JP2006206765A - Water-repellent composition, substrate having water-repellent layer, method for producing the same, and article for transportation equipment - Google Patents
Water-repellent composition, substrate having water-repellent layer, method for producing the same, and article for transportation equipment Download PDFInfo
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本発明は、撥水性組成物、該撥水性組成物から形成された撥水層を有する基材、該基材の製造方法および該基材からなる輸送機器用物品に関する。 The present invention relates to a water-repellent composition, a substrate having a water-repellent layer formed from the water-repellent composition, a method for producing the substrate, and an article for transport equipment comprising the substrate.
自動車用フロントガラス等の基材表面には、水滴滑落性（水滴転落性ともいう。）を付与することが強く求められている。基材表面に耐久性に優れる水滴滑落性を付与するために、ポリフルオロアルキル基含有シラン化合物の部分加水分解縮合物と、シラン化合物とからなるガラス表面の撥水撥油剤が提案されている（例えば、特許文献１参照。）。しかし、ポリフルオロアルキル基含有シラン化合物とシラン化合物との相溶性が充分でないため、塗布時に両成分を基材表面に均一に塗布することが難しく、水滴滑落性と耐磨耗性とを安定的に両立することができなかった。 There is a strong demand for imparting water droplet sliding property (also referred to as water droplet falling property) to the surface of a substrate such as an automobile windshield. In order to impart a water droplet sliding property having excellent durability to the substrate surface, a water / oil repellent on the glass surface composed of a partially hydrolyzed condensate of a polyfluoroalkyl group-containing silane compound and a silane compound has been proposed ( For example, see Patent Document 1.) However, since the compatibility between the polyfluoroalkyl group-containing silane compound and the silane compound is not sufficient, it is difficult to uniformly apply both components to the surface of the substrate during application, and stable water drop sliding resistance and abrasion resistance are achieved. It was not possible to achieve both.
また、シリカマトリックス中に、ジメチルシリコーンの末端にウレタン結合を介してシランカップリング剤を結合させてなる滑水成分を分散させた高滑水性被膜が提案されている（例えば、特許文献２参照。）。しかし、該高滑水性被膜は、自動車用ウィンドウガラスとしての耐久性、耐薬品性、耐候性、特にワイパー摺動やウィンドウ昇降に対する耐摩耗性が充分ではなかった。 Further, a highly water-slidable coating film in which a water-sliding component obtained by bonding a silane coupling agent to a terminal of dimethyl silicone via a urethane bond is dispersed in a silica matrix has been proposed (for example, see Patent Document 2). ). However, the high water-sliding coating film has not been sufficient in durability, chemical resistance, and weather resistance as an automotive window glass, and particularly, abrasion resistance against wiper sliding and window lifting.
本発明者らは、ポリフルオロアルキル基含有シラン化合物からなる撥水性組成物を提案した（例えば、特許文献３参照。）。該撥水性組成物は、耐摩耗性には優れるものの、水滴転落性が充分でなく、自動車用ウィンドウとしては視認性が充分ではなかった。 The present inventors have proposed a water-repellent composition comprising a polyfluoroalkyl group-containing silane compound (see, for example, Patent Document 3). Although the water-repellent composition is excellent in abrasion resistance, the water droplet fallability is not sufficient, and the visibility as an automobile window is not sufficient.
本発明の目的は、上記のような問題点を解決し、水滴滑落性と耐摩耗性に優れた撥水層を形成しうる撥水性組成物、該撥水性組成物から形成された撥水層を有する基材、該基材の製造方法および該基材からなる輸送機器用物品を提供することである。 The object of the present invention is to solve the above-mentioned problems and to form a water-repellent composition capable of forming a water-repellent layer excellent in water droplet sliding and abrasion resistance, and a water-repellent layer formed from the water-repellent composition It is providing the base material which has this, the manufacturing method of this base material, and the articles | goods for transport equipment which consist of this base material.
本発明は、下式１で表される化合物１および／または下式２で表される化合物２と、下式３で表される化合物３とを、（化合物１および／または化合物２の合計）／化合物３が２／１００〜１００／１００の質量比で部分共加水分解して得た部分共加水分解体をを含むことを特徴とする撥水性組成物を提供する。 The present invention comprises a compound 1 represented by the following formula 1 and / or a compound 2 represented by the following formula 2 and a compound 3 represented by the following formula 3 (total of compound 1 and / or compound 2): There is provided a water repellent composition comprising a partially cohydrolyzed product obtained by partial cohydrolysis of / compound 3 at a mass ratio of 2/100 to 100/100.
ＲｆＣＯＮ（Ｒ１）−Ａ−Ｓｉ（Ｒ２）ｐ（Ｘ１）３−ｐ・・・式１
ＲｆＳＯ２Ｎ（Ｒ３）−Ｂ−Ｓｉ（Ｒ４）ｑ（Ｘ２）３−ｑ・・・式２
（Ｒ５）ｒＳｉ（Ｘ３）４−ｒ・・・式３
ただし、式中の記号は以下の意味を示す。
Ｒｆ：炭素原子数３〜１７のポリフルオロアルキル基または酸素原子を含む炭素原子数３〜１７のポリフルオロアルキル基。
Ａ、Ｂ：それぞれ独立して、窒素原子を含む炭素数１〜４の２価有機基または炭素原子数１〜４の２価有機基。
Ｒ１、Ｒ３：それぞれ独立して、炭素原子数１〜３の１価炭化水素基または水素原子。
Ｒ２、Ｒ４、Ｒ５：それぞれ独立して、フッ素原子を含まない炭素原子数１〜６の１価炭化水素基。
Ｘ１、Ｘ２、Ｘ３：それぞれ独立して、ハロゲン原子、アルコキシ基またはイソシアネート基。
ｐ、ｑ、ｒ：それぞれ独立して、０、１または２。
R f CON (R 1) -A -Si (R 2) p (X 1) 3-p ··· Formula 1
R f SO 2 N (R 3 ) -B-Si (R 4) q (X 2) 3-q ··· Equation 2
(R 5 ) r Si (X 3 ) 4-r Formula 3
However, the symbols in the formulas have the following meanings.
R f : a polyfluoroalkyl group having 3 to 17 carbon atoms or a polyfluoroalkyl group having 3 to 17 carbon atoms including an oxygen atom.
A and B: each independently a divalent organic group having 1 to 4 carbon atoms or a divalent organic group having 1 to 4 carbon atoms containing a nitrogen atom.
R 1 and R 3 : each independently a monovalent hydrocarbon group having 1 to 3 carbon atoms or a hydrogen atom.
R 2 , R 4 , R 5 : each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms that does not contain a fluorine atom.
X 1 , X 2 , X 3 : each independently a halogen atom, an alkoxy group or an isocyanate group.
p, q, r: each independently 0, 1 or 2.
また、本発明は該撥水性組成物から形成された撥水層を有する基材を提供する。また、該撥水性組成物を基材に塗布し、ついで、温度０〜１００℃、相対湿度１０〜８０％の条件下に保持することを特徴とする撥水層を有する基材の製造方法を提供する。さらに、本発明は該撥水層を有する基材からなる輸送機器用物品を提供する。 The present invention also provides a substrate having a water repellent layer formed from the water repellent composition. A method for producing a substrate having a water-repellent layer, characterized in that the water-repellent composition is applied to a substrate and then maintained under conditions of a temperature of 0 to 100 ° C. and a relative humidity of 10 to 80%. provide. Furthermore, this invention provides the articles | goods for transport equipment which consist of a base material which has this water-repellent layer.
本発明の撥水性組成物を用いて形成された撥水層は、水滴滑落性に優れ、耐摩耗性に優れ、雨天走行時の視界確保が容易であり、水滴滑落性の耐久性に優れ、長期間雨天走行時の良好な視界が維持できる。また、基材に特別な前処理を必要とせず、０〜１００℃の温度、特に室温に保持することで撥水層を形成できるため、経済的にも優れる。 The water-repellent layer formed using the water-repellent composition of the present invention is excellent in water drop slidability, excellent wear resistance, easy to ensure visibility during rainy weather, excellent in water drop slidability, Good visibility during rainy weather for long periods can be maintained. Moreover, since a water-repellent layer can be formed by maintaining the substrate at a temperature of 0 to 100 ° C., particularly at room temperature, without requiring special pretreatment, it is economically excellent.
本発明における部分共加水分解体は、式１で表される化合物１（以下化合物１と記す。）および／または式２で表される化合物２（以下、化合物２と記す。）と、式３で表される化合物３（以下、化合物３と記す。）とを共加水分解して得る。 The partial co-hydrolyzate in the present invention includes compound 1 represented by formula 1 (hereinafter referred to as compound 1) and / or compound 2 represented by formula 2 (hereinafter referred to as compound 2) and formula 3. It is obtained by cohydrolyzing the compound 3 represented by the formula (hereinafter referred to as compound 3).
化合物１、化合物２におけるＲ１、Ｒ２、Ｒ３、Ｒ４は、水素原子または炭素原子数１〜３の１価炭化水素基が好ましく、水素原子またはメチル基がより好ましい。化合物３におけるＲ５は、炭素原子数１〜６の１価炭化水素基が好ましく、メチル基またはエチル基がより好ましい。化合物１、化合物２、化合物３におけるＸ１、Ｘ２、Ｘ３は、アルコキシ基が好ましい。アルコキシ基であると化合物１、化合物２、化合物３の取扱いが容易である。 R 1 , R 2 , R 3 and R 4 in Compound 1 and Compound 2 are preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. R 5 in the compound 3 is preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group. X 1 , X 2 and X 3 in Compound 1, Compound 2 and Compound 3 are preferably alkoxy groups. When it is an alkoxy group, it is easy to handle Compound 1, Compound 2, and Compound 3.
本発明における化合物１は、ポリフルオロアルキル基（以下、Ｒｆ基と記す。）含有化合物１ａとアミノシラン化合物１ｂとを反応させて得られる。化合物１ａとしては、ポリフルオロアルキルカルボン酸、ポリフルオロアルキルカルボン酸エステル、ポリフルオロアルキルカルボン酸フルオリド等が好ましく、ポリフルオロアルキルカルボン酸エステルがより好ましい。化合物１ｂとしては、分子内にアミノ基を１〜３個および加水分解性反応基を２〜３個有する化合物が好ましい。 The compound 1 in the present invention is obtained by reacting a polyfluoroalkyl group (hereinafter referred to as Rf group) -containing compound 1a and an aminosilane compound 1b. As compound 1a, polyfluoroalkyl carboxylic acid, polyfluoroalkyl carboxylic acid ester, polyfluoroalkyl carboxylic acid fluoride and the like are preferable, and polyfluoroalkyl carboxylic acid ester is more preferable. The compound 1b is preferably a compound having 1 to 3 amino groups and 2 to 3 hydrolyzable reactive groups in the molecule.
化合物２は、Ｒｆ基含有化合物２ａとアミノシラン化合物２ｂとを反応させて得られる。化合物２ａとしては、ポリフルオロアルキルスルホン酸、ポリフルオロアルキルスルホン酸エステル、ポリフルオロアルキルスルホン酸フルオリド等が好ましく、ポリフルオロアルキルスルホン酸エステルがより好ましい。化合物２ｂとしては、上記化合物１ｂと同様の化合物が好ましい。 Compound 2 is obtained by reacting Rf group-containing compound 2a with aminosilane compound 2b. As the compound 2a, polyfluoroalkylsulfonic acid, polyfluoroalkylsulfonic acid ester, polyfluoroalkylsulfonic acid fluoride and the like are preferable, and polyfluoroalkylsulfonic acid ester is more preferable. Compound 2b is preferably the same compound as Compound 1b.
化合物１ａ、化合物２ａにおけるＲｆ基の構造は特に制限されず、ＲｆとしてはＦ（ＣＦ２）ａ−Ｄ−（ただし、Ｄは単結合、炭素原子数１〜４の２価有機基、または、窒素原子および／または酸素原子を含む炭素原子数１〜４の２価有機基。ａは３〜１７の整数を示す。）が好ましい。上記Ｒｆの炭素原子数であるａは、４〜８がより好ましい。Ｒｆ基は、直鎖構造でも分岐構造でもよい。また、Ｒｆ基は酸素原子を含んでいてもよい。 The structure of the R f group in Compound 1a and Compound 2a is not particularly limited, and R f is F (CF 2 ) a -D- (where D is a single bond, a divalent organic group having 1 to 4 carbon atoms, Or a divalent organic group having 1 to 4 carbon atoms containing a nitrogen atom and / or an oxygen atom, and a is an integer of 3 to 17). As for a which is the number of carbon atoms of said Rf , 4-8 are more preferable. The R f group may have a linear structure or a branched structure. In addition, the R f group may contain an oxygen atom.
化合物１ａの具体例を以下に挙げるが、これらに限定されない。
Ｃ８Ｆ１７ＣＯ２Ｈ、Ｃ７Ｆ１５ＣＯ２Ｈ、Ｃ６Ｆ１３ＣＯ２Ｈ、Ｃ５Ｆ１１ＣＯ２Ｈ、Ｃ４Ｆ９ＣＯ２Ｈ、Ｃ８Ｆ１７ＣＯ２ＣＨ３、Ｃ７Ｆ１５ＣＯ２ＣＨ３、Ｃ６Ｆ１３ＣＯ２ＣＨ３、Ｃ５Ｆ１１ＣＯ２ＣＨ３、Ｃ４Ｆ９ＣＯ２ＣＨ３、Ｃ８Ｆ１７ＣＯＦ、Ｃ７Ｆ１５ＣＯＦ、Ｃ６Ｆ１３ＣＯＦ、Ｃ５Ｆ１１ＣＯＦ、Ｃ４Ｆ９ＣＯＦ、Ｃ４Ｆ９ＯＣ２Ｆ４ＯＣＦ２ＣＯ２Ｈ、Ｃ４Ｆ９ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣＦ２ＣＯ２Ｈ、Ｃ２Ｆ５ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣＦ２ＣＯ２Ｈ、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］２Ｃ２Ｆ４ＣＯ２Ｈ、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］Ｃ２Ｆ４Ｃ２Ｈ４ＯＣＨ２ＣＯ２Ｈ、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］６Ｃ２Ｆ４Ｃ２Ｈ４ＣＯ２Ｈ、Ｃ４Ｆ９ＯＣ２Ｆ４ＯＣＦ２ＣＯ２ＣＨ３、Ｃ４Ｆ９ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣＦ２ＣＯ２ＣＨ３、Ｃ２Ｆ５ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣＦ２ＣＯ２ＣＨ３、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］２Ｃ２Ｆ４ＣＯ２ＣＨ３、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］６Ｃ２Ｆ４Ｃ２Ｈ４ＣＯ２ＣＨ３、Ｃ４Ｆ９ＯＣ２Ｆ４ＯＣＦ２ＣＯＦ、Ｃ４Ｆ９ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣＦ２ＣＯＦ、Ｃ２Ｆ５ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣＦ２ＣＯＦ、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］２Ｃ２Ｆ４ＣＯＦ、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］６Ｃ２Ｆ４Ｃ２Ｈ４ＣＯＦ。
Specific examples of compound 1a are listed below, but are not limited thereto.
C 8 F 17 CO 2 H, C 7 F 15 CO 2 H, C 6 F 13 CO 2 H, C 5 F 11 CO 2 H, C 4 F 9 CO 2 H, C 8 F 17 CO 2 CH 3, C 7 F 15 CO 2 CH 3 , C 6 F 13 CO 2 CH 3 , C 5 F 11 CO 2 CH 3 , C 4 F 9 CO 2 CH 3 , C 8 F 17 COF, C 7 F 15 COF, C 6 F 13 COF, C 5 F 11 COF, C 4 F 9 COF, C 4 F 9 OC 2 F 4 OCF 2 CO 2 H, C 4 F 9 OC 2 F 4 OC 2 F 4 OCF 2 CO 2 H, C 2 F 5 OC 2 F 4 OC 2 F 4 OCF 2 CO 2 H, F [CF (CF 3) CF 2 O] 2 C 2 F 4 CO 2 H, F [CF (CF 3) CF 2 O] C 2 F 4 C 2 H 4 OCH 2 CO 2 H, F [CF (CF 3 ) CF 2 O] 6 C 2 F 4 C 2 H 4 CO 2 H, C 4 F 9 OC 2 F 4 OCF 2 CO 2 CH 3, C 4 F 9 OC 2 F 4 OC 2 F 4 OCF 2 CO 2 CH 3, C 2 F 5 OC 2 F 4 OC 2 F 4 OCF 2 CO 2 CH 3, F [CF (CF 3) CF 2 O] 2 C 2 F 4 CO 2 CH 3, F [CF (CF 3) CF 2 O] 6 C 2 F 4 C 2 H 4 CO 2 CH 3, C 4 F 9 OC 2 F 4 OCF 2 COF, C 4 F 9 OC 2 F 4 OC 2 F 4 OCF 2 COF, C 2 F 5 OC 2 F 4 OC 2 F 4 OCF 2 COF, F [CF (CF 3) CF 2 O] 2 C 2 F 4 COF, F [CF (CF 3) CF 2 O] 6 C 2 F 4 C 2 H 4 COF .
化合物２ａの具体例を以下に挙げるが、これらに限定されない。
Ｃ８Ｆ１７ＳＯ３Ｈ、Ｃ７Ｆ１５ＳＯ３Ｈ、Ｃ６Ｆ１３ＳＯ３Ｈ、Ｃ５Ｆ１１ＳＯ３Ｈ、Ｃ４Ｆ９ＳＯ３Ｈ、Ｃ８Ｆ１７ＳＯ３ＣＨ３、Ｃ７Ｆ１５ＳＯ３ＣＨ３、Ｃ６Ｆ１３ＳＯ３ＣＨ３、Ｃ５Ｆ１１ＳＯ３ＣＨ３、Ｃ４Ｆ９ＳＯ３ＣＨ３、Ｃ８Ｆ１７ＳＯ３Ｆ、Ｃ７Ｆ１５ＳＯ３Ｆ、Ｃ６Ｆ１３ＳＯ３Ｆ、Ｃ５Ｆ１１ＳＯ３Ｆ、Ｃ４Ｆ９ＳＯ３Ｆ、Ｃ４Ｆ９ＯＣ２Ｆ４ＯＣＦ２ＳＯ３Ｈ、Ｃ４Ｆ９ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣＦ２ＳＯ３Ｈ、Ｃ２Ｆ５ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣＦ２ＳＯ３Ｈ、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］２Ｃ２Ｆ４ＳＯ３Ｈ、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］Ｃ２Ｆ４Ｃ２Ｈ４ＯＣＨ２ＳＯ３Ｈ、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］６Ｃ２Ｆ４Ｃ２Ｈ４ＳＯ３Ｈ、Ｃ４Ｆ９ＯＣ２Ｆ４ＯＣＦ２ＳＯ３ＣＨ３、Ｃ４Ｆ９ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣＦ２ＳＯ３ＣＨ３、Ｃ２Ｆ５ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣＦ２ＳＯ３ＣＨ３、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］２Ｃ２Ｆ４ＳＯ３ＣＨ３、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］Ｃ２Ｆ４Ｃ２Ｈ４ＯＣＨ２ＳＯ３ＣＨ３、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］６Ｃ２Ｆ４Ｃ２Ｈ４ＳＯ３ＣＨ３、Ｃ４Ｆ９ＯＣ２Ｆ４ＯＣＦ２ＳＯ３Ｆ、Ｃ４Ｆ９ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣＦ２ＳＯ３Ｆ、Ｃ２Ｆ５ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣＦ２ＳＯ３Ｆ、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］２Ｃ２Ｆ４ＳＯ３Ｆ、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］Ｃ２Ｆ４Ｃ２Ｈ４ＯＣＨ２ＳＯ３Ｆ、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］６Ｃ２Ｆ４Ｃ２Ｈ４ＳＯ３Ｆ。
Specific examples of compound 2a are shown below, but are not limited thereto.
C 8 F 17 SO 3 H, C 7 F 15 SO 3 H, C 6 F 13 SO 3 H, C 5 F 11 SO 3 H, C 4 F 9 SO 3 H, C 8 F 17 SO 3 CH 3, C 7 F 15 SO 3 CH 3, C 6 F 13 SO 3 CH 3, C 5 F 11 SO 3 CH 3, C 4 F 9 SO 3 CH 3, C 8 F 17 SO 3 F, C 7 F 15 SO 3 F , C 6 F 13 SO 3 F , C 5 F 11 SO 3 F, C 4 F 9 SO 3 F, C 4 F 9 OC 2 F 4 OCF 2 SO 3 H, C 4 F 9 OC 2 F 4 OC 2 F 4 OCF 2 SO 3 H, C 2 F 5 OC 2 F 4 OC 2 F 4 OCF 2 SO 3 H, F [CF (CF 3) CF 2 O] 2 C 2 F 4 SO 3 H, F [CF (CF 3) CF 2 O] C 2 F 4 C 2 H 4 OCH 2 SO 3 H, F [CF (CF 3) CF 2 O] 6 C 2 F 4 C 2 H 4 SO 3 H, C 4 F 9 OC 2 F 4 OCF 2 SO 3 CH 3, C 4 F 9 OC 2 F 4 OC 2 F 4 OCF 2 SO 3 CH 3, C 2 F 5 OC 2 F 4 OC 2 F 4 OCF 2 SO 3 CH 3, F [CF (CF 3) CF 2 O] 2 C 2 F 4 SO 3 CH 3, F [ CF (CF 3) CF 2 O ] C 2 F 4 C 2 H 4 OCH 2 SO 3 CH 3, F [CF (CF 3) CF 2 O] 6 C 2 F 4 C 2 H 4 SO 3 CH 3, C 4 F 9 OC 2 F 4 OCF 2 SO 3 F, C 4 F 9 OC 2 F 4 OC 2 F 4 OCF 2 SO 3 F, C 2 F 5 OC 2 F 4 OC 2 F 4 OCF 2 SO 3 F, F [CF (CF 3 ) CF 2 O] 2 C 2 F 4 SO 3 F, F [CF (CF 3) CF 2 O] C 2 F 4 C 2 H 4 OCH 2 SO 3 F, F [CF (CF 3) CF 2 O] 6 C 2 F 4 C 2 H 4 SO 3 F.
化合物１ｂ、２ｂの具体例を以下に挙げるが、これらに限定されない。
ＮＨ２Ｃ３Ｈ６Ｓｉ（ＯＣＨ３）３、ＮＨ２Ｃ３Ｈ６Ｓｉ（ＣＨ３）（ＯＣＨ３）２、ＮＨ２Ｃ２Ｈ４ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、ＮＨ２Ｃ２Ｈ４ＮＨＣ３Ｈ６Ｓｉ（ＣＨ３）（ＯＣＨ３）２、（Ｃ６Ｈ５）ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、ＣＨ３Ｃ３Ｈ６ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、（ＣＨ３Ｏ）３ＳｉＣ３Ｈ６ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、ＮＨ２Ｃ３Ｈ６ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、ＮＨ２ＣＨ２Ｃ６Ｈ４ＣＨ２ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ６Ｈ５ＣＨ２ＮＨＣ２Ｈ４ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、ＮＨ２Ｃ２Ｈ４ＮＨＣ２Ｈ４ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３。
Specific examples of the compounds 1b and 2b are shown below, but are not limited thereto.
NH 2 C 3 H 6 Si ( OCH 3) 3, NH 2 C 3 H 6 Si (CH 3) (OCH 3) 2, NH 2 C 2 H 4 NHC 3 H 6 Si (OCH 3) 3, NH 2 C 2 H 4 NHC 3 H 6 Si (CH 3) (OCH 3) 2, (C 6 H 5) NHC 3 H 6 Si (OCH 3) 3, CH 3 C 3 H 6 NHC 3 H 6 Si (OCH 3) 3 , (CH 3 O) 3 SiC 3 H 6 NHC 3 H 6 Si (OCH 3 ) 3 , NH 2 C 3 H 6 NHC 3 H 6 Si (OCH 3 ) 3 , NH 2 CH 2 C 6 H 4 CH 2 NHC 3 H 6 Si (OCH 3 ) 3 , C 6 H 5 CH 2 NHC 2 H 4 NHC 3 H 6 Si (OCH 3 ) 3 , NH 2 C 2 H 4 NHC 2 H 4 NHC 3 H 6 Si (OCH 3 3 )
本発明における化合物１の具体例を以下に挙げるが、これらに限定されない。
Ｃ８Ｆ１７ＣＯＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ７Ｆ１５ＣＯＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ６Ｆ１３ＣＯＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ５Ｆ１１ＣＯＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ４Ｆ９ＣＯＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ８Ｆ１７ＣＯＮ（ＣＨ３）Ｃ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ７Ｆ１５ＣＯＮ（ＣＨ３）Ｃ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ６Ｆ１３ＣＯＮ（ＣＨ３）Ｃ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ５Ｆ１１ＣＯＮ（ＣＨ３）Ｃ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ４Ｆ９ＣＯＮ（ＣＨ３）Ｃ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ８Ｆ１７ＣＯＮＨＣ２Ｈ４Ｓｉ（ＯＣＨ３）３、Ｃ７Ｆ１５ＣＯＮＨＣ２Ｈ４Ｓｉ（ＯＣＨ３）３、Ｃ６Ｆ１３ＣＯＮＨＣ２Ｈ４Ｓｉ（ＯＣＨ３）３、Ｃ５Ｆ１１ＣＯＮＨＣ２Ｈ４Ｓｉ（ＯＣＨ３）３、Ｃ４Ｆ９ＣＯＮＨＣ２Ｈ４Ｓｉ（ＯＣＨ３）３、Ｃ８Ｆ１７ＣＯＮＨＣ２Ｈ４ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ８Ｆ１７ＣＯＮＨＣ２Ｈ４ＮＨＣ３Ｈ６Ｓｉ（ＣＨ３）（ＯＣＨ３）２、Ｃ７Ｆ１５ＣＯＮＨＣ２Ｈ４ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ７Ｆ１５ＣＯＮＨＣ２Ｈ４ＮＨＣ３Ｈ６Ｓｉ（ＣＨ３）（ＯＣＨ３）２、Ｃ６Ｆ１３ＣＯＮＨＣ２Ｈ４ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ６Ｆ１３ＣＯＮＨＣ２Ｈ４ＮＨＣ３Ｈ６Ｓｉ（ＣＨ３）（ＯＣＨ３）２、Ｃ５Ｆ１１ＣＯＮＨＣ２Ｈ４ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ５Ｆ１１ＣＯＮＨＣ２Ｈ４ＮＨＣ３Ｈ６Ｓｉ（ＣＨ３）（ＯＣＨ３）２、Ｃ４Ｆ９ＣＯＮＨＣ２Ｈ４ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ４Ｆ９ＣＯＮＨＣ２Ｈ４ＮＨＣ３Ｈ６Ｓｉ（ＣＨ３）（ＯＣＨ３）２、Ｃ４Ｆ９ＯＣ２Ｆ４ＯＣＦ２ＣＯＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ４Ｆ９ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣＦ２ＣＯＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ２Ｆ５ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣＦ２ＣＯＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］２Ｃ２Ｆ４ＣＯＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｆ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］６Ｃ２Ｆ４Ｃ２Ｈ４ＣＯＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３。
Although the specific example of the compound 1 in this invention is given below, it is not limited to these.
C 8 F 17 CONHC 3 H 6 Si (OCH 3) 3, C 7 F 15 CONHC 3 H 6 Si (OCH 3) 3, C 6 F 13 CONHC 3 H 6 Si (OCH 3) 3, C 5 F 11 CONHC 3 H 6 Si (OCH 3) 3, C 4 F 9 CONHC 3 H 6 Si (OCH 3) 3, C 8 F 17 CON (CH 3) C 3 H 6 Si (OCH 3) 3, C 7 F 15 CON (CH 3 ) C 3 H 6 Si (OCH 3 ) 3 , C 6 F 13 CON (CH 3 ) C 3 H 6 Si (OCH 3 ) 3 , C 5 F 11 CON (CH 3 ) C 3 H 6 Si ( OCH 3) 3, C 4 F 9 CON (CH 3) C 3 H 6 Si (OCH 3) 3, C 8 F 17 CONHC 2 H 4 Si (OCH 3) 3, C 7 F 15 CONHC 2 H Si (OCH 3) 3, C 6 F 13 CONHC 2 H 4 Si (OCH 3) 3, C 5 F 11 CONHC 2 H 4 Si (OCH 3) 3, C 4 F 9 CONHC 2 H 4 Si (OCH 3) 3, C 8 F 17 CONHC 2 H 4 NHC 3 H 6 Si (OCH 3) 3, C 8 F 17 CONHC 2 H 4 NHC 3 H 6 Si (CH 3) (OCH 3) 2, C 7 F 15 CONHC 2 H 4 NHC 3 H 6 Si ( OCH 3) 3, C 7 F 15 CONHC 2 H 4 NHC 3 H 6 Si (CH 3) (OCH 3) 2, C 6 F 13 CONHC 2 H 4 NHC 3 H 6 Si ( OCH 3) 3, C 6 F 13 CONHC 2 H 4 NHC 3 H 6 Si (CH 3) (OCH 3) 2, C 5 F 11 CONHC 2 H 4 NH 3 H 6 Si (OCH 3) 3, C 5 F 11 CONHC 2 H 4 NHC 3 H 6 Si (CH 3) (OCH 3) 2, C 4 F 9 CONHC 2 H 4 NHC 3 H 6 Si (OCH 3) 3, C 4 F 9 CONHC 2 H 4 NHC 3 H 6 Si (CH 3) (OCH 3) 2, C 4 F 9 OC 2 F 4 OCF 2 CONHC 3 H 6 Si (OCH 3) 3, C 4 F 9 OC 2 F 4 OC 2 F 4 OCF 2 CONHC 3 H 6 Si (OCH 3) 3, C 2 F 5 OC 2 F 4 OC 2 F 4 OCF 2 CONHC 3 H 6 Si (OCH 3) 3, F [CF ( CF 3) CF 2 O] 2 C 2 F 4 CONHC 3 H 6 Si (OCH 3) 3, F [CF (CF 3) CF 2 O] 6 C 2 F 4 C 2 H 4 CONHC 3 H 6 S (OCH 3) 3.
本発明における化合物２の具体例を以下に挙げるが、これらに限定されない。
Ｃ８Ｆ１７ＳＯ２ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ７Ｆ１５ＳＯ２ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ６Ｆ１３ＳＯ２ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ５Ｆ１１ＳＯ２ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ４Ｆ９ＳＯ２ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ８Ｆ１７ＳＯ２Ｎ（ＣＨ３）Ｃ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ７Ｆ１５ＳＯ２Ｎ（ＣＨ３）Ｃ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ６Ｆ１３ＳＯ２Ｎ（ＣＨ３）Ｃ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ５Ｆ１１ＳＯ２Ｎ（ＣＨ３）Ｃ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ４Ｆ９ＳＯ２Ｎ（ＣＨ３）Ｃ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ８Ｆ１７ＳＯ２ＮＨＣ２Ｈ４Ｓｉ（ＯＣＨ３）３、Ｃ７Ｆ１５ＳＯ２ＮＨＣ２Ｈ４Ｓｉ（ＯＣＨ３）３、Ｃ６Ｆ１３ＳＯ２ＮＨＣ２Ｈ４Ｓｉ（ＯＣＨ３）３、Ｃ５Ｆ１１ＳＯ２ＮＨＣ２Ｈ４Ｓｉ（ＯＣＨ３）３、Ｃ４Ｆ９ＳＯ２ＮＨＣ２Ｈ４Ｓｉ（ＯＣＨ３）３、Ｃ７Ｆ１５ＳＯ２Ｎ（Ｃ２Ｈ５）Ｃ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ７Ｆ１５ＳＯ２Ｎ（Ｃ３Ｈ７）Ｃ３Ｈ６Ｓｉ（ＯＣＨ３）３、Ｃ７Ｆ１５ＳＯ２Ｎ（Ｃ３Ｈ７）Ｃ３Ｈ６Ｓｉ（ＯＣＨ３）３。
Although the specific example of the compound 2 in this invention is given below, it is not limited to these.
C 8 F 17 SO 2 NHC 3 H 6 Si (OCH 3) 3, C 7 F 15 SO 2 NHC 3 H 6 Si (OCH 3) 3, C 6 F 13 SO 2 NHC 3 H 6 Si (OCH 3) 3 , C 5 F 11 SO 2 NHC 3 H 6 Si (OCH 3) 3, C 4 F 9 SO 2 NHC 3 H 6 Si (OCH 3) 3, C 8 F 17 SO 2 N (CH 3) C 3 H 6 Si (OCH 3 ) 3 , C 7 F 15 SO 2 N (CH 3 ) C 3 H 6 Si (OCH 3 ) 3 , C 6 F 13 SO 2 N (CH 3 ) C 3 H 6 Si (OCH 3 ) 3 , C 5 F 11 SO 2 N (CH 3) C 3 H 6 Si (OCH 3) 3, C 4 F 9 SO 2 N (CH 3) C 3 H 6 Si (OCH 3) 3, C 8 F 17 SO 2 NHC 2 H 4 Si (OCH 3 3, C 7 F 15 SO 2 NHC 2 H 4 Si (OCH 3) 3, C 6 F 13 SO 2 NHC 2 H 4 Si (OCH 3) 3, C 5 F 11 SO 2 NHC 2 H 4 Si (OCH 3 ) 3, C 4 F 9 SO 2 NHC 2 H 4 Si (OCH 3) 3, C 7 F 15 SO 2 N (C 2 H 5) C 3 H 6 Si (OCH 3) 3, C 7 F 15 SO 2 N (C 3 H 7) C 3 H 6 Si (OCH 3) 3, C 7 F 15 SO 2 N (C 3 H 7) C 3 H 6 Si (OCH 3) 3.
本発明における化合物３の具体例を以下に挙げるが、これらに限定されない。
テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン、メチルトリメトキシシラン、エチルトリメトキシシラン、フェニルトリメトキシシラン、ジメチルジメトキシシラン、ジエチルジメトキシシラン、ジフェニルジメトキシシラン、フェニルメチルジメトキシシラン、エチルメチルジメトキシシラン、エチルフェニルジメトキシシラン等。
Although the specific example of the compound 3 in this invention is given below, it is not limited to these.
Tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, ethylmethyl Dimethoxysilane, ethylphenyldimethoxysilane and the like.
部分共加水分解時の化合物１〜３の混合割合は、（化合物１および／または化合物２の合計）／化合物３の質量比として２／１００〜１００／１００であり、２／１００〜５０／１００が好ましく、２／１００〜３０／１００がより好ましい。該範囲であると、撥水層は、最表層に配向するＲｆ基が充分であり、撥水性に優れ、撥水層の内部のＲｆ基の割合が適度であり、撥水層の硬度が充分であり、耐久性に優れ、耐摩耗性に優れる。 The mixing ratio of compounds 1 to 3 at the time of partial cohydrolysis is 2/100 to 100/100 as a mass ratio of (compound 1 and / or compound 2) / compound 3, and 2/100 to 50/100. Is preferable, and 2/100 to 30/100 is more preferable. Within this range, the water repellent layer has sufficient R f groups oriented in the outermost layer, is excellent in water repellency, has an appropriate ratio of R f groups inside the water repellent layer, and has a hardness of the water repellent layer. Is sufficient, and has excellent durability and wear resistance.
また、化合物１と化合物２とを合わせて用いる場合、その混合割合は、化合物２／化合物１の質量比として、５／１０〜１０／１０が好ましい。該範囲であると、水滴滑落性に優れる。 Moreover, when using the compound 1 and the compound 2 together, the mixing ratio is preferably 5/10 to 10/10 as the mass ratio of the compound 2 / compound 1. Within this range, the water droplet sliding property is excellent.
本発明の撥水性組成物から形成された撥水層をＸ線光電子分光装置を用いて測定した結果（図１）、撥水層中のフッ素原子濃度が、撥水層の表面近くで高く、基材方向に向かって低くなる濃度分布を有することがわかった。
本発明における部分共加水分解体は、分子量が５００〜２０，０００であるのが好ましく、１，０００〜１５，０００がより好ましく、２，０００〜１０，０００が最も好ましい。
As a result of measuring the water repellent layer formed from the water repellent composition of the present invention using an X-ray photoelectron spectrometer (FIG. 1), the fluorine atom concentration in the water repellent layer is high near the surface of the water repellent layer, It was found to have a concentration distribution that decreases toward the substrate.
The partial cohydrolyzate in the present invention preferably has a molecular weight of 500 to 20,000, more preferably 1,000 to 15,000, and most preferably 2,000 to 10,000.
本発明における部分共加水分解体は、化合物１および／または化合物２と、化合物３とを、酸性触媒または塩基性触媒、水、溶媒の存在下、加水分解反応することにより製造できる。 The partial cohydrolyzate in the present invention can be produced by subjecting Compound 1 and / or Compound 2 and Compound 3 to a hydrolysis reaction in the presence of an acidic catalyst or a basic catalyst, water, and a solvent.
前記溶剤は、化合物１、化合物２、化合物３を溶解する化合物であれば特に限定されない。たとえば、アルコール類、ケトン類、芳香族炭化水素類、パラフィン系炭化水素類、酢酸エステル類等が好ましく、アルコール類または酢酸エステル類がより好ましく、炭素原子数１〜６のアルコールが最も好ましい。具体的には、イソプロピルアルコール（以下、ＩＰＡと記す。）が最も好ましい。溶剤は１種を使用してもよく、極性、蒸発速度等の異なる２種以上の溶剤を併用してもよい。
通常、仕込んだ原料は全て反応して部分共加水分解体が生成する。
The solvent is not particularly limited as long as it is a compound that dissolves Compound 1, Compound 2, and Compound 3. For example, alcohols, ketones, aromatic hydrocarbons, paraffin hydrocarbons, acetate esters and the like are preferable, alcohols or acetate esters are more preferable, and alcohols having 1 to 6 carbon atoms are most preferable. Specifically, isopropyl alcohol (hereinafter referred to as IPA) is most preferable. One type of solvent may be used, or two or more types of solvents having different polarities and evaporation rates may be used in combination.
Usually, all the charged raw materials react to produce a partial cohydrolyzate.
前記酸性触媒としては、塩酸、硝酸、酢酸、クエン酸、硫酸、燐酸、スルホン酸、メタンスルホン酸、ｐ−トルエンスルホン酸等が好ましく、最適な分子量に制御しやすく、揮発しやすいという点で、塩酸がより好ましい。また、前記塩基性触媒としては、アンモニア水が好ましい。触媒としては、塩酸が最も好ましい。 As the acidic catalyst, hydrochloric acid, nitric acid, acetic acid, citric acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, p-toluenesulfonic acid and the like are preferable, in that they can be easily controlled to an optimal molecular weight and easily volatilize. Hydrochloric acid is more preferred. The basic catalyst is preferably ammonia water. As the catalyst, hydrochloric acid is most preferred.
前記溶剤の割合は、化合物１および／または化合物２と化合物３との合計の１００質量部に対して、１，０００〜４，０００質量部が好ましく、１，０００〜２，０００質量部がより好ましい。該範囲であると、化合物１および／または化合物２と化合物３とが相分離せず、各成分単独の加水分解体が生成しにくく、均質な部分共加水分解体が生成しやすい。そのため、水滴滑落性、耐久性が充分に発現できる。また、重合度の制御が容易で、粘度制御が容易であり、撥水性組成物を塗布する際の作業性に優れる。 The proportion of the solvent is preferably 1,000 to 4,000 parts by mass, more preferably 1,000 to 2,000 parts by mass with respect to 100 parts by mass of the total of compound 1 and / or compound 2 and compound 3. preferable. Within this range, Compound 1 and / or Compound 2 and Compound 3 do not phase separate, making it difficult to produce a hydrolyzate of each component alone and to form a homogeneous partial cohydrolyzate. For this reason, water drop sliding properties and durability can be sufficiently exhibited. In addition, the degree of polymerization is easily controlled, the viscosity is easily controlled, and the workability when applying the water-repellent composition is excellent.
本発明における部分共加水分解体には、ジルコニウム、アルミニウム、チタニウム、セリウム等の塩化物、アルコキシド、アセチルアセトナート、酸化物等の添加物を添加してもよい。該添加物の添加量は、化合物１および／または化合物２と化合物３の合量の１００質量部に対して、０．０１〜２０質量部が好ましい。該範囲であると、撥水層の架橋密度が高く、水滴滑落性、耐久性に優れる。 You may add additives, such as chlorides, such as zirconium, aluminum, titanium, and cerium, an alkoxide, acetylacetonate, and an oxide, to the partial cohydrolyzate in this invention. The addition amount of the additive is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of Compound 1 and / or Compound 2 and Compound 3. Within such a range, the water repellent layer has a high crosslink density and is excellent in water drop sliding properties and durability.
本発明の撥水性組成物には、部分共加水分解体のほかに、原料化合物１〜３の混合物、水、酸性触媒または塩基性触媒、アルコール類等の溶剤を含むことが好ましい。 In addition to the partial cohydrolyzate, the water-repellent composition of the present invention preferably contains a mixture of raw material compounds 1 to 3, a solvent such as water, an acidic catalyst or a basic catalyst, and alcohols.
本発明の撥水性組成物には、目的に応じて界面活性剤、化合物１、化合物２以外のＲｆ基含有化合物、ポリジメチルシロキサン、色素等の着色用材料、各種樹脂等を含んでもよい。該含有量は、化合物１および／または化合物２と化合物３の合量の１００質量部に対して、０．０１〜２０質量部が好ましい。該範囲であると、水滴滑落性、耐久性に優れる。 The water-repellent composition of the present invention may contain a surfactant, an Rf group-containing compound other than Compound 1 and Compound 2, a coloring material such as polydimethylsiloxane and a dye, various resins, and the like. The content is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of Compound 1 and / or Compound 2 and Compound 3. Within this range, the water droplet sliding property and durability are excellent.
撥水性組成物における溶媒は、加水分解反応において用いた溶媒と同様の溶媒を用いることが好ましく、溶媒の含有量は、部分共加水分解体の１００質量部に対して１，０００〜５０，０００質量部が好ましく、１，０００〜２０，０００質量部がより好ましい。 The solvent in the water-repellent composition is preferably a solvent similar to the solvent used in the hydrolysis reaction, and the solvent content is 1,000 to 50,000 with respect to 100 parts by mass of the partially co-hydrolyzed product. Mass parts are preferable, and 1,000 to 20,000 parts by mass are more preferable.
撥水性組成物における水の含有量は、部分共加水分解体の１００質量部に対して３〜２０質量部が好ましく、３〜１０質量部がより好ましい。また、撥水性組成物に酸性触媒または塩基性触媒を含む場合の酸性触媒または塩基性触媒の含有量は、部分共加水分解体の１００質量部に対して１〜１０質量部が好ましく、２〜５質量部がより好ましい。 3-20 mass parts is preferable with respect to 100 mass parts of a partial cohydrolyzate, and, as for content of water in a water repellent composition, 3-10 mass parts is more preferable. In addition, when the water-repellent composition contains an acidic catalyst or a basic catalyst, the content of the acidic catalyst or the basic catalyst is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the partial cohydrolyzate, 5 parts by mass is more preferable.
また、撥水性組成物に界面活性剤を添加する場合の界面活性剤の添加量は、部分共加水分解体の１００質量部に対して０．１〜５質量部が好ましく、色素を添加する場合の色素の添加量は、部分共加水分解体の１００質量部に対して１〜１０質量部が好ましい。 In addition, when the surfactant is added to the water-repellent composition, the addition amount of the surfactant is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the partial cohydrolyzate, and the pigment is added. The added amount of the dye is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the partial cohydrolyzate.
前記、化合物１、化合物２以外のＲｆ基含有化合物の具体例としては以下の化合物が挙げられる。ただし、下式中のｎは１〜１０の整数を示す。
（ＣＨ３Ｏ）３ＳｉＣ２Ｈ４（ＣＦ２）ｎＣ２Ｈ４Ｓｉ（ＯＣＨ３）３、（ＣＨ３Ｏ）２（ＣＨ３）ＳｉＣ２Ｈ４（ＣＦ２）ｎＣ２Ｈ４Ｓｉ（ＣＨ３）（ＯＣＨ３）２、（ＣＨ３Ｏ）２（Ｒｆ）ＳｉＣ２Ｈ４（ＣＦ２）ｎＣ２Ｈ４Ｓｉ（Ｒｆ）（ＯＣＨ３）２、（ＣＨ３Ｏ）３ＳｉＣ２Ｈ４ＣＦ（ＣＦ３）ＣＦ２Ｏ（ＣＦ２）ｎＯＣＦ２ＣＦ（ＣＦ３）Ｃ２Ｈ４Ｓｉ（ＯＣＨ３）３、（ＣＨ３Ｏ）２（ＣＨ３）ＳｉＣ２Ｈ４ＣＦ（ＣＦ３）ＣＦ２Ｏ（ＣＦ２）ｎＯＣＦ２ＣＦ（ＣＦ３）Ｃ２Ｈ４Ｓｉ（ＣＨ３）（ＯＣＨ３）２、（ＣＨ３Ｏ）２（Ｒｆ）ＳｉＣ２Ｈ４ＣＦ（ＣＦ３）ＣＦ２Ｏ（ＣＦ２）ｎＯＣＦ２ＣＦ（ＣＦ３）Ｃ２Ｈ４Ｓｉ（Ｒｆ）（ＯＣＨ３）２、（ＣＨ３Ｏ）３ＳｉＣ２Ｈ４ＣＦ（ＣＦ３）（ＣＦ２）ｎＣＦ（ＣＦ３）Ｃ２Ｈ４Ｓｉ（ＯＣＨ３）３、（ＣＨ３Ｏ）２（ＣＨ３）ＳｉＣ２Ｈ４ＣＦ（ＣＦ３）（ＣＦ２）ｎＣＦ（ＣＦ３）Ｃ２Ｈ４Ｓｉ（ＣＨ３）（ＯＣＨ３）２、（ＣＨ３Ｏ）２（Ｒｆ）ＳｉＣ２Ｈ４ＣＦ（ＣＦ３）（ＣＦ２）ｎＣＦ（ＣＦ３）Ｃ２Ｈ４Ｓｉ（Ｒｆ）（ＯＣＨ３）２。
Specific examples of the R f group-containing compound other than the compounds 1 and 2 include the following compounds. However, n in the following formula represents an integer of 1 to 10.
(CH 3 O) 3 SiC 2 H 4 (CF 2 ) n C 2 H 4 Si (OCH 3 ) 3 , (CH 3 O) 2 (CH 3 ) SiC 2 H 4 (CF 2 ) n C 2 H 4 Si (CH 3 ) (OCH 3 ) 2 , (CH 3 O) 2 (R f ) SiC 2 H 4 (CF 2 ) n C 2 H 4 Si (R f ) (OCH 3 ) 2 , (CH 3 O) 3 SiC 2 H 4 CF (CF 3 ) CF 2 O (CF 2) n OCF 2 CF (CF 3) C 2 H 4 Si (OCH 3) 3, (CH 3 O) 2 (CH 3) SiC 2 H 4 CF (CF 3) CF 2 O ( CF 2) n OCF 2 CF (CF 3) C 2 H 4 Si (CH 3) (OCH 3) 2, (CH 3 O) 2 (R f) SiC 2 H 4 CF ( CF 3) CF 2 O (CF 2) n OCF 2 CF (CF 3) C 2 H 4 Si (R f) (OCH 3) 2, (CH 3 O) 3 SiC 2 H 4 CF (CF 3) (CF 2) n CF (CF 3) C 2 H 4 Si (OCH 3) 3, (CH 3 O) 2 (CH 3) SiC 2 H 4 CF (CF 3) (CF 2) n CF (CF 3) C 2 H 4 Si (CH 3) (OCH 3) 2, (CH 3 O) 2 (R f) SiC 2 H 4 CF (CF 3) (CF 2) n CF (CF 3) C 2 H 4 Si (R f) (OCH 3) 2.
本発明の撥水性組成物は公知の方法で基材に塗布できる。たとえば、はけ塗り、流し塗り、回転塗布、浸漬塗布、スキージ塗布、スプレー塗布等の方法を用いることができる。そして、塗布後に、大気中または窒素雰囲気中で乾燥させて、撥水層を形成できる。余剰の撥水性組成物は、溶剤含む布または溶剤を含まない布で拭きとる方法等で除去して、外観を調節することが好ましい。撥水層を有する基材の製造において、本発明の撥水性組成物を基材に塗布する際および塗布した後に、温度を０〜１００℃に保持することが好ましく、１０〜８０℃がより好ましく、２０〜４０℃が最も好ましい。また、相対湿度を１０〜１００％に保持することが好ましく、１０〜８０％がより好ましく、２０〜７０％がとりわけ好ましく、２５〜６０％が最も好ましい。温度、相対湿度が該範囲であると、撥水層内部および撥水層と基材との架橋反応が充分進行し、撥水層は基材との密着性に優れ、撥水層自体の硬度が充分高くなり、耐摩耗性に優れる。 The water-repellent composition of the present invention can be applied to a substrate by a known method. For example, methods such as brush coating, flow coating, spin coating, dip coating, squeegee coating, and spray coating can be used. And after application | coating, it can be made to dry in air | atmosphere or nitrogen atmosphere, and a water repellent layer can be formed. It is preferable to remove the excess water-repellent composition by wiping with a cloth containing a solvent or a cloth not containing a solvent to adjust the appearance. In the production of a substrate having a water repellent layer, the temperature is preferably maintained at 0 to 100 ° C., more preferably 10 to 80 ° C., when and after applying the water repellent composition of the present invention to the substrate. Most preferred is 20-40 ° C. The relative humidity is preferably maintained at 10 to 100%, more preferably 10 to 80%, particularly preferably 20 to 70%, and most preferably 25 to 60%. When the temperature and relative humidity are within these ranges, the crosslinking reaction between the water-repellent layer and the water-repellent layer and the substrate proceeds sufficiently, and the water-repellent layer has excellent adhesion to the substrate, and the hardness of the water-repellent layer itself. Is sufficiently high and wear resistance is excellent.
本発明の撥水性組成物を用いて基材上に形成される撥水層の厚さは、２〜１００ｎｍが好ましく、１０〜５０ｎｍがより好ましい。該範囲であると、撥水層は透明性に優れ、経済性にも優れる。 2-100 nm is preferable and, as for the thickness of the water-repellent layer formed on a base material using the water repellent composition of this invention, 10-50 nm is more preferable. Within this range, the water-repellent layer is excellent in transparency and economical.
本発明の撥水性組成物を用いて形成された撥水層表面の算術平均粗さ（Ｒａ）は、０．１〜１０ｎｍが好ましい。該範囲であると、自動車用ウィンドウとして用いた場合にワイパー摺動が円滑で、不快な摺動音を生じにくく、直径５ｍｍ以下の小さな水滴が残存しにくく視認性に優れる。 The arithmetic average roughness (R a ) of the surface of the water repellent layer formed using the water repellent composition of the present invention is preferably 0.1 to 10 nm. Within this range, when used as an automobile window, wiper sliding is smooth, uncomfortable sliding noise is less likely to occur, and small water droplets having a diameter of 5 mm or less do not remain, resulting in excellent visibility.
本発明の撥水層を有する基材において、撥水層と基材の間に下地層を有してもよいが、最外層が本発明の撥水性組成物から形成された撥水層であることが好ましい。撥水層の耐磨耗を向上させるために、下地層としてシリカ層を設けることが好ましい。 In the substrate having the water-repellent layer of the present invention, an undercoat layer may be provided between the water-repellent layer and the substrate, but the outermost layer is a water-repellent layer formed from the water-repellent composition of the present invention. It is preferable. In order to improve the abrasion resistance of the water repellent layer, it is preferable to provide a silica layer as a base layer.
撥水層と下地層とは、その境界線が厳密に分かれた状態で形成されるとは限らず、層界面の一部または全部が相互に入り交じっていてもよい。このような構成は、シリカ層と撥水層との密着性が高いため、特に耐摩耗性を向上させる効果がある。シリカ層に化合物１または化合物２等の成分に基づくＲｆ成分が含まれると、水に伴う各種劣化因子が下地層と基材との界面に浸透するのを防止する効果を有する。 The water repellent layer and the base layer are not necessarily formed with their boundary lines strictly separated, and part or all of the layer interface may be intermingled. Such a configuration is particularly effective in improving the wear resistance since the adhesion between the silica layer and the water repellent layer is high. When the Rf component based on components such as Compound 1 or Compound 2 is contained in the silica layer, it has an effect of preventing various deterioration factors accompanying water from penetrating into the interface between the underlayer and the substrate.
本発明における撥水層を有する基材の製造方法としては、以下の（１）〜（３）の工程を含む。（１）基材を洗浄および乾燥する工程、（２）化合物１および／または化合物２と化合物３との部分共加水分解体を含む撥水性組成物を基材に塗布する工程、（３）０〜室温、相対湿度１０〜８０％の条件下に該基材を保持する工程。 As a manufacturing method of the base material which has a water repellent layer in this invention, the process of the following (1)-(3) is included. (1) a step of washing and drying the substrate, (2) a step of applying a water-repellent composition containing Compound 1 and / or a partial cohydrolyzate of Compound 2 and Compound 3 to the substrate, (3) 0 -A step of holding the substrate under conditions of room temperature and relative humidity of 10 to 80%.
本発明における基材は特に限定されず、金属、プラスチック、ガラス、セラミック、またはその組み合わせ（複合材料、積層材料等）が好ましく、ガラスまたはプラスチック等の透明な基材がより好ましい。基材の形状は平板でもよく、全面または一部に曲率を有していてもよい。 The substrate in the present invention is not particularly limited, and metal, plastic, glass, ceramic, or a combination thereof (composite material, laminated material, etc.) is preferable, and a transparent substrate such as glass or plastic is more preferable. The shape of the substrate may be a flat plate or may have a curvature on the entire surface or a part thereof.
本発明の輸送機器用物品は撥水層を有する基材からなる。
本発明の撥水層を有する基材は、表面が水滴滑落性に優れる。その発現機構としては以下が考えられる。化合物１のアミド基、化合物２のスルホンアミド基は水素結合を形成し易く、最表面でＲｆ基が配向し易い。そのため、水との相互作用を引き起こすシラノール基等が最表面に存在しにくくなり、優れた水滴滑落性が発現すると考えられる。
本発明の撥水層を有する基材および輸送機器用物品は、その表面が撥水性、水滴滑落性、耐磨耗性に優れることから、水滴がすみやかにはじかれ、急速に移動する。特に、各種窓ガラス等の透視野部での用途において、低速走行時、霧雨時、多量の泥水がかかった場合に、視認性に優れ、車輌等の運行において安全性が向上する。また、本発明における撥水層の表面は撥油性にも優れ、指紋除去性に優れる。さらに、水滴が氷結するような環境下でも氷結しにくく、氷結したとしても解凍は著しく速い。さらに、汚れを含む水滴の付着がほとんどないため、清浄の作業回数を少なくでき、しかも清浄作業を容易に行うことができる。
The article for transport equipment according to the present invention comprises a substrate having a water repellent layer.
The base material having the water repellent layer of the present invention has excellent water droplet sliding properties. The expression mechanism is considered as follows. The amide group of compound 1 and the sulfonamide group of compound 2 are easy to form a hydrogen bond, and the Rf group is easily oriented on the outermost surface. Therefore, it is considered that silanol groups or the like that cause interaction with water are less likely to be present on the outermost surface, and excellent water droplet sliding properties are expressed.
Since the surface of the substrate having a water-repellent layer and the article for transportation equipment of the present invention are excellent in water repellency, water-drop sliding property, and abrasion resistance, water droplets are quickly repelled and move rapidly. In particular, when using a wide field of view such as various types of window glass, when the vehicle is traveling at a low speed, during drizzle, or when a large amount of muddy water is applied, the visibility is excellent, and the safety of driving a vehicle or the like is improved. Further, the surface of the water repellent layer in the present invention is excellent in oil repellency and excellent in fingerprint removability. Furthermore, it is difficult to freeze even in an environment where water droplets freeze, and even if it freezes, thawing is extremely fast. Further, since there is almost no adhesion of water droplets containing dirt, the number of cleaning operations can be reduced, and the cleaning operation can be easily performed.
以下に本発明を、実施例（例１〜８、１３、１４）、比較例（例９〜１２、１５〜１９）を挙げてさらに具体的に説明するが、この説明が本発明を限定するものではない。各例における各種物性の測定は以下の方法で行い、結果を表１に示した。 Hereinafter, the present invention will be described more specifically with reference to Examples (Examples 1 to 8, 13, and 14) and Comparative Examples (Examples 9 to 12, and 15 to 19). However, the description limits the present invention. It is not a thing. Various physical properties in each example were measured by the following methods, and the results are shown in Table 1.
１．基材
酸化セリウム系微粒子を含む研磨剤で研磨洗浄し、純水ですすいで風乾したソーダライムガラス板（１０ｃｍ×１０ｃｍ×厚さ３ｃｍ、Ｒａ＝０．１ｎｍ）。
1. Substrate A soda-lime glass plate (10 cm × 10 cm × thickness 3 cm, R a = 0.1 nm) that has been polished and washed with an abrasive containing cerium oxide fine particles, rinsed with pure water, and air-dried.
２．水滴滑落性
２−１．接触角
サンプル基材の表面に直径約１ｍｍの水滴を５滴置き、その接触角の測定値の平均値を示した。未処理のソーダライムガラス板の接触角は約３０°である。
2. 2. Water drop sliding property 2-1. Contact angle Five drops of water having a diameter of about 1 mm were placed on the surface of the sample substrate, and the average value of the measured values of the contact angle was shown. The contact angle of the untreated soda lime glass plate is about 30 °.
２−２．転落角
サンプル基材を水平に保持し、その表面に５０μＬの水滴を滴下した後、サンプル基材を徐々に傾け、水滴が転落しはじめた時のサンプル基材と水平面との角度（転落角）を測定した。転落角が小さいほど水滴滑落性に優れる。
2-2. Falling angle Hold the sample substrate horizontally, drop 50 μL of water droplets on the surface, then tilt the sample substrate gradually, and the angle between the sample substrate and the horizontal plane when the water droplet starts to fall (falling angle) Was measured. The smaller the falling angle, the better the water drop sliding property.
３．耐摩耗性
３−１．ケイエヌテー社往復式トラバース試験機を用いて、ネル布、荷重１ｋｇ、摩耗回数３０００往復の条件にてサンプル基材について磨耗試験を行った後、接触角および転落角を測定した。
3. 3. Abrasion resistance 3-1. Using a KT reciprocating traverse tester, a sample substrate was subjected to an abrasion test under the conditions of flannel cloth, a load of 1 kg, and a wear frequency of 3000 reciprocations, and then contact angle and sliding angle were measured.
３−２．ドア昇降試験機を用いてサンプル基材を、泥水、摩耗回数３０００回往復の条件にて摩耗試験を行った後、接触角および転落角を測定した。 3-2. The sample base material was subjected to a wear test under a reciprocating condition of 3000 times of muddy water and wear using a door elevating tester, and then the contact angle and the falling angle were measured.
４．膜厚
アルバック社製ＤＥＫＴＡＫ３０３０を用いて測定した。
4). Film thickness Measured using DEKTAK3030 manufactured by ULVAC.
５．表面平滑性
セイコー電子社製ＡＦＭ／ＳＰＩ３７００を用いコンタクトモードにて測定した。
5. Surface smoothness Measured in contact mode using AFM / SPI3700 manufactured by Seiko Denshi.
［使用化合物］
化合物１−１：Ｆ（ＣＦ２）８ＣＯＮＨ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
化合物１−２：Ｆ（ＣＦ２）７ＣＯＮＨ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
化合物１−３：Ｆ（ＣＦ２）６ＣＯＮＨ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
化合物１−４：Ｆ（ＣＦ２）５ＣＯＮＨ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
化合物１−５：Ｆ（ＣＦ２）４ＣＯＮＨ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
化合物１−６：Ｆ（ＣＦ２）３ＣＯＮＨ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
化合物１−７：Ｆ（ＣＦ２）６ＣＯＮＨ（ＣＨ２）３Ｓｉ（ＮＣＯ）３、
化合物１−８：Ｆ（ＣＦ２）６ＣＯＮＨ（ＣＨ２）３ＳｉＣｌ３、
化合物２−１：Ｆ（ＣＦ２）８ＳＯ２ＮＨ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
化合物２−２：Ｆ（ＣＦ２）６ＳＯ２ＮＨ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
化合物３−１：Ｓｉ（ＯＣ２Ｈ５）４、
化合物３−２：Ｓｉ（ＮＣＯ）４、
化合物３−３：ＳｉＣｌ４、
化合物４−１：Ｆ（ＣＦ２）８（ＣＨ２）２Ｓｉ（ＯＣＨ３）３、
化合物４−２：Ｆ（ＣＦ２）６（ＣＨ２）２Ｓｉ（ＯＣＨ３）３。
[Used compounds]
Compound 1-1: F (CF 2 ) 8 CONH (CH 2 ) 3 Si (OCH 3 ) 3 ,
Compound 1-2: F (CF 2 ) 7 CONH (CH 2 ) 3 Si (OCH 3 ) 3 ,
Compound 1-3: F (CF 2 ) 6 CONH (CH 2 ) 3 Si (OCH 3 ) 3 ,
Compound 1-4: F (CF 2 ) 5 CONH (CH 2 ) 3 Si (OCH 3 ) 3 ,
Compound 1-5: F (CF 2 ) 4 CONH (CH 2 ) 3 Si (OCH 3 ) 3 ,
Compound 1-6: F (CF 2 ) 3 CONH (CH 2 ) 3 Si (OCH 3 ) 3 ,
Compound 1-7: F (CF 2 ) 6 CONH (CH 2 ) 3 Si (NCO) 3 ,
Compound 1-8: F (CF 2 ) 6 CONH (CH 2 ) 3 SiCl 3 ,
Compound 2-1: F (CF 2 ) 8 SO 2 NH (CH 2 ) 3 Si (OCH 3 ) 3 ,
Compound 2-2: F (CF 2 ) 6 SO 2 NH (CH 2 ) 3 Si (OCH 3 ) 3 ,
Compound 3-1: Si (OC 2 H 5 ) 4 ,
Compound 3-2: Si (NCO) 4 ,
Compound 3-3: SiCl 4 ,
Compound 4-1: F (CF 2 ) 8 (CH 2 ) 2 Si (OCH 3 ) 3 ,
Compound 4-2: F (CF 2) 6 (CH 2) 2 Si (OCH 3) 3.
［撥水性組成物１〜１４の調整］
撹拌機、温度計がセットされたガラス容器に下記の原料および溶剤を下記の量（括弧内は質量比）入れ、２５℃にて１０分間撹拌し、次いで塩酸水溶液（０．０３ｍｏｌ／Ｌ）の３３．７２ｇを滴下して、５０℃にて３時間撹拌した。
[Adjustment of water-repellent compositions 1-14]
In a glass container in which a stirrer and a thermometer are set, the following raw materials and solvent are added in the following amounts (mass ratio in parentheses), stirred at 25 ° C. for 10 minutes, and then an aqueous hydrochloric acid solution (0.03 mol / L). 33.72g was dripped and it stirred at 50 degreeC for 3 hours.
撥水性組成物１：化合物１−１の０．３６ｇ、化合物３−１の２．７ｇ、ＩＰＡの９７．０ｇ（化合物１−１／化合物３−１＝１．３３／１０）。
撥水性組成物２：化合物２−１の０．３６ｇ、化合物３−１の２．７ｇ、ＩＰＡの９７．０ｇ（化合物２−１／化合物３−１＝１．３３／１０）。
撥水性組成物３：化合物１−２の０．３６ｇ、化合物３−１の２．７ｇ、ＩＰＡの９７．０ｇ（化合物１−２／化合物３−１＝１．３３／１０）。
撥水性組成物４：化合物１−３の０．３６ｇ、化合物３−１の２．７ｇ、ＩＰＡの９７．０ｇ（化合物１−３／化合物３−１＝１．３３／１０）。
Water repellent composition 1: 0.36 g of compound 1-1, 2.7 g of compound 3-1, and 97.0 g of IPA (compound 1-1 / compound 3-1 = 1.33 / 10).
Water-repellent composition 2: 0.36 g of compound 2-1, 2.7 g of compound 3-1, and 97.0 g of IPA (compound 2-1 / compound 3-1 = 1.33 / 10).
Water-repellent composition 3: 0.36 g of compound 1-2, 2.7 g of compound 3-1 and 97.0 g of IPA (compound 1-2 / compound 3-1 = 1.33 / 10).
Water-repellent composition 4: 0.36 g of compound 1-3, 2.7 g of compound 3-1 and 97.0 g of IPA (compound 1-3 / compound 3-1 = 1.33 / 10).
撥水性組成物５：化合物２−２の０．３６ｇ、化合物３−１の２．７ｇ、ＩＰＡの９７．０ｇ（化合物２−２／化合物３−１＝１．３３／１０）。
撥水性組成物６：化合物１−４の０．３６ｇ、化合物３−１の２．７ｇ、ＩＰＡの９７．０ｇ（化合物１−４／化合物３−１＝１．３３／１０）。
撥水性組成物７：化合物１−５の０．３６ｇ、化合物３−１の２．７ｇ、ＩＰＡの９７．０ｇ（化合物１−５／化合物３−１＝１．３３／１０）。
撥水性組成物８：化合物１−６の０．３６ｇ、化合物３−１の２．７ｇ、ＩＰＡの９７．０ｇ（化合物１−６／化合物３−１＝１．３３／１０）。
Water repellent composition 5: 0.36 g of compound 2-2, 2.7 g of compound 3-1, and 97.0 g of IPA (compound 2-2 / compound 3-1 = 1.33 / 10).
Water-repellent composition 6: 0.36 g of compound 1-4, 2.7 g of compound 3-1, and 97.0 g of IPA (compound 1-4 / compound 3-1 = 1.33 / 10).
Water-repellent composition 7: 0.36 g of compound 1-5, 2.7 g of compound 3-1 and 97.0 g of IPA (compound 1-5 / compound 3-1 = 1.33 / 10).
Water repellent composition 8: 0.36 g of compound 1-6, 2.7 g of compound 3-1, and 97.0 g of IPA (compound 1-6 / compound 3-1 = 1.33 / 10).
撥水性組成物９：化合物１−３の０．０５ｇ、化合物３−１の２．７ｇ、ＩＰＡの９７．０ｇ（化合物１−３／化合物３−１＝０．１８／１０）。
撥水性組成物１０：化合物１−３の３．０ｇ、化合物３−１の２．７ｇ、ＩＰＡの９７．０ｇ（化合物１−３／化合物３−１＝１１．１１／１０）。
撥水性組成物１１：化合物４−１の０．３６ｇ、化合物３−１の２．７ｇ、ＩＰＡの９７．０ｇ（化合物４−１／化合物３−１＝１．３３／１０）。
撥水性組成物１２：化合物４−２の０．３６ｇ、化合物３−１の２．７ｇ、ＩＰＡの９７．０ｇ（化合物４−２／化合物３−１＝１．３３／１０）。
Water-repellent composition 9: 0.05 g of compound 1-3, 2.7 g of compound 3-1 and 97.0 g of IPA (compound 1-3 / compound 3-1 = 0.18 / 10).
Water-repellent composition 10: 3.0 g of compound 1-3, 2.7 g of compound 3-1, and 97.0 g of IPA (compound 1-3 / compound 3-1 = 11.11 / 10).
Water-repellent composition 11: 0.36 g of compound 4-1, 2.7 g of compound 3-1, and 97.0 g of IPA (compound 4-1 / compound 3-1 = 1.33 / 10).
Water-repellent composition 12: 0.36 g of compound 4-2, 2.7 g of compound 3-1, and 97.0 g of IPA (compound 4-2 / compound 3-1 = 1.33 / 10).
撥水性組成物１３：化合物１−７の０．３６ｇ、化合物３−２の２．７ｇ、酢酸ブチルの９７．０ｇ（化合物１−７／化合物３−２＝１．３３／１０）。
撥水性組成物１４：化合物１−８の０．３６ｇ、化合物３−３の２．７ｇ、酢酸ブチルの９７．０ｇ（化合物１−８／化合物３−３＝１．３３／１０）。
Water-repellent composition 13: 0.36 g of compound 1-7, 2.7 g of compound 3-2, 97.0 g of butyl acetate (compound 1-7 / compound 3-2 = 1.33 / 10).
Water-repellent composition 14: 0.36 g of compound 1-8, 2.7 g of compound 3-3, 97.0 g of butyl acetate (compound 1-8 / compound 3-3 = 1.33 / 10).
［撥水性組成物１５の調整］
撹拌機、温度計がセットされたガラス容器に化合物１−７の０．３６ｇ、化合物３−２の２．７ｇ、酢酸ブチルの９７．０ｇを入れ、２５℃にて１０分間撹拌した（化合物１−７／化合物３−２＝１．３３／１０）。
[Adjustment of water repellent composition 15]
A glass container in which a stirrer and a thermometer were set was charged with 0.36 g of compound 1-7, 2.7 g of compound 3-2 and 97.0 g of butyl acetate, and the mixture was stirred at 25 ° C. for 10 minutes (compound 1 −7 / compound 3-2 = 1.33 / 10).
［撥水性組成物１６の調整］
撹拌機、温度計がセットされたガラス容器に、化合物１−３の０．３６ｇ、化合物３−１の２．７ｇ、ＩＰＡの９７．０ｇを入れ、２５℃にて１０分間撹拌し、塩酸水溶液（０．０３ｍｏｌ／Ｌ）の３３．７２ｇを滴下して、５０℃にて３時間撹拌した。さらにＩＰＡの１００ｇを添加して１０分間撹拌した（化合物１−３／化合物３−１＝１．３３／１０）。
[Adjustment of water repellent composition 16]
In a glass container in which a stirrer and a thermometer are set, 0.36 g of compound 1-3, 2.7 g of compound 3-1 and 97.0 g of IPA are put, and stirred at 25 ° C. for 10 minutes, and a hydrochloric acid aqueous solution. 33.72 g of (0.03 mol / L) was added dropwise and stirred at 50 ° C. for 3 hours. Further, 100 g of IPA was added and stirred for 10 minutes (Compound 1-3 / Compound 3-1 = 1.33 / 10).
［例１］
基材に撥水性組成物１を約１ｍＬ滴下し、スピンコート法（３０００ｒｐｍ）にて塗布して、１昼夜（２４時間）、室温（２０〜２５℃）、相対湿度（５０〜６０％）にて保持し、サンプル基材１を得た。
[Example 1]
About 1 mL of the water-repellent composition 1 was dropped on the base material and applied by spin coating (3000 rpm), and it was kept at room temperature (20-25 ° C.), relative humidity (50-60%) for one day and night (24 hours). To obtain a sample substrate 1.
［例２〜１６］
例１の撥水性組成物１の代わりに撥水性組成物２〜１６を用いた以外は、例１と同様にしてサンプル基材２〜１６を得た。
[Examples 2 to 16]
Sample substrates 2 to 16 were obtained in the same manner as in Example 1 except that the water repellent compositions 2 to 16 were used instead of the water repellent composition 1 of Example 1.
［例１７］
例４において、３０００ｒｐｍを１０００ｒｐｍにした以外は、例４と同様にしてサンプル基材１７を得た。
[Example 17]
A sample substrate 17 was obtained in the same manner as in Example 4 except that 3000 rpm was changed to 1000 rpm in Example 4.
［例１８］
例４において、基材をＲａ＝３０ｎｍのソーダライムガラス板にした以外は、例４と同様にしてサンプル基材１８を得た。
[Example 18]
A sample substrate 18 was obtained in the same manner as in Example 4 except that the substrate was a soda lime glass plate with R a = 30 nm.
［例１９］
例４で得られたサンプル基材４を、２００℃にて１時間熱処理してサンプル基材１９を得た。
[Example 19]
The sample substrate 4 obtained in Example 4 was heat-treated at 200 ° C. for 1 hour to obtain a sample substrate 19.
［例２０］
自動車用フロント合わせガラスの外側表面に、撥水性組成物４をフローコート法にて塗布して、１昼夜（２４時間）、室温（２０〜２５℃）、相対湿度５０〜６０％にて保持して撥水層を有する合わせガラスを得た。得られた合わせガラスを自動車のフロントに装着し、該自動車を用いて日中２時間の走行テストを３ケ月間行い、雨天時の水滴の付着状態を肉眼で観察した。その結果、特に低速走行時に表面の水滴がすみやかに移動し、ワイパーをほとんど使用することなく視野が確保できた。また付着した指紋もティッシュペーパーで軽く拭くだけで容易に除去できた。
[Example 20]
The water-repellent composition 4 is applied to the outer surface of a front laminated glass for automobiles by a flow coating method, and is kept at day and night (24 hours), room temperature (20 to 25 ° C.), and relative humidity of 50 to 60%. Thus, a laminated glass having a water repellent layer was obtained. The obtained laminated glass was mounted on the front of an automobile, a running test for 2 hours during the day was conducted for 3 months using the automobile, and the adhesion state of water droplets in the rain was observed with the naked eye. As a result, water droplets on the surface moved quickly, especially during low-speed running, and a field of view could be secured with almost no wiper used. Also, the attached fingerprint could be easily removed by lightly wiping with tissue paper.
［例２１］
例２０におけるフロント合わせガラスを、サイドガラスまたはリアガラスに変更して走行テストを行ったところ、例２０と同じ効果が確認できた。
[Example 21]
When the front laminated glass in Example 20 was changed to the side glass or the rear glass and a running test was performed, the same effect as in Example 20 was confirmed.
［例２２］
Ｘ線光電子分光装置を用いてサンプル基板４の表面の測定を行った。Ｘ線光電子分光による分析では、撥水層表面から基材方向へ向かって表面を削りながら存在する原子の強度を測定していく。結果を図１に示す。図１において横軸は撥水層の深さを示し、縦軸は存在する原子の強度を示す。Ｆ１ｓで示される撥水層中のフッ素原子濃度が、撥水層の表面近くで高く、基材方向に向かって低くなる濃度分布を有することがわかる。２５ｍｉｎ付近からは基材に達していることを示している。
[Example 22]
The surface of the sample substrate 4 was measured using an X-ray photoelectron spectrometer. In the analysis by X-ray photoelectron spectroscopy, the intensity of existing atoms is measured while the surface is scraped from the surface of the water repellent layer toward the substrate. The results are shown in FIG. In FIG. 1, the horizontal axis indicates the depth of the water-repellent layer, and the vertical axis indicates the intensity of the existing atoms. It can be seen that the fluorine atom concentration in the water repellent layer indicated by F1s has a concentration distribution that is high near the surface of the water repellent layer and decreases toward the substrate. It shows that it has reached the base material from around 25 min.
本発明の撥水性組成物を用いて形成された撥水層を有する基材は輸送機器用物品に最適である。輸送機器用物品としては、電車、自動車、船舶、航空機等におけるボディー、窓ガラス（フロントガラス、サイドガラス、リアガラス）、ミラー、バンパー等が挙げられる。 A substrate having a water-repellent layer formed using the water-repellent composition of the present invention is most suitable for articles for transportation equipment. Examples of articles for transportation equipment include bodies in trains, automobiles, ships, aircrafts, window glasses (front glass, side glass, rear glass), mirrors, bumpers, and the like.
Claims (6)
ＲｆＣＯＮ（Ｒ１）−Ａ−Ｓｉ（Ｒ２）ｐ（Ｘ１）３−ｐ・・・式１
ＲｆＳＯ２Ｎ（Ｒ３）−Ｂ−Ｓｉ（Ｒ４）ｑ（Ｘ２）３−ｑ・・・式２
（Ｒ５）ｒＳｉ（Ｘ３）４−ｒ・・・式３
ただし、式中の記号は以下の意味を示す。
Ｒｆ：炭素原子数３〜１７のポリフルオロアルキル基または酸素原子を含む炭素原子数３〜１７のポリフルオロアルキル基。
Ａ、Ｂ：それぞれ独立して、炭素原子数１〜４の２価有機基または窒素原子を含む炭素数１〜４の２価有機基。
Ｒ１、Ｒ３：それぞれ独立して、炭素原子数１〜３の１価炭化水素基または水素原子。
Ｒ２、Ｒ４、Ｒ５：それぞれ独立して、フッ素原子を含まない炭素原子数１〜６の１価炭化水素基。
Ｘ１、Ｘ２、Ｘ３：それぞれ独立して、ハロゲン原子、アルコキシ基またはイソシアネート基。
ｐ、ｑ、ｒ：それぞれ独立して、０、１または２。 The compound 1 represented by the following formula 1 and / or the compound 2 represented by the following formula 2 and the compound 3 represented by the following formula 3 are (total of compound 1 and / or compound 2) / compound 3 A water repellent composition comprising a partial cohydrolyzed product obtained by partial cohydrolysis at a mass ratio of 2/100 to 100/100.
R f CON (R 1) -A -Si (R 2) p (X 1) 3-p ··· Formula 1
R f SO 2 N (R 3 ) -B-Si (R 4) q (X 2) 3-q ··· Equation 2
(R 5 ) r Si (X 3 ) 4-r Formula 3
However, the symbols in the formulas have the following meanings.
R f : a polyfluoroalkyl group having 3 to 17 carbon atoms or a polyfluoroalkyl group having 3 to 17 carbon atoms including an oxygen atom.
A and B: each independently a divalent organic group having 1 to 4 carbon atoms or a divalent organic group having 1 to 4 carbon atoms containing a nitrogen atom.
R 1 and R 3 : each independently a monovalent hydrocarbon group having 1 to 3 carbon atoms or a hydrogen atom.
R 2 , R 4 , R 5 : each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms that does not contain a fluorine atom.
X 1 , X 2 , X 3 : each independently a halogen atom, an alkoxy group or an isocyanate group.
p, q, r: each independently 0, 1 or 2.
The transport equipment article according to claim 5, wherein the base material is a transparent material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009051174A (en) * | 2007-08-29 | 2009-03-12 | Nippon Sheet Glass Co Ltd | Water-repellent film coated article and method for manufacturing the same |
| JP2015205973A (en) * | 2014-04-18 | 2015-11-19 | キヤノンファインテック株式会社 | Water repellent and oil repellent compound and repellent film formed by using the same |
| JP2016166370A (en) * | 2016-04-28 | 2016-09-15 | キヤノンファインテック株式会社 | Water repellent and oil repellent composition and water repellent film formed by using the same |
| KR20190111893A (en) * | 2017-02-14 | 2019-10-02 | 에이지씨 가부시키가이샤 | Fluorine-containing ether compositions, coating solutions and articles |
| KR20190125297A (en) * | 2017-03-15 | 2019-11-06 | 에이지씨 가부시키가이샤 | Fluorine-containing ether compositions, coating solutions and articles |
| JP2021020831A (en) * | 2019-07-29 | 2021-02-18 | 日本板硝子株式会社 | Window pane for automobile |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58122979A (en) * | 1982-01-19 | 1983-07-21 | Asahi Glass Co Ltd | Water/oil repellent for glass surface |
-
2005
- 2005-01-28 JP JP2005021408A patent/JP2006206765A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58122979A (en) * | 1982-01-19 | 1983-07-21 | Asahi Glass Co Ltd | Water/oil repellent for glass surface |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009051174A (en) * | 2007-08-29 | 2009-03-12 | Nippon Sheet Glass Co Ltd | Water-repellent film coated article and method for manufacturing the same |
| JP2015205973A (en) * | 2014-04-18 | 2015-11-19 | キヤノンファインテック株式会社 | Water repellent and oil repellent compound and repellent film formed by using the same |
| JP2016166370A (en) * | 2016-04-28 | 2016-09-15 | キヤノンファインテック株式会社 | Water repellent and oil repellent composition and water repellent film formed by using the same |
| KR20190111893A (en) * | 2017-02-14 | 2019-10-02 | 에이지씨 가부시키가이샤 | Fluorine-containing ether compositions, coating solutions and articles |
| JP2022069480A (en) * | 2017-02-14 | 2022-05-11 | Ａｇｃ株式会社 | Fluorine-containing ether composition, coating liquid and article |
| KR102531226B1 (en) | 2017-02-14 | 2023-05-10 | 에이지씨 가부시키가이샤 | Fluorinated ether compositions, coating solutions and articles |
| KR20190125297A (en) * | 2017-03-15 | 2019-11-06 | 에이지씨 가부시키가이샤 | Fluorine-containing ether compositions, coating solutions and articles |
| KR102526826B1 (en) | 2017-03-15 | 2023-04-27 | 에이지씨 가부시키가이샤 | Fluorinated ether compositions, coating solutions and articles |
| JP2021020831A (en) * | 2019-07-29 | 2021-02-18 | 日本板硝子株式会社 | Window pane for automobile |
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