WO2019239487A1 - Water-repellent member production method, water-repellent member, and automotive components comprising said water-repellent member - Google Patents

Water-repellent member production method, water-repellent member, and automotive components comprising said water-repellent member Download PDF

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WO2019239487A1
WO2019239487A1 PCT/JP2018/022426 JP2018022426W WO2019239487A1 WO 2019239487 A1 WO2019239487 A1 WO 2019239487A1 JP 2018022426 W JP2018022426 W JP 2018022426W WO 2019239487 A1 WO2019239487 A1 WO 2019239487A1
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water
rare earth
repellent member
earth oxide
repellent
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PCT/JP2018/022426
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French (fr)
Japanese (ja)
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亮太 小林
宮本　隆司
村上　亮
野口　雄司
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日産自動車株式会社
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Priority to PCT/JP2018/022426 priority Critical patent/WO2019239487A1/en
Priority to JP2020524984A priority patent/JP7165308B2/en
Publication of WO2019239487A1 publication Critical patent/WO2019239487A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material

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  • the present invention relates to a method for producing a water-repellent member and a water-repellent member, and more particularly, to a method for producing a water-repellent member capable of forming a water-repellent film on a large-area substrate and a water-repellent member.
  • an antifouling structure that repels foreign matter by immobilizing silicone oil or fluorine oil on a porous substrate and forming a water-repellent surface on the surface of the substrate is known. Since the antifouling structure uses liquid oil or the like, the oil is easily lost, and it is difficult to improve durability over a long period of time. A method of imparting water repellency without using organic substances is desired.
  • Rare earth oxides are known as inorganic water repellent materials.
  • the water repellency of the rare earth oxide is considered to be because the 4f orbit is shielded by electrons on the outer 5s2p6 orbit and cannot interact with water.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2009-120866 of Patent Document 1 describes that a rare earth oxide film having a constant film thickness without cracks can be formed by oxidative decomposition of an organic complex of a rare earth element heated and melted. Has been.
  • the present inventor has made dehydration condensation of a part of the functional group of rare earth alkoxide with alcohol, so that the condensation reaction between hydrolyzed alkoxides is suppressed and sol-gel
  • the present inventors have found that the reaction can be delayed and have completed the present invention.
  • the method for producing a water-repellent member of the present invention includes a process for forming a water-repellent film by applying a rare earth oxide precursor solution to a substrate and baking it.
  • the rare earth oxide precursor solution includes a rare earth alkoxide and a reaction inhibitor, and the reaction inhibitor is a dialcohol having an ether bond.
  • the water repellent member of the present invention includes a water repellent film on the substrate.
  • the water repellent film includes a rare earth oxide having a thickness of 15 nm or more and less than 100 nm.
  • the automobile part of the present invention is characterized by comprising the above water-repellent member.
  • a water-repellent film can be formed by a sol-gel method, the film thickness can be easily controlled, no cracks occur, and a large area It is possible to provide a method for producing a water-repellent member capable of forming a rare earth oxide film on the substrate.
  • FIG. 2 is a cross-sectional SEM image of the water repellent member produced in Example 1.
  • the method for producing the water repellent member of the present invention will be described in detail.
  • the method for producing the water repellent member is a method of forming a water repellent film of a rare earth oxide on a substrate by a sol-gel method.
  • a metal alkoxide is used as a starting material, a sol is obtained by hydrolysis and dehydration condensation reaction, and the sol is applied to a substrate and dried to form a dry gel film, followed by baking to obtain a solvent.
  • This is a method of completely removing and forming a metal oxide thin film.
  • rare earth alkoxides have a high reaction activity with moisture and are easily hydrolyzed. The viscosity of the liquid will increase.
  • a rare earth oxide precursor solution containing a reaction inhibitor is used. Then, a rare-earth oxide precursor solution having a low viscosity in which gelation is suppressed is applied to a base material, and is subjected to hydrolysis and dehydration condensation reaction on the base material to cause gelation.
  • a thin gel film can be formed, and a water-repellent film of rare earth oxide without cracks or peeling can be formed.
  • a linear dialcohol can be used as the reaction inhibitor.
  • a linear dialcohol having 4 or more carbon atoms having at least one ether bond can be used, such as triethylene glycol, diethyl glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, Examples include 2,2′-oxide (benzyl alcohol), 1,3 bis (4-hydroxyphenoxy) benzene, 4,4′-oxydiphenol, 2,2′-oxydiphenol, and the like.
  • the reaction inhibitor for example, triethylene glycol, forms a cyclic structure by dehydration condensation with a rare earth alkoxide as shown in the following reaction formula (1), and suppresses the sol-gel reaction of the rare earth alkoxide.
  • the linear dialcohol does not have to have a large side chain that causes steric hindrance, the ether bond can freely rotate, and the two hydroxyl groups of the reaction inhibitor can be dehydrated and condensed with one rare earth alkoxide molecule. Further, it may have a small side chain that does not hinder the rotation of the ether bond or the dehydration reaction of two hydroxyl groups.
  • the content of the linear dialcohol in the rare earth oxide precursor solution is not particularly limited and is preferably 1% by mass to 10% by mass, although it depends on the coating conditions.
  • rare earth alkoxide examples include rare earth elements, that is, scandium (Sc) and Y yttrium (Y), and lanthanoid alkoxides from lanthanum (La) to lutetium (Lu).
  • Examples of the solvent for the rare earth oxide precursor solution include low-boiling organic solvents that can be removed at low temperatures, such as aromatic solvents such as toluene and xylene, nonpolar solvents such as hexane, and cyclic ether solvents such as tetrahydrofuran. .
  • the rare earth oxide precursor solution can contain an alcohol. By containing alcohol, the viscosity increase of the rare earth oxide precursor solution can be prevented and the viscosity can be lowered.
  • the alcohol to be added to the rare earth oxide precursor solution is preferably a low viscosity alcohol that does not volatilize during coating and increase the viscosity of the rare earth oxide precursor solution.
  • examples of such alcohols include ethanol, isopropyl alcohol, and butanol.
  • the content of the alcohol in the rare earth oxide precursor solution is not particularly limited and is preferably 50% by mass to 90% by mass, although it depends on the coating conditions.
  • Examples of the method for applying the rare earth oxide precursor solution to the substrate include conventionally known coating methods such as spin coating, spray coating, roll coater, flow coating, and dip coating.
  • the gel film is preferably baked at 480 ° C. to 515 ° C. By baking at 515 ° C. or lower, a water repellent film can be formed even on a low-melting glass having a softening point of about 520 ° C. to 600 ° C.
  • the gel film is considered to have a fine structure formed of secondary particles in which oligomers of several nm obtained by dehydration condensation of rare earth alkoxide are aggregated and connected in a daisy chain.
  • oligomers of several nm obtained by dehydration condensation of rare earth alkoxide are aggregated and connected in a daisy chain.
  • sputtering or organic complex melting Unlike a dense film formed by a film forming method, ultrafine pores of several nm are formed between the secondary particles.
  • the water-repellent film produced by the method for producing the water-repellent film has air entering the pores to form an air film on the surface, and the water repellency is improved in combination with the rare earth oxide.
  • a vacuum chamber is not required unlike sputtering, and therefore a uniform water-repellent film can be formed even on a large-area substrate. preferably applicable to 1000 cm 2 or more substrates, especially and 1500 cm 2 or more substrates, the length of one side can be preferably applied to the substrate over long 35 cm.
  • the water-repellent film of the present invention is a film containing a rare earth oxide formed on a substrate and has a thickness of 15 nm or more and less than 100 nm.
  • both water repellency and transparency can be achieved. If the film thickness is less than 15 nm, the water-repellent film is too thin to reduce the water repellency. If the film thickness exceeds 100 nm, cracks occur and the haze value increases.
  • a transparent plate glass or the like can be used as the substrate.
  • the haze value of the substrate is preferably 0.1% or less, and the total light transmittance is preferably 93% or more.
  • the water repellent member has a total light transmittance of 90% or more and a haze value of 0.5% or less, and further a total light transmittance of 91% or more and a haze value of 0.2% or less. preferable.
  • the total light transmittance and the haze value are in the above ranges, transparency required for automobile parts, optical parts and the like can be obtained.
  • the automobile component of the present invention includes the water repellent member.
  • the water-repellent member By providing the water-repellent member in the automobile part, water repellency and durability are improved, and not only a good field of view can be secured in rainy weather and bad roads, but also the number of times of washing and cleaning can be reduced.
  • small transparent parts such as a light cover, a meter panel, a mirror, and a camera lens can be cited in addition to a large area glass window such as a front window, a rear window, and a side window.
  • Example 1 (Preparation of rare earth oxide precursor solution) 1000 ⁇ L of triethylene glycol, 1000 ⁇ L of holmium butoxide (Hokuko Chemical Co., Ltd .: 0.503 mol / kg) and 500 ⁇ L of isopropyl alcohol are stirred in a screw tube, further heated at 80 ° C. for 30 minutes, then cooled to room temperature and mixed. A liquid was obtained.
  • holmium butoxide Hokuko Chemical Co., Ltd .: 0.503 mol / kg
  • Example 2 Preparation of rare earth oxide precursor solution 1000 ⁇ L of triethylene glycol, 1000 ⁇ L of erbium butoxide (Hokuko Chemical Co., Ltd .: 0.503 mol / kg), and 500 ⁇ L of isopropyl alcohol are stirred in a screw tube, further heated at 80 ° C. for 30 minutes, then cooled to room temperature and mixed. A liquid was obtained.
  • a water repellent member was obtained in the same manner as in Example 1 except that the rare earth oxide precursor solution was used.
  • Example 3 Preparation of rare earth oxide precursor solution 1000 ⁇ L of diethylene glycol, 1000 ⁇ L of holmium butoxide (made by Hokuko Chemical Co., Ltd .: 0.503 mol / kg) and 500 ⁇ L of isopropyl alcohol are stirred in a screw tube, further heated at 80 ° C. for 30 minutes, then cooled to room temperature and the mixed solution is Obtained.
  • a water repellent member was obtained in the same manner as in Example 1 except that the rare earth oxide precursor solution was used.
  • Example 4 (Preparation of rare earth oxide precursor solution) 1000 ⁇ L of triethylene glycol, 1000 ⁇ L of holmium butoxide (made by Hokuko Chemical Co., Ltd .: 0.503 mol / kg) and 500 ⁇ L of isopropyl alcohol are stirred in a screw tube, further heated at 80 ° C. for 30 minutes, and then cooled to room temperature for rare earth. An oxide precursor solution was obtained.
  • a water repellent member was obtained in the same manner as in Example 1 except that the rare earth oxide precursor solution was used.
  • Example 5 (Preparation of rare earth oxide precursor solution) 1000 ⁇ L of triethylene glycol, 1000 ⁇ L of holmium butoxide (Hokuko Chemical Co., Ltd .: 0.503 mol / kg) and 500 ⁇ L of isopropyl alcohol were placed in a screw tube and stirred to obtain a rare earth oxide precursor solution.
  • holmium butoxide Hokuko Chemical Co., Ltd .: 0.503 mol / kg
  • a water repellent member was obtained in the same manner as in Example 1 except that the rare earth oxide precursor solution was used.
  • Example 6 Preparation of rare earth oxide precursor solution 1000 ⁇ L of triethylene glycol, 1000 ⁇ L of holmium butoxide (manufactured by Hokuko Chemical Co., Ltd .: 0.503 mol / kg), and 500 ⁇ L of isopropyl alcohol were placed in a screw tube and stirred to obtain a mixed solution.
  • a water repellent member was obtained in the same manner as in Example 1 except that the rare earth oxide precursor solution was used.
  • Example 1 A water-repellent film was formed in the same manner as in Example 1 except that 1.5 mL of holmium butoxide (manufactured by Hokuko Chemical Co., Ltd .: 0.503 mol / kg) was spin-coated as it was.
  • 1.5 mL of holmium butoxide manufactured by Hokuko Chemical Co., Ltd .: 0.503 mol / kg
  • a water-repellent film was formed in the same manner as in Example 1 except that the rare earth oxide precursor solution was used.
  • the haze value and the total light transmittance of the water repellent member were measured with a haze / transmittometer (Murakami Color: HM-65W) equipped with an integrating sphere.
  • FIG. 1 shows a cross-sectional SEM image of the water-repellent member of Example 1.

Abstract

A water-repellent member production method according to the present invention comprises a process wherein a rare earth oxide precursor solution is applied to a base material and fired, forming a water-repellent film.　In addition, the rare earth oxide precursor solution includes a rare earth alkoxide and a reaction inhibitor, and inhibits a condensation reaction between hydrolyzed alkoxides and causes a sol-gel reaction to be delayed, enabling the suppression of an increase in the viscosity of the rare earth oxide precursor solution and thereby enabling the formation of a rare earth oxide water-repellent film that is thin and free from cracks.

Description

撥水部材の製造方法、撥水部材及び該撥水部材を備える自動車部品Water-repellent member manufacturing method, water-repellent member, and automotive part including the water-repellent member
　本発明は、撥水部材の製造方法、及び撥水部材に係り、更に詳細には、大面積の基材にも撥水膜を形成可能な撥水部材の製造方法、及び撥水部材に関する。 The present invention relates to a method for producing a water-repellent member and a water-repellent member, and more particularly, to a method for producing a water-repellent member capable of forming a water-repellent film on a large-area substrate and a water-repellent member.
　従来、多孔質な基材にシリコーンオイルやフッ素オイルなどを固定化させ、基材表面に撥水面を形成することで異物を撥ねる防汚構造体が知られている。
　上記防汚構造体は、液体のオイルなどを用いるため、オイルが滅失し易く長期に亘る耐久性の向上が困難であり、有機物を用いずに撥水性を付与する方法が望まれている。 Conventionally, an antifouling structure that repels foreign matter by immobilizing silicone oil or fluorine oil on a porous substrate and forming a water-repellent surface on the surface of the substrate is known.
Since the antifouling structure uses liquid oil or the like, the oil is easily lost, and it is difficult to improve durability over a long period of time. A method of imparting water repellency without using organic substances is desired.
　無機物の撥水材料として希土類酸化物が知られている。上記希土類酸化物の撥水性は、４ｆ軌道が外側の５ｓ２ｐ６軌道の電子にシールドされて水と相互作用できないためであると考えられている。 Rare earth oxides are known as inorganic water repellent materials. The water repellency of the rare earth oxide is considered to be because the 4f orbit is shielded by electrons on the outer 5s2p6 orbit and cannot interact with water.
　特許文献１の日本国特開２００９－１２０８６６号公報には、加熱溶融した希土類元素の有機錯体を酸化分解することで、クラックがなく一定の膜厚を有する希土類酸化物被膜を形成できる旨が記載されている。 Japanese Patent Application Laid-Open No. 2009-120866 of Patent Document 1 describes that a rare earth oxide film having a constant film thickness without cracks can be formed by oxidative decomposition of an organic complex of a rare earth element heated and melted. Has been.
日本国特開２００９－１２０８６６号公報Japanese Unexamined Patent Publication No. 2009-120866
　しかしながら、特許文献１に記載の方法にあっては、溶媒を用いずに希土類元素の有機錯体を加熱溶融するため、上記有機錯体の分解温度以上に加熱することができず、希土類元素の有機錯体の融液の粘度が高くなり、希土類酸化物被膜を薄膜化することが困難である。 However, in the method described in Patent Document 1, since the rare earth element organic complex is heated and melted without using a solvent, the organic complex of the rare earth element cannot be heated above the decomposition temperature of the organic complex. Thus, it is difficult to make the rare earth oxide film thinner.
　本発明は、このような従来技術の有する課題に鑑みてなされたものであり、その目的とするところは、膜厚の制御が容易でクラックが生じず、かつ大面積の基材にも形成可能な、希土類酸化物の撥水膜を備える撥水部材の製造方法を提供することにある。 The present invention has been made in view of such problems of the prior art, and the object of the present invention is to easily control the film thickness, to prevent cracks, and to be formed on a large-area substrate. Another object of the present invention is to provide a method for producing a water-repellent member comprising a water-repellent film of a rare earth oxide.
　本発明者は、上記目的を達成すべく鋭意検討を重ねた結果、希土類アルコキシドの官能基の一部をアルコールと脱水縮合させることで、加水分解したアルコキシド同士の縮合反応が抑制されてゾル‐ゲル反応を遅延できることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above-mentioned object, the present inventor has made dehydration condensation of a part of the functional group of rare earth alkoxide with alcohol, so that the condensation reaction between hydrolyzed alkoxides is suppressed and sol-gel The present inventors have found that the reaction can be delayed and have completed the present invention.
　即ち、本発明の撥水部材の製造方法は、希土類酸化物前駆体溶液を、基材に塗布し焼成して撥水膜を形成する処理を備える。
　そして、上記希土類酸化物前駆体溶液が、希土類アルコキシドと反応抑制剤とを含み、上記反応抑制剤が、エーテル結合を有するジアルコールであることを特徴とする。 That is, the method for producing a water-repellent member of the present invention includes a process for forming a water-repellent film by applying a rare earth oxide precursor solution to a substrate and baking it.
The rare earth oxide precursor solution includes a rare earth alkoxide and a reaction inhibitor, and the reaction inhibitor is a dialcohol having an ether bond.
　また、本発明の撥水部材は、基材上に撥水膜を備える。
　そして、上記撥水膜が、厚さが１５ｎｍ以上１００ｎｍ未満の希土類酸化物を含むことを特徴とする。 The water repellent member of the present invention includes a water repellent film on the substrate.
The water repellent film includes a rare earth oxide having a thickness of 15 nm or more and less than 100 nm.
　さらに、本発明の自動車部品は、上記撥水部材を備えることを特徴とする。 Furthermore, the automobile part of the present invention is characterized by comprising the above water-repellent member.
　本発明によれば、希土類アルコキシドの官能基の一部をアルコールと脱水縮合させることとしたため、ゾル‐ゲル法で撥水膜を形成でき、膜厚の制御が容易でクラックが生じず、大面積の基材にも希土類酸化物被膜を形成可能な、撥水部材の製造方法を提供することができる。 According to the present invention, since a part of the functional group of the rare earth alkoxide is dehydrated and condensed with alcohol, a water-repellent film can be formed by a sol-gel method, the film thickness can be easily controlled, no cracks occur, and a large area It is possible to provide a method for producing a water-repellent member capable of forming a rare earth oxide film on the substrate.
実施例１で作製した撥水部材の断面ＳＥＭ像である。2 is a cross-sectional SEM image of the water repellent member produced in Example 1. FIG.
＜製造方法＞
　本発明の撥水部材の製造方法について詳細に説明する。
　上記撥水部材の製造方法は、ゾル‐ゲル法により希土類酸化物の撥水膜を基材上に形成する方法である。 <Manufacturing method>
The method for producing the water repellent member of the present invention will be described in detail.
The method for producing the water repellent member is a method of forming a water repellent film of a rare earth oxide on a substrate by a sol-gel method.
　上記ゾル‐ゲル法は、金属アルコキシドを出発原料とし、加水分解、脱水縮合反応によりゾルを得て、上記ゾルを基材に塗布し乾燥させてドライゲルの膜を形成した後、焼成して溶媒を完全に除去し金属酸化物の薄膜を形成する方法である。 In the sol-gel method, a metal alkoxide is used as a starting material, a sol is obtained by hydrolysis and dehydration condensation reaction, and the sol is applied to a substrate and dried to form a dry gel film, followed by baking to obtain a solvent. This is a method of completely removing and forming a metal oxide thin film.
　しかし、希土類アルコキシドは、ケイ素アルコキシド、アルミニウムアルコキシド、チタニウムアルコキシドなどに比して、水分との反応活性が大きく加水分解し易いため、ゾル‐ゲル反応の反応速度が速く、すぐにゲル化して塗工液の粘度が上昇してしまう。 However, compared with silicon alkoxide, aluminum alkoxide, titanium alkoxide, etc., rare earth alkoxides have a high reaction activity with moisture and are easily hydrolyzed. The viscosity of the liquid will increase.
　したがって、ゲル膜の膜厚が厚くなり易く、加熱時の引張応力によってクラックや剥離が生じ、散乱のない透明な希土類酸化物の撥水膜を形成することは困難である。 Therefore, it is difficult to form a transparent water-repellent film made of a transparent rare earth oxide without scattering because the gel film tends to be thick and cracks and peeling occur due to tensile stress during heating.
　本発明の製造方法においては、反応抑制剤を含む希土類酸化物前駆体溶液を用いる。
　そして、ゲル化が抑制された低粘度の希土類酸化物前駆体溶液を基材に塗布し、基材上で加水分解、脱水縮合反応を進ませてゲル化させる。 In the production method of the present invention, a rare earth oxide precursor solution containing a reaction inhibitor is used.
Then, a rare-earth oxide precursor solution having a low viscosity in which gelation is suppressed is applied to a base material, and is subjected to hydrolysis and dehydration condensation reaction on the base material to cause gelation.
　したがって、希土類アルコキシドであっても膜厚が薄いゲル膜を形成することができ、クラックや剥離のない希土類酸化物の撥水膜を形成することができる。 Therefore, even if it is a rare earth alkoxide, a thin gel film can be formed, and a water-repellent film of rare earth oxide without cracks or peeling can be formed.
　上記反応抑制剤としては直鎖状ジアルコールを使用できる。
　具体的には、エーテル結合を一つ以上有する炭素数が４以上の直鎖状ジアルコールを使用することができ、例えば、トリエチレングリコール、ジエチルグリコール、ポリエチレングリコール、ジプロピレングリコール、トリプロピレグリコール、２，２’－オキシド（ベンジルアルコール）、１，３ビス（４－ハイドロキシフェノキシ）ベンゼン、４，４’－オキシジフェノール、２，２’－オキシジフェノールなどを挙げることができる。 A linear dialcohol can be used as the reaction inhibitor.
Specifically, a linear dialcohol having 4 or more carbon atoms having at least one ether bond can be used, such as triethylene glycol, diethyl glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, Examples include 2,2′-oxide (benzyl alcohol), 1,3 bis (4-hydroxyphenoxy) benzene, 4,4′-oxydiphenol, 2,2′-oxydiphenol, and the like.
　上記反応抑制剤、例えばトリエチレングリコールは、下記反応式（１）に示すように希土類アルコキシドと脱水縮合して環状構造を形成し、希土類アルコキシドのゾル‐ゲル反応を抑制する。 The reaction inhibitor, for example, triethylene glycol, forms a cyclic structure by dehydration condensation with a rare earth alkoxide as shown in the following reaction formula (1), and suppresses the sol-gel reaction of the rare earth alkoxide.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　本発明において、直鎖状ジアルコールとは、立体障害になるような大きな側鎖などがなくエーテル結合が自由に回転し、反応抑制剤の２つの水酸基が共に希土類アルコキシド１分子と脱水縮合できればよく、エーテル結合の回転や、２つの水酸基の脱水反応を妨げないような小さな側鎖を有していてもよい。 In the present invention, the linear dialcohol does not have to have a large side chain that causes steric hindrance, the ether bond can freely rotate, and the two hydroxyl groups of the reaction inhibitor can be dehydrated and condensed with one rare earth alkoxide molecule. Further, it may have a small side chain that does not hinder the rotation of the ether bond or the dehydration reaction of two hydroxyl groups.
　上記希土類酸化物前駆体溶液中の直鎖状ジアルコールの含有量は、特に制限はなく、塗工条件などにもよるが、１質量％～１０質量％であることが好ましい。 The content of the linear dialcohol in the rare earth oxide precursor solution is not particularly limited and is preferably 1% by mass to 10% by mass, although it depends on the coating conditions.
　希土類アルコキシドとしては、希土類元素、すなわち、スカンジウム（Ｓｃ）とＹイットリウム（Ｙ）と、ランタン（Ｌａ）からルテチウム（Ｌｕ）までのランタノイドのアルコキシドが挙げられる。 Examples of the rare earth alkoxide include rare earth elements, that is, scandium (Sc) and Y yttrium (Y), and lanthanoid alkoxides from lanthanum (La) to lutetium (Lu).
　上記希土類酸化物前駆体溶液の溶媒としては、トルエン、キシレン等の芳香族系溶媒、ヘキサンなどの非極性溶媒、テトラヒドロフラン等の環状エーテル系溶媒など、低温で除去可能な低沸点有機溶媒が挙げられる。 Examples of the solvent for the rare earth oxide precursor solution include low-boiling organic solvents that can be removed at low temperatures, such as aromatic solvents such as toluene and xylene, nonpolar solvents such as hexane, and cyclic ether solvents such as tetrahydrofuran. .
　希土類酸化物前駆体溶液は、アルコールを含有することができる。アルコールを含有させることで希土類酸化物前駆体溶液の粘度上昇を防止して低粘度化することができる。 The rare earth oxide precursor solution can contain an alcohol. By containing alcohol, the viscosity increase of the rare earth oxide precursor solution can be prevented and the viscosity can be lowered.
　希土類酸化物前駆体溶液に添加するアルコールとしては、塗工中に揮発して希土類酸化物前駆体溶液の粘度が上昇することがなく、かつ低粘度のアルコールであることが好ましい。このようなアルコールとしては、例えば、エタノール、イソプロピルアルコール、ブタノールなどを挙げることができる。 The alcohol to be added to the rare earth oxide precursor solution is preferably a low viscosity alcohol that does not volatilize during coating and increase the viscosity of the rare earth oxide precursor solution. Examples of such alcohols include ethanol, isopropyl alcohol, and butanol.
　上記希土類酸化物前駆体溶液中のアルコールの含有量は、特に制限はなく、塗工条件などにもよるが、５０質量％～９０質量％であることが好ましい。 The content of the alcohol in the rare earth oxide precursor solution is not particularly limited and is preferably 50% by mass to 90% by mass, although it depends on the coating conditions.
　上記希土類酸化物前駆体溶液を基材に塗布する方法としては、スピンコート、スプレー塗工、ロールコーター、フローコート、ディップコート等、従来公知の塗工方法を挙げることができる。 Examples of the method for applying the rare earth oxide precursor solution to the substrate include conventionally known coating methods such as spin coating, spray coating, roll coater, flow coating, and dip coating.
　上記ゲル膜の焼成は、４８０℃～５１５℃で行うことが好ましい。５１５℃以下で焼成することで、軟化点が５２０℃～６００℃程度の低融点ガラスにも撥水膜を形成できる。 The gel film is preferably baked at 480 ° C. to 515 ° C. By baking at 515 ° C. or lower, a water repellent film can be formed even on a low-melting glass having a softening point of about 520 ° C. to 600 ° C.
　また、上記ゲル膜は、希土類アルコキシドが脱水縮合した数ｎｍ程度のオリゴマーが凝集し、数珠つなぎになった二次粒子で形成された微細構造であると考えられ、例えば、スパッタリングや、有機錯体溶融成膜法で形成した緻密な膜とは異なり、上記二次粒子間に数ｎｍの極微細な細孔が形成される。 In addition, the gel film is considered to have a fine structure formed of secondary particles in which oligomers of several nm obtained by dehydration condensation of rare earth alkoxide are aggregated and connected in a daisy chain. For example, sputtering or organic complex melting Unlike a dense film formed by a film forming method, ultrafine pores of several nm are formed between the secondary particles.
　したがって、上記撥水膜の製造方法で作製した撥水膜は、上記細孔に空気が入り込んで表面に空気の膜が形成され、希土類酸化物と相俟って撥水性が向上する。 Therefore, the water-repellent film produced by the method for producing the water-repellent film has air entering the pores to form an air film on the surface, and the water repellency is improved in combination with the rare earth oxide.
　上記撥水膜の製造方法によれば、スパッタリングのように真空槽を必要としないため、大面積の基材にも均一な撥水膜を形成することができ、スパッタリングでは形成が困難な面積が１０００ｃｍ２以上の基材に好ましく適用でき、特に１５００ｃｍ２以上の基材や、一辺の長さが３５ｃｍ以上の長尺の基材に好ましく適用できる。 According to the method for producing a water-repellent film, a vacuum chamber is not required unlike sputtering, and therefore a uniform water-repellent film can be formed even on a large-area substrate. preferably applicable to 1000 cm 2 or more substrates, especially and 1500 cm 2 or more substrates, the length of one side can be preferably applied to the substrate over long 35 cm.
＜撥水膜＞
　本発明の撥水膜は、基材上に形成された希土類酸化物を含む膜であり、厚さが１５ｎｍ以上１００ｎｍ未満である。 <Water repellent film>
The water-repellent film of the present invention is a film containing a rare earth oxide formed on a substrate and has a thickness of 15 nm or more and less than 100 nm.
　膜厚が上記範囲内であることで、撥水性と透明性とを両立できる。
　膜厚が１５ｎｍ未満では、撥水膜が薄すぎて撥水性が低下し、また、膜厚が１００ｎｍを超えると、クラックが生じてヘイズ値が高くなる。 When the film thickness is within the above range, both water repellency and transparency can be achieved.
If the film thickness is less than 15 nm, the water-repellent film is too thin to reduce the water repellency. If the film thickness exceeds 100 nm, cracks occur and the haze value increases.
＜基材＞
　上記基材としては、透明な板ガラスなどを使用することができる。
　上記基材のヘイズ値は０．１％以下であることが好ましく、全光線透過率は９３％以上であることが好ましい。 <Base material>
A transparent plate glass or the like can be used as the substrate.
The haze value of the substrate is preferably 0.1% or less, and the total light transmittance is preferably 93% or more.
　上記撥水部材は、全光線透過率が９０％以上、かつヘイズ値が０．５％以下であり、さらに、全光線透過率が９１％以上、ヘイズ値が０．２％以下であることが好ましい。
　全光線透過率及びヘイズ値が上記範囲にあることで、自動車部品や光学部品等に要求される透明性が得られる。 The water repellent member has a total light transmittance of 90% or more and a haze value of 0.5% or less, and further a total light transmittance of 91% or more and a haze value of 0.2% or less. preferable.
When the total light transmittance and the haze value are in the above ranges, transparency required for automobile parts, optical parts and the like can be obtained.
＜自動車部品＞
　本発明の自動車部品は、上記撥水部材を備える。
　自動車部品が上記撥水部材を備えることで、撥水性や耐久性が向上し、雨天や悪路において良好な視界を確保することができるだけでなく、洗車や清掃の回数を減らすことができる。 <Auto parts>
The automobile component of the present invention includes the water repellent member.
By providing the water-repellent member in the automobile part, water repellency and durability are improved, and not only a good field of view can be secured in rainy weather and bad roads, but also the number of times of washing and cleaning can be reduced.
　上記自動車部品としては、フロントウィンドウ、リヤウィンドウ、サイドウィンドウなど大面積のガラスウィンドウの他、ライトカバー、メーターパネル、ミラー、カメラレンズなど、小型の透明部品を挙げることができる。 As the above-mentioned automobile parts, small transparent parts such as a light cover, a meter panel, a mirror, and a camera lens can be cited in addition to a large area glass window such as a front window, a rear window, and a side window.
　以下、本発明を実施例により詳細に説明するが、本発明は下記実施例に限定されるものではない。 Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to the following examples.
［実施例１］
（希土類酸化物前駆体溶液の作製）
　トリエチレングリコール１０００μＬ、ホルミウムブトキシド（北興化学社製：０．５０３ｍｏｌ／ｋｇ）１０００μＬ、及びイソプロピルアルコール５００μＬをスクリュー管に入れて撹拌し、さらに８０℃で３０分間加熱した後、室温まで冷却して混合液を得た。 [Example 1]
(Preparation of rare earth oxide precursor solution)
1000 μL of triethylene glycol, 1000 μL of holmium butoxide (Hokuko Chemical Co., Ltd .: 0.503 mol / kg) and 500 μL of isopropyl alcohol are stirred in a screw tube, further heated at 80 ° C. for 30 minutes, then cooled to room temperature and mixed. A liquid was obtained.
　上記混合液１０００μＬにイソプロピルアルコールを４０００μＬ入れて希釈し、撹拌して希土類酸化物前駆体溶液を得た。 4,000 μL of isopropyl alcohol was added to 1000 μL of the above mixed solution, diluted, and stirred to obtain a rare earth oxide precursor solution.
（成膜）
　上記希土類酸化物前駆体溶液１．５ｍｌを、プラズマ処理したソーダライムガラス上に、温度２５℃、湿度６０％の環境下でスピンコート（回転数１００ｒｐｍで３ｓｅｃ、５００ｒｐｍで５ｓｅｃ、１０００ｒｐｍで１５ｓｅｃ）し、１５０℃で１時間乾燥して室温まで冷却した後、５００℃で１時間焼成して撥水部材を得た。 (Film formation)
1.5 ml of the rare earth oxide precursor solution is spin-coated on a plasma-treated soda lime glass in an environment of a temperature of 25 ° C. and a humidity of 60% (3 sec at a rotational speed of 100 rpm, 5 sec at 500 rpm, and 15 sec at 1000 rpm). After drying at 150 ° C. for 1 hour and cooling to room temperature, it was fired at 500 ° C. for 1 hour to obtain a water-repellent member.
［実施例２］
（希土類酸化物前駆体溶液の作製）
　トリエチレングリコール１０００μＬ、エルビウムブトキシド（北興化学社製：０．５０３ｍｏｌ／ｋｇ）１０００μＬ、及びイソプロピルアルコール５００μＬをスクリュー管に入れて撹拌し、さらに８０℃で３０分間加熱した後、室温まで冷却して混合液を得た。 [Example 2]
(Preparation of rare earth oxide precursor solution)
1000 μL of triethylene glycol, 1000 μL of erbium butoxide (Hokuko Chemical Co., Ltd .: 0.503 mol / kg), and 500 μL of isopropyl alcohol are stirred in a screw tube, further heated at 80 ° C. for 30 minutes, then cooled to room temperature and mixed. A liquid was obtained.
　上記混合液１０００μＬにイソプロピルアルコールを４０００μＬ入れて希釈し、撹拌して希土類酸化物前駆体溶液を得た。 4,000 μL of isopropyl alcohol was added to 1000 μL of the above mixed solution, diluted, and stirred to obtain a rare earth oxide precursor solution.
　上記希土類酸化物前駆体溶液を用いる他は実施例１と同様にして撥水部材を得た。 A water repellent member was obtained in the same manner as in Example 1 except that the rare earth oxide precursor solution was used.
［実施例３］
（希土類酸化物前駆体溶液の作製）
　ジエチレングリコール１０００μＬ、ホルミウムブトキシド（北興化学社製：０．５０３ｍｏｌ／ｋｇ）１０００μＬ、及びイソプロピルアルコール５００μＬをスクリュー管に入れて撹拌し、さらに８０℃で３０分間加熱した後、室温まで冷却して混合液を得た。 [Example 3]
(Preparation of rare earth oxide precursor solution)
1000 μL of diethylene glycol, 1000 μL of holmium butoxide (made by Hokuko Chemical Co., Ltd .: 0.503 mol / kg) and 500 μL of isopropyl alcohol are stirred in a screw tube, further heated at 80 ° C. for 30 minutes, then cooled to room temperature and the mixed solution is Obtained.
　上記混合液１０００μＬにイソプロピルアルコールを４０００μＬ入れて希釈し、撹拌して希土類酸化物前駆体溶液を得た。 4,000 μL of isopropyl alcohol was added to 1000 μL of the above mixed solution, diluted, and stirred to obtain a rare earth oxide precursor solution.
　上記希土類酸化物前駆体溶液を用いる他は実施例１と同様にして撥水部材を得た。 A water repellent member was obtained in the same manner as in Example 1 except that the rare earth oxide precursor solution was used.
［実施例４］
（希土類酸化物前駆体溶液の作製）
　トリエチレングリコール１０００μＬ、ホルミウムブトキシド（北興化学社製：０．５０３ｍｏｌ／ｋｇ）１０００μＬ、及びイソプロピルアルコール５００μＬをスクリュー管に入れて撹拌し、さらに８０℃で３０分間加熱した後、室温まで冷却して希土類酸化物前駆体溶液を得た。 [Example 4]
(Preparation of rare earth oxide precursor solution)
1000 μL of triethylene glycol, 1000 μL of holmium butoxide (made by Hokuko Chemical Co., Ltd .: 0.503 mol / kg) and 500 μL of isopropyl alcohol are stirred in a screw tube, further heated at 80 ° C. for 30 minutes, and then cooled to room temperature for rare earth. An oxide precursor solution was obtained.
　上記希土類酸化物前駆体溶液を用いる他は実施例１と同様にして撥水部材を得た。 A water repellent member was obtained in the same manner as in Example 1 except that the rare earth oxide precursor solution was used.
［実施例５］
（希土類酸化物前駆体溶液の作製）
　トリエチレングリコール１０００μＬ、ホルミウムブトキシド（北興化学社製：０．５０３ｍｏｌ／ｋｇ）１０００μＬ、及びイソプロピルアルコール５００μＬをスクリュー管に入れて撹拌して希土類酸化物前駆体溶液を得た。 [Example 5]
(Preparation of rare earth oxide precursor solution)
1000 μL of triethylene glycol, 1000 μL of holmium butoxide (Hokuko Chemical Co., Ltd .: 0.503 mol / kg) and 500 μL of isopropyl alcohol were placed in a screw tube and stirred to obtain a rare earth oxide precursor solution.
　上記希土類酸化物前駆体溶液を用いる他は実施例１と同様にして撥水部材を得た。 A water repellent member was obtained in the same manner as in Example 1 except that the rare earth oxide precursor solution was used.
［実施例６］
（希土類酸化物前駆体溶液の作製）
　トリエチレングリコール１０００μＬ、ホルミウムブトキシド（北興化学社製：０．５０３ｍｏｌ／ｋｇ）１０００μＬ、及びイソプロピルアルコール５００μＬをスクリュー管に入れて撹拌して混合液を得た。 [Example 6]
(Preparation of rare earth oxide precursor solution)
1000 μL of triethylene glycol, 1000 μL of holmium butoxide (manufactured by Hokuko Chemical Co., Ltd .: 0.503 mol / kg), and 500 μL of isopropyl alcohol were placed in a screw tube and stirred to obtain a mixed solution.
　上記混合液１０００μＬにイソプロピルアルコールを４０００μＬ入れて希釈し、撹拌して希土類酸化物前駆体溶液を得た。 4,000 μL of isopropyl alcohol was added to 1000 μL of the above mixed solution, diluted, and stirred to obtain a rare earth oxide precursor solution.
　上記希土類酸化物前駆体溶液を用いる他は実施例１と同様にして撥水部材を得た。 A water repellent member was obtained in the same manner as in Example 1 except that the rare earth oxide precursor solution was used.
［比較例１］
　ホルミウムブトキシド（北興化学社製：０．５０３ｍｏｌ／ｋｇ）１．５ｍＬをそのままスピンコートする他は実施例１と同様にして撥水膜を形成したが剥離が生じ成膜できなかった。 [Comparative Example 1]
A water-repellent film was formed in the same manner as in Example 1 except that 1.5 mL of holmium butoxide (manufactured by Hokuko Chemical Co., Ltd .: 0.503 mol / kg) was spin-coated as it was.
［比較例２］
（希土類酸化物前駆体溶液の作製）
　ホルミウムブトキシド（北興化学社製：０．５０３ｍｏｌ／ｋｇ）１０００μＬ、及びイソプロピルアルコール４０００μＬをスクリュー管に入れて撹拌して希土類酸化物前駆体溶液を得た。 [Comparative Example 2]
(Preparation of rare earth oxide precursor solution)
1000 μL of holmium butoxide (Hokuko Chemical Co., Ltd .: 0.503 mol / kg) and 4000 μL of isopropyl alcohol were placed in a screw tube and stirred to obtain a rare earth oxide precursor solution.
　上記希土類酸化物前駆体溶液を用いる他は実施例１と同様にして撥水膜を形成したが剥離が生じ成膜できなかった。 A water-repellent film was formed in the same manner as in Example 1 except that the rare earth oxide precursor solution was used.
＜評価＞
　上記実施例１～６で作製した試験片の撥水部材を以下の方法で評価した。
　評価結果を表１に示す。 <Evaluation>
The water repellent members of the test pieces prepared in Examples 1 to 6 were evaluated by the following methods.
The evaluation results are shown in Table 1.
（撥水性）
　水平に設置した撥水部材に水５μＬを滴下し、その接触角を楕円近似法（共和界面製：Ｄｒｏｐ　Ｍａｓｔｅｒ）にて測定した。 (Water repellency)
5 μL of water was dropped on a horizontally installed water-repellent member, and the contact angle was measured by an ellipse approximation method (manufactured by Kyowa Interface: Drop Master).
（光学特性）
　撥水部材のヘイズ値及び全光線透過率を、積分球を備えたヘイズ・透過計（村上色彩製：ＨＭ－６５Ｗ）で測定した。 (optical properties)
The haze value and the total light transmittance of the water repellent member were measured with a haze / transmittometer (Murakami Color: HM-65W) equipped with an integrating sphere.
（膜厚）
　撥水部材の断面を、走査型電子顕微鏡（日立製作所社製：Ｓ４７００）を用いて観察し、撥水膜の膜厚を測定した。
　図１に実施例１の撥水部材の断面ＳＥＭ像を示す。 (Film thickness)
The cross section of the water repellent member was observed using a scanning electron microscope (manufactured by Hitachi, Ltd .: S4700), and the film thickness of the water repellent film was measured.
FIG. 1 shows a cross-sectional SEM image of the water-repellent member of Example 1.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　上記表１の結果から、本発明の撥水部材の製造方法によれば、水の接触角が９５°以上のクラックのない透明な撥水部材を形成できることがわかる。 From the results shown in Table 1, it can be seen that according to the method for producing a water-repellent member of the present invention, a transparent water-repellent member free from cracks having a water contact angle of 95 ° or more can be formed.

Claims (6)

  1. 　希土類酸化物前駆体溶液を基材に塗布し、焼成して撥水膜を形成する処理を備える撥水部材の製造方法であって、
    　上記希土類酸化物前駆体溶液が、希土類アルコキシドと反応抑制剤とを含み、
    　上記反応抑制剤が、エーテル結合を有するジアルコールであることを特徴とする撥水部材の製造方法。     A method for producing a water-repellent member comprising a process of applying a rare earth oxide precursor solution to a substrate and firing to form a water-repellent film,
    The rare earth oxide precursor solution includes a rare earth alkoxide and a reaction inhibitor,
    The method for producing a water-repellent member, wherein the reaction inhibitor is a dialcohol having an ether bond.
  2. 　上記希土類酸化物前駆体溶液が、エタノール、イソプロピルアルコール、ブタノールを含むことを特徴とする請求項１に記載の撥水部材の製造方法。 The method for producing a water-repellent member according to claim 1, wherein the rare earth oxide precursor solution contains ethanol, isopropyl alcohol, and butanol.
  3. 　基材上に撥水膜を備え、
    　上記撥水膜が、希土類酸化物を含み、厚さが１５ｎｍ以上１００ｎｍ未満であることを特徴とする撥水部材。     A water-repellent film is provided on the substrate,
    The water-repellent member, wherein the water-repellent film contains a rare earth oxide and has a thickness of 15 nm or more and less than 100 nm.
  4. 　全光線透過率が９０％以上、かつヘイズ値が０．５％以下であることを特徴とする請求項３に記載の撥水部材。 The water repellent member according to claim 3, wherein the total light transmittance is 90% or more and the haze value is 0.5% or less.
  5. 　上記基材が、面積１０００ｃｍ２以上の板ガラスであることを特徴とする請求項３又は４に記載の撥水部材。 The water repellent member according to claim 3 or 4, wherein the substrate is a plate glass having an area of 1000 cm 2 or more.
  6. 　撥水部材を備える自動車部品であって、
    　上記撥水部材が、請求項３～５のいずれか１つの項に記載の撥水膜であることを特徴とする自動車部品。     An automotive part provided with a water repellent member,
    An automobile part, wherein the water repellent member is the water repellent film according to any one of claims 3 to 5.
PCT/JP2018/022426 2018-06-12 2018-06-12 Water-repellent member production method, water-repellent member, and automotive components comprising said water-repellent member WO2019239487A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08104985A (en) * 1994-10-07 1996-04-23 Toyota Motor Corp Formation of water-repellent coating film on ferrous member
JPH11172455A (en) * 1997-12-03 1999-06-29 Kansai Shingijutsu Kenkyusho:Kk Surface reformation for base material
JP2007125537A (en) * 2005-10-05 2007-05-24 Nippon Sheet Glass Co Ltd Method for manufacturing article having organic-inorganic composite film
US20100239824A1 (en) * 2007-08-07 2010-09-23 President And Fellows Of Harvard College Metal Oxide Coating On Surfaces
JP2011063852A (en) * 2009-09-17 2011-03-31 Sumitomo Osaka Cement Co Ltd Product with soil resistant finish and manufacturing method therefor
JP2016121331A (en) * 2014-11-26 2016-07-07 ザ・ボーイング・カンパニーＴｈｅ Ｂｏｅｉｎｇ Ｃｏｍｐａｎｙ Corrosion-inhibiting sol-gel coating system and method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08104985A (en) * 1994-10-07 1996-04-23 Toyota Motor Corp Formation of water-repellent coating film on ferrous member
JPH11172455A (en) * 1997-12-03 1999-06-29 Kansai Shingijutsu Kenkyusho:Kk Surface reformation for base material
JP2007125537A (en) * 2005-10-05 2007-05-24 Nippon Sheet Glass Co Ltd Method for manufacturing article having organic-inorganic composite film
US20100239824A1 (en) * 2007-08-07 2010-09-23 President And Fellows Of Harvard College Metal Oxide Coating On Surfaces
JP2011063852A (en) * 2009-09-17 2011-03-31 Sumitomo Osaka Cement Co Ltd Product with soil resistant finish and manufacturing method therefor
JP2016121331A (en) * 2014-11-26 2016-07-07 ザ・ボーイング・カンパニーＴｈｅ Ｂｏｅｉｎｇ Ｃｏｍｐａｎｙ Corrosion-inhibiting sol-gel coating system and method

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