WO2005063903A1 - Water repellent agent and use thereof - Google Patents

Water repellent agent and use thereof Download PDF

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Publication number
WO2005063903A1
WO2005063903A1 PCT/JP2004/019745 JP2004019745W WO2005063903A1 WO 2005063903 A1 WO2005063903 A1 WO 2005063903A1 JP 2004019745 W JP2004019745 W JP 2004019745W WO 2005063903 A1 WO2005063903 A1 WO 2005063903A1
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WO
WIPO (PCT)
Prior art keywords
water repellent
water
fine particles
silicone oil
coating
Prior art date
Application number
PCT/JP2004/019745
Other languages
French (fr)
Japanese (ja)
Inventor
Seimei Shiratori
Jinho Kim
Shigeo Toujou
Original Assignee
Snt Co., Ltd.
Yokohama Oils & Fats Industry Co., Ltd.
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 Snt Co., Ltd., Yokohama Oils & Fats Industry Co., Ltd. filed Critical Snt Co., Ltd.
Priority to JP2005516722A priority Critical patent/JP4060333B2/en
Publication of WO2005063903A1 publication Critical patent/WO2005063903A1/en

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Classifications

    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • the present invention relates to a water repellent used for water repellent treatment of the surface of a solid article, a method of using the water repellent, a coated article treated with the water repellent, and a method of using the water repellent or the coated article. It relates to a manufacturing method.
  • Silicone oil is widely used as a material that imparts water repellency to the surface of a solid article made of metal, ceramic, plastic, fiber, or the like.
  • amino-modified silicone oil-based water repellents are commercially available for coating automotive bodies, but coatings obtained by spraying them have low water repellency and insufficient sustainability.
  • Patent Literature 1 discloses that “a resin solution having a water contact angle of 90 ° or more on a coating film surface and inorganic or organic fine particles capable of providing fine irregularities on the surface after the coating film is cured.
  • Aqueous coating composition "is described, and it is said that a heat exchanger coated with this composition can drop fine water droplets of about 1 mm in diameter from the fin surface.
  • Patent Document 2 discloses that, ⁇ at least a particle having a hydrophobic surface and having an average particle diameter of 1 nm to 1 mm is composed of a resin coating film, and the fine particles are in an area of 20% or more of the resin and the film surface area.
  • Patent Document 2 discloses that the average particle diameter of the fine particles is smaller, the effect of the concavo-convex shape is lower, the contact angle is smaller, and the larger the average particle diameter, the lower the water repellency against fine water droplets. It is stated that it is limited to ⁇ 1 mm.
  • Patent Document 3 discloses that “water has a contact angle of less than 120 ° When formed, the contact angle of water on the coating surface was 150.
  • a water-repellent coating that can be formed as described above, wherein the layer is formed on the surface and contains a water-repellent polymer having an adhesive property, and is fixed to a surface of the layer containing the water-repellent polymer having an adhesive property.
  • the contact angle of water on the surface of the layer containing the water-repellent polymer having the adhesive property is 120.
  • the average particle diameter of the water-repellent silica particles is selected from the range of 0.1 to 100 m, and the surface density of the water-repellent silica particles fixed on the surface is 10 it describes water-repellent film ", characterized in that the selected 2 to 1 0 in 8 / mm 2 range, the resulting water-repellent film is that the contact angle is 1 5 0 ° or more," sticky
  • the water-repellent polymer having tackiness which constitutes the layer containing the water-repellent polymer having water repellency, functions as a binder when the water-repellent sily particles are stably fixed to the surface thereof. It is more preferable to use an adhesive fluoropolymer or a mixture of the adhesive fluoropolymer and a viscous silicone resin. " .
  • Patent Document 4 describes a surface modifier comprising gel particles having a diameter in the range of 1 nm to 1 m and a hydrophobic polymer material, whereby at least 150 ° It is described that a coating having a contact angle of at least 160 ° and a contact angle of at least 160 ° is formed.
  • the coating film When applying a water repellent to the surface of an article, the coating film is required to be transparent and glossy so as not to impair the color and texture of the article itself. Further, it is desired that after the water repellent coating is performed, the water repellency can be maintained for a long time without peeling off from the article surface.
  • the water repellent has high water repellency, and has high transparency (glossiness) and strength after coating with the water repellent. Is to provide.
  • Another object of the present invention is to provide an article coated with such a water repellent having high water repellency, transparency, and strength, and a method for producing the same.
  • the present inventors have conducted intensive studies on the above problems, and have found that, in a water repellent containing silicone oil, fine particles, and a solvent, it is possible to enhance the binding between the fine particles and / or the fine particles and the silicone oil. It has been found that the strength of the water-repellent coating film can be enhanced by adding a fine particle binder, and the present invention has been accomplished.
  • the strength of the film in the present invention means that when a water repellent is coated on a solid surface, it does not peel off for a long time, does not peel off due to friction with water pressure or cloth, or is exposed to outside air or light. This means that the water repellent keeps water repellency for a long time without peeling off or deteriorating.
  • the present inventors have found that the surface of the water-repellent film after the coating with the water-repellent agent can exhibit high water-repellency when the surface has irregularities of a specific size. I found that there is. '
  • the present inventors have proposed that irregular reflection due to surface irregularities is possible in order to ensure transparency. It was found that it was necessary to be invisible with visual light, and it was found that a specific size of the surface depression was preferable for transparency.
  • the present inventors have found that by further adding a surfactant to the above-mentioned water repellent, the water repellent has good storage stability over a long period of time and has little clogging when sprayed.
  • the present invention has been made based on the above findings, and relates to the following.
  • a water repellent comprising silicone oil, fine particles, a fine particle binder, an aqueous solvent and water.
  • a water repellent comprising silicone oil, silica fine particles having an average particle diameter of 5 to 20 nm, wax and / or paraffin, an aqueous solvent and water.
  • silicone oil, an aqueous solvent, and water To the dried product, add silicone oil, an aqueous solvent, and water, and stir.
  • a surfactant is further added in one of the steps of mixing and heating and dissolving the mixture in an organic solvent, or adding and stirring silicone oil, an aqueous solvent, and water. 10.
  • (21) A method for using the water repellent according to any one of the above (1) to (10) for a car washer.
  • the water repellent of the present invention and the article coated with the water repellent of the present invention can have both high water repellency, transparency and strength, and even one month after coating. An excellent effect that the water repellency is not reduced can be obtained.
  • FIG. 1 shows an example of a spray device used for the coating of the present invention.
  • FIG. 2 shows an example of an apparatus for using the water repellent of the present invention in a car washer.
  • FIG. 3 shows a micrograph of a comparative example without binder.
  • FIG. 4 shows a micrograph of an example of the present invention.
  • the water repellent of the present invention is used for performing water repellent treatment on the surface of a solid article.
  • Solid articles can be applied to hard materials such as metals, ceramics, glass and plastics, as well as soft materials such as fibers.
  • it can be suitably used for treating vehicles such as ships, aircraft, and automobiles, buildings, mirrors, tiles, and fabrics.
  • the silicone oil (organopolysiloxane) used in the water repellent of the present invention may be any one that can form a viscous liquid by mixing with fine particles.
  • Amino-modified silicone oil, higher fatty acid-modified silicone oil Dimethyl silicone oil, alkyl-modified silicone oil, alkyl aralkyl-modified silicone oil, epoxy-modified silicone oil, carboxylyl-modified silicone oil, and the like.
  • the viscosity of the silicone oil is preferably from 5 to 100, OO Octs, and more preferably from 50 to 50 Octs.
  • the fine particles used in the present invention may be an inorganic substance or an organic substance, but an inorganic substance which does not deteriorate is preferable.
  • the material is not limited, inorganic oxides such as silica, alumina, and titania are preferable in order to obtain fine particles having a particle size on the order of nm.Since there is a commercially available product having an average particle size of 520 nm, the silica force is high. Most preferred.
  • These fine silica particles are made by Nippon Aerodil Co., Ltd., Aerodil 1 ⁇ 972, 972 ⁇ , 1 ⁇ 972 , 11974, R812, R805, RX200, RX300, RY200 (all of which are hydrophobic silica), among which aerosil R972 and RX200 are preferred.
  • Fine particles manufactured by Nippon Aerosil Co., Ltd., Aerosil 50, 90G, 130, 200, 200V, 200CF, 200FAD, 300, 300CF, 380, R202, R812S, 0X50, TT600, M0X80, MOX170, C0K84, Aluminum oxide C , Titanium dioxide T805, titanium dioxide # 25 and the like can also be used.
  • hydrophilic fine particles are preferably subjected to hydrophobic treatment with a silane coupling agent in advance.
  • Resins acrylic resin, epoxy resin, silicone resin, etc .
  • Surfactants monoalkyl ammonium chloride, dialkyl ammonium chloride, ethylene oxide-added ammonium chloride, amine acetates , Alkylamines, alkyldiamines, alkylamides, bisamides, alkylamine ethylene oxide adducts, fatty acid ethylenoxide adducts, fatty salts, etc .
  • Petrol isoparaffin, normal paraffin, paraffin wax, microcrystal wax, mineral oils such as petrolatum, monic acid and its ester wax, polyolefin wax, hydroxy And synthetic waxes stearic phosphate based Esuteruwakkusu the like.
  • the glassy state an organic substance which becomes solid at room temperature and becomes a liquid having a relatively low viscosity when heated. More preferably, a mixture of paraffin wax having a melting point of 115 ° F. to 155 ° F. (46.1 ° C. to 63.9 ° C.) and 10 to:! OOcts normal paraffin is used.
  • Paraffin has long been used as a water repellent (see, for example, JP-A-62-263279), but in the present invention, paraffin enhances the binding between fine particles and / or the fine particles and silicone oil. It is added in order to A water repellent consisting of only paraffin and fine particles or only silicone and fine particles cannot provide the desired strength.
  • the surfactant when a surfactant is added to the water repellent, the dispersibility of the fine particles is improved, and the particles are not separated even when stored for a long period of time, and the storage stability is improved. Further, the surfactant can also have an effect of preventing clogging of the spray nozzle when spraying the water repellent.
  • a cationic surfactant is preferable, and among them, mono-anolekylammonium chloride and dialkylammonium chloride are more preferable.
  • the aqueous solvent in the present invention is an organic solvent having affinity for water.
  • any of the solvents commonly used for water repellents such as alcohols, glycols, esters, ketones, and ethers, can be used.
  • 2-propanediol propylenedali cornole
  • 2-methinole 2,4-pentanediole / hexene hexylene glycolone
  • diethylene glycol monobutyl ether butyldiglycol
  • 1,5-pentanediol penentamethylene glycol
  • the average particle size of the fine particles to be used is preferably 1 to 100 nm, and in order to satisfy water repellency, gloss and strength with good balance, it is more preferably 5 to 20 nm. preferable.
  • the weight ratio of the binder to the fine particles is preferably in the range of 0.01% to 20%, more preferably 0.1% to 10%.
  • the binder is less than 0.1%, no strength is obtained, and when it exceeds 20%, the gloss decreases.
  • the weight ratio of silicone oil to fine particles is preferably in the range of 0.1 to 100%, more preferably 2 to 30%.
  • silicone oil content is less than 0.1%, the strength is not obtained, and when it exceeds 100%, the gloss decreases.
  • the amount of the aqueous solvent is not particularly limited as long as the fine particles show sufficient dispersibility, and is preferably 1 to 15 parts by weight, more preferably 5 to 10 parts by weight, per 1 part by weight of the fine particles. When the amount of the aqueous solvent is less than 1 part by weight, sufficient dispersibility is not exhibited. When the amount exceeds 15 parts by weight, the adhesion efficiency as a water repellent decreases.
  • the water repellent of the present invention comprises a step of mixing a binder of fine particles in a solvent, heating and dissolving the mixture, adding and mixing the fine particles, and drying the mixture under reduced pressure under stirring. It can be produced by adding and stirring a solvent and water.
  • a surfactant especially a cationic surfactant
  • any solvent may be used as long as the binder shows solubility, and a lipophilic solvent or an amphiphilic solvent having both hydrophilicity and lipophilicity is more preferable.
  • the lipophilic solvent include normal pentane and normal hexane
  • examples of the amphiphilic solvent include ethanol and hexyl alcohol. 4 019745
  • the binder is weighed in the range of 0.01 to 20% by weight of the fine particles, mixed with a lipophilic solvent, and dissolved by heating.
  • the amount of the solvent at this time is 15 to 20 times the weight of the fine particles.
  • fine particles are added, and the mixture is dried under reduced pressure with stirring. 1 to 15 parts by weight of an aqueous solvent is added to 1 part by weight of the obtained dried product, and the mixture is sufficiently stirred and mixed. Then, with stirring, 0.001 to 1 part by weight of silicone oil and 5 to 20 parts by weight of water are sequentially added. Stir.
  • the cationic surfactant is added, 0.01 to 20% by weight of the fine particles is added.
  • a water repellent is produced by adding 10 to 80 parts by weight of water to 1 part by weight of the obtained mixture.
  • the water repellent is obtained by applying a spray coating to a solid substance such as a metal, a ceramic, and a fabric to obtain a coated article.
  • the coating amount is more preferably per unit surface area 3 0 ⁇ 5 0 ng / m, 3 per unit of surface area 5-4 is 0 ng Z rn m 2.
  • the coating amount can be measured using QCM (Quartz Crystal Microbalance).
  • the surface unevenness is preferably 30 to 200 rim from the viewpoint of water repellency and gloss.
  • the depression can be measured using an atomic force microscope (AFM).
  • AFM atomic force microscope
  • any known method such as roller coating, impregnation, spraying and the like can be used, but spraying is preferred.
  • the nozzle position may be fixed, and the injection may be performed intermittently, or may be performed by moving the nozzle using a slider or the like.
  • a spray nozzle is placed on a slider or the like, and the water repellent is sprayed while the spray nozzle is reciprocated by the slider. Focusing on a certain point on the solid surface, if a certain point is sprayed for a certain period of time, the spray nozzle will pass through the point, and the water repellent will dry up to a certain degree before being sprayed on the return path. The water repellent is sprayed again on the dried water repellent. Reciprocate the spray nozzle until a suitable coating amount is obtained.
  • the injection can be performed intermittently while moving the nozzle position using the slider. By such an intermittent spray, a more preferable uneven surface is formed.
  • (1) is an article to be coated, and exemplifies a car body.
  • '(2) is the spray nozzle, and the spray nozzle (2) is fixed on the electric slider (3).
  • the electric slider (3) is reciprocated in the direction of the arrow by the motor (4).
  • a water repellent is sprayed from the spray nozzle (2) which reciprocates with the reciprocation of the electric slider (3).
  • the spray nozzle (2) is connected to the water repellent storage tank (5) and the pump (6).
  • the flow rate of the water repellent can be controlled by the discharge amount of the pump (6). It can also be controlled by a flow control pulp (not shown) provided in the pump (6).
  • the injection pressure of the water repellent in the nozzle (2) is controlled by a solenoid valve (not shown) provided in the compressor (7).
  • the article to be coated is equipped with a QCM (Quartz Crystal Microbalance) [8] for measuring the amount of water repellent attached.
  • the amount of adhesion is counted by the frequency counter (9) as the frequency fluctuation of QCM.
  • the discharge rate of the pump (6), the opening of the flow control valve, and the solenoid valve of the compressor are controlled by a personal computer based on the count of the frequency counter (9) to control the flow rate of the water repellent in accordance with the coating film thickness. be able to.
  • (10) is a motor for controlling the drive of the slider (3).
  • the control device (1 1) (1 2) is a power supply device.
  • the spray device of the present invention may further include a control means for controlling drying, for example, an intermittent timer according to the frequency fluctuation of QCM (not shown).
  • a coated article can be manufactured while controlling the amount of the water repellent to be attached by QCM.
  • the amount of adhesion can also be adjusted by adjusting the diameter and the spray pressure of the spray nozzle.
  • the particle size of the water repellent mist sprayed from the spray nozzle is preferably 80 izm or less, and more preferably adjusted to 6 to 14 / xm. By adjusting the mist particle size within this range, desired irregularities can be formed.
  • FIG. 2 shows an example of the case where the water repellent of the present invention is used in a car washer.
  • Fig. 2 (13) to (24) show the spray nozzles, and the car body to be washed gradually moves under the nozzles (13) to (24).
  • the water repellent is sent from the water repellent tank (25) to the nozzle by the ejector (28) together with the dilution water from the dilution water pipe (27), and is sprayed from the nozzle toward the vehicle body.
  • the dilution water discharge pressure was 0 to 5 kg / cm 2
  • the stock solution used was 20 to 50 Om1
  • the dilution ratio was 0.1 to 5 ° /.
  • the moving speed of the car washer is preferably 0.5 to 5 Omm / sec.
  • a water repellent was produced in the same manner as in Example 1 except that the particle size of the fine particles was changed to 7 nm (RX300: manufactured by Nippon Aerosil Co., Ltd.).
  • the water repellent produced in Examples 1 and 2 was sprayed intermittently while drying it until a predetermined thickness was obtained on a test piece for coating and coating composed of a metal substrate.
  • the properties of the obtained coatings were evaluated and summarized in Table 1.
  • the distance is the distance from the spray nozzle to the sample
  • the pressure is the spray pressure of the spray nozzle.
  • Gloss is Horiba, Model: IG-330
  • the contact angle was measured by dropping 101 water droplets on the contact angle meter.
  • the gloss meter of Horiba, Model: IG-330 measures the reflectance by irradiating 800 ⁇ m light from the LED to the surface, and the value without coating is assumed to be 100. It was indicated by the value of the reflectance of the coated article.
  • the contact angle is 1 4 5. As described above, a falling angle of 40 ° or less is sufficient for practical use, and a contact angle of 160 ° or more and a falling angle of 20 ° or less indicates more excellent water repellency. Water repellency is also called slipperiness, meaning that water droplets do not adhere to the surface and roll off easily. [table 1 ]
  • a water repellent was produced in the same manner as in Example 1 except that the amount of the binder was changed, and the effect of the presence or absence of the binder on the water repellency, gloss, and strength was tested.
  • H 2 0 spray lOmin is after spraying for 10 minutes a pressure of about 2 atm
  • H 2 0 spray 20min shows the results after 2 0 min spray.
  • the falling angle X indicates that the water droplet does not roll even if the substrate is tilted by 90 °.
  • Atomic force microscopy for coatings with 1 wt% binder 4 019745
  • the average roughness was 94 nm.
  • TEM electron microscope
  • a water repellent was produced in the same manner as in Example 1 except that the amount of silicone oil (polydimethylsiloxane) was changed in various ways, and the properties of the coating were evaluated in the same manner as in Example 3.
  • a water repellent was produced in the same manner as in Example 1 except that the particle size of the silica fine particles was changed to 300 nm, and the water repellency was measured. As a result, the contact angle was 65 ° and the water repellency was poor.
  • the water repellent of the present invention has sufficient water repellency even 20 days after coating.
  • Paraffin wax 0.05 g, 70 cts normal paraffin, 0.05 g, dialkylammonium chloride (trade name: Ercard, Lionaxo Co., Ltd.)
  • RX 200 fine particles with a particle size of 12 mn
  • To 1.0 g of the obtained dried product 9.0 g of diethylene glycol monobutyl ether (butyl diglycol; BDG) was added, and the mixture was stirred.
  • BDG diethylene glycol monobutyl ether
  • a water repellent is obtained by adding 22 parts by weight of water to 1 part by weight of the obtained mixture.
  • the water repellent stock solution 50 m 1 was diluted with dilution water discharge pressure 3. 0 k gZ cm 2 to 6000 m 1 (dilution ratio 0.83%) were sprayed from car wash nozzle of FIG.
  • the moving speed of the car washer was 1 ⁇ sec, and spraying was repeated three times.

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  • Organic Chemistry (AREA)
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Abstract

Disclosed is a water repellent agent with high water repellency whose coatings have both high transparency (gloss) and high strength. Specifically, the water repellent agent contains at least a silicone oil, fine particles, a binder for particles, an aqueous solvent and water. Also disclosed are a method for producing such a water repellent agent, an article coated with such a water repellent agent, and a car washing machine using such a water repellent agent.

Description

撥水剤とその使用  Water repellent and its use
[技術分野] [Technical field]
本発明は、 固体物品の表面を撥水処理するために用いる撥水剤、 撥水剤の使用 方法、 該撥水剤で処理されたコーティング物品、 及ぴ該撥水剤あるいは該コーテ ィング物品の製造方法に関する。 明  The present invention relates to a water repellent used for water repellent treatment of the surface of a solid article, a method of using the water repellent, a coated article treated with the water repellent, and a method of using the water repellent or the coated article. It relates to a manufacturing method. Light
[背景技術] 書 [Background Art]
シリコーンオイルは、 金属、 セラミック、 プラスチック、 あるいは繊維などか らなる固体物品表面に撥水性を付与する材料として広く用いられている。 例えば、 自動車ボディーのコーティング用としてアミノ変性シリコーンオイル系の撥水剤 が市販されているが、それをスプレーして得たコーティングでは、撥水性が低く、 また、 持続性が十分ではない。  Silicone oil is widely used as a material that imparts water repellency to the surface of a solid article made of metal, ceramic, plastic, fiber, or the like. For example, amino-modified silicone oil-based water repellents are commercially available for coating automotive bodies, but coatings obtained by spraying them have low water repellency and insufficient sustainability.
そこで、 シリコーンオイル中に無機または有機系微粒子を混ぜることによって、 シリコーンオイルの撥水性をより向上させようとする試みがなされている。  Therefore, attempts have been made to further improve the water repellency of silicone oil by mixing inorganic or organic fine particles in silicone oil.
例えば、 特許文献 1には、 「塗膜表面の水接触角が 9 0度以上となるような樹脂 溶液と、 塗膜硬化後表面に微細凹凸を付与しうる無機または有機系微粒子とから なる撥水性コーティング用組成物」 が記載され、 この組成物を塗布した熱交換器 では直径 1 m m程度の微細な水滴をフィン表面から落とすことができるという。 また、 特許文献 2では、 「少なく とも表面が疎水性である平均粒径 1 n m〜 1 m mの微粒子と樹脂塗膜からなり、 該微粒子が該樹脂と膜表面積の 2 0 %以上の領 域に露出されて固着されていること特徴とする撥水性被膜」 によって、 いわゆる 蓮の葉が水を弹くような撥水性を得ようとしている。 そして、 特許文献 2には、 微粒子の平均粒径について、 小さくなると凹凸形状の効果が低下して接触角が小 さくなり、 大きくなると細かい水滴に対する撥水性が低下するので 1 η π！〜 1 m mに限定されると記載されている。  For example, Patent Literature 1 discloses that “a resin solution having a water contact angle of 90 ° or more on a coating film surface and inorganic or organic fine particles capable of providing fine irregularities on the surface after the coating film is cured. Aqueous coating composition "is described, and it is said that a heat exchanger coated with this composition can drop fine water droplets of about 1 mm in diameter from the fin surface. Patent Document 2 discloses that, `` at least a particle having a hydrophobic surface and having an average particle diameter of 1 nm to 1 mm is composed of a resin coating film, and the fine particles are in an area of 20% or more of the resin and the film surface area. The water-repellent coating, which is characterized by being exposed and fixed, is trying to obtain the water-repellency of so-called lotus leaves. Patent Document 2 discloses that the average particle diameter of the fine particles is smaller, the effect of the concavo-convex shape is lower, the contact angle is smaller, and the larger the average particle diameter, the lower the water repellency against fine water droplets. It is stated that it is limited to ~ 1 mm.
さらに、特許文献 3には、 「水の接触角が 1 2 0 °に満たない材料からなる表面上 に形成した際、 その被膜表面における水の接触角を 1 5 0。以上とすることが可能 な撥水性被膜であって、 前記表面上に形成された、 粘着性を有する撥水性高分子 を含む層と、 前記粘着性を有する撥水性高分子を含む層表面に固着された、 撥水 性シリカ粒子とからなる被膜であり、 前記粘着性を有する撥水性高分子を含む層 自体の表面における水の接触角は、 1 2 0。以下であり、 前記撥水性シリカ粒子の 平均粒子径は、 0 . 1 ~ 1 0 0 mの範囲に選択され、 対応させて、 表面に固着 された前記撥水性シリカ粒子の面密度は、 1 0 2~ 1 0 8個/ mm2の範囲に選択さ れていることを特徴とする撥水性被膜」 が記載され、 得られる撥水性被膜は接触 角が 1 5 0 ° 以上であること、 「粘着性を有する撥水性高分子を含む層を構成する 粘着性を有する撥水性高分子は、 その表面に撥水性シリ力粒子を安定に固着する 際、 パインダ一として機能するものであり、 上記の粘着性含フッ素高分子、 ある いは、 この粘着性含フッ素高分子と粘性シリコーン樹脂との混合物を利用するこ とが一層好ましい」 ことが記載されている。. Further, Patent Document 3 discloses that “water has a contact angle of less than 120 ° When formed, the contact angle of water on the coating surface was 150. A water-repellent coating that can be formed as described above, wherein the layer is formed on the surface and contains a water-repellent polymer having an adhesive property, and is fixed to a surface of the layer containing the water-repellent polymer having an adhesive property. The contact angle of water on the surface of the layer containing the water-repellent polymer having the adhesive property is 120. The average particle diameter of the water-repellent silica particles is selected from the range of 0.1 to 100 m, and the surface density of the water-repellent silica particles fixed on the surface is 10 it describes water-repellent film ", characterized in that the selected 2 to 1 0 in 8 / mm 2 range, the resulting water-repellent film is that the contact angle is 1 5 0 ° or more," sticky The water-repellent polymer having tackiness, which constitutes the layer containing the water-repellent polymer having water repellency, functions as a binder when the water-repellent sily particles are stably fixed to the surface thereof. It is more preferable to use an adhesive fluoropolymer or a mixture of the adhesive fluoropolymer and a viscous silicone resin. " .
さらにまた、 特許文献 4には、 1 n m~ 1 mの範囲内にある径を有するゲル 粒子と疎水性ポリマー材料とからなる表面変性剤が記載され、 それによつて、 少 なく とも 1 5 0 ° の接触角、 さらには少なく とも 1 6 0 ° の接触角を有するコー ティングが形成されることが記載されている。  Furthermore, Patent Document 4 describes a surface modifier comprising gel particles having a diameter in the range of 1 nm to 1 m and a hydrophobic polymer material, whereby at least 150 ° It is described that a coating having a contact angle of at least 160 ° and a contact angle of at least 160 ° is formed.
しかしながら、 これらの従来技術は、 いずれもコーティング表面における疎水 性の向上を目的とするもので、 接触角が 1 6 0 ° を超えるような超撥水性の表面 を提供できるというが、 コーティングの透明性 （光沢） や強度については不明で のる。  However, these conventional techniques are all aimed at improving the hydrophobicity of the coating surface, and can provide a super water-repellent surface having a contact angle of more than 160 °. (Gloss) and strength are unknown.
撥水剤を物品表面に適用する際、 その物品自体の色、 材質感などを損なわない ために、 コーティング膜は、 透明で光沢を有することが要望される。 また、 ー且 撥水剤コーティングを行った後は、 物品表面から剥離することなく長時間撥水性 を維持できることが望まれる。  When applying a water repellent to the surface of an article, the coating film is required to be transparent and glossy so as not to impair the color and texture of the article itself. Further, it is desired that after the water repellent coating is performed, the water repellency can be maintained for a long time without peeling off from the article surface.
特に、 撥水剤を船舶、 航空機、 自動車などの車両、 建造物に適用する際などに おいては、 撥水性が高いのみでなく、 撥水剤コーティングの透明性や光沢性が髙 いことがユーザーにとって関心が高い。 また、 撥水剤コーティング後、 コーティ ング物品の洗浄や清拭によっても、 あるいは物品が外気や光に暴露されても、 撥 水剤が剥離したり変質することなく、 撥水性を長時間維持できることがユーザー の強い要望となる。 In particular, when a water repellent is applied to ships, aircraft, automobiles, and other vehicles and buildings, not only the water repellency is high, but also the transparency and gloss of the water repellent coating are low. High interest for users. Also, after coating the water repellent with the water repellent, the coated product can be repelled by washing or wiping, or even if the product is exposed to outside air or light. It is a strong demand from users to be able to maintain water repellency for a long time without exfoliation or deterioration of the liquid agent.
[特許文献 1]  [Patent Document 1]
特開平 7— 3 2853 2号公報  JP-A-7-328532
[特許文献 2]  [Patent Document 2]
特開平 3— 2446 79号公報  JP-A-3-244679
[特許文献 3]  [Patent Document 3]
特開 2003— 543 1 8号公報  JP 2003-54318A
[特許文献 4]  [Patent Document 4]
特開 2003— 50756 7号公報  JP 2003-50756 7
[発明の開示] [Disclosure of the Invention]
本発明の課題は、 上記の従来技術の問題点を解決することであって、 撥水性が 高く、 且つ、 撥水剤のコーティング後において、 高い透明性 （光沢性） と強度を 併せ持つ撥水剤を提供することにある。  An object of the present invention is to solve the above-mentioned problems of the prior art. The water repellent has high water repellency, and has high transparency (glossiness) and strength after coating with the water repellent. Is to provide.
さらに、 本発明は、 そのような撥水性、 透明性、 及ぴ強度の高い撥水剤をコー ティングした物品、 及びその製造方法を提供することも課題とする。  Further, another object of the present invention is to provide an article coated with such a water repellent having high water repellency, transparency, and strength, and a method for producing the same.
本発明者らは、 上記課題を鋭意研究した結果、 シリ コーンオイル、 微粒子、 及 ぴ溶剤を含む撥水剤において、 微粒子同士、 及ぴ または微粒子とシリ コーンォ ィルとの結合性を増強できるような微粒子結合剤を添加することによって、 撥水 剤コーティング膜の強度を増強できることを見出し、 本発明に至った。 なお、 本 発明において膜の強度とは、 撥水剤を固体表面にコーティングした際、 長時間剥 離することなく、 また、 水圧、 布による摩擦などによっても剥離せず、 あるいは 外気や光に暴露されても、 撥水剤が剥離したり変質することなく、 長時間撥水性 を維持することをいう。  The present inventors have conducted intensive studies on the above problems, and have found that, in a water repellent containing silicone oil, fine particles, and a solvent, it is possible to enhance the binding between the fine particles and / or the fine particles and the silicone oil. It has been found that the strength of the water-repellent coating film can be enhanced by adding a fine particle binder, and the present invention has been accomplished. The strength of the film in the present invention means that when a water repellent is coated on a solid surface, it does not peel off for a long time, does not peel off due to friction with water pressure or cloth, or is exposed to outside air or light. This means that the water repellent keeps water repellency for a long time without peeling off or deteriorating.
また、 本発明者らは、 撥水剤コーティング後の撥水性膜の表面が、 特定寸法の 凹凸を有するときに高い撥水性を発揮できることを見出し、 そのために撥水剤中 の微粒子に好ましい粒子径があることを見出した。 '  In addition, the present inventors have found that the surface of the water-repellent film after the coating with the water-repellent agent can exhibit high water-repellency when the surface has irregularities of a specific size. I found that there is. '
さらに、 本発明者らは、 透明性を確保するために、 表面凹凸による乱反射が可 視光によって見えないことが必要であることを見出し、 透明性のためにも、 表面 凹 ώは特定寸法が好ましいことを見出した。 Further, the present inventors have proposed that irregular reflection due to surface irregularities is possible in order to ensure transparency. It was found that it was necessary to be invisible with visual light, and it was found that a specific size of the surface depression was preferable for transparency.
さらにまた、 本発明者らは、 上記の撥水剤に界面活性剤をさらに添加すること で、 撥水剤が長期にわたって保存性が良く、 スプレーの際に目詰まりも少ないこ とを見出した。  Furthermore, the present inventors have found that by further adding a surfactant to the above-mentioned water repellent, the water repellent has good storage stability over a long period of time and has little clogging when sprayed.
本発明は、 以上の知見によりなされたもので、 以下に関する。  The present invention has been made based on the above findings, and relates to the following.
( 1 ) シリコーンオイル、 微粒子、 微粒子の結合剤、 水系溶剤及び水を含むこ とを特徴とする撥水剤。  (1) A water repellent comprising silicone oil, fine particles, a fine particle binder, an aqueous solvent and water.
(2) シリコーンオイルがポリジメチルシロキサンである上記 （1 ) 記載の撥 水剤。  (2) The water repellent according to the above (1), wherein the silicone oil is polydimethylsiloxane.
(3) 微粒子の平均粒子径が 1〜 1 0 0 nmである上記 （1 ) または （2) に 記載の撥水剤。  (3) The water repellent according to (1) or (2), wherein the fine particles have an average particle size of 1 to 100 nm.
(4) 微粒子の平均粒子径が 5 ~ 20 nmである上記 （3) 記载の撥水剤。 (4) The water repellent according to the above (3), wherein the average particle diameter of the fine particles is 5 to 20 nm.
(5) 微粒子が金属酸化物からなる請求項 1 ~4のいずれかに記載の撥水剤。(5) The water repellent according to any one of claims 1 to 4, wherein the fine particles are made of a metal oxide.
(6) 微粒子がシリカからなる上記 （1 ) 〜 （4) のいずれかに記載の撥水剤。(6) The water repellent according to any one of the above (1) to (4), wherein the fine particles are made of silica.
(7) 微粒子の結合剤がワックス及ぴ Zまたはパラフィンである上記 （1 ) ~ (6) のいずれかに記載の撥水剤。 (7) The water repellent according to any one of the above (1) to (6), wherein the binder of the fine particles is wax, Z or paraffin.
(8) シリ コーンオイル、 平均粒子径 5 ~ 2 0 nmのシリカ微粒子、 ワックス 及び/またはパラフィン、 水系溶剤及び水を含むことを特徴とする撥水剤。  (8) A water repellent comprising silicone oil, silica fine particles having an average particle diameter of 5 to 20 nm, wax and / or paraffin, an aqueous solvent and water.
(9) さらに界面活性剤を含む上記 （1) 〜 （8) のいずれかに記載の撥水剤。 (9) The water repellent according to any one of the above (1) to (8), further comprising a surfactant.
( 1 0) 界面活性 Jとしてジアルキルアンモニゥムクロライドを含む上記 （9) に記載の撥水剤。 (10) The water repellent according to the above (9), which comprises a dialkylammonium chloride as the surface activity J.
( 1 1 ) 微粒子の結合剤を有機溶剤に混合して加熱溶解し、 微粒子を添加混合 することにより得た混合物を乾燥する工程、 該乾燥物にシリ コーンオイル、 水系 溶剤、 及び水を添加攪拌する工程を含む上記 （1 ) 〜 （8) のいずれかに記載の 撥水剤の製造方法。  (11) A step of mixing a binder of fine particles with an organic solvent, heating and dissolving the mixture, and drying the mixture obtained by adding and mixing the fine particles.Adding silicone oil, an aqueous solvent, and water to the dried product and stirring. The method for producing a water repellent according to any one of the above (1) to (8), which comprises a step of:
( 1 2) 微粒子の結合剤を有機溶剤に混合して加熱溶解し、 微粒子を添加混合 することにより得た混合物を乾燥する工程、 該乾燥物にシリコーンオイル、 水系 溶剤、 及び水を添加攪拌する工程を含む撥水剤の製造方法において、 微粒子の結 合剤を有機溶剤に混合して加熱溶解する工程、 あるいはシリ コーンオイル、 水系 溶剤、 及ぴ水を添加攪拌する工程のいずれかの工程で、 界面活性剤をさらに添加 する上記 （9) または （1 0) に記載の撥水剤の製造方法。 (12) A step of mixing the binder of the fine particles in an organic solvent, heating and dissolving the mixture, and drying the mixture obtained by adding and mixing the fine particles. To the dried product, add silicone oil, an aqueous solvent, and water, and stir. In the method for producing a water repellent including the step of (9) or (9) wherein a surfactant is further added in one of the steps of mixing and heating and dissolving the mixture in an organic solvent, or adding and stirring silicone oil, an aqueous solvent, and water. 10. The method for producing a water repellent according to the above item 10).
( 1 3) 上記 （1 ) ~ ( 1 0) のいずれかに記載の撥水剤がコーティングされ てなるコーティング物品。  (13) A coated article coated with the water repellent according to any one of (1) to (10).
(1 4) コーティング量が単位表面積当たり 3 0 ~ 5 0 n g /mm 2である上記(1 4) coating amount above a unit surface area per 3 0 ~ 5 0 ng / mm 2
( 1 3) 記載のコーティング物品。 (13) The coated article as described in (13).
( 1 5) コーティング量が単位表面積当たり 3 5〜40 n g /mm 2である上記(1 5) coating amount above a 3 5~40 ng / mm 2 per unit surface area
( 1 4) に記载のコーティング物品。. The coated article described in (14). .
( 1 6) 3 0〜 2 0 0 nmの凹凸を表面に有する上記 （1 3) ~ ( 1 5) のい ずれかに記载のコーティング物品。  (16) The coated article according to any one of the above (13) to (15), wherein the surface has irregularities of 30 to 200 nm.
( 1 7) 上記 （1) 〜 （ 1 0) のいずれかに記載の撥水剤をスプレーしてコ一 ティング物品を製造する方法。  (17) A method for producing a coated article by spraying the water repellent according to any one of the above (1) to (10).
( 1 8) スプレーした撥水剤をすばやく乾燥させながらスプレーすることを特 徴とする上記 （1 7) 記載のコーティング物品の製造方法。  (18) The method for producing a coated article according to the above (17), wherein the sprayed water repellent is sprayed while being quickly dried.
( 1 9) 撥水剤を間欠的にスプレーすることを特徴とする上記 （1 7) または ( 1 8) 記載のコーティング物品の製造方法。  (19) The method for producing a coated article according to the above (17) or (18), wherein the water repellent is sprayed intermittently.
(2 0) スプレーノズルの径及ぴ Z又は噴射圧力を調整することによってコー ティング量を調整することを特徴とする上記 （1 7) 〜 （ 1 9) のいずれかに記 载のコ一ティング物品の製造方法。  (20) The coating according to any one of (17) to (19) above, wherein the coating amount is adjusted by adjusting the diameter and the Z of the spray nozzle or the injection pressure. Article manufacturing method.
(2 1 ) 上記 （1 ) ~ ( 1 0) のいずれかに記載の撥水剤を洗車機に用いる撥 水剤の使用方法。  (21) A method for using the water repellent according to any one of the above (1) to (10) for a car washer.
以上の構成により、 本発明の撥水剤、 及ぴ本発明の撥水剤によりコーティング された物品は、 高い撥水性と透明性と強度とを併せ持つことができ、 コーティン グ後 1ヶ月たつても撥水性能が低下しない優れた効果を奏することができた。  With the above configuration, the water repellent of the present invention and the article coated with the water repellent of the present invention can have both high water repellency, transparency and strength, and even one month after coating. An excellent effect that the water repellency is not reduced can be obtained.
[図面の簡単な説明〕 [Brief description of drawings]
図 1は、 本発明のコーティングに用いるスプレー装置の一例を示す。  FIG. 1 shows an example of a spray device used for the coating of the present invention.
図 2は、 本発明の撥水剤を洗車機に用いるための装置の一例を示す。 図 3は、 結合剤なしの比較例の顕微鏡写真を示す。 FIG. 2 shows an example of an apparatus for using the water repellent of the present invention in a car washer. FIG. 3 shows a micrograph of a comparative example without binder.
図 4は、 本発明の実施例の顕微鏡写真を示す。  FIG. 4 shows a micrograph of an example of the present invention.
[発明の実施における最良の形態] [Best mode for carrying out the invention]
以下に、 本発明を具体的に説明するが、 本発明はそれに限定されるわけではな い。  Hereinafter, the present invention will be described specifically, but the present invention is not limited thereto.
本発明の撥水剤は、 固体物品の表面を撥水処理するのに用いられる。 固体物品 は、 金属、 セラミック、 ガラス、 プラスチックなどの硬い素材でも、 繊維などの 柔らかい素材でもいずれでも適用できる。 特に、 船舶、 航空機、 自動車などの車 両、 建造物、 ミラー、 タイル、 布帛の処理に好適に使用できる。  The water repellent of the present invention is used for performing water repellent treatment on the surface of a solid article. Solid articles can be applied to hard materials such as metals, ceramics, glass and plastics, as well as soft materials such as fibers. In particular, it can be suitably used for treating vehicles such as ships, aircraft, and automobiles, buildings, mirrors, tiles, and fabrics.
本発明の撥水剤に用いるシリコーンオイル （オルガノポリシロキサン） として は、 微粒子と混合して粘性を有する液状物を形成できるものであればいずれでも 良く、 ァミノ変性シリコーンオイル、 高級脂肪酸変性シリ コーンオイル、 ジメチ ルシリ コーンオイノレ、 アルキル変' [·生シリ コーンオイル、 アルキルァラキル変性シ リ コーンオイル、 エポキシ変性シリコーンオイル、 カルボキシリル変性シリコー ンオイルなどが用いられる。  The silicone oil (organopolysiloxane) used in the water repellent of the present invention may be any one that can form a viscous liquid by mixing with fine particles. Amino-modified silicone oil, higher fatty acid-modified silicone oil Dimethyl silicone oil, alkyl-modified silicone oil, alkyl aralkyl-modified silicone oil, epoxy-modified silicone oil, carboxylyl-modified silicone oil, and the like.
好ましくはァミノ変性シリコーンオイル、 ジメチルシリコーンオイル （ポリジ メチルシロキサン） である。  Preferred are amino-modified silicone oil and dimethyl silicone oil (polymethylsiloxane).
シリコーンオイルの粘度は、 5 〜 1 0 0 ， O O O ctsが好ましく、 さらに好まし くは、 5 0 〜 5 0 O ctsである。  The viscosity of the silicone oil is preferably from 5 to 100, OO Octs, and more preferably from 50 to 50 Octs.
本発明で用いる微粒子としては、 無機物質でも有機物質でも構わないが、 変質 しない無機物質が好ましい。 材質は問わないが、 n mオーダーの粒径の微粒子を 得るためには、 シリカ、 アルミナ、 チタニアなどの無機酸化物が好ましく、 平均 粒子径が 5 2 0 n mの市販品がある点からシリ力が最も好ましい。 この微粒子 シリカとして、日本ァェロジル株式会社製、ァェロジル1^ 972、 972¥、 1?972じ？、11974、 R812、 R805, RX200、 RX300、 RY200 (いずれも疎水性シリカ） などが挙げられ、 中 でもァエロジル R 972、 RX200が好ましい。 微粒子として、 その他、 日本ァエロジ ル株式会社製、 ァエロジル 50、 90G、 130、 200、 200V、 200CF、 200FAD、 300、 300CF、 380、 R202、 R812S, 0X50、 TT600、 M0X80、 MOX170、 C0K84, 酸化アルミニウム C、 二酸化チタン T805、 二酸化チタン Ρ25等も用いることができる。 これらの微粒子 のうち親水性の微粒子は、 あらかじめシラン力ップリング剤で疎水処理しておく ことが好ましい。 The fine particles used in the present invention may be an inorganic substance or an organic substance, but an inorganic substance which does not deteriorate is preferable. Although the material is not limited, inorganic oxides such as silica, alumina, and titania are preferable in order to obtain fine particles having a particle size on the order of nm.Since there is a commercially available product having an average particle size of 520 nm, the silica force is high. Most preferred. These fine silica particles are made by Nippon Aerodil Co., Ltd., Aerodil 1 ^ 972, 972 ¥, 1 ~ 972 , 11974, R812, R805, RX200, RX300, RY200 (all of which are hydrophobic silica), among which aerosil R972 and RX200 are preferred. Other fine particles, manufactured by Nippon Aerosil Co., Ltd., Aerosil 50, 90G, 130, 200, 200V, 200CF, 200FAD, 300, 300CF, 380, R202, R812S, 0X50, TT600, M0X80, MOX170, C0K84, Aluminum oxide C , Titanium dioxide T805, titanium dioxide # 25 and the like can also be used. Among these fine particles, hydrophilic fine particles are preferably subjected to hydrophobic treatment with a silane coupling agent in advance.
微粒子の結合剤としては、 樹脂類、 界面活性剤類、 油脂類などが用いられる。 樹脂類として、 アクリル樹脂、 エポキシ樹脂、 シリコーン樹脂など；界面活性 剤としては、 モノアルキルアンモニゥムクロライ ド、 ジアルキルアンモニゥムク 口ライ ド、エチレンォキサイ ド付加型アンモニゥムクロライド、ァミン酢酸塩類、 アルキルァミン、 アルキルジァミン、 アルキルアミ ド、 ビスアミ ド、 アルキルァ ミンエチレンォキサイ ド付加物、脂肪酸ェチレノキサイ ド付加物、脂肪塩類など； 油脂類としては、 脂肪酸、 脂肪酸エステル、 カルナパ、 キャンデリラ、 ラノリン などの動植物油、 ぺトロール、 イソパラフィン、 ノルマルパラフィン、 パラフィ ンワックス、 マイクロクリスタルワックス、 ペトロラタムなどの鉱物油類、 モン タン酸やそのエステルワックス、 ポリオレフインワックス、 ヒ ドロキシステアリ ン酸系エステルヮックスなど合成ワックスが挙げられる。 好ましくはヮックス状 (常温で固体、 加熱時に比較的 低粘度の液体になる有機物） を有するもが良い。 さらに好ましくは融点 115° F〜155° F (46.1°C〜63.9°C) のパラフィンワックス と 10〜： !OOctsのノルマルパラフィンを混合したものが用いられる。  As the binder for the fine particles, resins, surfactants, fats and oils and the like are used. Resins: acrylic resin, epoxy resin, silicone resin, etc .; Surfactants: monoalkyl ammonium chloride, dialkyl ammonium chloride, ethylene oxide-added ammonium chloride, amine acetates , Alkylamines, alkyldiamines, alkylamides, bisamides, alkylamine ethylene oxide adducts, fatty acid ethylenoxide adducts, fatty salts, etc .; Petrol, isoparaffin, normal paraffin, paraffin wax, microcrystal wax, mineral oils such as petrolatum, monic acid and its ester wax, polyolefin wax, hydroxy And synthetic waxes stearic phosphate based Esuteruwakkusu the like. Preferably, it has a glassy state (an organic substance which becomes solid at room temperature and becomes a liquid having a relatively low viscosity when heated). More preferably, a mixture of paraffin wax having a melting point of 115 ° F. to 155 ° F. (46.1 ° C. to 63.9 ° C.) and 10 to:! OOcts normal paraffin is used.
パラフィンは、古くから撥水剤として用いられるが （例えば、特開昭 62-263279 号公報参照）、 本発明では、 パラフィンは、 微粒子同士、 及ぴ 又は微粒子とシリ コーンオイルとの結合性を増強するために添加するものである。 パラフィンと微 粒子のみ、 あるいはシリコーンと微粒子のみからなる撥水剤では、 所望の強度は 得られない。  Paraffin has long been used as a water repellent (see, for example, JP-A-62-263279), but in the present invention, paraffin enhances the binding between fine particles and / or the fine particles and silicone oil. It is added in order to A water repellent consisting of only paraffin and fine particles or only silicone and fine particles cannot provide the desired strength.
本発明において、 撥水剤に界面活性剤を添加すると、 微粒子の分散性がよくな り、 長期間保存しても分離せず保存性が向上する。 また、 界面活性剤は、 撥水剤 をスプレーするときスプレーノズルを目詰まりさせないという効果を奏すること もできる。 用いられる界面活性剤としては、 陽イオン界面活性剤が好ましく、 中 でも、 モノアノレキルアンモニゥムクロライ ド、 ジアルキルアンモニゥムクロライ ドがさらに好ましい。  In the present invention, when a surfactant is added to the water repellent, the dispersibility of the fine particles is improved, and the particles are not separated even when stored for a long period of time, and the storage stability is improved. Further, the surfactant can also have an effect of preventing clogging of the spray nozzle when spraying the water repellent. As the surfactant to be used, a cationic surfactant is preferable, and among them, mono-anolekylammonium chloride and dialkylammonium chloride are more preferable.
本発明における水系溶剤とは、 水親和性を有する有機溶剤のことである。 水系溶剤として、 アルコール、 グリコール、 エステル、 ケトン、 エーテルなど、 撥水剤に通常用いられる溶剤をいずれも用いることが出来るが、 沸点、 引火点が 高く、 毒性が低いという安全性の面から、 1,2-プロパンジオール （プロピレンダリ コーノレ） 、 2—メチノレー 2， 4一ペンタンジォ一/レ （へキシレングリコーノレ）、 ジエチレングリコールモノブチルエーテル （プチルジグリ コール）、 1， 5—ペン タンジオール （ペンタメチレングリコール） が好ましい。 The aqueous solvent in the present invention is an organic solvent having affinity for water. As the aqueous solvent, any of the solvents commonly used for water repellents, such as alcohols, glycols, esters, ketones, and ethers, can be used. , 2-propanediol (propylenedali cornole), 2-methinole 2,4-pentanediole / hexene (hexylene glycolone), diethylene glycol monobutyl ether (butyldiglycol), and 1,5-pentanediol (pentamethylene glycol) are preferred. .
本発明の撥水剤において、 用いる微粒子の平均粒子径は 1〜 1 0 0 n mが好ま しく、 撥水性と光沢と強度をパランスよく満足させるためには、 5〜2 0 n mで あることがさらに好ましい。  In the water repellent of the present invention, the average particle size of the fine particles to be used is preferably 1 to 100 nm, and in order to satisfy water repellency, gloss and strength with good balance, it is more preferably 5 to 20 nm. preferable.
本発明において、 結合剤は、 微粒子に対して重量比で 0 . 0 1〜2 0 %の範囲 が好ましく、 さらに 0 . 1〜 1 0 %が好ましい。 結合剤が 0 · 0 1 %以下の時は 強度が得られず、 2 0 %を超えると、 光沢度が低下する。  In the present invention, the weight ratio of the binder to the fine particles is preferably in the range of 0.01% to 20%, more preferably 0.1% to 10%. When the binder is less than 0.1%, no strength is obtained, and when it exceeds 20%, the gloss decreases.
本発明において、 シリコーンオイルは、 微粒子に対して重量比で 0 . 1 ~ 1 0 0 %の範囲が好ましく、 さらに 2 ~ 3 0 %が好ましい。 シリ コーンオイルが 0 . 1 %以下の時は強度が得られず、 1 0 0 %を超えると、 光沢度が低下する。  In the present invention, the weight ratio of silicone oil to fine particles is preferably in the range of 0.1 to 100%, more preferably 2 to 30%. When the silicone oil content is less than 0.1%, the strength is not obtained, and when it exceeds 100%, the gloss decreases.
水系溶剤の量は、 微粒子が十分分散性を示す量であれば良く、 微粒子 1重量部 に対して 1〜 1 5重量部が好ましく、 5 ~ 1 0重量部がより好ましい。 水系溶剤 が 1重量部以下の時は十分な分散性を示さず、 1 5重量部を超えると、 撥水剤と しての付着効率が低下する。  The amount of the aqueous solvent is not particularly limited as long as the fine particles show sufficient dispersibility, and is preferably 1 to 15 parts by weight, more preferably 5 to 10 parts by weight, per 1 part by weight of the fine particles. When the amount of the aqueous solvent is less than 1 part by weight, sufficient dispersibility is not exhibited. When the amount exceeds 15 parts by weight, the adhesion efficiency as a water repellent decreases.
本発明の撥水剤は、 微粒子の結合剤を溶媒に混合して加熱溶解し、 微粒子を添 加混合して得た混合物を攪拌下で減圧乾燥する工程、 該乾燥物にシリコーンオイ ル、 水系溶剤、 及ぴ水を添加攪拌する工程によって製造することが出来る。  The water repellent of the present invention comprises a step of mixing a binder of fine particles in a solvent, heating and dissolving the mixture, adding and mixing the fine particles, and drying the mixture under reduced pressure under stirring. It can be produced by adding and stirring a solvent and water.
界面活性剤、 特に陽イオン界面活性剤を添加するときには、 微粒子の結合剤を 溶媒に混合して加熱溶解工程、 または、 乾燥物にシリコーンオイル、 水系溶剤、 及ぴ水を添加攪拌する工程添加することが出来る。  When adding a surfactant, especially a cationic surfactant, add the binder of the fine particles to the solvent and heat and dissolve it, or add the silicone oil, aqueous solvent, and water to the dried product and add a stirring step. I can do it.
結合剤を溶解させる溶媒としては、 結合剤が溶解性を示すものであれば良く、 親油性溶剤や親水性と親油性を併せ持つ両親媒性溶剤がより好ましい。 親油性溶 剤として、 ノルマルペンタン、 ノルマルへキサン、 両親媒性溶剤としてエタノー ル、 へキシルアルコールを例示することが出来る。 4 019745 As a solvent for dissolving the binder, any solvent may be used as long as the binder shows solubility, and a lipophilic solvent or an amphiphilic solvent having both hydrophilicity and lipophilicity is more preferable. Examples of the lipophilic solvent include normal pentane and normal hexane, and examples of the amphiphilic solvent include ethanol and hexyl alcohol. 4 019745
具体的には、 結合剤を微粒子重量比 0 . 0 1〜 2 0 %の範囲で計り取り、 親油 性溶剤と混合し、 加熱溶解させる。 このときの溶媒量は微粒子重量比で 1 5 ~ 2 0倍量とする。 結合剤と親油性溶剤とを加熱溶解させた状態で、 微粒子を加え攪 拌しながら減圧乾燥させる。 得られた乾燥物 1重量部に水系溶剤を 1〜 1 5重量 部加え十分攪拌混合し、 さらに攪拌下でシリコーンオイル 0 . 0 0 1〜 1重量部、 水 5 ~ 2 0重量部を順次加え攪拌する。 陽イオン界面活性剤を添加するときには、 微粒子重量比で 0 . 0 1〜 2 0 %添加する。 得られた混合物 1重量部に水 1 0 ~ 8 0重量部加えることによって撥水剤を製造する。 Specifically, the binder is weighed in the range of 0.01 to 20% by weight of the fine particles, mixed with a lipophilic solvent, and dissolved by heating. The amount of the solvent at this time is 15 to 20 times the weight of the fine particles. In a state where the binder and the lipophilic solvent are dissolved by heating, fine particles are added, and the mixture is dried under reduced pressure with stirring. 1 to 15 parts by weight of an aqueous solvent is added to 1 part by weight of the obtained dried product, and the mixture is sufficiently stirred and mixed. Then, with stirring, 0.001 to 1 part by weight of silicone oil and 5 to 20 parts by weight of water are sequentially added. Stir. When the cationic surfactant is added, 0.01 to 20% by weight of the fine particles is added. A water repellent is produced by adding 10 to 80 parts by weight of water to 1 part by weight of the obtained mixture.
上記撥水剤は、 金属、 セラミック、 布帛などの固体物質にスプレーコーティン グなどすることによってコーティング物品を得る。  The water repellent is obtained by applying a spray coating to a solid substance such as a metal, a ceramic, and a fabric to obtain a coated article.
コーティング量によって、 表面の凹凸の大きさが異なってきて、 撥水性 （接触 角） や光沢に差が出てくるので、 コーティング量を調節することが重要である。 コーティング量は、 単位表面積当たり 3 0〜 5 0 n g / m より好ましくは、 単位表面積当たり 3 5〜4 0 n g Z rn m 2である。 Depending on the amount of coating, the size of the unevenness on the surface will differ, resulting in differences in water repellency (contact angle) and gloss, so it is important to adjust the amount of coating. The coating amount is more preferably per unit surface area 3 0~ 5 0 ng / m, 3 per unit of surface area 5-4 is 0 ng Z rn m 2.
本発明でコーティング量は、 Q C M (水晶振動子マイク ロパランス ： Quartz Crystal Microbalance) を用いて測定することができる。  In the present invention, the coating amount can be measured using QCM (Quartz Crystal Microbalance).
表面の凹凸は、 3 0 ~ 2 0 0 ri mが撥水性及ぴ光沢の面から好ましい。  The surface unevenness is preferably 30 to 200 rim from the viewpoint of water repellency and gloss.
凹 ώは、 原子間力顕微鏡 （A F M) を用いて測定することができる。  The depression can be measured using an atomic force microscope (AFM).
コーティング方法は、 ローラーコーティング、 含浸、 スプレーなど周知のいず れの手段でも使用できるが、 スプレーが好ましい。  As a coating method, any known method such as roller coating, impregnation, spraying and the like can be used, but spraying is preferred.
スプレーしてコーティング物品を製造するに際しては、 通常にスプレーするだ けでも良いが、 スプレーした撥水剤をすばやく乾燥させながらスプレーすること が好ましい。 スプレーした撥水剤をすばやく乾燥させながらスプレーを行うこと で、 乾燥して凹凸を形成した撥水剤コーティングの上にさらにスプレーするとい う状況が維持できるために、 表面に好ましい凹凸を形成することができる。 すば やく乾燥させながらスプレーを行うためには、 撥水剤をスプレーすると同時に乾 燥空気を吹き付けるなどの方法をとることができる。  When producing a coated article by spraying, normal spraying may be sufficient, but spraying while sprayed water repellent is dried quickly is preferred. Spraying the sprayed water repellent while drying it quickly, so that the situation of spraying on the water repellent coating that has been dried to form irregularities can be maintained. Can be. In order to spray while drying quickly, a method such as spraying a dry air while spraying a water repellent can be used.
また、 スプレーを固体表面に対して間欠的に行うことによつても、 すばやく乾 燥させながらスプレーするという状況を実現できる。 間欠的にスプレーするため には、 ノズル位置を固定してお-いて、 噴射を間欠的に行っても良いし、 スライダ 一などを利用してノズルを移動させることによって行っても良い。 具体的には、 スライダーなどにスプレーノズルを载置し、 スプレーノズルをスライダーにより 往復移動させながら撥水剤をスプレーする。 固体表面上のあるボイントに着目す れば、 あるポイントに一定時間スプレーされたらスプレーノズルはそのボイント を通過してしまい、 復路でスプレーされるまでの間に撥水剤は乾燥され、 ある程 度乾燥した撥水剤の上に再度撥水剤がスプレーされることになる。 適当なコーテ イング量が得られるまで、 スプレ一ノズルの往復を行う。 また、 スライダーを用 いノズル位置を移動させながら、 かつ、 噴射も間欠的に行うこともできる。 この ような間欠的スプレーによって、 より好ましい凹凸表面が形成される。 Also, by intermittently spraying the solid surface, it is possible to realize a situation in which the spray is quickly dried and sprayed. To spray intermittently In this case, the nozzle position may be fixed, and the injection may be performed intermittently, or may be performed by moving the nozzle using a slider or the like. Specifically, a spray nozzle is placed on a slider or the like, and the water repellent is sprayed while the spray nozzle is reciprocated by the slider. Focusing on a certain point on the solid surface, if a certain point is sprayed for a certain period of time, the spray nozzle will pass through the point, and the water repellent will dry up to a certain degree before being sprayed on the return path. The water repellent is sprayed again on the dried water repellent. Reciprocate the spray nozzle until a suitable coating amount is obtained. In addition, the injection can be performed intermittently while moving the nozzle position using the slider. By such an intermittent spray, a more preferable uneven surface is formed.
このような間欠スプレーを行うためのスプレー装置の一例を図 1を参照しなが ら、 以下に説明する。  An example of a spray device for performing such an intermittent spray will be described below with reference to FIG.
図 1において、（ 1 )は、被コーティング物品であり、車のボディーを例示した。' (2) がスプレーノズルであり、 スプレーノズル （2) は、 電動スライダー （3) 上に固定されている。 電動スライダー （3) は、 モーター （4) により矢印方向 に往復駆動される。 電動スライダー （3) の往復動と共に往復するスプレーノズ ル （2) からは、 撥水剤がスプレーされる。 スプレーノズル （2) は、 撥水剤貯 槽 （5) およびポンプ （6) と連結されており、 撥水剤流量は、 該ポンプ （6) の吐出量で制御することもできるし、,該ポンプ （6) に設けた流量調節パルプ （図 示せず） によって制御することもできる。  In FIG. 1, (1) is an article to be coated, and exemplifies a car body. '(2) is the spray nozzle, and the spray nozzle (2) is fixed on the electric slider (3). The electric slider (3) is reciprocated in the direction of the arrow by the motor (4). A water repellent is sprayed from the spray nozzle (2) which reciprocates with the reciprocation of the electric slider (3). The spray nozzle (2) is connected to the water repellent storage tank (5) and the pump (6). The flow rate of the water repellent can be controlled by the discharge amount of the pump (6). It can also be controlled by a flow control pulp (not shown) provided in the pump (6).
ノズル （2) における撥水剤の噴射圧力は、 コンプレッサー （7) に設けられ た電磁弁 （図示せず） により制御される。 一方、 被コーティング物品には、 撥水 剤付着量を測定するための QCM (水晶振動子マイクロパランス： Quartz Crystal Microbalance) (8) が取り付けられている。 付着量は Q C Mの周波数変動として 周波数カウンタ （9) でカウントする。  The injection pressure of the water repellent in the nozzle (2) is controlled by a solenoid valve (not shown) provided in the compressor (7). On the other hand, the article to be coated is equipped with a QCM (Quartz Crystal Microbalance) [8] for measuring the amount of water repellent attached. The amount of adhesion is counted by the frequency counter (9) as the frequency fluctuation of QCM.
周波数カウンタ （9) のカウントに基づきポンプ （6) の吐出量や流量調節パ ルブの開度、 コンプレッサーの電磁弁をパソコン制御することによって、 コーテ ィング膜厚に応じた撥水剤流量を制御することができる。  The discharge rate of the pump (6), the opening of the flow control valve, and the solenoid valve of the compressor are controlled by a personal computer based on the count of the frequency counter (9) to control the flow rate of the water repellent in accordance with the coating film thickness. be able to.
図 1において、 （1 0) は、 スライダー （3) の駆動を制御するためのモーター 制御装置、 （1 1) (1 2) は、 電源装置である。 In Fig. 1, (10) is a motor for controlling the drive of the slider (3). The control device (1 1) (1 2) is a power supply device.
また、 本発明のスプレー装置は、 Q CMの周波数変動に応じて、 乾燥を制御す る制御手段、 例えば間欠タイマーをさらに設けることができる （図示せず）。 このような装置によって、 撥水剤の付着量を Q CMにより制御しながら、 コー ティング物品を製造することができる。  Further, the spray device of the present invention may further include a control means for controlling drying, for example, an intermittent timer according to the frequency fluctuation of QCM (not shown). With such an apparatus, a coated article can be manufactured while controlling the amount of the water repellent to be attached by QCM.
付着量は、 スプレーノズルの径及ぴ 又は噴射圧力を調整することによつても 調整することができる。  The amount of adhesion can also be adjusted by adjusting the diameter and the spray pressure of the spray nozzle.
本発明で、 スプレーノズルから噴射される撥水剤ミス トの粒径は 80 izm以下 が好ましく、 6~14 /xmに調整することがより好ましい。 ミス ト粒径をこの範 囲に調整することで、 望ましい凹凸を形成することができる。  In the present invention, the particle size of the water repellent mist sprayed from the spray nozzle is preferably 80 izm or less, and more preferably adjusted to 6 to 14 / xm. By adjusting the mist particle size within this range, desired irregularities can be formed.
また、 本発明の撥水剤を洗車機に用いる場合の一例を図 2に示した。  FIG. 2 shows an example of the case where the water repellent of the present invention is used in a car washer.
図 2において （1 3) 〜 （24) は、 スプレー用のノズルを示し、 洗車される 車体はノズル （1 3) 〜 （24) の下を徐々にくぐり移動することになる。 撥水 剤は、 '希釈水配管 （27) からの希釈水と共に撥水剤タンク （25) からェジェ クタ一 （28) によりノズルに送られ、 ノズルから車体に向けてスプレーされる。 このとき、 希釈水吐出圧 0~ 5 k g/ c m2, 原液使用量 20〜50 Om 1、 希釈 倍率 0. 1〜 5 °/。で、 洗車機の移動速度 0. 5〜 5 Omm/ s e cが好ましい。 In Fig. 2, (13) to (24) show the spray nozzles, and the car body to be washed gradually moves under the nozzles (13) to (24). The water repellent is sent from the water repellent tank (25) to the nozzle by the ejector (28) together with the dilution water from the dilution water pipe (27), and is sprayed from the nozzle toward the vehicle body. At this time, the dilution water discharge pressure was 0 to 5 kg / cm 2 , the stock solution used was 20 to 50 Om1, and the dilution ratio was 0.1 to 5 ° /. The moving speed of the car washer is preferably 0.5 to 5 Omm / sec.
[実施例] [Example]
以下に、 実施例を記載して、 本発明をより詳細に説明するが、 本発明はこれに 限られるわけではない。  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
[実施例 1]  [Example 1]
(撥水剤の製造）  (Manufacture of water repellent)
融点 1 1 5° F (46. 1。C) ノ ラフィンワックス 0. lg、 70 c t sのノル マルパラフィン 0. 1 gをノルマルへキサン 20 Ogに加え、 60でに加熱溶解さ せる。 さらに撩拌下で粒径 1 2nmのシリカ微粒子 （RX 200 ; 日本ァエロジル 株式会社製） を 10. Ogカ卩え、 ロータリーエバポレーターで減圧乾燥させる。 得 られた乾燥物 1. Ogにジエチレングリコールモノブチルエーテル （プチルジグリ コール； BDG) 9. 0g を加え攪拌し、 さらにポリジメチルシロキサン （G.E.シ リコーン製 TSF451-350) 0. ' 1 g、 水 1 5. O g加え 3時間攪拌する。 得られ た混合物 1重量部に水 2 2重量部加えることによって撥水剤とする。 Melting point: 115 ° F (46. 1.C) 0.1 g of normal wax, 0.1 gram of normal paraffin of 70 cts, is added to 20 Og of normal hexane, and dissolved by heating at 60 ° C. Further, under agitation, silica fine particles (RX 200; manufactured by Nippon Aerosil Co., Ltd.) having a particle size of 12 nm are 10. Og kagane and dried under reduced pressure with a rotary evaporator. Obtained dried product 1. 9.0 g of diethylene glycol monobutyl ether (butyl diglycol; BDG) was added to Og, and the mixture was stirred. 0. 1 g, 1 5. O g of water, and stir for 3 hours. A water repellent is obtained by adding 22 parts by weight of water to 1 part by weight of the obtained mixture.
[実施例 2]  [Example 2]
実施例 1の微粒子の粒径を 7 nm (RX300： 日本ァエロジル株式会社製） に変え た以外は、 同様にして撥水剤を製造した。  A water repellent was produced in the same manner as in Example 1 except that the particle size of the fine particles was changed to 7 nm (RX300: manufactured by Nippon Aerosil Co., Ltd.).
[実施例 3]  [Example 3]
実施例 1 ~ 2によって製造された撥水剤を金属基材からなる塗装被覆用テスト ピースに所定厚さが得られるまで乾燥させながら間欠スプレーした。 得られたコ 一チイングの特性を評価して表 1にまとめた。  The water repellent produced in Examples 1 and 2 was sprayed intermittently while drying it until a predetermined thickness was obtained on a test piece for coating and coating composed of a metal substrate. The properties of the obtained coatings were evaluated and summarized in Table 1.
以下の表において、距離は、 スプレーノズルからサンプルまでの距離、圧力は、 スプレーノズルの噴射圧力である。  In the following table, the distance is the distance from the spray nozzle to the sample, and the pressure is the spray pressure of the spray nozzle.
接触角は、 Kyoma Interface Science Co. LTD. Model: CA-DT  Contact angle is Kyoma Interface Science Co. LTD.Model: CA-DT
光沢は、 Horiba, Model: IG-330  Gloss is Horiba, Model: IG-330
転落角は、 Kyoma Interface Science Co. LTD. Model: CA-DT  Fall angle is Kyoma Interface Science Co. LTD.Model: CA-DT
ミスト径は、 LDSA Win 5.04L  Mist diameter is LDSA Win 5.04L
によって、 測定した。 接触角は、 上記の接触角計に 1 0 1の水滴を滴下するこ とで測定した。 なお、 Horiba, Model: IG-330の光沢計は、 LEDからの 8 0 0 η mの光を表面に照射して反射率を測るものであり、 コーティングなしの値を 1 0 0としたときのコーティング物品の反射率の値で示した。 Measured. The contact angle was measured by dropping 101 water droplets on the contact angle meter. The gloss meter of Horiba, Model: IG-330 measures the reflectance by irradiating 800 ηm light from the LED to the surface, and the value without coating is assumed to be 100. It was indicated by the value of the reflectance of the coated article.
。 接触角は 1 4 5。 以上、転落角は 4 0° 以下であれば実用上十分であり、接触角 1 6 0° 以上、転落角 2 0° 以下であればより優れた撥水性であることを示してい る。 撥水性は滑水性ともいわれ、 水滴が表面に付着せず、 転がり落ち易くなる性 質を示す。 [表 1 ] . The contact angle is 1 4 5. As described above, a falling angle of 40 ° or less is sufficient for practical use, and a contact angle of 160 ° or more and a falling angle of 20 ° or less indicates more excellent water repellency. Water repellency is also called slipperiness, meaning that water droplets do not adhere to the surface and roll off easily. [table 1 ]
Figure imgf000014_0001
Figure imgf000014_0001
[実施例 4 ] [Example 4]
結合剤量を変えた以外は、 実施例 1 と同様に撥水剤を製造し、 結合剤の有無あ るいはその量が、 撥水性、 光沢、 強度に与える影響を試験した。  A water repellent was produced in the same manner as in Example 1 except that the amount of the binder was changed, and the effect of the presence or absence of the binder on the water repellency, gloss, and strength was tested.
結果を表 2にまとめた。  Table 2 summarizes the results.
ここで、 H20 spray lOminは、 約 2気圧の水圧を 1 0分間スプレーした後の、 H20 spray 20min は、 2 0分スプレーした後の結果を示している。 また、 転落角 Xは、 基板を 9 0 ° 傾斜させても水滴が転がらないことを示している。 Here, H 2 0 spray lOmin is after spraying for 10 minutes a pressure of about 2 atm, H 2 0 spray 20min shows the results after 2 0 min spray. The falling angle X indicates that the water droplet does not roll even if the substrate is tilted by 90 °.
[表 2 ]  [Table 2]
Figure imgf000014_0002
この結果から、 結合剤なしのときは、 コーティング直後では十分は撥水性を示 すものの、 水圧による耐久試験によると、 撥水性が落ちることが分かる。 それに 対して、 結合剤を 1重量％以上添加することによって、 耐久性が向上しているこ とが分かる。 また、 結合剤を 2 0重量。 /0添加すると撥水性が低下してく るので、 結合剤添加量は 2 0重量％より少ないことが好ましいことが分かる。
Figure imgf000014_0002
From these results, it can be seen that when no binder is used, water repellency is sufficiently high immediately after coating, but the water repellency decreases according to a water pressure durability test. On the other hand, it can be seen that the durability is improved by adding 1% by weight or more of the binder. 20 weight of binder. Since the water repellency decreases when / 0 is added, it is understood that the amount of the binder added is preferably less than 20% by weight.
結合剤量が 1 w t %のコーティングについて、 原子間力顕微鏡 （A F M) を用 4 019745 Atomic force microscopy (AFM) for coatings with 1 wt% binder 4 019745
いて表面の凹凸を測定したところ、 平均 9 4 n mの凹凸であった。 When the surface roughness was measured, the average roughness was 94 nm.
また、 結合剤なしの例と結合剤パラブインを 1 w t %添加した例との電子顕微 鏡 （T E M) 写真を撮影した。 図 3が結合剤なし、 図 4が結合剤添加の例である。 図 3では、 微粒子が凝集してしまっているが、 図 4では、 微粒子がつながつてい るのが分かる。 この微粒子のつながりが、 コーティング物品表面に適度な凹凸を 与えることになる。  In addition, electron microscope (TEM) photographs were taken of the case without the binder and the case with the addition of 1 wt% of the binder parabuin. Fig. 3 shows an example without binder, and Fig. 4 shows an example with binder added. In Fig. 3, the particles are agglomerated, while in Fig. 4, the particles are connected. The connection of the fine particles gives the coated article a moderate unevenness.
[実施例 5 ]  [Example 5]
シリコーンオイル （ポリジメチルシロキサン） の量を種々に変更した以外は、 実施例 1と同様にして撥水剤を製造し、 実施例 3と同様にコーティングの特性を 評価した。  A water repellent was produced in the same manner as in Example 1 except that the amount of silicone oil (polydimethylsiloxane) was changed in various ways, and the properties of the coating were evaluated in the same manner as in Example 3.
[表 3 ]  [Table 3]
Figure imgf000015_0001
この結果から、 シリコーンオイルなしのときは、 コーティング直後では十分は 撥水性を示すものの、 水圧による耐久試験によると、 撥水性が落ちることが分か る。 それに対して、 シリコーンオイルを添加することによって、 耐久性が向上し ていることが分かる。
Figure imgf000015_0001
From these results, it can be seen that when no silicone oil is used, water repellency is sufficient immediately after coating, but the water repellency is reduced in a water pressure durability test. On the other hand, it can be seen that the durability was improved by adding the silicone oil.
[比較例 1 ]  [Comparative Example 1]
シリカ微粒子の粒径を 3 0 0 n mに変えた以外は実施例 1 と同様に撥水剤を製 造して、 撥水性を測定したところ、 接触角 6 5 ° と撥水性が劣っていた。  A water repellent was produced in the same manner as in Example 1 except that the particle size of the silica fine particles was changed to 300 nm, and the water repellency was measured. As a result, the contact angle was 65 ° and the water repellency was poor.
[実施例 6 ]  [Example 6]
実施例 1 の撥水剤を金属基材からなる塗装被覆用テス トピースにスプレーして 得られたコーティングの耐久性を試験した。 結果を表 4に示す。 The durability of the coating obtained by spraying the water repellent of Example 1 on a test piece for coating and coating composed of a metal substrate was tested. Table 4 shows the results.
[表 4]  [Table 4]
Figure imgf000016_0001
本発明の撥水剤は、 コーティング後 20日たつても、 十分な撥水性を有してい ることが分かる。
Figure imgf000016_0001
It can be seen that the water repellent of the present invention has sufficient water repellency even 20 days after coating.
また、 目視観察を続けたところ、 1力月半後でも、 超撥水性を維持し、 光沢度 においても十分な透明性を維持していた。  In addition, as a result of continuous visual observation, it was found that even after one and a half months, the super water repellency was maintained and the glossiness was sufficiently transparent.
[実施例 7]  [Example 7]
(撥水剤の製造）  (Manufacture of water repellent)
融点 1 1 5° F (46. 1。C) パラフィンワックス 0. 05 g、 70 c t sのノ ルマルパラフィン 0. 05g、 ジアルキルアンモニゥムクロライ ド （商品名 ：ァー カード、 ライオンァクゾ （株）） をノルマルへキサン 200g に加え、 60°Cに加 熱溶解させる。 さらに攪拌下で粒径 1 2mnのシリ力微粒子 （RX 200 ； 日本ァ エロジル株式会社製） を 1 0. 0g加え、 ロータリーェパポレーターで減圧乾燥さ せる。 得られた乾燥物 1. 0gにジエチレングリコールモノプチルエーテル （プチ ルジグリコール； BDG) 9. 0g を加え攪拌し、 さらにポリジメチルシロキサン Melting point: 115 ° F (46. 1.C) Paraffin wax: 0.05 g, 70 cts normal paraffin, 0.05 g, dialkylammonium chloride (trade name: Ercard, Lionaxo Co., Ltd.) Add 200 g of normal hexane and heat and dissolve at 60 ° C. Further, under stirring, 10.0 g of fine particles with a particle size of 12 mn (RX 200; manufactured by Nippon Aerosil Co., Ltd.) is added, and the mixture is dried under reduced pressure using a rotary evaporator. To 1.0 g of the obtained dried product, 9.0 g of diethylene glycol monobutyl ether (butyl diglycol; BDG) was added, and the mixture was stirred.
(G.E.シリコーン製 TSF451-350) 0. 1 g、 7 1 5. O g加え 3時間攪拌する。 得られた混合物 1重量部に水 22重量部加えることによって撥水剤とする。 (TSE451-350, manufactured by G.E. Silicone) 0.1 g, 71.5Og were added and stirred for 3 hours. A water repellent is obtained by adding 22 parts by weight of water to 1 part by weight of the obtained mixture.
(コーティング）  (Coating)
撥水剤原液 50 m 1を吐出圧 3. 0 k gZ c m2の希釈水で 6000 m 1 (希釈 倍率 0. 83%) に希釈して、 図 2の洗車機ノズルよりスプレーした。 洗車機の 移動速度は 1 ΟηιιαΖ s e cで、 3回繰り返しスプレーした。 The water repellent stock solution 50 m 1 was diluted with dilution water discharge pressure 3. 0 k gZ cm 2 to 6000 m 1 (dilution ratio 0.83%) were sprayed from car wash nozzle of FIG. The moving speed of the car washer was 1 ΖηιιαΖ sec, and spraying was repeated three times.
上記の撥水剤の製造法でシリコーン 0 · 05 gのもの、 比較としてシリコーン なしのときのものも調製して同様にコーティングした。  Using the above method for producing a water-repellent agent, one with 0.05 g of silicone and one without silicone were also prepared and coated in the same manner.
実施例 3と同様にコーティングの特性を評価して、 結果を表 5に示した。 [表 5 ] The properties of the coating were evaluated in the same manner as in Example 3, and the results are shown in Table 5. [Table 5]
Figure imgf000017_0001
この結果から、 本発明の撥水剤を洗車機のノズルに用いてスプレーすることで、 撥水性、 耐久性が十分なコーティングが得られることが分かった。
Figure imgf000017_0001
From these results, it was found that by spraying the water repellent of the present invention on the nozzle of the car washer, a coating having sufficient water repellency and durability could be obtained.
[産業上の利用可能性] . [Industrial applicability].
本発明により、 撥水性が良好で、 光沢、 強度も高い撥水剤及ぴコーティング物 品が得られた。  According to the present invention, a water repellent and a coated product having good water repellency, high gloss and high strength were obtained.

Claims

請 求 の 範 囲 The scope of the claims
1 . シリコーンオイル、 微粒子、 微粒子の結合剤、 水系溶剤及ぴ水を含むこと を特徴とする撥水剤。 1. A water repellent comprising silicone oil, fine particles, a fine particle binder, an aqueous solvent and water.
2 . シリコーンオイルがポリジメチルシロキサンである請求項 1記載の撥水剤。  2. The water repellent according to claim 1, wherein the silicone oil is polydimethylsiloxane.
3 . 微粒子の平均粒子径が 1 ~ 1 0 0 n mである請求項 1または 2に記載の撥 水剤。 3. The water repellent according to claim 1, wherein the fine particles have an average particle diameter of 1 to 100 nm.
4 . 微粒子の平均粒子径が 5 ~ 2 0 n mである請求項 3記載の撥水剤。  4. The water repellent according to claim 3, wherein the fine particles have an average particle size of 5 to 20 nm.
5 , 微粒子が金属酸化物からなる請求項 1〜4のいずれかに記載の撥水剤。 5. The water repellent according to claim 1, wherein the fine particles are made of a metal oxide.
6 . 微粒子がシリカからなる請求項 1 ~ 4のいずれかに記載の撥水剤。 6. The water repellent according to any one of claims 1 to 4, wherein the fine particles are made of silica.
7 . 微粒子の結合剤がヮックス及び/またはパラフィンである請求項 1 ~ 6の いずれかに記載の撥水剤。  7. The water repellent according to any one of claims 1 to 6, wherein the binder of the fine particles is a box and / or paraffin.
8 . シリコーンオイル、 平均粒子径 5 ~ 2 0 n mのシリカ微粒子、 ワックス及 ぴノまたはパラフィン、 水系溶剤及び水を含むことを特徴とする撥水剤。  8. A water repellent comprising silicone oil, silica fine particles having an average particle diameter of 5 to 20 nm, wax and phenol or paraffin, an aqueous solvent and water.
9 . さらに界面活性剤を含む請求項 1〜8のいずれかに記載の撥水剤。  9. The water repellent according to any one of claims 1 to 8, further comprising a surfactant.
1 0 . 界面活性剤としてジアルキルアンモニゥムクロライ ドを含む請求項 9に 記載の撥水剤。  10. The water repellent according to claim 9, comprising a dialkylammonium chloride as a surfactant.
1 1 . 微粒子の結合剤を有機溶剤に混合して加熱溶解し、 微粒子を添加混合す ることにより得た混合物を乾燥する工程、 該乾燥物にシリコーンオイル、 水系溶 剤、 及ぴ水を添加攪拌する工程を含む請求項 1 ~ 8のいずれかに記載の撥水剤の 製造方法。  11. Mixing the binder of the microparticles with the organic solvent, heating and dissolving the mixture, and adding and mixing the microparticles to dry the obtained mixture. Adding silicone oil, aqueous solvent, and water to the dried product 9. The method for producing a water repellent according to claim 1, comprising a step of stirring.
1 2 . 微粒子の結合剤を有機溶剤に混合して加熱溶解し、 微粒子を添加混合す ることにより得た混合物を乾燥する工程、 該乾燥物にシリ コーンオイル、 水系溶 剤、 及び水を添加攪拌する工程を含む撥水剤の製造方法において、 微粒子の結合 剤を有機溶剤に混合して加熱溶解する工程、 あるいはシリコーンオイル、 水系溶 剤、 及ぴ水を添加攪拌する工程のいずれかの工程で、 界面活性剤をさらに添加す る請求項 9または 1 0に記載の撥水剤の製造方法。  12. Mixing the binder of the fine particles into the organic solvent, heating and dissolving the mixture, and drying the mixture obtained by adding and mixing the fine particles; adding silicone oil, aqueous solvent, and water to the dried product In the method for producing a water-repellent agent including a step of stirring, any one of a step of mixing and heating and dissolving a binder of fine particles in an organic solvent, or a step of adding and stirring silicone oil, an aqueous solvent, and water. 10. The method for producing a water repellent according to claim 9, wherein a surfactant is further added.
1 3 . 請求項 1 ~ 1 0のいずれかに記載の撥水剤がコーティングされてなるコ 一ティング物品。 13. A coated article coated with the water repellent according to any one of claims 1 to 10.
1 4. コーティング量が単位表面積当たり 3 0〜5 0 n g /rnm2である請求項 1 3に記載のコーティング物品。 1 4. The coating article of claim 1 3 coating weight of unit surface area per 3 0~5 0 ng / rnm 2.
1 5. コーティング量が単位表面積当たり 3 5〜4 0 n g/mm2である請求項 1 4に記載のコーティング物品。 1 5. The coating article of claim 1 4 coating amount is 3 5~4 0 ng / mm 2 per unit surface area.
1 6. 3 0〜 2 0 0 nmの凹凸を表面に有する請求項 1 3 ~ 1 5のいずれかに 記載のコーティング物品。  The coated article according to any one of claims 13 to 15, which has irregularities of 16.30 to 200 nm on its surface.
1 7. 請求項 1 ~ 1 0のいずれかに記載の撥水剤をスプレーしてコーティング 物品を製造する方法。  1 7. A method for producing a coated article by spraying the water repellent according to any one of claims 1 to 10.
1 8. スプレーした撥水剤をすばやく乾燥させながらスプレーすることを特徴 とする請求項 1 7記載のコーティング物品の製造方法。  18. The method for producing a coated article according to claim 17, wherein the sprayed water repellent is sprayed while drying quickly.
1 9. 撥水剤を間欠的にスプレーすることを特徴とする請求項 1 7または 1 8 記載のコーティング物品の製造方法。  19. The method for producing a coated article according to claim 17 or 18, wherein the water repellent is sprayed intermittently.
20. スプレーノズルの径及ぴ 又は噴射圧力を調整することによってコーテ イング量を調整することを特徴とする請求項 1 7〜 1 9のいずれかに記載のコ一 ティング物品の製造方法。  20. The method for producing a coated article according to any one of claims 17 to 19, wherein the amount of coating is adjusted by adjusting the diameter and the spray pressure of the spray nozzle.
2 1. 請求項 1〜 1 0のいずれかに記載の撥水剤を洗車機に用いる撥水剤の使 用方法。  2 1. A method for using a water repellent according to any one of claims 1 to 10 for a car washer.
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JP2009185201A (en) * 2008-02-07 2009-08-20 Soft99 Corporation Water-repellent treatment composition for aerosol, and aerosol type water-repellent treatment agent
JP2009241943A (en) * 2008-03-31 2009-10-22 Snt Co Coating agent and packaging material having dried coating film of the coating agent formed on surface thereof
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JP2007106844A (en) * 2005-10-12 2007-04-26 Parker Corp Coating agent composition for surface of vehicle
JP2008038096A (en) * 2006-08-09 2008-02-21 Soft99 Corporation Agent for water-repelling treatment and method for water-repelling treatment
JP2011507865A (en) * 2007-12-20 2011-03-10 エイボン プロダクツ インコーポレーテッド Cosmetic composition for imparting a superhydrophobic film
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JP2009185201A (en) * 2008-02-07 2009-08-20 Soft99 Corporation Water-repellent treatment composition for aerosol, and aerosol type water-repellent treatment agent
JP2011513407A (en) * 2008-03-04 2011-04-28 エイボン プロダクツ インコーポレーテッド Cosmetic composition for providing a superhydrophobic film
JP2009241943A (en) * 2008-03-31 2009-10-22 Snt Co Coating agent and packaging material having dried coating film of the coating agent formed on surface thereof
WO2016170882A1 (en) * 2015-04-24 2016-10-27 東洋製罐株式会社 Structure with solid particles distributed on surface
JP2016203527A (en) * 2015-04-24 2016-12-08 東洋製罐株式会社 Structure having surface with solid particles distributed thereon
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WO2023145932A1 (en) * 2022-01-31 2023-08-03 国立研究開発法人物質・材料研究機構 Coating composition, production method thereof, production method of coating film using same, lubricating article kit using same, and washer fluid using same

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