output 80 W, oscillation frequency 40 KHz
  • a transparent acrylic plate (length 5 cm, width 5 cm, thickness 2 mm) is sprayed using Mitsubishi Chemical Co., Ltd. “Acrilite” (trade name) to form a coated film so that the coating after drying is 30 ⁇ m. (Spray amount: 6.7 g / m 2 ) It was dried at 60 ° C. for 30 minutes to prepare a test piece with a membrane.
  • Examples 2 to 5 Hydrophobic fine particles were obtained in the same manner as in Example 1, except that the content ratio of attapulgite to the silane coupling agent and the content ratio of tetraethoxysilane to hexadecyltrimethoxysilane were changed as described in Table 1.
  • Example 2 For Examples 2 to 5 and Comparative Examples 1 to 11, as in Example 1, the ratio of hexadecyltrimethoxysilane to atapulgite of hydrophobic fine particles, and the contact angle, permeability, and haze of the membrane to water were measured. The results are shown in Table 1. Further, SEM images of the hydrophobic fine particles obtained in Examples 2 and 3 and Comparative Example 1 taken with a scanning electron microscope are shown in FIGS.
  • Examples 1 to 5 are hydrophobic fine particles having a contact angle to water of 90 ° or more when formed into a coating film, and since the transmittance is also high, the transparency is also excellent. .
  • the hydrophobic fine particles of the present invention are useful for preventing the adhesion of snow or ice to the surface of an aircraft, a railway, a car, a wind power generator, a house, a traffic light, a signboard and the like.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Combustion & Propulsion (AREA)
  • Dispersion Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

L'invention concerne : des particules fines hydrophobes pour conférer un caractère hydrofuge à un objet au moyen de la surface de l'objet en cours de traitement avec celles-ci, et par lesquelles un film hydrofuge ayant à la fois un caractère hydrofuge et une transparence peut être obtenu ; et une composition d'agent hydrofuge qui comprend les particules fines hydrophobes. Ces particules fines hydrophobes comprennent un composé inorganique qui est de structure aciculaire et revêtu d'un agent de traitement hydrophobe sur leurs surfaces, et ont une taille moyenne de 100 nm ou moins dans la direction orthogonale à la direction longitudinale.
PCT/JP2019/000559 2018-01-11 2019-01-10 Particules fines hydrophobes et composition d'agent hydrofuge WO2019139092A1 (fr)

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IT201900024754A1 (it) * 2019-12-19 2021-06-19 Consiglio Nazionale Ricerche Materiale ibrido multifunzionale basato su sepiolite per il recupero ed il biorisanamento ambientale
IT201900024802A1 (it) * 2019-12-19 2021-06-19 Consiglio Nazionale Ricerche Materiale ibrido multifunzionale basato su argille naturali per il recupero ed il biorisanamento ambientale
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