JP2012177062A - Antifouling coating composition and method of forming antifouling coating - Google Patents
Antifouling coating composition and method of forming antifouling coating Download PDFInfo
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本発明は、耐汚染性、耐温水性に優れた、自己洗浄能力を有する防汚層を形成することのできる防汚塗料組成物及び防汚塗膜の形成方法に関する。 The present invention relates to an antifouling coating composition capable of forming an antifouling layer having a self-cleaning ability, which is excellent in stain resistance and hot water resistance, and a method for forming an antifouling coating film.
オルガノポリシロキサン系の無機樹脂を結合剤とする塗膜は、耐候性や耐汚染性等に優れるものの、初期の親水性発現までに時間を要する。また、オルガノシラン及び／又はその部分加水分解縮合物と、シリル基含有化合物を加水分解縮合反応させて得られる有機無機複合樹脂を結合剤とする塗膜は、クラックが生じ難いものの、耐汚染性や、耐候性、耐溶剤性を更に向上させることが求められていた（例えば、特許文献１及び２参照）。 A coating film using an organopolysiloxane-based inorganic resin as a binder is excellent in weather resistance, stain resistance, and the like, but takes time to develop the initial hydrophilicity. In addition, a coating film using an organic-inorganic composite resin obtained by hydrolytic condensation reaction of organosilane and / or its partial hydrolysis-condensation product and a silyl group-containing compound as a binder is resistant to contamination. In addition, it has been required to further improve the weather resistance and solvent resistance (see, for example, Patent Documents 1 and 2).
本発明の目的は、このような従来技術の課題を背景になされたもので、特定のコロイド状シリカと特定の界面活性剤、水とを用いることにより、耐汚染性や、耐温水性に優れた、自己洗浄能力を有する防汚層を形成し、また、有機系溶剤を使用しないため環境面においても優しく、更に有機溶剤に脆弱な下地塗膜が溶解や膨潤等を起こすことのない防汚塗料組成物及び防汚塗膜の形成方法を提供することである。 The object of the present invention is based on the background of the problems of the prior art, and by using a specific colloidal silica, a specific surfactant, and water, it is excellent in stain resistance and hot water resistance. In addition, it forms an antifouling layer that has a self-cleaning ability, and is environmentally friendly because it does not use organic solvents.Furthermore, an antifouling agent that does not cause dissolution or swelling of an undercoating film that is fragile to organic solvents. It is providing the coating composition and the formation method of an antifouling coating film.
本発明に従って、
（ａ）水分散コロイダルシリカ（固形分換算）０．１〜１０．０質量％と、
（ｂ）１種類以上のノニオン系界面活性剤（固形分換算）０．０１〜１．０質量％と、
（ｃ）水８９〜９９質量％と
を主成分として含有し、
該ノニオン系界面活性剤が、ポリオキシアルキレンモノアルキルエーテルを含有し、かつ、有機系溶剤を含有しないことを特徴とする防汚塗料組成物が提供される。
In accordance with the present invention,
(A) water-dispersed colloidal silica (in terms of solid content) 0.1 to 10.0% by mass;
(B) one or more kinds of nonionic surfactants (in terms of solid content) 0.01 to 1.0% by mass;
(C) containing 89 to 99% by mass of water as a main component,
An antifouling paint composition is provided in which the nonionic surfactant contains a polyoxyalkylene monoalkyl ether and does not contain an organic solvent.
また、本発明に従って、上記の防汚塗料組成物を、基材又は下塗塗膜上に塗布・乾燥し、防汚塗膜を形成することを特徴とする防汚塗膜の形成方法が提供される。 In addition, according to the present invention, there is provided a method for forming an antifouling coating film characterized in that the antifouling coating composition is applied to a substrate or an undercoat coating film and dried to form an antifouling coating film. The
本発明によって、耐汚染性や、耐温水性に優れた、自己洗浄能力を有する防汚層を形成し、また、有機系溶剤を使用しないため環境面においても優しく、更に有機溶剤に脆弱な下地塗膜が溶解や膨潤等を起こすことのない防汚塗料組成物及び防汚塗膜の形成方法を提供することが可能となった。 According to the present invention, an antifouling layer having excellent antifouling property and hot water resistance and having a self-cleaning ability is formed, and since it does not use an organic solvent, it is environmentally friendly, and further, a base that is fragile to an organic solvent. It became possible to provide an antifouling paint composition and a method for forming an antifouling coating film in which the coating film does not cause dissolution or swelling.
以下、本発明の実施形態について、詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明の防汚塗料組成物の各構成成分について説明する。 Each component of the antifouling coating composition of the present invention will be described.
まず、本発明の防汚塗料組成物の主剤となる（ａ）水分散コロイダルシリカについて説明する。 First, (a) water-dispersed colloidal silica which is the main component of the antifouling coating composition of the present invention will be described.
（ａ）水分散コロイダルシリカについて
（ａ）成分の水分散コロイダルシリカは、シリカ粒子が、水媒体中に分散したものである。コロイダルシリカは、通常、平均粒子径が、５〜１００ｎｍのほぼ球状のシリカ粒子が分散したタイプと、シリカ粒子が太さ５〜５０ｎｍ、長さ４０〜４００ｎｍ程度に鎖状に凝集して溶液中に分散したタイプと、平均粒子径１０〜５０ｎｍの球状シリカ粒子がパールネックレス状に５０〜４００ｎｍの長さに連なったパールネックレス状タイプと、平均粒子径５〜５０ｎｍのシリカ粒子が環状に凝集して溶液中に分散した環状タイプ等がある。本発明においては、球状コロイダルシリカを使用することが耐汚染性の観点から好ましい。また、異なるタイプの物も少量であれば混合して使用することができる。水分散コロイダルシリカの平均粒子径は１０〜４０ｎｍであることが好ましい。平均粒子径が１０ｎｍ未満であると耐汚染性が低下し、４０ｎｍを超えると塗膜外観が低下する傾向がある。
(A) About water-dispersed colloidal silica (a) The water-dispersed colloidal silica of component (a) is a dispersion of silica particles in an aqueous medium. Colloidal silica usually has a type in which approximately spherical silica particles having an average particle diameter of 5 to 100 nm are dispersed, and silica particles aggregate in a chain shape with a thickness of about 5 to 50 nm and a length of about 40 to 400 nm. A pearl necklace type in which spherical silica particles having an average particle diameter of 10 to 50 nm are connected in a pearl necklace shape with a length of 50 to 400 nm and silica particles having an average particle diameter of 5 to 50 nm aggregate in a ring shape. There are ring types dispersed in the solution. In the present invention, it is preferable to use spherical colloidal silica from the viewpoint of stain resistance. Different types of products can also be mixed and used in small amounts. The average particle size of the water-dispersed colloidal silica is preferably 10 to 40 nm. When the average particle size is less than 10 nm, the stain resistance decreases, and when it exceeds 40 nm, the appearance of the coating film tends to decrease.
ほぼ球状のシリカ粒子が水に分散したコロイダルシリカは、市販品として容易に入手することができ、具体例としては、例えば、日産化学工業（株）製のスノーテックス−２０、スノーテックス−Ｏ、スノーテックス−Ｃ、スノーテックス−Ｓや、旭電化工業（株）製のアデライトＡＴ−２０、ＡＴ−２０Ｎ、ＡＴ−２０Ａ、ＡＴ−３００等が挙げられる。 Colloidal silica in which substantially spherical silica particles are dispersed in water can be easily obtained as a commercial product. Specific examples include, for example, SNOWTEX-20, SNOWTEX-O, manufactured by Nissan Chemical Industries, Ltd. Examples include Snowtex-C, Snowtex-S, and Adelite AT-20, AT-20N, AT-20A, AT-300 manufactured by Asahi Denka Kogyo Co., Ltd.
鎖状コロイダルシリカは、水中にシリカ粒子が分散したものであり、市販品として容易に入手することができる。その具体例としては、例えば、日産化学工業（株）製のスノーテックス−ＵＰ、スノーテックス−ＯＵＰ（以上、水分散系）等が挙げられる。 Chain colloidal silica is obtained by dispersing silica particles in water, and can be easily obtained as a commercial product. Specific examples thereof include, for example, Snowtex-UP, Snowtex-OUP (above, water dispersion) manufactured by Nissan Chemical Industries, Ltd.
パールネックレス状コロイダルシリカは、市販品として容易に入手することができ、具体例としては、例えば、日産化学工業（株）製のスノーテックス−ＰＳ−Ｓ、スノーテックス−ＰＳ−Ｍ、スノーテックス−ＰＳ−ＳＯ、スノーテックス−ＰＳ−ＭＯ等が挙げられる。 The pearl necklace-shaped colloidal silica can be easily obtained as a commercial product. Specific examples thereof include, for example, SNOWTEX-PS-S, SNOWTEX-PS-M, SNOWTEX- manufactured by Nissan Chemical Industries, Ltd. PS-SO, Snowtex-PS-MO, etc. are mentioned.
本発明の防汚塗料組成物においては、水系の塗料組成物であり、塗膜外観が低下するため、水分散コロイダルシリカの分散溶媒としては、有機溶媒を含むものは使用できない。 In the antifouling paint composition of the present invention, it is a water-based paint composition, and the appearance of the coating film is lowered. Therefore, a dispersion solvent of water-dispersed colloidal silica cannot contain a solvent containing an organic solvent.
（ａ）成分は、塗膜の硬化性や耐汚染性を向上させるためのものであり、その配合量は、固形分換算で、防汚塗料組成物中、０．１〜１０．０質量％、好ましくは、０．５〜２．０質量％が適当である。（ａ）成分の配合量が、前記範囲より少ないと、塗膜の硬化性や、耐汚染性を向上させる効果が発揮されず、逆に多過ぎると、塗膜の外観が悪くなる傾向にある。 (A) A component is for improving the sclerosis | hardenability and stain resistance of a coating film, The compounding quantity is 0.1-10.0 mass% in antifouling coating composition in conversion of solid content. Preferably, 0.5 to 2.0% by mass is appropriate. When the blending amount of the component (a) is less than the above range, the effect of improving the curability and stain resistance of the coating film is not exhibited, and conversely, when it is too much, the appearance of the coating film tends to deteriorate. .
一般に水分散コロイダルシリカは製造方法によりＮａを含むが、本発明においてはそのＮａを含んだアルカリ性タイプの水分散コロイダルシリカを用いることがシリカ粒子の分散性が向上するため好ましい。よって、（ａ）成分の水分散コロイダルシリカ溶液のｐＨは、８〜１０であることが好ましく、更には、ｐＨが８．５〜９．５であることがより好ましい。 In general, the water-dispersed colloidal silica contains Na depending on the production method. In the present invention, it is preferable to use an alkaline type water-dispersed colloidal silica containing Na because the dispersibility of the silica particles is improved. Therefore, the pH of the water-dispersed colloidal silica solution of component (a) is preferably 8 to 10, and more preferably 8.5 to 9.5.
（ｂ）ノニオン系界面活性剤について
（ｂ）成分は、（ａ）成分の水分散コロイダルシリカの分散性向上や塗膜の耐汚染性、塗膜形成時のフロー性を向上させるために含有される。
(B) Nonionic surfactant (b) The component (b) is contained in order to improve the dispersibility of the water-dispersed colloidal silica of the component (a), the stain resistance of the coating film, and the flowability during coating film formation. The
（ｂ）ノニオン系界面活性剤としては、ポリオキシアルキレンモノアルキルエーテルを含有することが必須である。これ以外にも、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリールエーテル、ポリオキシエチレンアルキルフェニルエーテル、プロピレンオキサイド・エチレンオキサイドブロックポリマー、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、アルキル（ポリ）グリコシド等のノニオン系界面活性剤を用いても構わない。これらの中でもプロピレンオキサイド・エチレンオキサイドブロックポリマーを含有すると耐雨筋汚染性が向上するため好ましい。 (B) As a nonionic surfactant, it is essential to contain a polyoxyalkylene monoalkyl ether. Other than this, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl phenyl ether, propylene oxide / ethylene oxide block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol Nonionic surfactants such as fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and alkyl (poly) glycosides may be used. Among these, it is preferable to contain a propylene oxide / ethylene oxide block polymer because rain-stain stain resistance is improved.
（ｂ）成分の配合量は、固形分換算で、防汚塗料組成物中０．０１〜１．０質量％、好ましくは、０．０５〜０．５質量％が適当である。（ｂ）成分の配合量が、前記範囲より少ないと、塗膜の成膜性、外観が悪くなる。逆に前記範囲より多いと、塗膜の耐水性が低下し、塗膜の耐久性が悪くなる。 (B) The compounding quantity of a component is 0.01-1.0 mass% in an antifouling coating composition in conversion of solid content, Preferably, 0.05-0.5 mass% is suitable. When the blending amount of the component (b) is less than the above range, the film formability and appearance of the coating film are deteriorated. On the other hand, when the amount is more than the above range, the water resistance of the coating film is lowered and the durability of the coating film is deteriorated.
（ｃ）成分について
希釈剤としての（ｃ）成分の水は、純水や蒸留水、イオン交換水、水道水等を使用することができる。
About (c) component Pure water, distilled water, ion-exchange water, tap water, etc. can be used for the water of (c) component as a diluent.
（ｃ）水の配合量は、防汚塗料組成物中、８９〜９９質量％であり、更に好ましくは、９５〜９９質量％である。（ｃ）成分の配合量が、前記範囲より少ないと、塗料粘度が高くなり塗装作業性が悪くなり、逆に多過ぎると、防汚塗料成分が希薄となり、均一な塗膜が得られなくなる。 (C) The compounding quantity of water is 89-99 mass% in an antifouling coating composition, More preferably, it is 95-99 mass%. When the blending amount of the component (c) is less than the above range, the coating viscosity becomes high and the coating workability is deteriorated. On the contrary, when the blending amount is too large, the antifouling coating component is diluted and a uniform coating film cannot be obtained.
本発明の防汚塗料組成物は、更にフッ素系界面活性剤を含有することが好ましい。ここで言うフッ素系界面活性剤は、分子内にＣＦ３（ＣＦ２）ｎ−で構成されるパーフルオロアルキル基を含有する界面活性剤であり、これを添加することで、表面張力を更に低下させることができ、塗膜の親水性が向上し塗膜の耐汚染性も向上する。 The antifouling coating composition of the present invention preferably further contains a fluorine-based surfactant. The fluorosurfactant mentioned here is a surfactant containing a perfluoroalkyl group composed of CF 3 (CF 2 ) n — in the molecule, and by adding this, the surface tension is further reduced. The hydrophilicity of the coating film is improved and the stain resistance of the coating film is also improved.
このようなフッ素系界面活性剤としては、例えば、パーフルオロアルキルカルボン酸塩、パーフルオロアルキルスルホン酸塩、パーフルオロアルキルリン酸エステル、パーフルオロアルケニルスルホン酸塩、パーフルオロアルケニルカルボン酸塩等のアニオン型フッ素系界面活性剤；パーフルオロアルキルベタイン等の両性型フッ素系界面活性剤；パーフルオロアルキルトリメチルアンモニウム等のカチオン型フッ素系界面活性剤；パーフルオロアルキルエチレンオキシド付加物、パーフルオロアルキルアミンオキサイド、パーフルオロアルキル基を含有するオリゴマー等のノニオン型フッ素系界面活性剤が挙げられる。これらの中でもパーフルオロアルケニル基を有するフッ素系界面活性剤が、特に塗膜の耐汚染性に優れるため好ましい。 Examples of such a fluorosurfactant include anions such as perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl phosphate, perfluoroalkenyl sulfonate, and perfluoroalkenyl carboxylate. Type fluorosurfactant; amphoteric type fluorosurfactant such as perfluoroalkylbetaine; cationic type fluorosurfactant such as perfluoroalkyltrimethylammonium; perfluoroalkylethylene oxide adduct, perfluoroalkylamine oxide, perfluoroalkyl surfactant Nonionic fluorine-type surfactants, such as an oligomer containing a fluoroalkyl group, are mentioned. Among these, a fluorosurfactant having a perfluoroalkenyl group is particularly preferable because of excellent stain resistance of the coating film.
本発明の防汚塗料組成物は、更に酸化錫粒子を含有することが好ましい。ここで言う酸化錫粒子は、光触媒機能を有しない酸化錫（ＳｎＯ）を主成分とする微粒子であり、その態様は粉末やゾル等の分散体のタイプであっても構わない。これを添加することで、更に塗膜の耐汚染性が向上するため好ましい。塗料中へは固形分で、０．０１〜１％添加するのが望ましい。 The antifouling paint composition of the present invention preferably further contains tin oxide particles. The tin oxide particles referred to here are fine particles mainly composed of tin oxide (SnO) having no photocatalytic function, and the mode thereof may be a dispersion type such as powder or sol. Addition of this is preferable because the stain resistance of the coating film is further improved. It is desirable to add 0.01 to 1% as a solid content in the paint.
本発明の防汚塗料組成物は、高分子重合体（樹脂）成分を含有しないことが好ましい。高分子重合体（樹脂）成分を含むと、防汚塗料組成物を塗布後、硬化・乾燥の工程に時間を要するため、塗装した基材同士を積み重ねる際のブロッキング（塗膜の付着）が起こり易くなるためである。ここで言う高分子重合体とは、被膜形成成分としてのバインダー樹脂成分であり、その態様は水中に分散する成分でも水溶性成分であってもよい。 The antifouling coating composition of the present invention preferably does not contain a polymer (resin) component. When a polymer (resin) component is included, it takes time for the curing and drying process after the antifouling coating composition is applied, so blocking occurs when the coated substrates are stacked. This is because it becomes easier. The high molecular polymer referred to here is a binder resin component as a film forming component, and the mode thereof may be a component dispersed in water or a water-soluble component.
そのような高分子重合体成分としては、例えば、アクリルエマルション、エポキシエマルション、ポリエステルエマルション、ポリウレタンエマルション、シリコン系エマルション、フッ素樹脂エマルション等の水分散性樹脂、水溶性アクリル、水溶性ポリエステル、水溶性ポリウレタン、水溶性アクリルシリコーン、水溶性フッ素樹脂等の水溶性樹脂が挙げられ、これらには変性されているものも含む。 Examples of such a polymer component include water-dispersible resins such as acrylic emulsions, epoxy emulsions, polyester emulsions, polyurethane emulsions, silicone emulsions, fluororesin emulsions, water-soluble acrylics, water-soluble polyesters, and water-soluble polyurethanes. And water-soluble resins such as water-soluble acrylic silicone and water-soluble fluororesin are included, and these include those that have been modified.
また、本発明の防汚塗料組成物は、光触媒機能材料を含有しないことが好ましい。光触媒機能材料を保持できるバインダー成分を含有しないことで、防汚塗料組成物中の界面活性剤成分等が光触媒機能により分解され、塗膜の外観が悪くなる恐れがなくなる。ここで言う光触媒機能材料とは、紫外線や可視光等を照射すると電子及び正孔が生じ、この電子が空気中の酸素を還元することで活性酸素や水酸基ラジカルを発生し、それによる有機物の分解や消臭効果、抗菌・防カビ効果、塗膜表面の親水性付与（防汚機能）や帯電防止効果等を有する材料のことである。 Moreover, it is preferable that the antifouling coating composition of the present invention does not contain a photocatalytic functional material. By not containing a binder component that can hold the photocatalytic functional material, the surfactant component in the antifouling coating composition is decomposed by the photocatalytic function, and the appearance of the coating film is not deteriorated. The photocatalytic functional material mentioned here generates electrons and holes when irradiated with ultraviolet rays, visible light, etc., and these electrons reduce oxygen in the air to generate active oxygen and hydroxyl radicals, thereby decomposing organic substances. It is a material having a deodorizing effect, an antibacterial / antifungal effect, imparting hydrophilicity to the coating film surface (antifouling function), an antistatic effect, and the like.
光触媒機能を有する材料としては、主に酸化チタンがあり、それ以外に、チタン酸ストロンチウム、酸化亜鉛、酸化スズ、酸化タングステン、酸化ジルコニウム、酸化ニオブ、酸化ニッケル、酸化ビスマス等の酸化物半導体が挙げられる。 As a material having a photocatalytic function, there is mainly titanium oxide, and in addition, oxide semiconductors such as strontium titanate, zinc oxide, tin oxide, tungsten oxide, zirconium oxide, niobium oxide, nickel oxide, and bismuth oxide are listed. It is done.
本発明の防汚塗料組成物は、例えば、メタノール、エタノール、プロパノール、ブタノール、トルエン、キシレン等の有機系溶剤を含有しないことを特徴の一つとする。有機系溶剤を含んでいると、塗膜の成膜性が低下し、塗膜の外観等が悪くなる。また、有機系溶剤を含んでいると、下地塗膜の溶解や膨潤等により下地に悪影響を与える場合があり、特に有機塗膜上に塗装する場合は注意を要するが、本発明の防汚塗料組成物は有機系溶剤を含まないため、そのような課題は生じない。更に、揮発性の有機溶剤を含まないため、被塗物に付着しなかった塗料（オーバースプレー）も回収し再利用することが可能であり、環境に対して非常に優しい塗料である。 One of the characteristics of the antifouling coating composition of the present invention is that it does not contain, for example, an organic solvent such as methanol, ethanol, propanol, butanol, toluene, and xylene. When the organic solvent is contained, the film formability of the coating film is lowered and the appearance of the coating film is deteriorated. In addition, if it contains an organic solvent, it may have an adverse effect on the base due to dissolution or swelling of the base coating, especially when it is applied on the organic coating, but the antifouling paint of the present invention Since the composition does not contain an organic solvent, such a problem does not occur. Furthermore, since it does not contain a volatile organic solvent, it is possible to collect and reuse paint that has not adhered to the object to be coated (overspray), and is very environmentally friendly.
本発明の防汚塗料組成物は、表面張力が、２５〜４０ｄｙｎ／ｃｍ（２５℃）であることが好ましく、更には、２５〜３５ｄｙｎ／ｃｍ（２５℃）であることがより好ましい。表面張力が、２５ｄｙｎ／ｃｍ（２５℃）未満であると薄膜の場合、塗装が困難になる場合があり、４０ｄｙｎ／ｃｍ（２５℃）よりも大きいと均一な塗膜形成が困難となるため、十分な塗膜性能が発揮できない。 The antifouling coating composition of the present invention preferably has a surface tension of 25 to 40 dyn / cm (25 ° C.), and more preferably 25 to 35 dyn / cm (25 ° C.). When the surface tension is less than 25 dyn / cm (25 ° C.), in the case of a thin film, coating may be difficult, and when it is greater than 40 dyn / cm (25 ° C.), it becomes difficult to form a uniform coating film. Insufficient coating performance.
本発明の防汚塗料組成物は、１５０℃、３０分間の加熱残分が、０．１〜１０．０質量％であることが好ましく、更には、０．５〜５．０質量％であることがより好ましい。加熱残分が、０．１質量％未満であると、塗膜の硬化性や、耐汚染性を向上させる効果が少なく、１０．０質量％超過であると塗膜の外観が悪くなる傾向がある。 In the antifouling coating composition of the present invention, the heating residue at 150 ° C. for 30 minutes is preferably 0.1 to 10.0% by mass, and further 0.5 to 5.0% by mass. It is more preferable. If the heating residue is less than 0.1% by mass, the effect of improving the curability and stain resistance of the coating film is small, and if it exceeds 10.0% by mass, the appearance of the coating film tends to deteriorate. is there.
本発明の防汚塗料組成物は、塗膜形成時に（ａ）成分の水分散コロイダルシリカが塗膜表面に偏析し、コロイダルシリカが互いにネットワーク構造を形成することで、膜厚が薄くても強固な塗膜を形成するため、優れた耐汚染性、耐水性を発現することが可能となり、雨水により（ａ）成分の水分散コロイダルシリカが洗い流されることがなく、耐汚染機能の維持性にも優れると考えられる。しかしながら、防汚塗料組成物中に有機系溶剤を含んでいると、そのコロイダルシリカのネットワーク構造が形成されず、雨水により（ａ）成分の水分散コロイダルシリカが洗い流され易く良好な塗膜が形成されないと考えられる。 In the antifouling coating composition of the present invention, the water-dispersed colloidal silica of component (a) segregates on the coating surface during coating film formation, and the colloidal silica forms a network structure with each other. It is possible to express excellent stain resistance and water resistance, and the water-dispersed colloidal silica of the component (a) is not washed away by rainwater, and it is possible to maintain the stain resistance function. It is considered excellent. However, when an organic solvent is contained in the antifouling paint composition, the network structure of the colloidal silica is not formed, and the water-dispersed colloidal silica of the component (a) is easily washed away by rainwater, and a good coating film is formed. It is thought that it is not done.
本発明の防汚塗料組成物は、以上説明した（ａ）成分、（ｂ）成分及び（ｃ）成分の３成分を主成分とし、有機系溶剤を含有しない。更に、必要に応じて、塗膜物性の向上や着色等のために、充填剤や、染料、硬化剤、更には、硬化促進剤、増粘剤、顔料分散剤等の各種添加剤等を配合することができる。 The antifouling paint composition of the present invention comprises the three components (a), (b) and (c) described above as the main components and does not contain an organic solvent. Furthermore, if necessary, in order to improve the coating film properties, coloring, etc., fillers, dyes, curing agents, and various additives such as curing accelerators, thickeners, pigment dispersants, etc. can do.
充填材としては、例えば、タルクや、硫酸バリウム、炭酸カルシウム、炭酸バリウム、ベントナイト、酸化チタン（光触媒機能を有さない顔料）、カーボンブラック、ベンガラ、リトポン等の各種塗料用体質顔料や、着色顔料が使用可能である。 As fillers, for example, talc, barium sulfate, calcium carbonate, barium carbonate, bentonite, titanium oxide (pigments not having a photocatalytic function), carbon black, bengara, lithopone, and other extender pigments for paints, and colored pigments Can be used.
次に、防汚塗料組成物が塗装される基材や下塗塗膜について説明する。本発明に使用される基材は、主に建材等に使用されるものに適用され、例えば、フレキシブルボードや、珪酸カルシウム板、石膏スラグバーライト板、木片セメント板、石綿セメント板、パルプセメント板、プレキャストコンクリート板、軽量気泡コンクリート板、ＡＬＣ板、石膏ボード等の無機建材や、アルミニウム、鉄、ステンレス等の金属建材等が代表的なものとして挙げられる。これらはその表面が平滑なものであっても、凹凸形状を有するものであってもよい。 Next, the base material and undercoat film on which the antifouling paint composition is applied will be described. The base material used in the present invention is mainly applied to materials used for building materials and the like, for example, flexible board, calcium silicate board, gypsum slag bar light board, wood chip cement board, asbestos cement board, pulp cement board Typical examples include inorganic building materials such as precast concrete plates, lightweight cellular concrete plates, ALC plates, and gypsum boards, and metal building materials such as aluminum, iron, and stainless steel. These may have a smooth surface or may have an uneven shape.
基材上に下塗塗膜が形成される場合は、複数の塗膜から形成されていてもよい。下塗塗膜を形成する塗膜としては、基材と塗膜との長期間密着性を発現させる働きをなすものであり、ビニル樹脂、アクリルスチレン樹脂、エポキシ／ポリアミン樹脂、ウレタン樹脂等を結合剤とする各種の溶剤系又は水系塗料等が挙げられ、塗膜機能としては基材密着性や耐アルカリ性、耐エフロレッセンス性等が要求される。 When an undercoat coating film is formed on a substrate, it may be formed from a plurality of coating films. As a coating film that forms an undercoat coating film, it serves to develop long-term adhesion between the substrate and the coating film, and is a binder of vinyl resin, acrylic styrene resin, epoxy / polyamine resin, urethane resin, etc. Various solvent-based or water-based paints and the like are mentioned, and the coating film function requires substrate adhesion, alkali resistance, efflorescence resistance, and the like.
特に外壁基材等の塗膜に耐候性や耐凍害性等が要求される場合には、アクリル樹脂、アクリルウレタン樹脂、ウレタン樹脂、フッ素樹脂、有機無機複合系樹脂等を結合剤とする溶剤系又は水系塗料が塗装される。 In particular, when weather resistance, frost damage resistance, etc. are required for a coating film such as an outer wall base material, a solvent system using an acrylic resin, an acrylic urethane resin, a urethane resin, a fluororesin, an organic-inorganic composite resin, etc. as a binder Or a water-based paint is painted.
本発明の防汚塗料組成物は、下塗塗膜の水に対する接触角１２０°以下のものに適用することが好ましい。そのような塗膜を形成する塗料としては、結合剤として無機系樹脂、特にＳｉ−ＯＲ基（Ｒは水素原子又は炭素数１〜１２の炭化水素基）を有する化合物が、塗膜形成成分換算で０．１〜５０質量％含有することが、防汚塗料組成物から形成される防汚塗膜との密着がより優れるため好ましい。Ｓｉ−ＯＲ基（Ｒは水素原子又は炭素数１〜１２の炭化水素基）を有する化合物を含有する塗料としては、加水分解性シリル基含有ビニル系塗料や、オルガノポリシロキサン系塗料、更には、シランカップリング剤添加塗料等が挙げられる。 The antifouling coating composition of the present invention is preferably applied to a primer coating having a contact angle of 120 ° or less with respect to water. As a paint for forming such a coating film, an inorganic resin as a binder, particularly a compound having a Si-OR group (R is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms) is converted into a coating film forming component. It is preferable to contain 0.1 to 50% by mass because the adhesion with the antifouling coating film formed from the antifouling coating composition is more excellent. As a paint containing a compound having a Si-OR group (R is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms), a hydrolyzable silyl group-containing vinyl paint, an organopolysiloxane paint, Examples include silane coupling agent-added paints.
これらの塗料は、各種機能を付与させるために、防カビ剤や、防腐剤、紫外線吸収剤、光安定剤、更に体質顔料や、着色顔料、防錆顔料を配合する場合は、分散剤や沈降防止剤、増粘剤等の各種添加剤を配合することができる。 In order to impart various functions, these paints have a fungicide, a preservative, a UV absorber, a light stabilizer, a body pigment, a color pigment, and a rust preventive pigment. Various additives such as an inhibitor and a thickener can be blended.
本発明の防汚塗料組成物は、基材上に１つあるいは複数の下塗塗料を塗布し、硬化・乾燥後、塗膜を形成した下塗塗膜の上から塗装し、硬化・乾燥させて防汚塗膜を形成する。形成された防汚塗膜上の水に対する接触角は、１°〜４０°であることが好ましく、より好ましくは５°〜３０°である。接触角が４０°より大きいと塗膜の防汚性能が低下する。 The antifouling paint composition of the present invention is applied by applying one or more undercoat paints on a substrate, curing and drying, and then applying the paint on the undercoat paint film on which a coating film has been formed, and curing and drying the paint. A dirty coating is formed. The contact angle of water on the formed antifouling coating film is preferably 1 ° to 40 °, more preferably 5 ° to 30 °. When the contact angle is larger than 40 °, the antifouling performance of the coating film is lowered.
下塗塗料や防汚塗料の塗装方法は、刷毛や、スプレー、ロール、ディッピング等の塗装手段により塗装し、例えば、常温もしくは３００℃以下の温度で焼付けることにより、硬化塗膜を形成することが可能である。場合により、予め基材を加熱しておき（プレヒート）、その上から塗料を塗装し、硬化塗膜を形成することもできる。 The coating method of the undercoat paint or antifouling paint can be applied by a brush, spray, roll, dipping or other coating means, for example, by baking at room temperature or a temperature of 300 ° C. or lower to form a cured coating film. Is possible. In some cases, the base material may be heated in advance (preheating), and a paint may be applied thereon to form a cured coating film.
下塗塗膜の膜厚は、数μｍ〜数百μｍであり、特に制限されない。防汚塗料組成物により形成される防汚塗膜の膜厚は、０．１〜１μｍであることが好ましい。 The thickness of the undercoat coating film is from several μm to several hundred μm and is not particularly limited. The film thickness of the antifouling coating film formed from the antifouling coating composition is preferably 0.1 to 1 μm.
以下、本発明について、実施例により更に詳細に説明する。なお、実施例中の「部」や「％」は、特に断らない限り、質量基準で示す。 Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “parts” and “%” are based on mass unless otherwise specified.
（ｉ）防汚塗料組成物の調製
＜実施例１〜１１及び比較例１〜５＞
表１〜表２に示すように各成分を配合し、実施例１〜１１及び比較例１〜５の防汚塗料組成物を得た。得られた各防汚塗料組成物について、表面張力や加熱残分の測定を、以下のように行った。
(I) Preparation of antifouling coating composition <Examples 1 to 11 and Comparative Examples 1 to 5>
Each component was mix | blended as shown in Table 1-Table 2, and the antifouling coating composition of Examples 1-11 and Comparative Examples 1-5 was obtained. About each obtained antifouling coating composition, the measurement of surface tension and a heating residue was performed as follows.
＜表面張力の測定方法＞
表面張力の測定は、協和界面科学（株）製の表面張力計（ＣＢＶＰ−Ａ３型）を用いて、２５℃で測定した。
<Method for measuring surface tension>
The surface tension was measured at 25 ° C. using a surface tension meter (CBVP-A3 type) manufactured by Kyowa Interface Science Co., Ltd.
＜加熱残分の測定方法＞
加熱残分は、試料約３グラムをアルミニウムカップに精秤し、１５０℃オーブンを用いて３０分間乾燥後の質量を精秤し、元の質量に対する残分の質量から計算し、加熱残分（％）を求めた。
<Measurement method of heating residue>
The heating residue is precisely weighed about 3 grams of the sample in an aluminum cup, weighed after drying for 30 minutes using a 150 ° C. oven, calculated from the weight of the residue with respect to the original mass, and the heating residue ( %).
各防汚塗料組成物の塗膜性能評価は、以下のように行った。
＜性能評価試験＞
（ｉｉ）防汚塗料組成物の塗膜性能評価用試験板の作製
素材として石膏スラグパーライト板（厚さ１２ｍｍ）を用い、その表面にポリイソシアネートプレポリマー溶液シーラー「Ｖセラン＃１００シーラー」（大日本塗料（株）製、酢酸ブチル：キシレン＝１：１の溶剤で１００％希釈）を塗着量が９０〜１００ｇ／ｍ２（ｗｅｔ質量）となるように吹付塗装した。これを１００℃で５分間乾燥した。次いで下塗塗料としてアクリルシリコーン樹脂系塗料「Ｖセラン＃５００エナメル」（大日本塗料（株）製、酢酸ブチル：キシレン＝１：１の溶剤で４０％希釈）を塗着量が８０〜９０ｇ／ｍ２（ｗｅｔ質量）となるように吹付塗装した。これを１２０℃で１５分間乾燥した。得られた下塗塗膜の水に対する接触角は６０°（２０℃）、またその塗膜中のＳｉ−ＯＲ基の含有量は１．５質量％であった。
The coating film performance evaluation of each antifouling paint composition was performed as follows.
<Performance evaluation test>
(Ii) Preparation of test plate for evaluating coating film performance of antifouling paint composition A gypsum slag perlite plate (thickness 12 mm) is used as a material, and a polyisocyanate prepolymer solution sealer “V-Selan # 100 sealer” (large) Nippon Paint Co., Ltd., butyl acetate: xylene = 1: 1 diluted with a solvent) was spray-coated so that the coating amount was 90-100 g / m 2 (wet mass). This was dried at 100 ° C. for 5 minutes. Next, an acrylic silicone resin-based paint “V-Selan # 500 Enamel” (Dainippon Paint Co., Ltd., diluted 40% with a solvent of butyl acetate: xylene = 1: 1) as an undercoat paint is applied in an amount of 80 to 90 g / m. 2 (wet mass) was spray-painted. This was dried at 120 ° C. for 15 minutes. The contact angle with water of the obtained undercoat coating film was 60 ° (20 ° C.), and the content of Si—OR groups in the coating film was 1.5% by mass.
次いで、前述の各調製した溶液に界面活性剤や希釈剤等を添加し、表１〜表２に示す配合の上塗り塗料を、塗着量７０〜８０ｇ／ｍ２（ｗｅｔ質量）となるように吹付塗装した。これを１２０℃で１５分間乾燥した後、室温で３日間乾燥し、得られた塗膜の外観、耐温水性、耐汚染性、耐候性、耐凍害性及び接触角の各性能評価試験を行い、その結果を表１〜表２に示した。 Next, a surfactant, a diluent, or the like is added to each of the prepared solutions, and the top coating composition shown in Tables 1 and 2 is applied to a coating amount of 70 to 80 g / m 2 (wet mass). Spray painted. After drying this at 120 ° C. for 15 minutes, it is dried at room temperature for 3 days, and each performance evaluation test of appearance, warm water resistance, stain resistance, weather resistance, frost damage resistance and contact angle of the obtained coating film is performed. The results are shown in Tables 1 and 2.
なお、各性能評価試験の試験方法及び評価基準は、以下に基づいて行った。
＜塗膜外観＞
得られた塗膜の外観を、以下のように目視で評価した。
◎・・・良好（透明な膜）
○・・・やや良好（一部白濁）
△・・・不良（全体的にやや白濁）
×・・・不良（全体的に白濁）
In addition, the test method and evaluation criteria of each performance evaluation test were performed based on the following.
<Appearance of coating film>
The appearance of the obtained coating film was visually evaluated as follows.
◎ ・ ・ ・ Good (transparent film)
○: Slightly good (partly cloudy)
Δ: Poor (slightly cloudy overall)
× ... Defective (overall cloudy)
＜耐温水性＞
上記のように作製した塗板を８０℃の温水中に３時間浸漬した後の塗膜外観を、浸漬中及び塗膜乾燥後において、以下のように目視判定した。
◎・・・浸漬中及び塗膜乾燥後、共に変化無し
○・・・浸漬中軽微な白化は有るが、塗膜乾燥後では変化無し
△・・・浸漬中での白化が酷く、塗膜乾燥後では光沢低下、白化等の軽微な変化有り
×・・・浸漬中での白化が酷く、塗膜乾燥後では光沢低下、白化等の変化大
<Hot water resistance>
The appearance of the coating film after the coated plate produced as described above was immersed in warm water at 80 ° C. for 3 hours was visually judged as follows during the immersion and after the coating film was dried.
◎ ・ ・ ・ No change during soaking and drying of coating film ○ ・ ・ ・ Slight whitening during soaking, but no change after drying of coating film △ ・ ・ ・ Severe whitening during soaking, drying of coating film After that, there are minor changes such as gloss reduction and whitening. × ・ ・ ・ Whitening during immersion is severe, and after drying the film, changes such as gloss reduction and whitening are large.
＜耐汚染性＞
塗板上にカーボンブラック分散液（ターペン溶液）をスポイトで数滴滴下して流し塗りした後、水の霧吹きでそれを洗い流し、その除染性を以下のように目視判定した。
◎・・・完全除去
○・・・極く軽微な汚染
△・・・少し汚染
×・・・汚染著しい
<Contamination resistance>
A few drops of a carbon black dispersion (terpene solution) was dropped onto the coated plate with a dropper, and then washed off with a spray of water. The decontamination property was visually determined as follows.
◎ ・ ・ ・ Complete removal ○ ・ ・ ・ Minimum contamination △ ・ ・ ・ Slight contamination × ・ ・ ・ Significant contamination
＜耐雨筋汚染性＞
水平面に対して１０度に傾斜し、かつ、長さ３０ｃｍで深さ３ｍｍの溝が３ｍｍピッチで刻まれた屋根を有する架台上に、上記の各塗板を、降雨が塗膜表面に筋状に流れ落ちるように南向きに垂直に取り付け、その状態で１２ヶ月間暴露した後、塗膜外観を試験前の塗膜と比較し、塗膜表面の汚染状態を、以下のように目視判定した。
◎・・・汚れは無く、雨筋も確認されない
○・・・わずかな汚れは有るが、雨筋は確認されない
△・・・局所的な汚れが有り、雨筋が薄く確認される
×・・・全面にかなりの汚れが有り、雨筋がはっきりと確認される
<Rain-stain stain resistance>
The above-mentioned coated plates are streaked on the surface of the coating film on a frame having a roof inclined at 10 degrees with respect to the horizontal plane and having a groove with a length of 30 cm and a depth of 3 mm carved at a pitch of 3 mm. After mounting vertically and facing southward for 12 months, the appearance of the coating film was compared with the coating film before the test, and the contamination state of the coating film surface was visually determined as follows.
◎ ・ ・ ・ There is no dirt and no rain streak is confirmed. ○ ・ ・ ・ Slight dirt is observed, but no rain streak is confirmed. △ ・ ・ ・ There is local dirt and the rain streak is thin.・ There is considerable dirt on the entire surface, and rain lines are clearly confirmed.
＜耐候性＞
サンシャインウェザー−オーメーターにより５０００時間行い、その耐候性を以下のように判定した。
○・・・塗膜外観に変化は無く、光沢保持率９５％以上
△・・・塗膜外観の変化が軽微にあり、光沢保持率８０％以上９５％未満
×・・・塗膜外観の変化が著しく、光沢保持率８０％未満
<Weather resistance>
The weather resistance was determined as follows using a sunshine weather-ometer for 5000 hours.
○: No change in coating film appearance, gloss retention of 95% or more Δ: Change in coating film appearance is minor, gloss retention of 80% or more and less than 95% ×: Change in coating film appearance Remarkably, gloss retention less than 80%
＜耐凍害性＞
ＡＳＴＭ−Ｃ６６６Ａ法（凍結−融解サイクル）により、１００サイクルの耐凍害性を実施し、以下のように目視判定した。
○・・・塗膜にクラックの発生無し
△・・・極く軽微なクラックの発生有り
×・・・クラックの発生又は塗膜の部分剥離
<Frost resistance>
By the ASTM-C666A method (freezing-thawing cycle), 100 cycles of frost damage resistance were carried out and visually judged as follows.
○ ・ ・ ・ No cracks occurred in the coating film △ ・ ・ ・ A very slight cracking occurred × ・ ・ ・ Crack generation or partial peeling of the coating film
＜水に対する静的接触角の測定＞
塗板表面に０．１ｃｃの蒸留水を滴下し、２０℃の雰囲気下で滴下１分後の接触角を協和界面化学株式会社ＣＡ−Ｘ接触角測定装置にて測定した。
<Measurement of static contact angle with water>
0.1 cc of distilled water was dropped on the surface of the coated plate, and the contact angle after 1 minute of dropping was measured at 20 ° C. with a Kyowa Interface Chemical Co., Ltd. CA-X contact angle measuring device.
１）水分散コロイダルシリカＡ（日産化学工業（株）製、スノーテックス−Ｏ、固形分２０％、ｐＨ３．８、平均粒子径１０〜２０ｎｍ、形状：球状、酸性タイプ）
２）水分散コロイダルシリカＢ（日産化学工業（株）製、スノーテックス−Ｃ、固形分２０％、ｐＨ９．０、平均粒子径１０〜２０ｎｍ、形状：球状）
３）水分散コロイダルシリカＣ（日産化学工業（株）製、スノーテックス−ＰＳ−ＳＯ、固形分２０％、ｐＨ３．０、平均粒子径８０〜１２０ｎｍ、形状：パールネックレス状）
４）水分散コロイダルシリカＤ（日産化学工業（株）製、スノーテックス−ＵＰ、固形分２０％、ｐＨ１０．０、平均粒子径４０〜１００ｎｍ、形状：鎖状）
５）イソプロパノール分散コロイダルシリカＥ（日産化学工業（株）製、ＩＰＡ−ＳＴ、固形分３０％、ｐＨ３．２、平均粒子径１０〜２０ｎｍ、形状：球状）
６）酸化錫粒子（Ｎ．Ｔ．Ｓ．社製、酸化スズゾル、固形分２０％）
７）光触媒酸化チタン粒子（石原産業（株）製、光触媒ＴｉＯ２、平均粒径８μｍ）
８）ノニオン系界面活性剤Ａ（ＴＥＧＯ社製、ポリフローＫＬ−５１０、固形分１００％、成分：ポリオキシアルキレンモノアルキルエーテル）
９）ノニオン系界面活性剤Ｂ（サンノプコ（株）製、ＳＮ９８４、固形分１００％、成分：ポリエーテル系化合物）
１０）ノニオン系界面活性剤Ｃ（第一工業製薬（株）、ニューコール１００４、固形分１００％、成分：ポリオキシエチレン−２−エチルヘキシルエーテル）
１１）ノニオン系界面活性剤Ｄ（第一工業製薬（株）、ネオノイゲン１４０Ａ、固形分１００％、成分：ポリオキシエチレン−アルキルフェニルエーテル）
１２）ノニオン系界面活性剤Ｅ（株式会社ＡＤＥＫＡ製、プルロニックＬ−４４、固形分１００％、成分：プロピレンオキサイド・エチレンオキサイドブロックポリマー）
１３）カチオン系界面活性剤Ｆ（ライオン（株）製、サンノール ＬＭＴ−１４３０、固形分２７％、成分：ポリオキシエチレンアルキルエーテル硫酸塩）
１４）アニオン系界面活性剤Ｇ（株式会社ＡＤＥＫＡ製、アデカコール ＥＣ−８６００、固形分７０％、成分：ジオクチルスルホコハク酸エステル塩）
１５）アニオン系界面活性剤Ｈ（サンノプコ（株）製、ウェット５０、固形分１００％、成分：アルキルスルホコハク酸ナトリウム）
１６）フッ素系界面活性剤Ｉ（株式会社ネオス製、フタージェント１００Ｃ、パーフルオロアルケニル基含有フッ素系界面活性剤、固形分１００％）
１７）フッ素系界面活性剤Ｊ（ＤＩＣ（株）製、メガファックＦ−４４４、パーフルオロアルキルエチレンオキシド付加物、有効成分１００％）
１８）アクリルエマルジョン（日本触媒（株）製、ユーダブルＥ−６７０、固形分４５％）
1) Water-dispersed colloidal silica A (manufactured by Nissan Chemical Industries, Snowtex-O, solid content 20%, pH 3.8, average particle size 10-20 nm, shape: spherical, acidic type)
2) Water-dispersed colloidal silica B (manufactured by Nissan Chemical Industries, Ltd., Snowtex-C, solid content 20%, pH 9.0, average particle size 10-20 nm, shape: spherical)
3) Water-dispersed colloidal silica C (manufactured by Nissan Chemical Industries, Ltd., Snowtex-PS-SO, solid content 20%, pH 3.0, average particle size 80-120 nm, shape: pearl necklace)
4) Water-dispersed colloidal silica D (manufactured by Nissan Chemical Industries, Ltd., Snowtex-UP, solid content 20%, pH 10.0, average particle size 40-100 nm, shape: chain)
5) Isopropanol-dispersed colloidal silica E (manufactured by Nissan Chemical Industries, Ltd., IPA-ST, solid content 30%, pH 3.2, average particle size 10-20 nm, shape: spherical)
6) Tin oxide particles (manufactured by NTS, tin oxide sol, solid content 20%)
7) Photocatalytic titanium oxide particles (Ishihara Sangyo Co., Ltd., photocatalyst TiO 2 , average particle size 8 μm)
8) Nonionic surfactant A (manufactured by TEGO, Polyflow KL-510, solid content 100%, component: polyoxyalkylene monoalkyl ether)
9) Nonionic surfactant B (manufactured by San Nopco, SN984, solid content 100%, component: polyether compound)
10) Nonionic surfactant C (Daiichi Kogyo Seiyaku Co., Ltd., New Coal 1004, solid content 100%, component: polyoxyethylene-2-ethylhexyl ether)
11) Nonionic surfactant D (Daiichi Kogyo Seiyaku Co., Ltd., Neonoigen 140A, solid content 100%, component: polyoxyethylene-alkylphenyl ether)
12) Nonionic surfactant E (manufactured by ADEKA Corporation, Pluronic L-44, solid content 100%, component: propylene oxide / ethylene oxide block polymer)
13) Cationic surfactant F (manufactured by Lion Corporation, Sannol LMT-1430, solid content 27%, component: polyoxyethylene alkyl ether sulfate)
14) Anionic surfactant G (manufactured by ADEKA Corporation, Adekacol EC-8600, solid content 70%, component: dioctylsulfosuccinate ester salt)
15) Anionic surfactant H (manufactured by San Nopco, wet 50, solid content 100%, component: sodium alkylsulfosuccinate)
16) Fluorosurfactant I (manufactured by Neos, Footent 100C, perfluoroalkenyl group-containing fluorosurfactant, solid content 100%)
17) Fluorosurfactant J (manufactured by DIC Corporation, MegaFuck F-444, perfluoroalkylethylene oxide adduct, active ingredient 100%)
18) Acrylic emulsion (manufactured by Nippon Shokubai Co., Ltd., U Double E-670, solid content 45%)
＜評価結果＞
表１〜表２より明らかな通り、本発明の防汚塗料組成物を使用した実施例１〜１１は、優れた塗膜性能を有していた。一方、比較例１及び４の溶剤系コロイダルシリカを含有する塗料では、耐汚染性や耐雨筋汚染性が悪かった。比較例２及び５の有機溶剤としてエタノールを含有する塗料では、塗膜外観、耐汚染性が非常に悪かった。また、比較例３のノニオン系界面活性剤を使用しない塗料では、耐温水性及び耐雨筋汚染性が非常に悪かった。
<Evaluation results>
As is clear from Tables 1 and 2, Examples 1 to 11 using the antifouling coating composition of the present invention had excellent coating performance. On the other hand, in the paint containing the solvent-based colloidal silica of Comparative Examples 1 and 4, the stain resistance and rain-stain stain resistance were poor. In the paint containing ethanol as the organic solvent of Comparative Examples 2 and 5, the appearance of the coating film and the stain resistance were very poor. Moreover, in the coating material which does not use the nonionic surfactant of the comparative example 3, warm water resistance and rain-stain stain resistance were very bad.
本発明に従って、
（ａ）水分散コロイダルシリカ（固形分換算）０．１〜１０．０質量％と、
（ｂ）１種類以上のノニオン系界面活性剤（固形分換算）０．０１〜１．０質量％と、
（ｃ）水８９〜９９質量％と
を主成分として含有し、
該ノニオン系界面活性剤が、ポリオキシアルキレンモノアルキルエーテルを含有するものであり、かつ、
有機系溶剤及び光触媒機能材料を含有しないことを特徴とする防汚塗料組成物が提供される。
In accordance with the present invention,
(A) water-dispersed colloidal silica (in terms of solid content) 0.1 to 10.0% by mass;
(B) one or more kinds of nonionic surfactants (in terms of solid content) 0.01 to 1.0% by mass;
(C) containing 89 to 99% by mass of water as a main component,
The nonionic surfactant contains a polyoxyalkylene monoalkyl ether, and
There is provided an antifouling paint composition characterized by not containing an organic solvent and a photocatalytic functional material .
また、本発明の防汚塗料組成物は、光触媒機能材料を含有しない。光触媒機能材料を保持できるバインダー成分を含有しないことで、防汚塗料組成物中の界面活性剤成分等が光触媒機能により分解され、塗膜の外観が悪くなる恐れがなくなる。ここで言う光触媒機能材料とは、紫外線や可視光等を照射すると電子及び正孔が生じ、この電子が空気中の酸素を還元することで活性酸素や水酸基ラジカルを発生し、それによる有機物の分解や消臭効果、抗菌・防カビ効果、塗膜表面の親水性付与（防汚機能）や帯電防止効果等を有する材料のことである。
Moreover, the antifouling coating composition of the present invention, have such contains a photocatalytic functional material. By not containing a binder component that can hold the photocatalytic functional material, the surfactant component in the antifouling coating composition is decomposed by the photocatalytic function, and the appearance of the coating film is not deteriorated. The photocatalytic functional material mentioned here generates electrons and holes when irradiated with ultraviolet rays, visible light, etc., and these electrons reduce oxygen in the air to generate active oxygen and hydroxyl radicals, thereby decomposing organic substances. It is a material having a deodorizing effect, an antibacterial / antifungal effect, imparting hydrophilicity to the coating film surface (antifouling function), an antistatic effect, and the like.
（ｉ）防汚塗料組成物の調製
＜実施例１〜９、１１、参考例１０及び比較例１〜５＞
表１〜表２に示すように各成分を配合し、実施例１〜９、１１、参考例１０及び比較例１〜５の防汚塗料組成物を得た。得られた各防汚塗料組成物について、表面張力や加熱残分の測定を、以下のように行った。
(I) Preparation of antifouling coating composition <Examples 1 to 9, 11 , Reference Example 10 and Comparative Examples 1 to 5>
Each component was mix | blended as shown in Table 1-Table 2, and the antifouling-coating composition of Examples 1-9 , 11 , Reference Example 10, and Comparative Examples 1-5 was obtained. About each obtained antifouling coating composition, the measurement of surface tension and a heating residue was performed as follows.
＜評価結果＞
表１〜表２より明らかな通り、本発明の防汚塗料組成物を使用した実施例１〜９、１１は、優れた塗膜性能を有していた。一方、比較例１及び４の溶剤系コロイダルシリカを含有する塗料では、耐汚染性や耐雨筋汚染性が悪かった。比較例２及び５の有機溶剤としてエタノールを含有する塗料では、塗膜外観、耐汚染性が非常に悪かった。また、比較例３のノニオン系界面活性剤を使用しない塗料では、耐温水性及び耐雨筋汚染性が非常に悪かった。
<Evaluation results>
As is clear from Tables 1 and 2, Examples 1 to 9 and 11 using the antifouling coating composition of the present invention had excellent coating performance. On the other hand, in the paint containing the solvent-based colloidal silica of Comparative Examples 1 and 4, the stain resistance and rain-stain stain resistance were poor. In the paint containing ethanol as the organic solvent of Comparative Examples 2 and 5, the appearance of the coating film and the stain resistance were very poor. Moreover, in the coating material which does not use the nonionic surfactant of the comparative example 3, warm water resistance and rain-stain stain resistance were very bad.
Claims (12)
（ｂ）１種類以上のノニオン系界面活性剤（固形分換算）０．０１〜１．０質量％と、
（ｃ）水８９〜９９質量％と
を主成分として含有し、
該ノニオン系界面活性剤が、ポリオキシアルキレンモノアルキルエーテルを含有し、かつ、有機系溶剤を含有しないことを特徴とする防汚塗料組成物。 (A) water-dispersed colloidal silica (in terms of solid content) 0.1 to 10.0% by mass;
(B) one or more kinds of nonionic surfactants (in terms of solid content) 0.01 to 1.0% by mass;
(C) containing 89 to 99% by mass of water as a main component,
The antifouling coating composition, wherein the nonionic surfactant contains a polyoxyalkylene monoalkyl ether and does not contain an organic solvent.
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