JP5609816B2 - Water permeation preventive film forming agent capable of holding hydrophilic film on porous body surface, water permeation preventive film and film laminate using the same, and member provided with the film or the laminate - Google Patents
Water permeation preventive film forming agent capable of holding hydrophilic film on porous body surface, water permeation preventive film and film laminate using the same, and member provided with the film or the laminate Download PDFInfo
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Description
本発明は、多孔質基材上にも光触媒被膜等の親水性被膜が形成されることを可能とする透水防止被膜形成剤に関するものである。 The present invention relates to a water permeation prevention film forming agent that enables a hydrophilic film such as a photocatalyst film to be formed on a porous substrate.
本発明の透水防止被膜形成剤の乾燥硬化物は、撥水性でありながら、光触媒等の無機物をその上に強固に保持することができる。したがって、前記乾燥硬化物からなる被膜を多孔体上に形成させ、さらにその上に光触媒を塗布し固着させることができる。これにより該多孔体内部への汚水の浸透を防止すると同時に該多孔体の表面付着汚染を防ぐこともできる。 The dry cured product of the water permeation preventive film forming agent of the present invention is capable of firmly holding an inorganic substance such as a photocatalyst thereon while being water repellent. Therefore, a film made of the dried cured product can be formed on the porous body, and a photocatalyst can be applied and fixed thereon. As a result, it is possible to prevent sewage from penetrating into the porous body and at the same time prevent surface adhesion contamination of the porous body.
更に、本発明により得られる透水防止被膜は、従来のものより透明度の点でも優れており、白濁しづらい。よって、本発明の透水防止被膜形成剤を用いることで、着色された煉瓦や着色されたモルタル等の意匠性多孔体に対しても、透水防止処理と光触媒処理を同時に行うことができる。 Furthermore, the water permeation preventive coating obtained by the present invention is superior in transparency to conventional ones and is not easily clouded. Therefore, by using the water permeation preventive film forming agent of the present invention, the water permeation preventive treatment and the photocatalytic treatment can be simultaneously performed on a design porous body such as a colored brick or a colored mortar.
本発明の透水防止被膜形成剤は水を主溶媒とする液体である上、従来使用される金属化合物系の硬化触媒を添加する必要がないために取扱い性および安全性が高い。該透水防止被膜形成剤は、あらゆる多孔体上に光触媒被膜等の親水性被膜を形成させるための下地を与え得る。 The water permeation preventive film forming agent of the present invention is a liquid containing water as a main solvent and has high handling and safety since it is not necessary to add a conventionally used metal compound-based curing catalyst. The water permeation preventive film forming agent can provide a base for forming a hydrophilic film such as a photocatalyst film on any porous material.
主に住宅建材として用いられるガラスや外壁等の基材を対象とした各種防汚性コート剤が上市されて久しい。殊に光触媒に代表されるような親水性のコート剤は、帯電を防止する効果および汚れを降雨により洗い落とす効果が高いことから、前述の各種基材に対する施工例が多くある。 It has been a long time since various antifouling coating agents targeting mainly base materials such as glass and outer walls used as housing building materials have been put on the market. In particular, hydrophilic coating agents such as photocatalysts have many examples of application to the above-mentioned various substrates because they have a high effect of preventing electrification and the effect of washing away dirt by rain.
このような親水性コート剤の成分は、多くの親水性基を有する化合物であることが多い。そのため、該コート剤をコンクリートやモルタルのような吸水性の高い素材へ直接施工した場合、その親水性によって汚水が基材の奥まで浸透してしまうため、有効な防汚作用が得られなかった。 The component of such a hydrophilic coating agent is often a compound having many hydrophilic groups. Therefore, when the coating agent is directly applied to a material having high water absorption, such as concrete or mortar, the dirty water penetrates deep into the base material due to its hydrophilicity, so an effective antifouling action could not be obtained. .
このような多孔体、特にコンクリートやモルタルといった無機基材に親水化処理を施すため、透水防止剤と呼ばれる、本来コンクリートの劣化防止用である薬剤を用いて“水の浸透を防止する層”を該多孔体表面に設け、その上に光触媒等の防汚コートを施工する技術が、一部で用いられ始めている（特許文献１）。 In order to hydrophilize such porous materials, especially inorganic substrates such as concrete and mortar, a “layer that prevents water penetration” is used with a chemical called a water permeation preventive, which is originally intended to prevent concrete deterioration. A technique for providing an antifouling coat such as a photocatalyst on the surface of the porous body has begun to be used in part (Patent Document 1).
しかしながら、上述の“透水防止剤”は本来、水の浸透を防ぐ目的で使用される材料であって、その被膜の表面に何かをコーティングできるように設計されていない。すなわち、多くの透水防止剤はアルキルシリコーン成分を多く含んでいるために、その被膜の表面は撥水性であり、反応性官能基を有しない。よって、該表面上に別の被膜剤を塗布しても、離型作用によって剥離してしまうことが多く、長期にわたる表面汚染の防止は期待できない。 However, the above-mentioned “water permeation preventive agent” is originally a material used for the purpose of preventing water penetration, and is not designed to be able to coat something on the surface of the film. That is, since many water permeation preventive agents contain a lot of alkyl silicone components, the surface of the coating is water repellent and does not have reactive functional groups. Therefore, even if another coating agent is applied on the surface, it often peels off due to the releasing action, and it is not expected to prevent surface contamination over a long period of time.
透水防止剤自体は、そもそも汚水の浸透を防ぐのが主な目的の材料であるために、特に汚染防止処理はされておらず、透水防止剤の被膜単独では表面の防汚作用はさほど高いものではない（特許文献２）。 The permeation preventive agent itself is a material whose main purpose is to prevent the penetration of sewage in the first place, so it has not been specially treated to prevent contamination, and the surface of the permeation preventive coating alone has a very high antifouling effect. Not (Patent Document 2).
すなわち、多孔体への防汚処理に係る問題とは、
１．多孔体を親水処理すれば、同時に該多孔体への汚水の染み込みを許すことになり、該多孔体が汚れる、および
２．多孔体を予め撥水処理して汚水浸透を防ぐと、更に該多孔体上に防汚コート液を施工できない、
という2点を同時に解決できないことである。斯様な問題を解決できるような下地処理液および施工法はいずれも現在のところ存在せず、解決すべき課題である。
That is, the problem related to the antifouling treatment to the porous body is
1. 1. Hydrophilic treatment of the porous body will permit the permeation of sewage into the porous body at the same time, and the porous body will become dirty; If the porous body is treated with water repellent in advance to prevent permeation of sewage, an antifouling coating solution cannot be applied on the porous body.
The two points cannot be solved at the same time. None of the ground treatment solutions and construction methods that can solve such problems currently exist, and are problems to be solved.
本発明は、上記問題に鑑みなされたもので、多孔体表面に親水性被膜を保持させつつ、該多孔体内部への水の浸透を防止できる透水防止被膜形成剤、これを用いた透水防止被膜及び被膜積層体、並びに該被膜または該積層体を備えた部材を提供することを課題とする。 The present invention has been made in view of the above problems, and a water permeation preventive film forming agent capable of preventing the penetration of water into the porous body while retaining a hydrophilic film on the surface of the porous body, and a water permeation preventive film using the same It is another object of the present invention to provide a coating laminate and a member provided with the coating or the laminate.
本発明者らは、上記の課題を解決すべく鋭意検討を行った結果、撥水性シリコーンエマルション粒子と反応性シリコーンレジンエマルション粒子との混合液を多孔体に塗布し硬化させて得られる被膜が、該多孔体内部への水の浸透防止性に優れ、かつ親水性防汚コーティングを該多孔体の最表面にのみ定着させることができることを見いだし、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have obtained a coating film obtained by applying a liquid mixture of water-repellent silicone emulsion particles and reactive silicone resin emulsion particles to a porous body and curing it. The inventors have found that the water penetration into the porous body is excellent and that a hydrophilic antifouling coating can be fixed only on the outermost surface of the porous body, and the present invention has been completed.
即ち、本発明は第一に、
（Ａ）撥水性シリコーンエマルション粒子、
（Ｂ）反応性シリコーンレジンエマルション粒子、および
（Ｃ）水
を含む常温硬化性の透水防止被膜形成剤であって、
該透水防止被膜形成剤において、（Ａ）成分および（Ｂ）成分の合計の量が0.5〜10質量%の範囲であり、（Ｃ）成分の量が80質量%以上である前記透水防止被膜形成剤を提供する。
本発明は第二に、前記透水防止被膜形成剤の硬化物からなる透水防止被膜を提供する。
本発明は第三に、前記透水防止被膜と、該透水防止被膜上に設けられた光触媒被膜とからなる被膜積層体を提供する。
本発明は第四に、基材と、前記透水防止被膜または前記被膜積層体とを備え、該基材の一部または全部が該透水防止被膜または該被膜積層体で被覆されている部材を提供する。
That is, the present invention firstly
(A) water-repellent silicone emulsion particles,
(B) Reactive silicone resin emulsion particles, and (C) a room temperature-curing water-preventing film-forming agent containing water,
In the water permeation prevention film forming agent, the total amount of the component (A) and the component (B) is in the range of 0.5 to 10% by mass, and the amount of the component (C) is 80% by mass or more. Provide the agent.
Secondly, the present invention provides a water permeation preventive film comprising a cured product of the water permeation preventive film forming agent.
Thirdly, the present invention provides a film laminate comprising the water permeation preventive film and a photocatalyst film provided on the water permeation preventive film.
Fourthly, the present invention provides a member comprising a base material and the water permeation preventive coating or the film laminate, wherein a part or all of the base material is coated with the water permeation preventive coating or the film laminate. To do.
本発明の透水防止被膜形成剤によって多孔体を処理したのちに、親水性コート液を塗布すると、多孔体の内部への水の浸透が効果的に防止されるにもかかわらず、多孔体表面のみに水膜を形成させることができる。即ち、防汚性に優れた特異的な表面状態を多孔体について維持することができ、多孔体内部への汚水の浸透を防止しつつも、多孔体表面における付着汚れを防止できる。
本発明の透水防止被膜形成剤を使用すれば、コンクリート、モルタル、煉瓦等の、吸水性の高さ故に防汚処理ができなかった基材上に、防汚性親水性コーティングを施すことができ、これらの基材の美観を維持する手段が提供される。
After the porous body is treated with the water permeation preventive film forming agent of the present invention, when a hydrophilic coating liquid is applied, only the surface of the porous body is obtained, although water penetration into the inside of the porous body is effectively prevented. A water film can be formed. That is, a specific surface state excellent in antifouling property can be maintained for the porous body, and adhering dirt on the surface of the porous body can be prevented while preventing the penetration of sewage into the porous body.
By using the water permeation preventive film forming agent of the present invention, it is possible to apply an antifouling hydrophilic coating on a substrate such as concrete, mortar, brick, etc., which could not be antifouled due to its high water absorption. A means of maintaining the aesthetics of these substrates is provided.
以下、本発明について詳細に説明する。本明細書において常温とは10〜30℃をいう。 Hereinafter, the present invention will be described in detail. In this specification, normal temperature means 10-30 degreeC.
［（Ａ）撥水性シリコーンエマルション粒子］
（Ａ）成分の撥水性シリコーンエマルション粒子としては、従来知られているいずれのものも使用することができる。（Ａ）成分のイオン性は、アニオン性、カチオン性、ノニオン性のいずれであってもよい。（Ａ）成分は１種単独でも２種以上を組み合わせて使用してもよい。
[(A) Water-repellent silicone emulsion particles]
As the water-repellent silicone emulsion particles of component (A), any conventionally known particles can be used. The ionicity of the component (A) may be any of anionic, cationic and nonionic. (A) A component may be used individually by 1 type or in combination of 2 or more types.
（Ａ）成分の撥水性シリコーンエマルション粒子に好適に使用されうる材料としては、例えば、ジメチルシリコーン（ポリジメチルシロキサン）、アミノ変性シリコーン、エポキシ変性シリコーン、エポキシ/ポリエーテル変性シリコーン、メタクリル変性シリコーン、アクリル変性シリコーン、メルカプト変性シリコーン、フェニル変性シリコーン、アルキル変性シリコーン、ヒドリド変性シリコーン、ヒドロキシ変性シリコーン、シラノール変性シリコーン、カルボキシ変性シリコーン、フッ素変性シリコーン、これらの組み合わせからなる変性シリコーン、更にこれらをゴム変性した変性シリコーンなどが挙げられる。（Ａ）成分としては、中でも特に自己架橋型アニオン性シリコーンエマルションが好適に用いられる。 Examples of materials that can be suitably used for the water-repellent silicone emulsion particles of component (A) include, for example, dimethyl silicone (polydimethylsiloxane), amino-modified silicone, epoxy-modified silicone, epoxy / polyether-modified silicone, methacryl-modified silicone, acrylic Modified silicone, mercapto-modified silicone, phenyl-modified silicone, alkyl-modified silicone, hydride-modified silicone, hydroxy-modified silicone, silanol-modified silicone, carboxy-modified silicone, fluorine-modified silicone, modified silicone composed of a combination of these, and rubber-modified Examples include silicone. As the component (A), a self-crosslinking type anionic silicone emulsion is particularly preferably used.
［（Ｂ）反応性シリコーンレジンエマルション粒子］
反応性シリコーンレジンエマルションとは、シリコーンレジンをエマルション化したものをいう。シリコーンレジンとは官能基変性シリコーンとアルコキシシランとが任意の割合で縮合した化合物を指す。（Ｂ）成分としては、従来知られているいずれのものも使用することができる。（Ｂ）成分のイオン性は、アニオン性、カチオン性、ノニオン性のいずれであってもよい。（Ｂ）成分は１種単独でも２種以上を組み合わせて使用してもよい。
[(B) Reactive silicone resin emulsion particles]
A reactive silicone resin emulsion refers to an emulsion of a silicone resin. The silicone resin refers to a compound in which a functional group-modified silicone and an alkoxysilane are condensed at an arbitrary ratio. As the component (B), any conventionally known component can be used. The ionicity of component (B) may be any of anionic, cationic or nonionic. (B) A component may be used individually by 1 type or in combination of 2 or more types.
（Ｂ）成分の反応性シリコーンレジンエマルション粒子に好適に使用されうる材料としては、例えば、MQレジン、アルキルレジン、フェニルレジン、エポキシレジン、アミノレジン、ポリエーテルレジン、エポキシ/ポリエーテルレジン、メタクリルレジン、アクリルレジン、メルカプトレジン、ヒドリドレジン、カルボキシレジン、フッ素レジン、これらの組み合わせからなる変性レジン、更にこれらに対し、ゴム変性成分を加えたレジンなどが挙げられる。（Ｂ）成分としては、中でも特にシラノール含有ノニオン性シリコーンレジンエマルション粒子が好適に用いられる。 Examples of materials that can be suitably used for the reactive silicone resin emulsion particles (B) include, for example, MQ resins, alkyl resins, phenyl resins, epoxy resins, amino resins, polyether resins, epoxy / polyether resins, and methacrylic resins. An acrylic resin, a mercaptoresin, a hydride resin, a carboxy resin, a fluorine resin, a modified resin composed of a combination thereof, and a resin obtained by adding a rubber-modified component to these. As the component (B), silanol-containing nonionic silicone resin emulsion particles are particularly preferably used.
[混合条件]
上記（Ａ）成分と（Ｂ）成分との混合比は、本発明の透水防止被膜および被膜積層体の特性が得られる限り、特に制限されない。本発明の透水防止被膜形成剤において、（Ａ）成分および（Ｂ）成分の合計の量は、0.5〜10質量%、好ましくは1〜5質量%の範囲であり、（Ｃ）成分の量は80質量%以上、好ましくは80〜99.5質量%、より好ましくは90〜99.5質量%、更により好ましくは95〜99質量%である。
[Mixing conditions]
The mixing ratio of the component (A) and the component (B) is not particularly limited as long as the characteristics of the water permeation preventive coating and the coating laminate of the present invention are obtained. In the water permeation preventive film forming agent of the present invention, the total amount of the component (A) and the component (B) is 0.5 to 10% by mass, preferably 1 to 5% by mass, and the amount of the component (C) is 80 mass% or more, preferably 80 to 99.5 mass%, more preferably 90 to 99.5 mass%, and still more preferably 95 to 99 mass%.
中でも、撥水性シリコーンエマルション粒子と親水性シリコーンレジンエマルション粒子とを混合することが好ましく、特に、自己架橋型アニオン性シリコーンエマルション粒子とシラノール含有ノニオン性シリコーンレジンエマルション粒子との質量比が10:90〜90：10の範囲の質量比であることが好ましい。自己架橋型アニオン性シリコーンエマルション粒子の濃度が90質量%より高い場合、極性を与えるシラノール含有ノニオン性シリコーンレジンエマルション粒子が十分量露出せず、その上に親水性コート液を施工したときの定着性が悪くなることがある。また、自己架橋型アニオン性シリコーンエマルション粒子の濃度が10質量%より低い場合、極性の高いシラノール含有ノニオン性シリコーンレジンエマルション粒子が多く、被膜がやや親水性となるために透水防止能力が低下することがある。 Among them, it is preferable to mix the water-repellent silicone emulsion particles and the hydrophilic silicone resin emulsion particles, and particularly the mass ratio of the self-crosslinking type anionic silicone emulsion particles to the silanol-containing nonionic silicone resin emulsion particles is 10:90 to A mass ratio in the range of 90:10 is preferred. When the concentration of self-crosslinking type anionic silicone emulsion particles is higher than 90% by mass, a sufficient amount of silanol-containing nonionic silicone resin emulsion particles giving polarity will not be exposed, and fixability when hydrophilic coating liquid is applied on top May get worse. In addition, when the concentration of self-crosslinking type anionic silicone emulsion particles is lower than 10% by mass, there are many highly polar silanol-containing nonionic silicone resin emulsion particles, and the water-permeable preventing ability is lowered because the coating is slightly hydrophilic. There is.
［親水性コート液の塗布］
本発明の透水防止被膜の上に形成される親水性被膜を与える防汚性親水性コート液としては、従来公知のいずれのものも用いることができる。親水性コート液は１種単独でも２種以上を組み合わせて用いることもできる。形成された親水性被膜の表面に対する水の接触角は３０°以下である。接触角が３０°を超えるような親水性被膜は防汚性能が不十分の場合がある。親水性コート液としては、無機質のシリケート系の溶液が好適に使用される。無機物からなる親水性コート液から得られる親水性被膜は、有機物からなる親水性コート液から得られる親水性被膜と比較して、耐久性が高くなりやすい。
[Application of hydrophilic coating solution]
Any conventionally known antifouling hydrophilic coating solution for providing a hydrophilic coating formed on the water permeation preventive coating of the present invention can be used. The hydrophilic coating liquid can be used alone or in combination of two or more. The contact angle of water with respect to the surface of the formed hydrophilic coating is 30 ° or less. A hydrophilic film having a contact angle exceeding 30 ° may have insufficient antifouling performance. As the hydrophilic coating solution, an inorganic silicate solution is preferably used. A hydrophilic film obtained from a hydrophilic coating liquid made of an inorganic substance tends to have higher durability than a hydrophilic film obtained from a hydrophilic coating liquid made of an organic substance.
［光触媒］
前記親水性被膜は光触媒被膜で有ってもよい。
光触媒粒子としては、従来知られているいずれのものも使用することができる。光触媒粒子は1種単独で使用しても2種類以上を併用してもよい。光触媒粒子としては、例えば酸化チタン系、酸化タングステン系、酸化亜鉛系、または酸化ニオブ系の光触媒粒子等の、ｎ型半導体である金属酸化物の結晶微粒子が使用できる。例えば、アナターゼ型の二酸化チタン（ＴｉＯ2）、ルチル型の二酸化チタン（ＴｉＯ2）、三酸化タングステン（ＷＯ3）、酸化亜鉛（ＺｎＯ）、Ｇａドープ酸化亜鉛（ＧＺＯ）、酸化ニオブ（Ｎｂ2Ｏ5）等を使用し得る。
[photocatalyst]
The hydrophilic coating may be a photocatalytic coating.
Any conventionally known photocatalyst particles can be used. The photocatalyst particles may be used alone or in combination of two or more. As the photocatalyst particles, crystal fine particles of metal oxide which is an n-type semiconductor such as titanium oxide, tungsten oxide, zinc oxide, or niobium oxide photocatalyst particles can be used. For example, anatase type titanium dioxide (TiO 2 ), rutile type titanium dioxide (TiO 2 ), tungsten trioxide (WO 3 ), zinc oxide (ZnO), Ga-doped zinc oxide (GZO), niobium oxide (Nb 2 O) 5 ) etc. can be used.
中でも、可視光活性の高いものとしてこれら金属酸化物の結晶内に窒素、硫黄、リン、炭素等をドーピングしたもの、又は表面に銅、鉄、ニッケル、金、銀、白金、パラジウム、ロジウム、ルテニウム、炭素等を担持したものが好適に使用し得る。更に詳しくは、白金を担持したルチル型酸化チタン、鉄を担持したルチル型酸化チタン、銅を担持したルチル型酸化チタン、水酸化銅を担持したルチル型酸化チタン、金を担持したアナターゼ型酸化チタン、白金を担持した三酸化タングステン等が挙げられる。更に、該微粒子の一次粒子径が微細なもの、即ち一次粒径が１〜１００ｎｍの範囲、更に好ましくは１〜５０ｎｍの範囲にあるものが好適に使用される。一次粒径が１００ｎｍ以下であると塗膜の透明度が低下しにくく外観を損ねにくい。なお、本明細書において、「平均粒子径」とは、動的光散乱法を用いた粒度分布測定装置によって求めた累積分布の50%に相当する体積基準の平均粒子径をいう。更に、光触媒性微粒子を固定するために、シリケートや非晶質チタニア等、無機系のバインダーを含んでいてもよい。 Among them, those having high visible light activity, those doped with nitrogen, sulfur, phosphorus, carbon, etc. in the crystal of these metal oxides, or copper, iron, nickel, gold, silver, platinum, palladium, rhodium, ruthenium on the surface Those carrying carbon or the like can be suitably used. More specifically, rutile-type titanium oxide carrying platinum, rutile-type titanium oxide carrying iron, rutile-type titanium oxide carrying copper, rutile-type titanium oxide carrying copper hydroxide, anatase-type titanium oxide carrying gold And tungsten trioxide carrying platinum. Further, fine particles having a fine primary particle diameter, that is, those having a primary particle diameter in the range of 1 to 100 nm, more preferably in the range of 1 to 50 nm are preferably used. When the primary particle size is 100 nm or less, the transparency of the coating film is hardly lowered and the appearance is hardly impaired. In the present specification, the “average particle diameter” refers to a volume-based average particle diameter corresponding to 50% of the cumulative distribution obtained by a particle size distribution measuring apparatus using a dynamic light scattering method. Further, in order to fix the photocatalytic fine particles, an inorganic binder such as silicate or amorphous titania may be included.
[塗膜の形成]
本発明の透水防止被膜形成剤が塗布される基材は、被膜を形成することができる限り、特に制限されない。該基材が多孔体（多孔質基材）である場合、該多孔体は、被膜を形成することができる限り、特に制限されず、例えば、表面に直径0.05〜5mmの空孔または凹凸を有する多孔体が挙げられる。基材の材料としては、無機材料、有機材料いずれも挙げられ、無機材料には例えば、非金属無機材料および金属無機材料が包含される。これらはそれぞれの目的、用途に応じた様々な形状を有することができる。
非金属無機材料としては、例えばガラス、セラミック等の多孔質材料が挙げられる。これらは意匠性建築材料、フィルター材等の様々な形に製品化され得る。
また、建築の外装、内装材料として用いられる、コンクリート、軽量発泡コンクリート、煉瓦、モルタル、珪藻土、漆喰、スレート、粘土、シラスバルーン、石膏プラスターボード、木材、天然石材、紙、布のいずれであってもよい。
金属無機材料としては、例えば鋳鉄、鋼材、鉄、鉄合金、アルミニウム、アルミニウム合金、ニッケル、ニッケル合金、亜鉛ダイキャスト等からなる多孔体が挙げられ、これらはメッキが施されてもよいし、有機塗料が塗布されていてもよい。また、非金属無機材料又は有機材料の表面に施された金属メッキ皮膜であってもよい。
有機材料としては、例えば塩化ビニル樹脂、ポリエチレン、ポリプロピレン、ポリカーボネート、アクリル樹脂、ポリスチレン、アクリル、ポリアセタール、フッ素樹脂、シリコーン樹脂、エチレン−酢酸ビニル共重合体（ＥＶＡ）、アクリロニトリル−ブタジエンゴム（ＮＢＲ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリビニルブチラール（ＰＶＢ）、エチレン−ビニルアルコール共重合体（ＥＶＯＨ）、ポリイミド、ポリフェニレンサルファイド（ＰＰＳ）、ポリエーテルイミド（ＰＥＩ）、ポリエーテルエーテルイミド（ＰＥＥＩ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、メラミン樹脂、アクリロニトリル−ブタジエン−スチレン（ＡＢＳ）樹脂等の合成樹脂材料；天然、合成若しくは半合成の繊維材料及び繊維製品、その多孔質加工品が挙げられる。これらは、網状、布状、フィルム、シート、その他の成型品、積層体などの所要の形状、構成に製品化されていてよい。
[Formation of coating film]
The base material to which the water-permeable prevention film forming agent of the present invention is applied is not particularly limited as long as a film can be formed. When the substrate is a porous body (porous substrate), the porous body is not particularly limited as long as it can form a film, and has, for example, pores or irregularities having a diameter of 0.05 to 5 mm on the surface. A porous body is mentioned. Examples of the material for the substrate include both inorganic materials and organic materials. Examples of inorganic materials include non-metallic inorganic materials and metallic inorganic materials. These can have various shapes according to their purposes and applications.
Examples of non-metallic inorganic materials include porous materials such as glass and ceramics. These can be commercialized into various forms such as a design building material and a filter material.
In addition, any of concrete, lightweight foamed concrete, brick, mortar, diatomaceous earth, plaster, slate, clay, shirasu balloon, gypsum plaster board, wood, natural stone, paper, cloth used as building exterior and interior materials Good.
Examples of the metal inorganic material include porous bodies made of cast iron, steel, iron, iron alloy, aluminum, aluminum alloy, nickel, nickel alloy, zinc die cast, etc., and these may be plated or organic A paint may be applied. Moreover, the metal plating film provided on the surface of nonmetallic inorganic material or organic material may be sufficient.
Examples of the organic material include vinyl chloride resin, polyethylene, polypropylene, polycarbonate, acrylic resin, polystyrene, acrylic, polyacetal, fluorine resin, silicone resin, ethylene-vinyl acetate copolymer (EVA), acrylonitrile-butadiene rubber (NBR), Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyvinyl butyral (PVB), ethylene-vinyl alcohol copolymer (EVOH), polyimide, polyphenylene sulfide (PPS), polyether imide (PEI), polyether ether imide ( Synthetic resin materials such as PEEI), polyetheretherketone (PEEK), melamine resin, acrylonitrile-butadiene-styrene (ABS) resin; natural, synthetic Semisynthetic fiber materials and fiber products, the porous workpiece and the like. These may be commercialized into required shapes and configurations such as nets, cloths, films, sheets, other molded products, and laminates.
本発明の透水防止被膜形成剤を基材に塗布するには、従来公知のいずれの方法も用いることができる。具体的には、ディップコーティング法、スピンコーティング法、スプレーコーティング法、印毛塗り法、ローラー法、含浸法、ロール法、ワイヤーバー法、ダイコーティング法、グラビア印刷法、インクジェット法等を利用して塗膜を基材上に形成させることができる。 Any conventionally known method can be used to apply the water permeation prevention film forming agent of the present invention to a substrate. Specifically, using the dip coating method, spin coating method, spray coating method, stamping method, roller method, impregnation method, roll method, wire bar method, die coating method, gravure printing method, ink jet method, etc. A coating film can be formed on a substrate.
本発明の透水防止被膜形成剤の硬化物からなる透水防止被膜はその表面に直径50nm〜1,000nmの球状の構造体を有することが好ましい。 It is preferable that the water permeation preventive film made of the cured product of the water permeation preventive film forming agent of the present invention has a spherical structure having a diameter of 50 nm to 1,000 nm on the surface thereof.
形成される透水防止被膜は、多孔質基材表面から１mm〜200mm程度の深さ、特には、1mm〜50mmの深さ範囲まで浸透していることが好ましい。透水防止被膜の浸透の深さが前記の範囲内であると、透水防止能力が不足しにくいため汚水が侵入しにくく、また、透水防止被膜の白色が顕在化しにくく意匠性が低下しにくい。本発明の透水防止被膜形成剤の硬化物からなる透水防止被膜は、表面に露出している空孔の直径が0.01〜2mmである多孔体の表面に設けられたとき、該透水防止被膜が設けられた前記表面から1mm以上の深さには水を浸透させないことが好ましい。 It is preferable that the formed water permeation preventive coating penetrates from the surface of the porous base material to a depth of about 1 mm to 200 mm, particularly a depth range of 1 mm to 50 mm. If the penetration depth of the water-permeable coating is within the above-mentioned range, the water-permeable preventing ability is hardly insufficient, so that sewage is difficult to enter, and the white color of the water-permeable coating is difficult to be revealed and the design is difficult to deteriorate. The water permeation preventive film comprising a cured product of the water permeation preventive film forming agent of the present invention is provided on the surface of a porous body having a diameter of pores exposed on the surface of 0.01 to 2 mm. It is preferable that water does not permeate to a depth of 1 mm or more from the formed surface.
本発明の透水防止被膜形成剤を塗布して形成される被膜上の水接触角は、その多孔質上にて80°以上であることが好ましい。水接触角が80°以上であると、汚水が浸透しにくい。 The water contact angle on the film formed by applying the water permeation preventive film forming agent of the present invention is preferably 80 ° or more on the porous surface. When the water contact angle is 80 ° or more, the sewage hardly penetrates.
また、本発明の透水防止被膜形成剤を塗布して形成される透水防止被膜の透明度に関しては、この被膜の厚さが10μmであるときに、該被膜単独について測定した全光線透過率およびヘイズ率がそれぞれ80％以上および１０％以下であることが好ましい。全光線透過率が８０％以上、かつ、ヘイズ率が１０％以下であると、被膜の白色が顕在化しにくく、基材の意匠性が低下しにくい。 Further, regarding the transparency of the water-permeation preventive film formed by applying the water-permeability preventive film forming agent of the present invention, the total light transmittance and haze ratio measured for the film alone when the thickness of the film is 10 μm. Are preferably 80% or more and 10% or less, respectively. When the total light transmittance is 80% or more and the haze ratio is 10% or less, the white color of the coating is difficult to be revealed, and the design of the substrate is difficult to be lowered.
親水性被膜または光触媒被膜を形成する場合には、前記の如く多孔体上に形成された透水防止層の上に、親水性コート液または光触媒コート液を前記同様の手法によって塗布し、乾燥する。常温静置でも加熱してもよく、加熱する場合は５０〜２００℃の温度範囲で１〜１２０分間処理することが好ましく、特には、６０〜１１０℃の温度範囲で５〜６０分間処理することが好ましい。 When forming a hydrophilic film or a photocatalyst film, the hydrophilic coating liquid or the photocatalyst coating liquid is applied on the water permeation preventive layer formed on the porous body as described above, and dried. It may be heated at room temperature or when heated, it is preferably treated at a temperature range of 50 to 200 ° C. for 1 to 120 minutes, particularly at a temperature range of 60 to 110 ° C. for 5 to 60 minutes. Is preferred.
本発明の透水防止被膜形成剤の硬化物からなる透水防止被膜と、該透水防止被膜上に設けられた親水性被膜とからなる被膜積層体は、表面に露出している空孔の直径が0.01〜2mmである多孔体の表面に該透水防止被膜と該表面とが接するように設けられたとき、該被膜積層体が設けられた前記表面から1mm以上の深さには水を浸透させず、水接触角が30°以下であることが好ましい。また、前記被膜積層体は、JIS K 7350-4に規定の、オープンフレームカーボンアーク灯を用いたサンシャインウェザーメータによるブラックパネル温度63±3℃、200時間の曝露試験後も水接触角が30°以下であることが好ましい。 The film laminate comprising a water permeation preventive film comprising a cured product of the water permeation preventive film forming agent of the present invention and a hydrophilic film provided on the water permeation preventive film has a diameter of pores exposed on the surface of 0.01. When the surface of the porous body having a thickness of ˜2 mm is provided so that the water permeation preventive coating and the surface are in contact with each other, water is not permeated to a depth of 1 mm or more from the surface where the coating laminate is provided The water contact angle is preferably 30 ° or less. Further, the coating laminate has a black panel temperature of 63 ± 3 ° C. by a sunshine weather meter using an open frame carbon arc lamp as defined in JIS K 7350-4, and a water contact angle of 30 ° even after a 200 hour exposure test. The following is preferable.
以下、実施例及び比較例により本発明を具体的に説明する。ただし、本発明はこれらの例により制限されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited by these examples.
［実施例１］
自己架橋型アニオン性シリコーンエマルションとして、PolonMF56（製品名、40質量%、信越化学工業製）を用い、シラノール含有ノニオン性シリコーンレジンエマルションとして、X-52-8148（製品名、47質量%、信越化学工業製）を用いた。
両成分を質量比が表１記載のとおりとなるように（即ち、両成分の質量比が50:50となるように）混合し、総固形分濃度が3.0質量%となるように脱イオン水で希釈して、透水防止被膜形成剤を調製した。得られた透水防止被膜形成剤をシポレックス50（製品名、軽量発泡コンクリート、住友金属鉱山シポレックス製）製の基材の一部の面に50g/m2程度、スプレーコート法にて塗布し、常温にて24時間乾燥させて、前記基材の一部の面に透水防止被膜が形成されたテストブロックを得た。
[Example 1]
PolonMF56 (product name, 40% by mass, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a self-crosslinking type anionic silicone emulsion, and X-52-8148 (product name, 47% by mass, Shin-Etsu Chemical) was used as a silanol-containing nonionic silicone resin emulsion. Kogyo) was used.
Both components are mixed so that the mass ratio is as shown in Table 1 (that is, the mass ratio of both components is 50:50), and deionized water so that the total solid content concentration is 3.0% by mass. Was diluted with a water permeation prevention film forming agent. Apply the obtained water permeation prevention film-forming agent to a part of the surface of Sipolex 50 (product name, lightweight foamed concrete, manufactured by Sumitomo Metal Mining Sipolex) by spray coating method at about 50 g / m 2 Was dried for 24 hours to obtain a test block in which a water permeation preventive film was formed on a part of the surface of the substrate.
［実施例２］
自己架橋型アニオン性シリコーンエマルションとして、KM-2002T（製品名、43質量%、信越化学工業製）を用い、シラノール含有ノニオン性シリコーンレジンエマルションとして、X-52-8148を用いた。
両成分を質量比が表１記載のとおりとなるように混合し、総固形分濃度が3.0質量%となるように脱イオン水で希釈して、透水防止被膜形成剤を調製した。得られた透水防止被膜形成剤をシポレックス50製の基材の一部の面に50g/m2程度、スプレーコート法にて塗布し、常温にて24時間乾燥させて、前記基材の一部の面に透水防止被膜が形成されたテストブロックを得た。
[Example 2]
KM-2002T (product name, 43 mass%, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the self-crosslinking type anionic silicone emulsion, and X-52-8148 was used as the silanol-containing nonionic silicone resin emulsion.
Both components were mixed so that the mass ratio was as shown in Table 1, and diluted with deionized water so that the total solid content concentration was 3.0% by mass to prepare a water permeation prevention film forming agent. The obtained water permeation prevention film forming agent was applied to about 50 g / m 2 on a part of the surface of the base material made of Sipolex 50 by a spray coating method and dried at room temperature for 24 hours, and a part of the base material A test block having a water permeation preventive coating formed on the surface was obtained.
［実施例３］
実施例１と同様にして作製したテストブロックの透水防止被膜上に、親水性コート剤UG-05（製品名、0.5質量%、信越化学工業製）を25g/m2程度、スプレーコート法にて塗布し、常温にて24時間乾燥させて、前記基材の一部の面に透水防止被膜と親水性被膜とからなる被膜積層体が形成されたテストブロックを得た。
[Example 3]
On permeability preventing coating of the test blocks were prepared in the same manner as in Example 1, the hydrophilic coating agent UG-05 (product name, 0.5 wt%, manufactured by Shin-Etsu Chemical Co.) and 25 g / m 2 approximately, by a spray coating method It was applied and dried at room temperature for 24 hours to obtain a test block in which a film laminate composed of a water permeation preventive film and a hydrophilic film was formed on a part of the surface of the substrate.
［実施例４］
実施例２と同様にして作製したテストブロックの透水防止被膜上に、親水性コート剤UG-05を25g/m2程度、スプレーコート法にて塗布し、常温にて24時間乾燥させて、前記基材の一部の面に透水防止被膜と親水性被膜とからなる被膜積層体が形成されたテストブロックを得た。
[Example 4]
On permeability preventing coating of the test blocks were prepared in the same manner as in Example 2, the hydrophilic coating agent UG-05 to 25 g / m 2 approximately, was applied by spray coating, dried for 24 hours at room temperature, the A test block was obtained in which a coating laminate composed of a water permeation prevention coating and a hydrophilic coating was formed on a part of the surface of the substrate.
［実施例５］
実施例１と同様にして作製したテストブロックの透水防止被膜上に、光触媒コート剤TPX-85（製品名、0.85質量%、鯤コーポレーション製）を25g/m2程度、スプレーコート法にて塗布し、常温にて24時間乾燥させて、前記基材の一部の面に透水防止被膜と光触媒被膜とからなる被膜積層体が形成されたテストブロックを得た。
[Example 5]
On permeability preventing coating of the test blocks were prepared in the same manner as in Example 1, the photocatalytic coating agent TPX-85 (product name, 0.85 wt%, manufactured by鯤Corporation) and 25 g / m 2 approximately, was applied by spray coating Then, it was dried at room temperature for 24 hours to obtain a test block in which a film laminate comprising a water permeation preventive film and a photocatalyst film was formed on a part of the surface of the substrate.
［実施例６］
実施例２と同様にして作製したテストブロックの透水防止被膜上に、光触媒コート剤TPX-85を25g/m2程度、スプレーコート法にて塗布し、常温にて24時間乾燥させて、前記基材の一部の面に透水防止被膜と光触媒被膜とからなる被膜積層体が形成されたテストブロックを得た。
[Example 6]
A photocatalyst coating agent TPX-85 was applied at about 25 g / m 2 by a spray coating method on a water-preventing coating of a test block produced in the same manner as in Example 2 and dried at room temperature for 24 hours. A test block was obtained in which a coating laminate comprising a water permeation prevention coating and a photocatalytic coating was formed on a part of the surface of the material.
［比較例１］
自己架橋型アニオン性シリコーンエマルションKM-2002Tを総固形分濃度が3.0質量%となるように脱イオン水で希釈して、希釈液を調製した。得られた希釈液をシポレックス50製の基材の一部の面に50g/m2程度、スプレーコート法にて塗布し、常温にて24時間乾燥させて、前記基材の一部の面に被膜が形成されたテストブロックを得た。
[Comparative Example 1]
A self-crosslinking type anionic silicone emulsion KM-2002T was diluted with deionized water so that the total solid content concentration was 3.0% by mass to prepare a diluted solution. The obtained diluted solution was applied to a part of the surface of the base material made of Sipolex 50 by about 50 g / m 2 by a spray coating method, and dried at room temperature for 24 hours. A test block with a coating formed thereon was obtained.
［比較例２］
シラノール含有ノニオン性シリコーンレジンエマルションX-52-8148を総固形分濃度が3.0質量%となるように脱イオン水で希釈して、希釈液を調製した。得られた希釈液をシポレックス50製の基材の一部の面に50g/m2程度、スプレーコート法にて塗布し、常温にて24時間乾燥させて、前記基材の一部の面に被膜が形成されたテストブロックを得た。
[Comparative Example 2]
A silanol-containing nonionic silicone resin emulsion X-52-8148 was diluted with deionized water to a total solid content concentration of 3.0% by mass to prepare a diluted solution. The obtained diluted solution was applied to a part of the surface of the base material made of Sipolex 50 by about 50 g / m 2 by a spray coating method, and dried at room temperature for 24 hours. A test block with a coating formed thereon was obtained.
［比較例３］
市販の透水防止剤FJ-150（製品名、シリコーンエマルション系の透水防止剤、Grandex製）をシポレックス50製の基材の一部の面に50g/m2程度、スプレーコート法にて塗布し、常温にて24時間乾燥させて、前記基材の一部の面に透水防止被膜を形成させた。該透水防止被膜上に、親水性コート剤UG-05を25g/m2程度、スプレーコート法にて塗布し、常温にて24時間乾燥させて、前記基材の一部の面に透水防止被膜と親水性被膜とからなる被膜積層体が形成されたテストブロックを得た。
[Comparative Example 3]
Apply a commercially available water permeation preventive FJ-150 (product name, water permeation preventive of silicone emulsion system, made by Grandex) to a part of Sipolex 50 base material by about 50g / m 2 by spray coating, The film was dried at room temperature for 24 hours to form a water permeation preventive film on a part of the surface of the substrate. A hydrophilic coating agent UG-05 is applied to the water-preventing coating at a rate of about 25 g / m 2 by a spray coating method, and is dried at room temperature for 24 hours. And a test block in which a film laminate comprising a hydrophilic film was formed.
［比較例４］
市販の透水防止剤FJ-150をシポレックス50製の基材の一部の面に50g/m2程度、スプレーコート法にて塗布し、常温にて24時間乾燥させて、前記基材の一部の面に透水防止被膜を形成させた。該透水防止被膜上に、光触媒コート剤TPX-85を25g/m2程度、スプレーコート法にて塗布し、常温にて24時間乾燥させて、前記基材の一部の面に透水防止被膜と光触媒被膜とからなる被膜積層体が形成されたテストブロックを得た。
[Comparative Example 4]
50 g / m 2 approximately to a part of the surface of a commercially available water permeation inhibitor FJ-0.99 Shiporekkusu 50 made of a substrate, was applied by spray coating, dried for 24 hours at room temperature, a portion of the substrate A water permeation preventive coating was formed on the surface. On the water-proof coating, a photocatalyst coating agent TPX-85 is applied at about 25 g / m 2 by a spray coating method, and dried at room temperature for 24 hours. A test block in which a film laminate including a photocatalyst film was formed was obtained.
［比較例５］
市販の透水防止剤FJ-150と市販のコロイダルシリカ（製品名：スノーテックス、日産化学製、粒子径8-11nm、SiO2 20質量％、表１では「シリカ」と表記）とを質量比が表１記載のとおりとなるように混合し、得られた混合液をシポレックス50製の基材の一部の面に50g/m2程度、スプレーコート法にて塗布し、常温にて24時間乾燥させて、前記基材の一部の面に透水防止被膜を形成させた。該透水防止被膜上に、光触媒コート剤TPX-85を25g/m2程度、スプレーコート法にて塗布し、常温にて24時間乾燥させて、前記基材の一部の面に透水防止被膜と光触媒被膜とからなる被膜積層体が形成されたテストブロックを得た。
[Comparative Example 5]
Mass ratio of commercially available water permeation preventive agent FJ-150 and commercially available colloidal silica (product name: Snowtex, manufactured by Nissan Chemical Co., Ltd., particle size 8-11nm, SiO 2 20% by mass, in Table 1, “silica”) Table 1 mixed so that as described, the resulting mixture of about 50 g / m 2 on a part of the surface of Shiporekkusu 50 made of a base material, was applied by spray coating, 24 hours at ambient temperature drying Thus, a water permeation preventive film was formed on a part of the surface of the substrate. On the water-proof coating, a photocatalyst coating agent TPX-85 is applied at about 25 g / m 2 by a spray coating method, and dried at room temperature for 24 hours. A test block in which a film laminate including a photocatalyst film was formed was obtained.
［球状の構造体の有無］
親水性被膜または光触媒被膜を形成する前の透水防止被膜について走査型電子顕微鏡（製品名：S-3400NX、日立ハイテクノロジーズ製）にて表面を観察した。下記の基準で評価した結果を表１に示す。
○：直径50nm〜1,000nmの球状の構造体が観察された
×：直径50nm〜1,000nmの球状の構造体が観察されなかった
[Presence or absence of spherical structure]
The surface of the water permeation preventive coating before forming the hydrophilic coating or the photocatalytic coating was observed with a scanning electron microscope (product name: S-3400NX, manufactured by Hitachi High-Technologies). The results of evaluation based on the following criteria are shown in Table 1.
○: A spherical structure having a diameter of 50 nm to 1,000 nm was observed. ×: A spherical structure having a diameter of 50 nm to 1,000 nm was not observed.
［汚水浸透防止性の確認］
前記テストブロックの被膜を形成した面上に、メチレンブルー色素（10μmol/L）にて着色した水を滴下・静置し、乾燥後に滴下部分を切り出して着色されている深さを定規にて計測した。下記の基準で評価した結果を表１に示す。
○：前記深さが1mm未満
×：前記深さが1mm以上
[Confirmation of sewage penetration prevention]
On the surface on which the test block film was formed, water colored with methylene blue dye (10 μmol / L) was dropped and allowed to stand, and the dried portion was cut out after drying and the colored depth was measured with a ruler. . The results of evaluation based on the following criteria are shown in Table 1.
○: The depth is less than 1 mm ×: The depth is 1 mm or more
［透水防止被膜の水接触角の測定］
親水性被膜または光触媒被膜を形成する前の透水防止被膜について水接触角を接触角計CA-A（製品名、協和界面科学製）を用いて常温にて測定した。結果を表１に示す。
[Measurement of water contact angle of water-permeable coating]
The water contact angle of the water permeation preventive coating before forming the hydrophilic coating or the photocatalytic coating was measured at room temperature using a contact angle meter CA-A (product name, manufactured by Kyowa Interface Science). The results are shown in Table 1.
［全光線透過率およびヘイズ］
親水性被膜または光触媒被膜を形成する前の透水防止被膜について全光線透過率およびヘイズ率をデジタルヘイズメーターＮＤＨ−２０Ｄ（日本電色工業（株）製）を用いて測定した。厚さ10μmの透水防止被膜を作製し測定に用いた。結果を表１に示す。
[Total light transmittance and haze]
The total light transmittance and haze ratio of the water permeation preventive coating before forming the hydrophilic coating or the photocatalytic coating were measured using a digital haze meter NDH-20D (manufactured by Nippon Denshoku Industries Co., Ltd.). A water permeation preventive film having a thickness of 10 μm was prepared and used for measurement. The results are shown in Table 1.
［防汚作用の維持］
透水防止被膜と親水性被膜または光触媒被膜とからなる被膜積層体が形成されたテストブロックについて、前記と同様にして水接触角を測定した。下記の基準で評価した結果を表１に示す。
○：水接触角が30°以下
×：水接触角が30°超
また、透水防止被膜と光触媒被膜とからなる被膜積層体が形成されたテストブロック中の光触媒被膜上にメチレンブルーの1.0mmol/L水溶液を塗布し、60℃で乾燥させることで該光触媒被膜表面に充分量のメチレンブルーを吸着させた。その後、このようにしてメチレンブルーを吸着させた光触媒被膜に紫外線（波長：190〜400nm、1mW/cm2）または可視光（波長400〜600nm、1mW/cm2）を照射し、光触媒評価チェッカーPCC-2（商品名、ULVAC理工社製）を用い、メチレンブルー吸着面における青色色素の吸光度（波長664nm）の減少を測定した。下記の基準で評価した結果を表１に示す。
○：測定開始10分後の前記吸光度の減少量×103の値が1以上
×：測定開始10分後の前記吸光度の減少量×103の値が1未満
[Maintenance of antifouling action]
The water contact angle was measured in the same manner as described above for a test block on which a film laminate comprising a water permeation preventive film and a hydrophilic film or a photocatalytic film was formed. The results of evaluation based on the following criteria are shown in Table 1.
○: Water contact angle is 30 ° or less ×: Water contact angle is more than 30 ° Further, 1.0 mmol / L of methylene blue on the photocatalyst film in the test block in which the film laminate composed of the water permeation prevention film and the photocatalyst film is formed An aqueous solution was applied and dried at 60 ° C. to adsorb a sufficient amount of methylene blue on the surface of the photocatalyst film. After that, the photocatalyst film thus adsorbed with methylene blue is irradiated with ultraviolet rays (wavelength: 190 to 400 nm, 1 mW / cm 2 ) or visible light (wavelength 400 to 600 nm, 1 mW / cm 2 ), and the photocatalyst evaluation checker PCC- 2 (trade name, manufactured by ULVAC Riko Co., Ltd.), the decrease in the absorbance (wavelength 664 nm) of the blue dye on the methylene blue adsorption surface was measured. The results of evaluation based on the following criteria are shown in Table 1.
○: The amount of decrease in absorbance x 10 3 10 minutes after the start of measurement is 1 or more ×: The amount of decrease in absorbance 10 min after the start of measurement x 10 3 is less than 1
［曝露試験］
透水防止被膜と親水性被膜または光触媒被膜とからなる被膜積層体が形成されたテストブロックに対して、JIS K 7350-4の規定に準じて、オープンフレームカーボンアーク灯を用いたサンシャインウェザーメータによるブラックパネル温度63±3℃、200時間の曝露試験を行った。曝露試験後に前記と同様にして水接触角を測定した。下記の基準で評価した結果を表１に示す。
○：水接触角が30°以下
×：水接触角が30°超
[Exposure test]
In accordance with the provisions of JIS K 7350-4, black with a sunshine weather meter using an open frame carbon arc lamp for a test block in which a film laminate consisting of a water permeation prevention film and a hydrophilic film or a photocatalyst film is formed An exposure test was performed at a panel temperature of 63 ± 3 ° C. for 200 hours. After the exposure test, the water contact angle was measured in the same manner as described above. The results of evaluation based on the following criteria are shown in Table 1.
○: Water contact angle is 30 ° or less ×: Water contact angle is more than 30 °
Claims (13)
（Ｂ）反応性シリコーンレジンエマルション粒子、および
（Ｃ）水
を含む常温硬化性の透水防止被膜形成剤であって、
（Ａ）成分が自己架橋型アニオン性シリコーンエマルション粒子であり、
（Ｂ）成分がシラノール含有ノニオン性シリコーンレジンエマルション粒子であり、
（Ａ）成分および（Ｂ）成分の合計の量が0.5〜10質量%の範囲であり、（Ｃ）成分の量が80質量%以上である前記透水防止被膜形成剤。 (A) water-repellent silicone emulsion particles,
(B) Reactive silicone resin emulsion particles, and (C) a room temperature-curing water-preventing film-forming agent containing water,
(A) component is self-crosslinking type anionic silicone emulsion particles,
(B) component is silanol-containing nonionic silicone resin emulsion particles,
The water permeation prevention film-forming agent, wherein the total amount of the component ( A) and the component (B) is in the range of 0.5 to 10% by mass, and the amount of the component (C) is 80% by mass or more.
該透水防止被膜形成剤の硬化物からなる透水防止被膜はその表面に直径50nm〜1,000nmの球状の構造体を有する前記透水防止被膜形成剤。 A water-permeable prevention film forming agent according to claim 1 or 2,
The water permeation prevention film forming agent comprising a cured product of the water permeation prevention film forming agent has a spherical structure having a diameter of 50 nm to 1,000 nm on the surface thereof.
該透水防止被膜形成剤の硬化物からなる透水防止被膜は、表面に露出している空孔の直径が0.01〜2mmである多孔体の表面に設けられたとき、該透水防止被膜が設けられた前記表面から1mm以上の深さには水を浸透させず、水接触角が80°以上である前記透水防止被膜形成剤。 A water permeation prevention film forming agent according to any one of claims 1 to 3 ,
When the water permeation preventive film comprising a cured product of the water permeation preventive film forming agent is provided on the surface of a porous body having a diameter of pores exposed on the surface of 0.01 to 2 mm, the water permeation preventive film is provided. The water permeation preventive film forming agent which does not penetrate water at a depth of 1 mm or more from the surface and has a water contact angle of 80 ° or more.
該透水防止被膜形成剤の硬化物からなる透水防止被膜は、厚さが10μmであるとき、全光線透過率が80%以上、かつ、ヘイズ率が10%以下である前記透水防止被膜形成剤。 A water permeation prevention film forming agent according to any one of claims 1 to 4 ,
The water permeation prevention film forming agent comprising a cured product of the water permeation prevention film forming agent, having a thickness of 10 μm, has a total light transmittance of 80% or more and a haze ratio of 10% or less.
該透水防止被膜形成剤の硬化物からなる透水防止被膜と、該透水防止被膜上に設けられた親水性被膜とからなる被膜積層体は、表面に露出している空孔の直径が0.01〜2mmである多孔体の表面に該透水防止被膜と該表面とが接するように設けられたとき、該被膜積層体が設けられた前記表面から1mm以上の深さには水を浸透させず、水接触角が30°以下である前記透水防止被膜形成剤。 A water permeation prevention film forming agent according to any one of claims 1 to 5 ,
The film laminate composed of a water-permeation-preventing film made of a cured product of the water-permeation-preventing film-forming agent and a hydrophilic film provided on the water-permeation-preventing film has a pore diameter of 0.01 to 2 mm exposed on the surface. When the surface of the porous body is provided so that the water permeation preventive coating and the surface are in contact with each other, water does not permeate to a depth of 1 mm or more from the surface on which the coating laminate is provided. The water permeation preventive film forming agent having an angle of 30 ° or less.
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