JP4518466B2 - Super water-repellent film forming composition - Google Patents
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- JP4518466B2 JP4518466B2 JP2003312817A JP2003312817A JP4518466B2 JP 4518466 B2 JP4518466 B2 JP 4518466B2 JP 2003312817 A JP2003312817 A JP 2003312817A JP 2003312817 A JP2003312817 A JP 2003312817A JP 4518466 B2 JP4518466 B2 JP 4518466B2
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Description
本発明は、撥水被膜形成組成物及びその製造方法に関する。さらに詳しくは、本発明は、接触角が１５０°以上の超撥水被膜形成組成物に関し、自動車塗装面、家屋の屋根等降雨や降雪にさらされる表面や水中で絶えず水に接触している表面等に塗布することによって、被塗物の表面を水の侵入から保護できる超撥水被膜形成組成物及びその製造方法に関する。 The present invention relates to a water-repellent film-forming composition and a method for producing the same. More specifically, the present invention relates to a super-water-repellent film-forming composition having a contact angle of 150 ° or more, such as an automobile paint surface, a roof of a house, a surface exposed to rain or snow, or a surface that is constantly in contact with water. The present invention relates to a super-water-repellent film-forming composition that can protect the surface of an object to be coated from water intrusion and the method for producing the same.
疎水性シリカ等の疎水性微粒子と樹脂から成るコーティング組成物や塗料の考案は古くから行なわれている。
空調機の熱交換器（アルミニウム製フィン）の表面に撥水性を付与する目的で、シリコーン系樹脂化合物に疎水性シリカ微粒子を配合した撥水性コーティング組成物が考案されている。（特許文献１参照）
また、同じ用途で、樹脂の種類をフッ素樹脂、ポリプロピレン樹脂、ポリエチレン樹脂として、疎水性シリカ微粒子を配合した撥水性コーティング組成物が考案されている。（特許文献２参照）
さらに、同じ用途で、熱硬化性樹脂に疎水性シリカ微粒子とパーフルオロアルキル基を有する撥水化剤を配合して撥水性と撥油性を付与した塗料等が考案されている。（特許文献３、特許文献４参照）
これらは、いずれも樹脂をバインダーとするコーティング組成物で、塗布後100℃以上の温度で加熱乾燥することによって、強靭な撥水、撥油被膜を得ようとするものである。したがって、被膜形成には加熱乾燥設備が必要であり、簡単に加工できる方法とはいい難い。また、このような撥水表面には微細な凸凹が形成されているため、汚れが付着しやすく、付着した汚れはとれにくい。さらに、被膜が強靭であるために、汚れが付着して撥水性が低下しても容易に剥離して再処理することは困難であり、用途が限定されるという問題があった。
また、２液硬化型樹脂、光硬化型樹脂、溶剤乾燥型樹脂を用いて、先に樹脂層を塗布後に疎水性シリカ微粒子を付着させる方法、塵埃の付着防止を目的として上記樹脂に帯電防止性を付与した方法などが考案されている（特許文献５、特許文献６参照）が、塗膜形成方法や剥離性に問題があった。
一方、ワックス又は油脂の結晶を基材表面で析出させて、撥水させる方法が提案されている（特許文献７参照）が、疎水性微粒子による凹凸構造と異なり、成膜と同時に撥水性が発現するのではなく、経時的に撥水性が増大するという弱点があった。
The invention of coating compositions and paints composed of hydrophobic fine particles such as hydrophobic silica and resins has been practiced for a long time.
For the purpose of imparting water repellency to the surface of a heat exchanger (aluminum fin) of an air conditioner, a water repellent coating composition in which hydrophobic silica fine particles are blended with a silicone resin compound has been devised. (See Patent Document 1)
In addition, for the same application, a water-repellent coating composition has been devised in which hydrophobic silica fine particles are blended with a resin type of fluorine resin, polypropylene resin, or polyethylene resin. (See Patent Document 2)
Furthermore, for the same application, paints and the like have been devised in which water repellency and oil repellency are imparted by blending a thermosetting resin with hydrophobic silica fine particles and a water repellent having a perfluoroalkyl group. (See Patent Document 3 and Patent Document 4)
These are all coating compositions containing a resin as a binder, and are intended to obtain a tough, water- and oil-repellent coating by heating and drying at a temperature of 100 ° C. or higher after coating. Therefore, heat drying equipment is required for film formation, and it is difficult to say that the method can be easily processed. Moreover, since fine unevenness is formed on such a water-repellent surface, dirt is likely to adhere, and the attached dirt is difficult to remove. Furthermore, since the film is tough, even if dirt adheres and the water repellency is lowered, it is difficult to easily peel and reprocess, and there is a problem that the application is limited.
In addition, using a two-component curable resin, a photo-curable resin, and a solvent-drying resin, a method of attaching hydrophobic silica fine particles after first applying a resin layer, and antistatic property to the above resin for the purpose of preventing dust adhesion Has been devised (see Patent Document 5 and Patent Document 6), but there are problems with the coating film forming method and the peelability.
On the other hand, a method of depositing wax or oil crystals on the surface of the substrate to make it water repellent has been proposed (see Patent Document 7). Instead, there was a weak point that water repellency increased over time.
このように前記従来の撥水性被膜組成物は、撥水性微粒子を被膜上に固定化するために樹脂を配合しており、被膜の強靭性はあるが、被膜の形成方法が簡単ではない。また、自由に剥離することが困難であるために、汚れが付着しやすい環境では使用しにくい、用途が限定されるなどの問題があった。
本発明は、かかる事情に鑑みなされたものであって、被膜の超撥水性や基材表面の保護性が優れ、簡単に塗布または剥離ができる超撥水性被膜形成用組成物及びその製造方法を提供することを目的とする。
これによって、様々な基材表面を簡単に超撥水性被膜で被覆することができるとともに、被膜が汚れたり、必要がなくなれば簡単に剥離することができる。
As described above, the conventional water-repellent coating composition contains a resin in order to immobilize the water-repellent fine particles on the coating and has a toughness of the coating, but the method of forming the coating is not simple. In addition, since it is difficult to peel freely, there are problems such as difficulty in use in environments where dirt easily adheres, and limited applications.
The present invention has been made in view of such circumstances, and has a super-water-repellent film-forming composition that has excellent super-water repellency of a film and excellent protection of a substrate surface, and can be easily applied or peeled off, and a method for producing the same. The purpose is to provide.
As a result, various substrate surfaces can be easily coated with the super water-repellent coating, and can be easily peeled off when the coating becomes dirty or unnecessary.
本発明者は、鋭意研究した結果、疎水性微粒子、ワックス、有機溶剤から成る超撥水被膜形成組成物とすることにより、目的が達成できることを見出した。
すなわち、疎水性微粒子、ワックス、ワックスの融点より高い沸点を持つ有機溶剤から成る超撥水被膜形成用組成物が上記の課題を解決できることを見出した。
より好ましくは、ワックスの融点と有機溶剤の沸点の温度差が、２０〜１８０℃である超撥水被膜形成用組成物が、より良い結果をもたらす。
As a result of diligent research, the present inventor has found that the object can be achieved by using a super water-repellent film forming composition comprising hydrophobic fine particles, wax, and an organic solvent.
That is, it has been found that a composition for forming a super water-repellent film comprising hydrophobic fine particles, wax, and an organic solvent having a boiling point higher than the melting point of the wax can solve the above problems.
More preferably, the composition for forming a super water-repellent film having a temperature difference between the melting point of the wax and the boiling point of the organic solvent gives a better result.
本発明の超撥水被膜形成組成物は、表１の結果から明らかなように、被膜の超撥水性に優れ、撥水効果を一定期間持続させることができるとともに、被膜が残っている間は被塗物の表面を保護し、不要になれば簡単に剥離することができるという極めて有用な効果をもたらした。 As is apparent from the results in Table 1, the super water-repellent film forming composition of the present invention is excellent in super water repellency of the film, can maintain the water repellency effect for a certain period, and while the film remains. The surface of the object to be coated was protected, and when it became unnecessary, it was able to be easily peeled off and brought about an extremely useful effect.
本発明の超撥水性被膜形成用組成物は、疎水性微粒子、ワックス、有機溶剤からなり、有機溶剤中に疎水性微粒子とワックスが分散している。疎水性微粒子とワックスとワックスの融点より高い沸点を持つ有機溶剤の配合比率は、ワックスが溶剤に溶ける範囲であり、疎水性微粒子がワックスでつなぎとめられ保持される範囲内であればとくに問題は無いが、好ましくは、疎水性微粒子とワックスとワックスの融点より高い沸点を持つ有機溶剤の配合比率は、１〜３：１：１０〜８００（質量比）である。
本発明の超撥水性被膜形成用組成物を基板に塗布し、乾燥させた基板の表面を電子顕微鏡で観察すると、疎水性微粒子とワックスが渾然一体となった状態で葡萄の房状に凝集しており、これが超撥水性を引き起こしていると考えられる。
本発明で用いる疎水性微粒子は、疎水性シリカ微粒子、フッ素樹脂微粒子、ポリオレフィン樹脂微粒子、シリコーン樹脂微粒子等で、水との接触角が９０°以上である基材からなる微粒子が好ましく、特に好ましくは、水との接触角が９５°以上である。水との接触角が９０°より小さいと撥水性がなくなる。
本発明で用いる疎水性微粒子は、粒子径についてはとくに制限は無く、粒子径１ｎｍ〜２０μｍのものであれば何でも良いが、疎水性微粒子が３０ｎｍ以下の小さいものが凹凸の少ない美しい表面を形成するので好ましい。
これらは、単独で使用しても良いし、複数組み合わせてもよい。有機溶剤に対する分散性、疎水性などの点から、疎水性シリカ微粒子が好ましい。疎水性シリカの中でも親水性のシリカ表面をトリメチルシリル化もしくはジメチルシリル化して疎水化度を向上したものが特に好ましい。
市販されている疎水性シリカは、一般に気相反応で生成されるが、液相中で反応させてもよい。また、疎水化は上記のようなアルキル基の他、フッ化アルキル基でもよい。
疎水性微粒子の粒度は特に限定されないが、凝集して塗膜表面に微細な凹凸を形成するものが望ましい。
疎水性シリカ微粒子の例としては、具体的には、Ｒ９７２、ＲＸ２００（以上日本アエロジル株式会社製）、Ｎｉｐｓｉｌ ＳＳ−５０（日本シリカ工業株式会社製）ＳＩＰＥＲＮＡＴ
Ｄ１０、ＳＩＰＥＲＮＡＴ Ｄ１７（以上デグサジャパン製）などが挙げられる。
The composition for forming a super water-repellent film of the present invention comprises hydrophobic fine particles, wax, and an organic solvent, and the hydrophobic fine particles and the wax are dispersed in the organic solvent. The mixing ratio of the hydrophobic fine particles and the organic solvent having a boiling point higher than the melting point of the wax is within the range where the wax is soluble in the solvent, and there is no problem as long as the hydrophobic fine particles are within the range where the fine particles are held together and held by the wax. However, the blending ratio of the hydrophobic fine particles, the wax, and the organic solvent having a boiling point higher than the melting point of the wax is 1 to 3: 1: 10 to 800 (mass ratio).
When the superhydrophobic coating film-forming composition of the present invention is applied to a substrate and the surface of the dried substrate is observed with an electron microscope, the hydrophobic particles and the wax are agglomerated in a cocoon-like shape in a state of being united. This is considered to cause super water repellency.
The hydrophobic fine particles used in the present invention are preferably hydrophobic silica fine particles, fluororesin fine particles, polyolefin resin fine particles, silicone resin fine particles, and the like, preferably fine particles comprising a substrate having a contact angle with water of 90 ° or more. The contact angle with water is 95 ° or more. If the contact angle with water is smaller than 90 °, the water repellency is lost.
Hydrophobic fine particles used in the present invention are not particularly limited with respect to the particle size, and any particle having a particle size of 1 nm to 20 μm may be used, but small particles having a size of 30 nm or less form a beautiful surface with less irregularities. Therefore, it is preferable.
These may be used alone or in combination. Hydrophobic silica fine particles are preferred from the viewpoints of dispersibility in organic solvents and hydrophobicity. Among the hydrophobic silicas, those in which the hydrophilic silica surface is trimethylsilylated or dimethylsilylated to improve the degree of hydrophobicity are particularly preferable.
Commercially available hydrophobic silica is generally produced by a gas phase reaction, but may be reacted in a liquid phase. Further, the hydrophobization may be a fluorinated alkyl group in addition to the alkyl group as described above.
The particle size of the hydrophobic fine particles is not particularly limited, but those that aggregate to form fine irregularities on the surface of the coating film are desirable.
Specific examples of the hydrophobic silica fine particles include R972, RX200 (manufactured by Nippon Aerosil Co., Ltd.), Nipsil SS-50 (manufactured by Nippon Silica Industry Co., Ltd.) SIPRNAT
D10, SIPERNAT D17 (manufactured by Degussa Japan) and the like.
本発明で用いるワックスは、天然ワックス、石油ワックス、合成ワックスのいずれでもよいが、融点は４０℃〜１３０℃が好ましく、より好ましくは６０〜９０℃である。融点が４０℃より小さいと気温が上昇する屋外では、塗膜が流動して脱落したり、溶融化することによって表面の微細な凹凸構造が破壊され、超撥水状態を維持できなくなったり、水滴の滑落性が低下する。融点が１３０℃より大きいと基材への付着性が低下する。
このような天然ワックスの例としては、キャンデリラワックス、カルナウバワックス、木蝋、蜜蝋、晒し蜜蝋、鯨蝋、セレシン等が挙げられる。石油ワックスの例としては、パラフィンワックス、マイクロワックス等が挙げられる。合成ワックスの例としては、モンタンワックス、酸ワックス、エステルワックス、ポリエチレンワックス、サゾールワックス、硬化ひまし油、１２−ヒドロキシステアリン酸、１２−ヒドロキシステアリン酸エステル、ジアルキルケトン類、脂肪酸エステル類等が挙げられる。これらは、単独で使用しても良いし、複数組み合わせてもよい。とくに、蜜蝋が好ましく用いられる。
The wax used in the present invention may be any of natural wax, petroleum wax, and synthetic wax, but the melting point is preferably 40 to 130 ° C, more preferably 60 to 90 ° C. When the melting point is lower than 40 ° C, the temperature rises outdoors, and the coating film flows and falls off. When melted, the fine uneven structure on the surface is destroyed and the super water-repellent state cannot be maintained. The slipperiness of is reduced. When the melting point is higher than 130 ° C., the adhesion to the substrate is lowered.
Examples of such natural waxes include candelilla wax, carnauba wax, wood wax, beeswax, bleached beeswax, spermaceti, ceresin and the like. Examples of petroleum waxes include paraffin wax and micro wax. Examples of synthetic waxes include montan wax, acid wax, ester wax, polyethylene wax, sazol wax, hydrogenated castor oil, 12-hydroxystearic acid, 12-hydroxystearic acid ester, dialkyl ketones, fatty acid esters and the like. . These may be used alone or in combination. In particular, beeswax is preferably used.
本発明で用いる有機溶剤は、疎水性微粒子とワックスを均一に分散させることができるものであれば良く、塗布する基材に合わせて自由に選択できる。有機溶剤の沸点は、ワックスの融点より高いものから選ばれる。このような有機溶剤の例としては、脂肪族有機溶剤、テルペン系有機溶剤、芳香族有機溶剤、エステル系有機溶剤、ケトン系有機溶剤等が挙げられる。
脂肪族有機溶剤の例としては、ソルベントナフサ、ストッダードソルベント、ノルマルパラフィン、イソパラフィン、シクロパラフィン、ナフテン、アルファオレフィン等が挙げられる。テルペン系有機溶剤の例としては、テレビン油、ショウノウ油、パイン油、α―ピネン、ｄ−リモネン、ジペンテンなどが挙げられる。
芳香族有機溶剤の例としては、トルエン、キシレンなどが挙げられる。エステル系有機溶剤の例としては、酢酸ブチル、酢酸ペンチル、酢酸２−エチルヘキシルなどが挙げられる。ケトン系有機溶剤の例としては、メチルイソブチルケトン、シクロヘキサノン、ホロンなどが挙げられる。
これらの有機溶剤は単独で使用しても良いし、複数を組み合わせても良い。
また、目的に応じて他のグリコールエーテル系溶剤、アルコール系溶剤等を、性能を損なわない範囲で添加しても良い。
ワックスの融点と有機溶剤の沸点の温度差は、２０〜１８０℃であることが好ましい。 この温度差のものは、とくに、疎水性微粒子がワックスと渾然一体となった状態で葡萄の房状に凝集する割合が高くなり、結果としてより疎水性になることが判っている。
The organic solvent used in the present invention may be any organic solvent that can uniformly disperse the hydrophobic fine particles and the wax, and can be freely selected according to the substrate to be coated. The boiling point of the organic solvent is selected from those higher than the melting point of the wax. Examples of such organic solvents include aliphatic organic solvents, terpene organic solvents, aromatic organic solvents, ester organic solvents, ketone organic solvents, and the like.
Examples of the aliphatic organic solvent include solvent naphtha, stocked solvent, normal paraffin, isoparaffin, cycloparaffin, naphthene, and alpha olefin. Examples of the terpene organic solvent include turpentine oil, camphor oil, pine oil, α-pinene, d-limonene, dipentene and the like.
Examples of the aromatic organic solvent include toluene, xylene and the like. Examples of the ester organic solvent include butyl acetate, pentyl acetate, and 2-ethylhexyl acetate. Examples of the ketone organic solvent include methyl isobutyl ketone, cyclohexanone, and holon.
These organic solvents may be used alone or in combination.
Further, other glycol ether solvents, alcohol solvents and the like may be added within a range not impairing the performance depending on the purpose.
The temperature difference between the melting point of the wax and the boiling point of the organic solvent is preferably 20 to 180 ° C. It has been found that those having this temperature difference have a higher ratio of agglomerates in the tuft shape of the hydrophobic particles, particularly in a state where the hydrophobic fine particles are integrally integrated with the wax, resulting in a more hydrophobic result.
本発明の組成物には、外観向上のために着色剤、耐光性向上のために紫外線吸収剤、粘度調整のための増粘剤などを必要に応じて添加してもよい。
本発明の組成物は、通常、スプレー、ハケ塗り、ディッピング等の方法によって塗布される。塗布後は自然乾燥により成膜し、特別な乾燥設備は必要としない。
塗膜が汚れたり、損傷したり、必要がなくなった場合は、ウエス等で簡単に拭き取ることができる。
If necessary, a colorant for improving the appearance, an ultraviolet absorber for improving light resistance, a thickener for adjusting viscosity, and the like may be added to the composition of the present invention.
The composition of the present invention is usually applied by a method such as spraying, brushing or dipping. After coating, the film is formed by natural drying, and no special drying equipment is required.
If the coating becomes dirty, damaged, or no longer necessary, it can be easily wiped off with a waste cloth or the like.
本発明の実施の形態をまとめると以下の通りである。（１）疎水性微粒子、蜜蝋、蜜蝋の融点より高い沸点を持つ有機溶剤から成る超撥水被膜形成用組成物であって、蜜蝋の融点と有機溶剤の沸点の温度差が、２０〜１８０℃であり、かつ、疎水性微粒子と蜜蝋と蜜蝋の融点より高い沸点を持つ有機溶剤の配合比率が１〜３：１：１０〜８００（質量比）であって、シリコーンオイルを含まないことを特徴とする非シリコーンオイル系超撥水被膜形成用組成物。（２）疎水性微粒子が、疎水性シリカ微粒子、フッ素樹脂微粒子、ポリオレフィン樹脂微粒子、シリコーン樹脂微粒子からなる群れより選ばれる１種若しくは２種以上の疎水性微粒子であることを特徴とする上記（１）に記載した超撥水被膜形成用組成物。（３）有機溶剤が、ソルベントナフサ、ストッダードソルベント、ノルマルパラフィン、イソパラフィン、シクロパラフィン、ナフテン、アルファオレフィンからなる脂肪族有機溶剤、テレビン油、ショウノウ油、パイン油、α―ピネン、ｄ−リモネン、ジペンテンからなるテルペン系有機溶剤、ベンゼン、トルエン、キシレンからなる芳香族有機溶剤、酢酸ブチル、酢酸ペンチル、酢酸２−エチルヘキシルからなるエステル系有機溶剤、メチルイソブチルケトン、シクロヘキサノン、ホロンからなるケトン系有機溶剤の１種又は２種以上である上記（１）または上記（２）に記載した超撥水被膜形成用組成物。 The embodiments of the present invention are summarized as follows. (1) A composition for forming a super water-repellent film comprising an organic solvent having a boiling point higher than the melting point of hydrophobic fine particles, beeswax, and beeswax, wherein the temperature difference between the melting point of beeswax and the boiling point of the organic solvent is 20 to 180 ° C. The blending ratio of the organic solvent having a boiling point higher than the melting point of hydrophobic fine particles, beeswax and beeswax is 1-3: 1: 10-800 (mass ratio) and does not contain silicone oil. A non-silicone oil-based super-water-repellent coating composition. (2) The above (1), wherein the hydrophobic fine particles are one or more hydrophobic fine particles selected from the group consisting of hydrophobic silica fine particles, fluororesin fine particles, polyolefin resin fine particles, and silicone resin fine particles. The composition for forming a super water-repellent film described in (1). (3) The organic solvent is an aliphatic organic solvent composed of solvent naphtha, stocked solvent, normal paraffin, isoparaffin, cycloparaffin, naphthene, alpha olefin, turpentine oil, camphor oil, pine oil, α-pinene, d-limonene, dipentene. Terpene organic solvent consisting of benzene, toluene, xylene aromatic organic solvent, butyl acetate, pentyl acetate, ester organic solvent consisting of 2-ethylhexyl acetate, methyl isobutyl ketone, cyclohexanone, ketone organic solvent consisting of holon The composition for forming a super water-repellent film as described in (1) or (2) above, which is one type or two or more types.
Ｄ−リモネン（沸点１７６℃）９７ｇ中に、１号カルナウバワックス（融点８３℃）１ｇ及び疎水性シリカ微粒子Ｒ９７２（粒子径１６ｎｍ、ジメチルシリル化疎水性シリカ／日本アエロジル製）２ｇを配合し、約９０℃まで加熱してカルナウバワックスを完全に溶解させた。その後、攪拌しながら室温まで冷却して超撥水被膜形成用組成物を得た。
この組成物をアクリルメラミン製塗装板及び普通乗用車のボンネット部分にエアーガンで均一にスプレー塗装して、自然乾燥させた後、水滴の接触角、転落角、実車における撥水の持続性、塗膜の剥離性、塗装表面の保護性について評価した。
In 97 g of D-limonene (boiling point: 176 ° C.), 1 g of No. 1 carnauba wax (melting point: 83 ° C.) and 2 g of hydrophobic silica fine particles R972 (particle diameter 16 nm, dimethylsilylated hydrophobic silica / manufactured by Nippon Aerosil) were blended, The carnauba wax was completely dissolved by heating to about 90 ° C. Then, it cooled to room temperature, stirring, and obtained the composition for super-water-repellent film formation.
After spraying this composition uniformly on the bonnet part of an acrylic melamine plate and the passenger car's bonnet with an air gun and letting it dry naturally, the contact angle of water droplets, the falling angle, the water repellency of the actual vehicle, The peelability and the paint surface protection were evaluated.
イソパラフィン（ＩＰソルベント１６２０、沸点範囲１６６〜２０２℃／出光石油化学社製）９７ｇ中に、パラフィンワックス１２０Ｆ（融点５０℃）１ｇ及び疎水性シリカ微粒子Ｒ９７２（粒子径１６ｎｍ、ジメチルシリル化疎水性シリカ／日本アエロジル製）２ｇを配合し、約６０℃まで加熱してパラフィンワックスを完全に溶解させた。その後、攪拌しながら室温まで冷却して実施例２の組成物を得た。
この組成物をアクリルメラミン製塗装板及び普通乗用車のボンネット部分にエアーガンで均一にスプレー塗装して、自然乾燥させた後、水滴の接触角、転落角、実車における撥水の持続性、塗膜の剥離性、塗装表面の保護性について評価した。
In 97 g of isoparaffin (IP solvent 1620, boiling point range: 166 to 202 ° C./manufactured by Idemitsu Petrochemical Co., Ltd.), 1 g of paraffin wax 120F (melting point: 50 ° C.) and hydrophobic silica fine particles R972 (particle diameter 16 nm, dimethylsilylated hydrophobic silica / 2 g of Nippon Aerosil Co., Ltd. was blended and heated to about 60 ° C. to completely dissolve the paraffin wax. Then, it cooled to room temperature, stirring, and obtained the composition of Example 2.
After spraying this composition uniformly on the bonnet part of an acrylic melamine plate and the passenger car's bonnet with an air gun and letting it dry naturally, the contact angle of water droplets, the falling angle, the water repellency of the actual vehicle, The peelability and the paint surface protection were evaluated.
ナフテン系溶剤（ナフテゾール１６０、沸点範囲１５０〜１８０℃／新日本石油化学社製）９７ｇ中に、蜜蝋（融点６０〜６７℃）１ｇ及び疎水性シリカ微粒子Ｒ９７２（粒子径１６ｎｍ、ジメチルシリル化疎水性シリカ／日本アエロジル製）２ｇを配合し、約７５℃まで加熱して蜜蝋を完全に溶解させた。その後、攪拌しながら室温まで冷却して実施例３の組成物を得た。
この組成物をアクリルメラミン製塗装板及び普通乗用車のボンネット部分にエアーガンで均一にスプレー塗装して、自然乾燥させた後、水滴の接触角、転落角、実車における撥水の持続性、塗膜の剥離性、塗装表面の保護性について評価した。
1 g of beeswax (melting point 60-67 ° C.) and hydrophobic silica fine particles R972 (particle size 16 nm, dimethylsilylated hydrophobicity) in 97 g of naphthenic solvent (naphthethol 160, boiling range 150-180 ° C./manufactured by Nippon Petrochemical Co., Ltd.) 2 g of silica / manufactured by Nippon Aerosil) and heated to about 75 ° C. to completely dissolve the beeswax. Then, it cooled to room temperature, stirring, and obtained the composition of Example 3.
After spraying this composition uniformly on the bonnet part of an acrylic melamine plate and the passenger car's bonnet with an air gun and letting it dry naturally, the contact angle of water droplets, the falling angle, the water repellency of the actual vehicle, The peelability and the paint surface protection were evaluated.
ナフテン系溶剤（ナフテゾール１６０、沸点範囲１５０〜１８０℃／新日本石油化学社製）９７ｇ中に、蜜蝋（融点６０〜６７℃）１ｇ及び疎水性シリカ微粒子ＲＸ２００（粒子径１２ｎｍ、トリメチルシリル化疎水性シリカ／日本アエロジル社製）２ｇを配合し、約７５℃まで加熱して蜜蝋を完全に溶解させた。その後、攪拌しながら室温まで冷却して実施例４の組成物を得た。
この組成物をアクリルメラミン製塗装板及び普通乗用車のボンネット部分にエアーガンで均一にスプレー塗装して、自然乾燥させた後、水滴の接触角、転落角、実車における撥水の持続性、塗膜の剥離性、塗装表面の保護性について評価した。
1 g of beeswax (melting point: 60-67 ° C.) and hydrophobic silica fine particles RX200 (particle size: 12 nm, trimethylsilylated hydrophobic silica) in 97 g of naphthenic solvent (Naphthezol 160, boiling range: 150-180 ° C./manufactured by Nippon Petrochemical Co., Ltd.) (Manufactured by Nippon Aerosil Co., Ltd.) 2 g was mixed and heated to about 75 ° C. to completely dissolve the beeswax. Then, it cooled to room temperature, stirring, and obtained the composition of Example 4.
After spraying this composition uniformly on the bonnet part of an acrylic melamine plate and the passenger car's bonnet with an air gun and letting it dry naturally, the contact angle of water droplets, the falling angle, the water repellency of the actual vehicle, The peelability and the paint surface protection were evaluated.
ナフテン系溶剤（ナフテゾール１６０、沸点範囲１５０〜１８０℃／新日本石油化学社製）９７ｇ中に、蜜蝋（融点６０〜６７℃）１ｇ及びテフロン微粒子（粒子径１μｍ、デュポン社製）２ｇを配合し、約７５℃まで加熱して蜜蝋を完全に溶解させた。その後、攪拌しながら室温まで冷却して実施例５の組成物を得た。
この組成物をアクリルメラミン製塗装板及び普通乗用車のボンネット部分にエアーガンで均一にスプレー塗装して、自然乾燥させた後、水滴の接触角、転落角、実車における撥水の持続性、塗膜の剥離性、塗装表面の保護性について評価した。
1 g of beeswax (melting point: 60-67 ° C.) and 2 g of Teflon fine particles (particle size: 1 μm, manufactured by DuPont) are blended in 97 g of a naphthenic solvent (Naphthezol 160, boiling range: 150-180 ° C./manufactured by Shin Nippon Petrochemical) And heated to about 75 ° C. to completely dissolve the beeswax. Then, it cooled to room temperature, stirring, and obtained the composition of Example 5.
After spraying this composition uniformly on the bonnet part of an acrylic melamine plate and the passenger car's bonnet with an air gun and letting it dry naturally, the contact angle of water droplets, the falling angle, the water repellency of the actual vehicle, The peelability and the paint surface protection were evaluated.
（比較例１）
ナフテン系溶剤（ナフテゾール１６０、沸点範囲１５０〜１８０℃／新日本石油化学社製）９７ｇ中に、蜜蝋（融点６０〜６７℃）１ｇ及び親水性シリカ微粒子アエロジル２００（粒子径１６ｎｍ、日本アエロジル社製）２ｇを配合し、約７５℃まで加熱して蜜蝋を完全に溶解させた。その後、攪拌しながら室温まで冷却して比較例１の組成物を得た。
この組成物をアクリルメラミン製塗装板及び普通乗用車のボンネット部分にエアーガンで均一にスプレー塗装して、自然乾燥させた後、水滴の接触角、転落角、実車における撥水の持続性、塗膜の剥離性、塗装表面の保護性について評価した。
(Comparative Example 1)
1 g of beeswax (melting point 60-67 ° C.) and hydrophilic silica fine particles Aerosil 200 (particle size 16 nm, manufactured by Nippon Aerosil Co., Ltd.) in 97 g of naphthenic solvent (naphthethol 160, boiling range 150-180 ° C./manufactured by Nippon Petrochemical Co., Ltd.) 2g) was mixed and heated to about 75 ° C to completely dissolve the beeswax. Then, it cooled to room temperature, stirring, and obtained the composition of the comparative example 1.
After spraying this composition uniformly on the bonnet part of an acrylic melamine plate and the passenger car's bonnet with an air gun and letting it dry naturally, the contact angle of water droplets, the falling angle, the water repellency of the actual vehicle, The peelability and the paint surface protection were evaluated.
（比較例２）
ナフテン系溶剤（ナフテゾール１６０、沸点範囲１５０〜１８０℃／新日本石油化学社製）９７ｇ中に、ブチルメタアクリレート樹脂（パラロイドＦ−１０／ロームアンドハースジャパン社製）１ｇを完全に溶解させた後、疎水性シリカ微粒子Ｒ９７２（粒子径１６ｎｍ、ジメチルシリル化疎水性シリカ／日本アエロジル製）２ｇを攪拌しながら配合し、比較例２の組成物を得た。
この組成物をアクリルメラミン製塗装板及び普通乗用車のボンネット部分にエアーガンで均一にスプレー塗装して、自然乾燥させた後、水滴の接触角、転落角、実車における撥水の持続性、塗膜の剥離性、塗装表面の保護性について評価した。
(Comparative Example 2)
After completely dissolving 1 g of butyl methacrylate resin (Paraloid F-10 / Rohm and Haas Japan) in 97 g of naphthenic solvent (Naphthesol 160, boiling range 150-180 ° C./manufactured by Nippon Petrochemical Co., Ltd.) 2 g of hydrophobic silica fine particles R972 (particle diameter 16 nm, dimethylsilylated hydrophobic silica / manufactured by Nippon Aerosil Co., Ltd.) were mixed with stirring to obtain a composition of Comparative Example 2.
After spraying this composition uniformly on the bonnet part of an acrylic melamine plate and the passenger car's bonnet with an air gun and letting it dry naturally, the contact angle of water droplets, the falling angle, the water repellency of the actual vehicle, The peelability and the paint surface protection were evaluated.
（比較例３）
ナフテン系溶剤（ナフテゾール１６０、沸点範囲１５０〜１８０℃／新日本石油化学社製）９８ｇ中に、蜜蝋（融点６０〜６７℃）２ｇを配合し、約７５℃まで加熱して蜜蝋を完全に溶解させた。その後、攪拌しながら室温まで冷却して比較例３の組成物を得た。
この組成物をアクリルメラミン製塗装板及び普通乗用車のボンネット部分にエアーガンで均一にスプレー塗装して、自然乾燥させた後、水滴の接触角、転落角、実車における撥水の持続性、塗膜の剥離性、塗装表面の保護性について評価した。
(Comparative Example 3)
2g of beeswax (melting point 60-67 ° C) is blended in 98g of naphthenic solvent (naphthethol 160, boiling range 150-180 ° C / manufactured by Nippon Petrochemical Co., Ltd.) and heated to about 75 ° C to completely dissolve the beeswax. I let you. Then, it cooled to room temperature, stirring, and obtained the composition of the comparative example 3.
After spraying this composition uniformly on the bonnet part of an acrylic melamine plate and the passenger car's bonnet with an air gun and letting it dry naturally, the contact angle of water droplets, the falling angle, the water repellency of the actual vehicle, The peelability and the paint surface protection were evaluated.
それぞれの評価結果を表１に表わす。
（１）水滴の接触角：水滴量0.02ml、自動接触角計CAZ-150（協和界面科学社製）で測定
（２）水滴の転落角：水滴量1ml、手動式転落角測定装置で測定
（３）塗膜の密着性：目視評価
○・・・異常なし
△・・・部分的にワレ、剥がれがある
（４）撥水の持続性（実車ホ゛ンネット）：散水後の目視評価（１ヶ月経過後）
○・・・水滴が真球状になり転がり落ちる
△・・・水滴が付着したまま塗面に残る
×・・・撥水しない
（５）塗膜の剥離性（実車ホ゛ンネット）：塗膜をウエスで拭き取る（１ヶ月経過後）
○・・・軽く拭き取れる
×・・・拭き残りが生じる
（６）塗膜の保護性（実車ホ゛ンネット）：拭き取り後の目視評価及び色差測定
（１ヶ月経過後）
色彩色差計CR-200（ミノルタ社製）使用
○・・・変化なし／ΔＥ：0.5未満
×・・・変色、汚れあり／ΔＥ：0.5以上
Each evaluation result is shown in Table 1.
(1) Water drop contact angle: 0.02 ml of water drop, measured with an automatic contact angle meter CAZ-150 (Kyowa Interface Science Co., Ltd.)
(2) Drop angle of water drops: 1 ml of water drops, measured with a manual drop angle measuring device
(3) Adhesion of coating film: visual evaluation
○ ・ ・ ・ No abnormality
△ ・ ・ ・ Partial cracks and peeling
(4) Water repellency (actual vehicle bonnet): Visual evaluation after sprinkling (after 1 month)
○ ... Water drops become spherical and roll down
Δ: Water drops remain on the paint surface
× ・ ・ ・ No water repellency
(5) Peelability of paint film (actual vehicle bonnet): Wipe the paint film with waste cloth (after 1 month)
○ ・ ・ ・ Lightly wipeable
× ・ ・ ・ Which residue is left
(6) Coating film protection (actual vehicle bonnet): Visual evaluation after wiping and color difference measurement (after one month)
Use color difference meter CR-200 (Minolta)
○ ・ ・ ・ No change / ΔE: Less than 0.5
× ・ ・ ・ discolored, dirty / ΔE: 0.5 or more
本発明の超撥水被膜形成組成物は、自動車の塗装膜のみならず、例えば屋根瓦の表面に塗布すると、雨や雪の粒を瓦の表面に留まらせることがないので、雪が積もることがないことが確認されており、雪国において冬に雪おろしをする必要が無くなる。 The super water-repellent film-forming composition of the present invention is not only applied to automobile paint films, but, for example, when it is applied to the surface of a roof tile, rain and snow particles do not remain on the surface of the tile, so that snow may accumulate. It has been confirmed that there is no need to remove snow in the winter in snowy countries.
Claims (3)
Terpene organic solvent is solvent naphtha, stocked solvent, normal paraffin, isoparaffin, cycloparaffin, naphthene, aliphatic organic solvent consisting of alpha olefin, turpentine oil, camphor oil, pine oil, α-pinene, d-limonene, dipentene Organic solvent, aromatic organic solvent consisting of benzene, toluene, xylene, ester organic solvent consisting of butyl acetate, pentyl acetate, 2-ethylhexyl acetate, ketone organic solvent consisting of methyl isobutyl ketone, cyclohexanone, and holon, or The composition for forming a super water-repellent film according to claim 1 or 2, wherein there are two or more kinds.
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| JP3787793B2 (en) * | 1996-04-11 | 2006-06-21 | 株式会社ソフト９９コーポレーション | Protective water repellent for coatings |
| JP4860018B2 (en) * | 1999-01-25 | 2012-01-25 | 株式会社タイホーコーザイ | Water repellent antifouling agent |
| JP2000248270A (en) * | 1999-02-26 | 2000-09-12 | Soft 99 Corporation:Kk | Water repellency-imparting treatment to coating film |
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2003
- 2003-09-04 JP JP2003312817A patent/JP4518466B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571291A (en) * | 2012-07-27 | 2014-02-12 | 比亚迪股份有限公司 | Waterproof coating |
| CN103571291B (en) * | 2012-07-27 | 2016-05-04 | 比亚迪股份有限公司 | A kind of water-repellent paint |
| CN111218208A (en) * | 2020-01-17 | 2020-06-02 | 四川农业大学 | Reversibly switchable super-wettability super-amphiphobic coating and preparation and application thereof |
| CN111218208B (en) * | 2020-01-17 | 2021-10-22 | 四川农业大学 | A reversibly switchable super-wetting super-amphiphobic coating and its preparation and application |
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| JP2005082616A (en) | 2005-03-31 |
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