JP7231422B2 - antifouling membrane - Google Patents
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本発明は、撥水撥油性を有し、特に油性マジックの汚れを簡便に落とすことができる防汚性膜及びこうした防汚性膜に関するものである。 TECHNICAL FIELD The present invention relates to an antifouling film having water and oil repellency, and particularly to an antifouling film capable of easily removing stains from permanent markers, and to such an antifouling film .
従来、撥水撥油性を付与することができる化合物として、特定のペルフルオロアミン構造を有する含フッ素シラン化合物が開示されている（例えば特許文献１（要約）参照。）。この含フッ素シラン化合物は、炭素数８以上のペルフルオロアルキル基を含有せず、生体蓄積性や環境適応性の点で問題となるペルフルオロオクタンスルホン酸（ＰＦＯＳ）又はペルフルオロオクタン酸（ＰＦＯＡ）を生成する懸念がない化学構造でありながら、優れた撥水撥油性を付与することが可能であり、多種多様な用途に適用可能性を有するフッ素系シランカップリング剤として有用である特徴がある。 Conventionally, a fluorine-containing silane compound having a specific perfluoroamine structure has been disclosed as a compound capable of imparting water and oil repellency (see, for example, Patent Document 1 (abstract)). This fluorine-containing silane compound does not contain a perfluoroalkyl group having 8 or more carbon atoms, and generates perfluorooctane sulfonic acid (PFOS) or perfluorooctanoic acid (PFOA), which are problematic in terms of bioaccumulation and environmental adaptability. Although it has a safe chemical structure, it can impart excellent water and oil repellency, and is useful as a fluorine-based silane coupling agent with applicability to a wide variety of uses.
特許文献１に示される含フッ素シラン化合物を少量だけ添加して液組成物を調製すると、この液組成物により形成した膜に撥水撥油性を付与することができる。しかしこの含フッ素シラン化合物を一般的なアルコール溶媒とを混合して液組成物を調製した場合、この含フッ素シラン化合物の表面張力がアルコール溶媒の表面張力と大きく異なってしまう。このため、この液組成物を基材上にバーコーターで塗布した場合、塗膜に水玉模様やコーター筋が生じて、成膜性に劣る。更に含フッ素シラン化合物と溶媒だけを混合した液組成物で塗膜を形成した場合、塗膜の強度が低いうえ、塗膜の基材への密着性が十分でない。更に成膜した後の膜厚が、可視光線の波長程度（１００ｎｍ～８００ｎｍ）である場合、液組成物を塗布した後の溶媒が揮発する乾燥過程でウェット膜厚が薄い部位から徐々に揮発していくときに、膜に虹色の干渉縞を発生する問題があった。 By adding a small amount of the fluorine-containing silane compound disclosed in Patent Document 1 to prepare a liquid composition, it is possible to impart water and oil repellency to a film formed from this liquid composition. However, when the fluorine-containing silane compound is mixed with a general alcohol solvent to prepare a liquid composition, the surface tension of the fluorine-containing silane compound is greatly different from that of the alcohol solvent. Therefore, when this liquid composition is applied onto a substrate with a bar coater, polka dot patterns and coater streaks occur in the coating film, resulting in poor film-forming properties. Furthermore, when a coating film is formed from a liquid composition in which only a fluorine-containing silane compound and a solvent are mixed, the strength of the coating film is low and the adhesion of the coating film to the substrate is not sufficient. Furthermore, when the film thickness after film formation is about the wavelength of visible light (100 nm to 800 nm), the solvent after applying the liquid composition evaporates gradually from the part where the wet film thickness is thin during the drying process. There was a problem that rainbow-colored interference fringes were generated on the film when the film was heated.
この問題を解決するために、本出願人は、シリカゾルゲルを主とする成分並びに溶媒を含み、シリカゾルゲルを１００質量％とするときに、このシリカゾルゲルが下記の一般式（１）で示されるペルフルオロアミン構造のフッ素含有官能基成分（Ｆ）を０．５質量％～１０質量％と炭素数２～７のアルキレン基成分（Ｇ）を０．５質量％～２０質量％含み、溶媒が、水と炭素数１～４のアルコールとの混合溶媒であるか、或いは炭素数１～４のアルコールと前記アルコール以外の有機溶媒との混合溶媒であることを特徴とする膜形成用液組成物を提案した（特許文献２（請求項１）参照。）。 In order to solve this problem, the present applicant contains a component mainly composed of silica sol-gel and a solvent, and when the silica sol-gel is 100% by mass, the silica sol-gel is represented by the following general formula (1) 0.5% to 10% by mass of a fluorine-containing functional group component (F) having a perfluoroamine structure and 0.5% to 20% by mass of an alkylene group component (G) having 2 to 7 carbon atoms, and the solvent is A film-forming liquid composition characterized by being a mixed solvent of water and an alcohol having 1 to 4 carbon atoms, or a mixed solvent of an alcohol having 1 to 4 carbon atoms and an organic solvent other than the alcohol. proposed (see Patent Document 2 (claim 1)).
特許文献２に示される膜形成用液組成物を基材上に塗布して塗膜を形成した後、塗膜に油性マジックの汚れが付着して長期間経過したときに、油性マジックの汚れは、布で基材を複数回強く擦らないと、落とすことができないまだ解決すべき課題があった。 After the film-forming liquid composition disclosed in Patent Document 2 is applied onto a substrate to form a coating film, when a long period of time elapses after the coating film has been stained with an oil-based marker, the stain of the oil-based marker is However, there is still a problem that needs to be solved in order to remove it unless the base material is strongly rubbed several times with a cloth .
本発明の目的は、撥水撥油性を有し、特に油性マジックの汚れを簡便に落とすことがで きる防汚性膜を提供することにある。 SUMMARY OF THE INVENTION An object of the present invention is to provide an antifouling film which has water and oil repellency and which is particularly easy to remove stains of permanent markers.
本発明の第１の観点は、膜表面に平均粒径０．１μｍ～５．０μｍのシロキサン骨格の成分を含む粒が１００μｍ2当り７０個～５００個存在し、表面粗さＳｑが４５ｎｍ～９５ｎｍであって、膜成分中のフッ素（Ｆ）と炭素（Ｃ）とケイ素（Ｓｉ）の質量比が、Ｆ：Ｃ：Ｓｉ＝（０．５～８）：（１４～２１）：（７５～８５）であることを特徴とする防汚性膜である。 A first aspect of the present invention is that the film surface has 70 to 500 particles per 100 μm 2 containing a siloxane skeleton component with an average particle diameter of 0.1 μm to 5.0 μm, and the surface roughness Sq is 45 nm to 95 nm. and the mass ratio of fluorine (F), carbon (C) and silicon (Si) in the film components is F:C:Si=(0.5-8):(14-21):(75- 85).
本発明の第２の観点は、シリカゾルゲルを主とする成分並びに溶媒を含み、前記シリカ ゾルゲルを１００質量％とするときに、前記シリカゾルゲル下記の一般式（１－１）で示 されるペルフルオロアミン構造のフッ素含有官能基成分又は下記の一般式（１－２）で示 されるペルフルオロエーテル構造のフッ素含有官能基成分を０．５質量％～１０質量％と 炭素数２～７のアルキレン基成分を０．５質量％～２０質量％とメチル基成分を０．２質 量％～１０質量％含み、前記溶媒が、炭素数１～４のアルコール及び／又は前記アルコー ル以外の溶媒であることを特徴とする防汚性膜形成用液組成物の乾燥物である防汚性膜である。 A second aspect of the present invention includes a component mainly composed of silica sol-gel and a solvent, and when the silica sol-gel is 100% by mass, the silica sol-gel contains perfluoro 0.5% to 10% by mass of a fluorine-containing functional group component of an amine structure or a fluorine-containing functional group component of a perfluoroether structure represented by the following general formula (1-2) and an alkylene group having 2 to 7 carbon atoms 0.5% by mass to 20% by mass of the component and 0.2% by mass to 10% by mass of the methyl group component, and the solvent is an alcohol having 1 to 4 carbon atoms and/or a solvent other than the alcohol The antifouling film is a dried product of the liquid composition for forming an antifouling film characterized by:
上記式（１－１）中、ｍ及びｎは、それぞれ同一又は互いに異なる１～６の整数である。また、Ｒｆ1は、炭素数１～６のペルフルオロアルキレン基であって、直鎖状又は分枝状であってもよい。また上記式（１－１）中、Ｘ１は、炭素数２～１０の炭化水素基であって、エーテル結合、ＣＯ－ＮＨ結合、Ｏ－ＣＯ－ＮＨ結合及びスルホンアミド結合から選択される１種以上の結合を含んでいてもよい。 In formula (1-1) above, m and n are the same or different integers of 1 to 6, respectively. Rf 1 is a perfluoroalkylene group having 1 to 6 carbon atoms and may be linear or branched. Further, in the above formula (1-1), X1 is a hydrocarbon group having 2 to 10 carbon atoms and is selected from an ether bond, a CO—NH bond, an O—CO—NH bond and a sulfonamide bond. It may contain the above combination.
上記式（１－２）中、ｍ及びｎは、それぞれ同一又は互いに異なる１～６の整数である。また上記式（１－２）中、Ｘ１は、炭素数２～１０の炭化水素基であって、エーテル結合、ＣＯ－ＮＨ結合、Ｏ－ＣＯ－ＮＨ結合及びスルホンアミド結合から選択される１種以上の結合を含んでいてもよい。 In formula (1-2) above, m and n are the same or different integers of 1 to 6, respectively. Further, in the above formula (1-2), X1 is a hydrocarbon group having 2 to 10 carbon atoms and is selected from an ether bond, a CO—NH bond, an O—CO—NH bond and a sulfonamide bond. It may contain the above combination.
本発明の第１の観点の防汚性膜では、膜表面に平均粒径０．１μｍ～５．０μｍのシロキサン骨格の成分を含む粒が１００μｍ2当り７０個～５００個存在するため、膜表面凹凸が生じることで、油性マジックの汚れのふき取り性（以下、単に「油性マジックの拭き取り性」という。）の効果を有する。また防汚性膜の表面粗さＳｑが４５ｎｍ～９５ｎｍであるため、良好な外観を維持しつつ油性マジックのふき取り性の効果を有する。更に膜成分中のフッ素（Ｆ）と炭素（Ｃ）とケイ素（Ｓｉ）の質量比が、Ｆ：Ｃ：Ｓｉ＝（０．５～８）：（１４～２１）：（７５～８５）であるため、適切なフッ素含有量と適切な炭素含有量により、撥水並びに撥油性が付与され、良好な外観を維持しつつ油性マジックのふき取り性の効果を有する。 In the antifouling film of the first aspect of the present invention, 70 to 500 particles per 100 μm 2 containing a siloxane skeleton component with an average particle diameter of 0.1 μm to 5.0 μm are present on the film surface. Due to the unevenness, it has the effect of wiping off the dirt of the permanent marker (hereinafter simply referred to as "wiping performance of the permanent marker") . In addition, since the surface roughness Sq of the antifouling film is 45 nm to 95 nm, it has the effect of wiping off permanent markers while maintaining a good appearance. Furthermore, the mass ratio of fluorine (F), carbon (C) and silicon (Si) in the film components is F:C:Si=(0.5-8):(14-21):(75-85). Therefore, an appropriate fluorine content and an appropriate carbon content impart water repellency and oil repellency, and have the effect of wiping off permanent marker while maintaining a good appearance.
本発明の第２の観点の防汚性膜形成用液組成物では、液組成物がシリカゾルゲルを主成分とするため、高い強度の防汚性膜が得られ、かつ防汚性膜の基材への密着性が良好となる。また液組成物が上記の一般式（１－１）で示されるペルフルオロアミン構造のフッ素含有官能基成分又は上記の一般式（１－２）で示されるペルフルオロエーテル構造のフッ素含有官能基成分を０．５質量％～１０質量％と炭素数２～７のアルキレン基成分を０．５質量％～２０質量％含むため、形成した防汚性膜に優れた撥水撥油性を付与することができる。またメチル基成分を０．２質量％～１０質量％含むため、油性マジックの汚れを簡便に落とすことができる。また溶媒が、炭素数１～４のアルコール及び／又は前記アルコール以外の溶媒であるため、防汚性膜を成膜性良く形成することができる。 In the liquid composition for forming an antifouling film according to the second aspect of the present invention, since the liquid composition contains silica sol-gel as a main component, a high-strength antifouling film can be obtained, and the base of the antifouling film can be Good adhesion to materials. Further, the liquid composition contains 0 fluorine-containing functional group components of the perfluoroamine structure represented by the above general formula (1-1) or fluorine-containing functional group components of the perfluoroether structure represented by the above general formula (1-2). .5% to 10% by mass and 0.5% to 20% by mass of an alkylene group component having 2 to 7 carbon atoms, so that the formed antifouling film can be imparted with excellent water and oil repellency. . In addition, since it contains 0.2% by mass to 10% by mass of a methyl group component, it is possible to easily remove oil-based marker stains. Further, since the solvent is an alcohol having 1 to 4 carbon atoms and/or a solvent other than the alcohol, the antifouling film can be formed with good film-forming properties.
次に本発明を実施するための形態を説明する。 Next, a mode for carrying out the present invention will be described.
〔防汚性膜形成用液組成物の製造方法〕
本実施形態の防汚性膜形成用液組成物の製造方法を説明する。この製造方法では、先ず、ケイ素アルコキシドとしてのテトラメトキシシラン又はテトラエトキシシランと、下記の一般式（２－１）又は下記の一般式（２－２）で示されるフッ素含有基成分としてのフッ素含有シランと、アルキレン基含有成分としてのエポキシ基含有シランと、メチル基成分としてのメチル基含有シランと、エタノール、２－プロパノール等のアルコールと、トルエン、キシレン等の芳香族炭化水素と、水とを混合して混合液を調製する。上記アルキレン基含有成分は、エポキシ基の開環反応によって得られるため、アルキレン基の元になるエポキシ基含有シランで混合する。次いでこの混合液と有機酸、無機酸又はチタン化合物からなる触媒とを混合してケイ素アルコキシドとエポキシ基含有シランとメチル基含有シランとを加水分解することにより加水分解物を調製する。この時点で、エポキシ基は、開環反応が生じ、アルキレン基が得られる。次にこの加水分解物に、炭素数１～４のアルコール及び／又は前記アルコール以外の溶媒とを混合して、シリカゾルゲルを含む防汚性膜形成用液組成物を製造する。
[Method for producing liquid composition for forming antifouling film]
A method for producing the antifouling film-forming liquid composition of the present embodiment will be described. In this production method, first, tetramethoxysilane or tetraethoxysilane as a silicon alkoxide, and fluorine-containing as a fluorine-containing group component represented by the following general formula (2-1) or the following general formula (2-2) silane, an epoxy group-containing silane as an alkylene group-containing component, a methyl group-containing silane as a methyl group component, alcohols such as ethanol and 2-propanol, aromatic hydrocarbons such as toluene and xylene, and water. Mix to prepare a mixture. Since the alkylene group-containing component is obtained by a ring-opening reaction of an epoxy group, it is mixed with an epoxy group-containing silane that is the source of the alkylene group. Next, this mixture is mixed with a catalyst comprising an organic acid, an inorganic acid, or a titanium compound to hydrolyze the silicon alkoxide, the epoxy group-containing silane, and the methyl group-containing silane to prepare a hydrolyzate. At this point, the epoxy group undergoes a ring-opening reaction to give an alkylene group. Next, this hydrolyzate is mixed with an alcohol having 1 to 4 carbon atoms and/or a solvent other than the alcohol to prepare a liquid composition for forming an antifouling film containing silica sol-gel.
上記式（２－１）中、ｍ及びｎは、それぞれ同一又は互いに異なる１～６の整数である。また、Ｒｆ1は、炭素数１～６のペルフルオロアルキレン基であって、直鎖状又は分枝状であってもよい。また上記式（２－１）中、Ｘ１は、炭素数２～１０の炭化水素基であって、エーテル結合、ＣＯ－ＮＨ結合、Ｏ－ＣＯ－ＮＨ結合及びスルホンアミド結合から選択される１種以上の結合を含んでいてもよい。更に上記式（２－１）中、Ｒ1及びＺはアルコキシ基である（ただし、ａは０～３の整数）。 In formula (2-1) above, m and n are the same or different integers of 1 to 6, respectively. Rf 1 is a perfluoroalkylene group having 1 to 6 carbon atoms and may be linear or branched. Further, in the above formula (2-1), X1 is a hydrocarbon group having 2 to 10 carbon atoms and is selected from an ether bond, a CO—NH bond, an O—CO—NH bond and a sulfonamide bond. It may contain the above combination. Furthermore, in the above formula (2-1), R 1 and Z are alkoxy groups (where a is an integer of 0 to 3).
上記式（２－２）中、ｍ及びｎは、それぞれ同一又は互いに異なる１～６の整数である。また上記式（２－２）中、Ｘ１は、炭素数２～１０の炭化水素基であって、エーテル結合、ＣＯ－ＮＨ結合、Ｏ－ＣＯ－ＮＨ結合及びスルホンアミド結合から選択される１種以上の結合を含んでいてもよい。更に上記式（２－２）中、Ｒ1及びＺはアルコキシ基である（ただし、ａは０～３の整数）。 In formula (2-2) above, m and n are the same or different integers of 1 to 6, respectively. Further, in the above formula (2-2), X1 is a hydrocarbon group having 2 to 10 carbon atoms and is selected from an ether bond, a CO—NH bond, an O—CO—NH bond and a sulfonamide bond. It may contain the above combination. Furthermore, in the above formula (2-2), R 1 and Z are alkoxy groups (where a is an integer of 0 to 3).
上記ケイ素アルコキシドとしては、具体的には、テトラメトキシシラン、そのオリゴマー又はテトラエトキシシラン、そのオリゴマーが挙げられる。例えば、硬度の高い防汚性膜を得る目的には、テトラメトキシシランを用いることが好ましく、一方、加水分解時に発生するメタノールを避ける場合は、テトラエトキシシランを用いることが好ましい。 Specific examples of the silicon alkoxide include tetramethoxysilane and its oligomers, and tetraethoxysilane and its oligomers. For example, tetramethoxysilane is preferably used for the purpose of obtaining a highly hard antifouling film, while tetraethoxysilane is preferably used for avoiding methanol generated during hydrolysis.
上記アルキレン基成分として用いるエポキシ基含有シランとしては、具体的には、２－(３，４－エポキシシクロヘキシル)エチルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン又は多官能エポキシシランが挙げられる。エポキシ基含有シランは、シリカゾル中のアルキレン基成分が０．５質量％～２０質量％になるように添加する。アルキレン基成分が下限値の０．５質量％未満では、形成した膜に虹色の干渉縞が依然として発生しやすく、上限値の２０質量％を超えると、形成した膜の強度が低くなりやすい。アルキレン基成分を上記０．５質量％～２０質量％の範囲含むと、形成した膜は虹色の干渉縞を発生しにくくなるのは、アルキレン基の成分となるエポキシ基が、加水分解重合過程において開環し重合に寄与し、膜成分中にアルキレン基として含有されることで、乾燥過程にレベリング性が改善し膜厚さが均一化されることによる。 Specific examples of the epoxy group-containing silane used as the alkylene group component include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyl Diethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane or polyfunctional epoxysilanes may be mentioned. The epoxy group-containing silane is added so that the alkylene group component in the silica sol becomes 0.5% by mass to 20% by mass. If the alkylene group component is less than the lower limit of 0.5% by mass, the formed film still tends to have rainbow interference fringes, and if it exceeds the upper limit of 20% by mass, the strength of the formed film tends to be low. When the alkylene group component is included in the above range of 0.5% by mass to 20% by mass, the formed film is less likely to generate iridescent interference fringes because the epoxy group, which is a component of the alkylene group, is in the hydrolytic polymerization process. The ring-opening contributes to the polymerization in the film component, and is contained as an alkylene group in the film component, thereby improving the leveling property in the drying process and making the film thickness uniform.
上記メチル基成分として用いるメチル基含有シランとしては、メチルトリメトキシシラン、ジメチルトリエトキシシラン、のモノマーや、ＪＮＣ社製ＦＭ－０４４１、ＦＭ－４４１１、ＦＭ－ＤＡ２６、信越化学工業社製ＫＲ－５００等メチル基含有オリゴマー、重合体が挙げられる。メチル基成分は、シリカゾルゲル中に０．２質量％～１０．０質量％含まれる。０．２質量％未満では、油性マジックのふき取り性の改善が現れず、１０．０質量％を超えると、膜外観が悪化する。 Examples of the methyl group-containing silane used as the methyl group component include monomers of methyltrimethoxysilane and dimethyltriethoxysilane, FM-0441, FM-4411 and FM-DA26 manufactured by JNC, and KR-500 manufactured by Shin-Etsu Chemical Co., Ltd. isomethyl group-containing oligomers and polymers. The methyl group component is contained in silica sol-gel in an amount of 0.2% by mass to 10.0% by mass. If it is less than 0.2% by mass, no improvement in the wiping off property of permanent marker is observed, and if it exceeds 10.0% by mass, the appearance of the film deteriorates.
上記フッ素含有官能基成分は加水分解物のシリカゾルゲル１００質量％に対して０．５質量％～１０質量％含まれる。好ましい含有割合は１．０質量％～１０質量％である。フッ素含有官能基成分が下限値の０．５質量％未満では、形成した膜に撥水撥油性の防汚性が生じにくく、上限値の１０質量％を超えると、成膜性に劣り、防汚性の機能を発現しにくい。 The fluorine-containing functional group component is contained in an amount of 0.5% by mass to 10% by mass with respect to 100% by mass of silica sol-gel in the hydrolyzate. A preferred content is 1.0% by mass to 10% by mass. When the fluorine-containing functional group component is less than the lower limit of 0.5% by mass, the formed film is unlikely to have water and oil repellency and antifouling properties. It is difficult to express the function of staining.
フッ素含有官能基成分として用いるフッ素含有シランは、上記一般式（２－１）で示される。上記式（２－１）中の含窒素ペルフルオロアルキル基としては、より具体的には、下記式（３）～（１４）で示されるペルフルオロアミン構造を挙げることができる。 The fluorine-containing silane used as the fluorine-containing functional group component is represented by the above general formula (2-1). More specific examples of the nitrogen-containing perfluoroalkyl group in formula (2-1) include perfluoroamine structures represented by formulas (3) to (14) below.
また、上記式（２－１）中のＸ１としては、下記式（１５）～（１９）で示される構造を挙げることができる。なお、下記式（１５）はエーテル結合、下記式（１６）はエステル結合、下記式（１７）はアミド結合、下記式（１８）はウレタン結合、下記式（１９）はスルホンアミド結合を含む例を示している。 Further, examples of X1 in the above formula (2-1) include structures represented by the following formulas (15) to (19). In addition, the following formula (15) is an ether bond, the following formula (16) is an ester bond, the following formula (17) is an amide bond, the following formula (18) is an urethane bond, and the following formula (19) is an example containing a sulfonamide bond. is shown.
ここで、上記式（１５）～（１９）中、Ｒ2及びＲ3は炭素数が０から１０の炭化水素基、Ｒ4は水素原子または炭素数１から６の炭化水素基である。Ｒ2及びＲ3の炭化水素基の例とは、メチレン基、エチレン基等のアルキレン基が挙げられ、Ｒ4の炭化水素基の例とは、メチル基、エチル基等のアルキル基の他、フェニル基も挙げられる。 In formulas (15) to (19), R 2 and R 3 are hydrocarbon groups having 0 to 10 carbon atoms, and R 4 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Examples of hydrocarbon groups for R 2 and R 3 include alkylene groups such as methylene group and ethylene group, and examples of hydrocarbon groups for R 4 include alkyl groups such as methyl group and ethyl group, Also included are phenyl groups .
また、上記式（２－１）中、Ｒ1は、加水分解基のメトキシ基、エトキシ基等が挙げられる。 In the above formula (2-1), R 1 includes hydrolyzable groups such as a methoxy group and an ethoxy group.
また、上記式（２－１）中、Ｚは、加水分解されてＳｉ－Ｏ－Ｓｉ結合を形成可能な加水分解性基であれば特に限定されるものではない。このような加水分解性基としては、具体的には、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基などのアルコキシ基、フェノキシ基、ナフトキシ基などのアリールオキシ基、ベンジルオキシ基、フェネチルオキシ基などのアラルキルオキシ基、アセトキシ基、プロピオニルオキシ基、ブチリルオキシ基、バレリルオキシ基、ピバロイルオキシ基、ベンゾイルオキシ基などのアシルオキシ基等が挙げられる。これらの中でも、メトキシ基、エトキシ基を適用することが好ましい。 In the above formula (2-1), Z is not particularly limited as long as it is a hydrolyzable group capable of forming a Si--O--Si bond upon hydrolysis. Specific examples of such hydrolyzable groups include alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; aryloxy groups such as phenoxy and naphthoxy; and acyloxy groups such as aralkyloxy group, acetoxy group, propionyloxy group, butyryloxy group, valeryloxy group, pivaloyloxy group, and benzoyloxy group. Among these, it is preferable to apply a methoxy group and an ethoxy group.
ここで、上記式（２－１）で表されるペルフルオロアミン構造を有するフッ素含有シランの具体例としては、例えば、下記式（２０）～（３４）で表される構造が挙げられる。なお、下記式（２０）～（３４）中、Ｒはメチル基又はエチル基である。 Specific examples of fluorine-containing silanes having a perfluoroamine structure represented by the above formula (2-1) include structures represented by the following formulas (20) to (34). In formulas (20) to (34) below, R is a methyl group or an ethyl group.
またフッ素含有シランは、上記一般式（２－２）で示される。上記式（２－２）中のペルフルオロエーテル基としては、より具体的には、下記式（３５）～（４１）で示されるペルフルオロエーテル構造を挙げることができる。 Fluorine-containing silane is represented by the above general formula (2-2). More specific examples of the perfluoroether group in formula (2-2) above include perfluoroether structures represented by the following formulas (35) to (41).
ここで、上記式（２－２）で表されるペルフルオロエーテル構造を有するフッ素含有シランの具体例としては、例えば、下記式（４２）～（４９）で表される構造が挙げられる。 Specific examples of fluorine-containing silanes having a perfluoroether structure represented by formula (2-2) above include structures represented by formulas (42) to (49) below.
上記炭素数１～４の範囲にあるアルコールは、この範囲にある１種又は２種以上のアルコールが挙げられる。このアルコールとしては、例えば、メタノール（沸点６４．７℃）、エタノール（沸点約７８．３℃）、プロパノール（ｎ－プロパノール（沸点９７－９８℃）、イソプロパノール（沸点８２．４℃））が挙げられる。特にメタノール又はエタノールが好ましい。これらのアルコールは、ケイ素アルコキドとの混合がしやすいためである。ケイ素アルコキシド及びエポキシ基含有シランに炭素数１～４の範囲にあるアルコールを添加して、好ましくは１０℃～３０℃の温度で５分～２０分間撹拌することにより混合液を調製する。 The alcohol having 1 to 4 carbon atoms includes one or two or more alcohols within this range. Examples of this alcohol include methanol (boiling point 64.7° C.), ethanol (boiling point about 78.3° C.), propanol (n-propanol (boiling point 97-98° C.), isopropanol (boiling point 82.4° C.)). be done. Methanol or ethanol are particularly preferred. This is because these alcohols are easily mixed with silicon alkoxides. A mixed solution is prepared by adding an alcohol having a carbon number of 1 to 4 to a silicon alkoxide and an epoxy group-containing silane and stirring the mixture at a temperature of preferably 10° C. to 30° C. for 5 to 20 minutes.
〔加水分解物の調製〕
上記調製された混合液と有機酸、無機酸又はチタン化合物からなる触媒とを混合する。このとき液温を好ましくは３０℃～８０℃の温度に保持して好ましくは１時間～２４時間撹拌する。これにより、混合液中のケイ素アルコキシドとエポキシ基含有シランとメチル基含有シランとが加水分解される。有機酸、無機酸又はチタン化合物は加水分解反応を促進させるための触媒として機能する。有機酸としてはギ酸、シュウ酸が例示され、無機酸としては塩酸、硝酸、リン酸が例示され、チタン化合物としてはテトラプロポキシチタン、テトラブトキシチタン、テトライソプロポキシチタン、乳酸チタン等が例示される。触媒は上記のものに限定されない。
[Preparation of hydrolyzate]
The mixed solution prepared above is mixed with a catalyst comprising an organic acid, an inorganic acid, or a titanium compound. At this time, the liquid temperature is preferably maintained at a temperature of 30° C. to 80° C. and stirred for preferably 1 hour to 24 hours. As a result, the silicon alkoxide, epoxy group-containing silane, and methyl group-containing silane in the mixed liquid are hydrolyzed. The organic acid, inorganic acid or titanium compound functions as a catalyst to promote the hydrolysis reaction. Examples of organic acids include formic acid and oxalic acid; examples of inorganic acids include hydrochloric acid, nitric acid, and phosphoric acid; and examples of titanium compounds include tetrapropoxytitanium, tetrabutoxytitanium, tetraisopropoxytitanium, and titanium lactate. . Catalysts are not limited to those listed above.
炭素数１～４の範囲にあるアルコールは、加水分解物を１００質量％とするときに、２０質量％～９８質量％含まれることが好ましい。このアルコールの割合を前記範囲に限定したのは、アルコールの割合が下限値未満では、ケイ素アルコキシドが、溶液中に溶解せずに分離しやすく、加水分解反応中に反応液がゲル化しやすい。一方、上限値を超えると、加水分解に必要な水、触媒量が相対的に少なくなるために、加水分解の反応性が低下して、重合が進みにくく、防汚性膜の密着性が低下しやすくなる。 The alcohol having a carbon number of 1 to 4 is preferably contained in an amount of 20% to 98% by mass when the hydrolyzate is taken as 100% by mass. The reason why the proportion of alcohol is limited to the above range is that if the proportion of alcohol is less than the lower limit, the silicon alkoxide tends to separate without dissolving in the solution, and the reaction solution tends to gel during the hydrolysis reaction. On the other hand, when the upper limit is exceeded, the amount of water and catalyst required for hydrolysis is relatively small, so the reactivity of hydrolysis is lowered, polymerization is difficult to proceed, and the adhesion of the antifouling film is lowered. easier to do.
加水分解物中のＳｉＯ2濃度（ＳｉＯ2分）は１質量％～４０質量％であるものが好ましい。加水分解物のＳｉＯ2濃度が下限値未満では、重合が不十分であり、防汚性膜の密着性の低下やクラックの発生が起こりやすく、上限値を超えると、加水分解により生じた水の割合が相対的に高くなりケイ素アルコキシドが溶解しにくく、反応液がゲル化しやすくなる。 The SiO 2 concentration (SiO 2 minute) in the hydrolyzate is preferably 1% by mass to 40% by mass. If the SiO 2 concentration of the hydrolyzate is less than the lower limit, polymerization is insufficient, and the adhesion of the antifouling film is likely to decrease and cracks are likely to occur. As the ratio becomes relatively high, the silicon alkoxide becomes difficult to dissolve, and the reaction solution tends to gel.
上述したように、本実施の形態のフッ素含有シランは、窒素原子に炭素数が６以下の短鎖長のペルフルオロアルキル基、又は酸素原子に炭素数が６以下の短鎖長のペルフルオロエーテル基をそれぞれ１以上有する構造となっていて、分子内のフッ素含有率が高いため、形成した防汚性膜に優れた撥水撥油性を付与することができる。 As described above, the fluorine-containing silane of the present embodiment includes a short-chain perfluoroalkyl group having 6 or less carbon atoms on the nitrogen atom or a short-chain perfluoroether group having 6 or less carbon atoms on the oxygen atom. The structure has one or more of each, and the fluorine content in the molecule is high, so that the formed antifouling film can be imparted with excellent water and oil repellency.
炭素数１～４のアルコールとともに用いられるアルコール以外の溶媒としては、沸点が１２０℃以上１６０℃未満の第１溶媒と、沸点が１６０℃以上２２０℃以下の第２溶媒が挙げられる。第１溶媒は沸点が１２０℃未満の炭素数１～４の範囲にあるアルコールと第２溶媒の中間の沸点を有することから、塗膜の乾燥時に前記アルコールと第２溶媒の沸点差に伴う塗膜の乾燥速度の大きな差を緩和する作用があり、第２溶媒は第１溶媒よりも高沸点であり、塗膜の乾燥速度が遅いことから塗膜の急激な乾燥を防止して急激な乾燥に伴う膜の不均一性を防止する作用があり、前記アルコールは沸点が最も低いことから塗膜の乾燥を速くする作用がある。このように沸点の異なる３種類の溶媒を用いることにより溶媒の乾燥速度を調整して、より的確にかつ効率的に塗膜を成膜性良く形成することができる。この他、アルコール以外の溶媒として、イオン交換水ような水、トルエン等の沸点が１２０℃未満の有機溶媒が挙げられる。 Solvents other than alcohols used together with alcohols having 1 to 4 carbon atoms include a first solvent having a boiling point of 120° C. or more and less than 160° C. and a second solvent having a boiling point of 160° C. or more and 220° C. or less. Since the first solvent has an intermediate boiling point between the second solvent and an alcohol having a boiling point of less than 120 ° C. and a carbon number of 1 to 4, the coating due to the difference in boiling points between the alcohol and the second solvent when drying the coating film. The second solvent has a higher boiling point than the first solvent, and the drying speed of the coating film is slow, so it prevents the coating film from drying rapidly. Since the alcohol has the lowest boiling point, it has the effect of speeding up the drying of the coating film. By using three kinds of solvents having different boiling points in this manner, the drying rate of the solvent can be adjusted, and a coating film can be formed more accurately and efficiently with good film-forming properties. Other solvents than alcohol include water such as ion-exchanged water, and organic solvents such as toluene having a boiling point of less than 120°C.
第１溶媒を例示すれば、２－メトキシエタノール（沸点１２５℃）、２－エトキシエタノール（沸点１３６℃）、２－イソプロポキシエタノール（沸点１４２℃）、１－メトキシ－２－プロパノール（沸点１２０℃）及び１－エトキシ－２－プロパノール（沸点１３２℃）からなる群より選ばれた１種又は２種以上の溶媒が挙げられる。また第２溶媒を例示すれば、ジアセトンアルコール（沸点１６９℃）、ジエチレングリコールモノメチルエーテル（沸点１９４℃）、Ｎ－メチルピロリドン（沸点２０２℃）及び３－メトキシ－３－メチル－１－ブタノール（沸点１７３℃）からなる群より選ばれた１種又は２種以上の溶媒が挙げられる。 Examples of the first solvent include 2-methoxyethanol (boiling point 125° C.), 2-ethoxyethanol (boiling point 136° C.), 2-isopropoxyethanol (boiling point 142° C.), 1-methoxy-2-propanol (boiling point 120° C. ) and 1-ethoxy-2-propanol (boiling point 132° C.). Examples of the second solvent include diacetone alcohol (boiling point 169° C.), diethylene glycol monomethyl ether (boiling point 194° C.), N-methylpyrrolidone (boiling point 202° C.) and 3-methoxy-3-methyl-1-butanol (boiling point 173° C.), or one or more solvents selected from the group consisting of
〔防汚性膜形成用液組成物〕
本実施の形態の防汚性膜形成用液組成物は、上記製造方法で製造され、シリカゾルゲルを主とする成分並びに溶媒を含み、このシリカゾルゲルを１００質量％とするときに、シリカゾルゲルが上記の一般式（１－１）で示されるペルフルオロアミン構造のフッ素含有官能基成分又は上記の一般式（１－２）で示されるペルフルオロエーテル構造のフッ素含有官能基成分を０．５質量％～１０質量％と炭素数２～７のアルキレン基を０．５質量％～２０質量％とメチル基成分を０．２質量％～１０質量％含み、上記溶媒が、炭素数１～４のアルコール及び／又は前記アルコール以外の溶媒であることを特徴とする。
[Anti-fouling film-forming liquid composition]
The antifouling film-forming liquid composition of the present embodiment is produced by the production method described above, and contains a component mainly composed of silica sol-gel and a solvent. 0.5% by mass to 10% by mass, 0.5% to 20% by mass of an alkylene group having 2 to 7 carbon atoms, and 0.2% to 10% by mass of a methyl group component, and the solvent is an alcohol having 1 to 4 carbon atoms and / Or it is characterized by being a solvent other than the said alcohol.
上記シリカゾルゲルは、上記の一般式（１－１）で示されるペルフルオロアミン構造のフッ素含有官能基成分と炭素数２～７のアルキレン基成分を含む。より具体的には、上述した式（３）～（３４）で示されるペルフルオロアミン構造を挙げることができる。
また上記シリカゾルゲルは、上記の一般式（１－２）で示されるペルフルオロエーテル構造のフッ素含有官能基成分と炭素数２～７のアルキレン基成分を含む。より具体的には、上述した式（３５）～（４９）で示されるペルフルオロエーテル構造を挙げることができる。
The silica sol-gel contains a fluorine-containing functional group component having a perfluoroamine structure represented by the general formula (1-1) and an alkylene group component having 2 to 7 carbon atoms. More specifically, perfluoroamine structures represented by formulas (3) to (34) above can be mentioned.
Further, the silica sol-gel contains a fluorine-containing functional group component having a perfluoroether structure represented by the general formula (1-2) and an alkylene group component having 2 to 7 carbon atoms. More specifically, perfluoroether structures represented by formulas (35) to (49) above can be mentioned.
本実施の形態の防汚性膜形成用液組成物がシリカゾルゲルを主成分として含むため、防汚性膜の基材への密着性に優れ、高い強度の防汚性膜が得られる。またシリカゾルゲルが上記一般式（１－１）で示されるペルフルオロアミン構造又は上記一般式（１－２）で示されるペルフルオロエーテル構造であるため、撥水並びに撥油の効果がある。シリカゾルゲル中のフッ素含有官能基成分の含有割合が０．５質量％未満では形成した膜に撥水撥油性の防汚機能を付与できず、１０質量％を超えると防汚性膜の弾き等が発生し成膜性に劣る。好ましいフッ素含有官能基成分の含有割合は０．６質量％～５質量％である。またシリカゾルゲル中の炭素数２～７のアルキレン基成分の含有割合が０．５質量％未満では、防汚性膜の干渉縞が発生する不具合があり、２０質量％を超えると膜強度が不足する不具合がある。好ましい炭素数２～７のアルキレン基成分の含有割合は１質量％～１０質量％である。一方、炭素数が８以上では膜強度が不足する不具合がある。好ましいアルキレン基の炭素数は３～５である。またシリカゾルゲル中のメチル基成分の含有割合が１質量％未満では、油性マジックの汚れが簡便に落ちず、１０質量％を超えると成膜後、膜が白化し、外観を損ねる。 Since the antifouling film-forming liquid composition of the present embodiment contains silica sol-gel as a main component, the antifouling film has excellent adhesion to the substrate and a high-strength antifouling film can be obtained. Further, since the silica sol-gel has a perfluoroamine structure represented by the above general formula (1-1) or a perfluoroether structure represented by the above general formula (1-2), it has a water-repellent and oil-repellent effect. If the content of the fluorine-containing functional group component in the silica sol-gel is less than 0.5% by mass, the formed film cannot be provided with a water- and oil-repellent antifouling function. occurs, resulting in poor film formability. A preferable content ratio of the fluorine-containing functional group component is 0.6% by mass to 5% by mass. If the content of the alkylene group component having 2 to 7 carbon atoms in the silica sol-gel is less than 0.5% by mass, there is a problem that interference fringes are generated in the antifouling film, and if it exceeds 20% by mass, the film strength is insufficient. There is a problem that The content of the alkylene group component having 2 to 7 carbon atoms is preferably 1% to 10% by mass. On the other hand, if the number of carbon atoms is 8 or more, there is a problem that the film strength is insufficient. A preferred alkylene group has 3 to 5 carbon atoms. If the content of the methyl group component in the silica sol-gel is less than 1% by mass, oil-based marker stains will not be easily removed, and if it exceeds 10% by mass, the film will turn white after film formation, detracting from its appearance.
〔防汚性膜の形成方法〕
本実施の形態の防汚性膜は、例えば、基材であるステンレス鋼（ＳＵＳ）、鉄、アルミニウム等の金属板上、窓ガラス、鏡等のガラス上、タイル上、ポリ塩化ビニル（ＰＶＣ）等のプラスチック上、又はポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム上に、上記液組成物を、スクリーン印刷法、バーコート法、ダイコート法、ドクターブレード、スピン法等により塗布した後に、室温乾燥もしくは乾燥機等により室温～１３０℃の温度で乾燥させることにより、形成される。
[Method for forming antifouling film]
The antifouling film of the present embodiment can be applied, for example, on metal plates such as stainless steel (SUS), iron, and aluminum that are substrates, on glass such as window glass and mirrors, on tiles, and on polyvinyl chloride (PVC). The above liquid composition is applied onto a plastic such as polyethylene terephthalate (PET), polybutylene terephthalate, or a polyester film such as polyethylene naphthalate by a screen printing method, a bar coating method, a die coating method, a doctor blade, a spin method, or the like. After coating, the coating is formed by drying at room temperature or drying at a temperature of room temperature to 130° C. using a dryer or the like.
〔防汚性膜〕
本実施の形態の防汚性膜は、膜表面に平均粒径０．１μｍ～５．０μｍのシロキサン骨格の成分を含む粒が１００μｍ2当り７０個～５００個存在する。粒がシロキサン骨格の成分であることは、走査型電子顕微鏡・エネルギー分散型Ｘ線分光装置（ＳＥＭ－ＥＤＸ）による元素分析により測定することができる。粒の平均粒径が０．１μｍ未満では、膜の凹凸が少過ぎるため、油性マジックのふき取り性に劣り、５．０μｍを超えると膜表面が荒れて外観が悪化する。好ましい平均粒径は０．２μｍ～４μｍである。この平均粒径はレーザー顕微鏡にて観察した粒子サイズを計測し、算術平均して求められる。また１００μｍ2当りの粒の数が７０個未満では、膜の凹凸が少過ぎるため、油性マジックのふき取り性の改善が見られず、又は膜表面が荒れて外観が悪化する。５００個を超えると、膜の凹凸が多過ぎるため、外観が悪化する。好ましい粒の個数は１００個～４００個である。防汚性膜の表面粗さＳｑは４５ｎｍ～９５ｎｍである。この表面粗さが４５ｎｍ未満では、凹凸が小さ過ぎるため、油性マジックのふき取り性に劣り、９５ｎｍを超えると、凹凸が大き過ぎるため、外観が悪化する。好ましい表面粗さは５０ｎｍ～８０ｎｍである。更に膜成分中のフッ素（Ｆ）と炭素（Ｃ）とケイ素（Ｓｉ）の質量比が、Ｆ：Ｃ：Ｓｉ＝（０．５～８）：（１４～２１）：（７５～８５）である。この範囲内であれば、適切な撥水撥油性の膜が得られ、油性マジックのふき取り性と膜の良好な外観性を両立した効果を有し、フッ素が少過ぎる場合には、撥油性に劣り、滑り性も悪くなる。炭素が多過ぎる場合には、親油性が強くなり過ぎ、油性マジックの拭き取り性も悪化する。好ましい質量比は、Ｆ：Ｃ：Ｓｉ＝（０．６～６）：（５～２０）：（７７～８４）である。
[Anti-fouling film]
In the antifouling film of the present embodiment, 70 to 500 particles per 100 μm 2 containing siloxane skeleton components with an average particle diameter of 0.1 μm to 5.0 μm are present on the surface of the film. Whether or not the particles are a component of the siloxane skeleton can be determined by elemental analysis using a scanning electron microscope/energy dispersive X-ray spectrometer (SEM-EDX). If the average particle size of the particles is less than 0.1 μm, the film has too little unevenness, and the ability to wipe off the permanent marker is poor. A preferred average particle size is 0.2 μm to 4 μm. This average particle diameter is obtained by measuring the particle size observed with a laser microscope and calculating the arithmetic mean. If the number of grains per 100 μm 2 is less than 70, the unevenness of the film is too small to improve the ability to wipe off the permanent marker, or the surface of the film becomes rough and the appearance deteriorates. If the number exceeds 500, the film has too many irregularities, resulting in poor appearance. The preferred number of grains is 100-400. The surface roughness Sq of the antifouling film is 45 nm to 95 nm. If the surface roughness is less than 45 nm, the unevenness is too small, resulting in poor wiping performance of the permanent marker. A preferred surface roughness is 50 nm to 80 nm. Furthermore, the mass ratio of fluorine (F), carbon (C) and silicon (Si) in the film components is F:C:Si=(0.5-8):(14-21):(75-85). be. Within this range, a film with appropriate water and oil repellency can be obtained, and it has the effect of achieving both the ability to wipe off the permanent marker and the good appearance of the film. It is inferior, and slipperiness also worsens. If the amount of carbon is too high, the lipophilicity becomes too strong, and the wiping property of the permanent marker deteriorates. A preferred mass ratio is F:C:Si=(0.6-6):(5-20):(77-84).
次に本発明の実施例を比較例とともに詳しく説明する。
＜実施例１＞
ケイ素アルコキシドとしてのテトラメトキシシラン（ＴＭＯＳ）の３～５量体（三菱化学社製、商品名：ＭＫＣシリケートＭＳ５１）８．０１ｇと、メチル基含有シランのオリゴマータイプ（ＪＮＣ社製、商品名：ＦＭ－４４１１）０．０９ｇと、式（３１）で表わされるフッ素含有シラン０．０９ｇと、エポキシ基含有シランとして、γ―グリシドキシプロピルトリメトキシシラン（信越化学工業社製、商品名：ＫＢＭ－４０３）０．８１ｇと、エタノール（ＥｔＯＨ）（沸点７８．３℃）１０．５ｇとに、トルエン１０．５ｇを有機溶媒として添加し、更にイオン交換水０．００６ｇを添加して、セパラブルフラスコ内で２５℃の温度で５分間撹拌することにより混合液を調製した。またこの混合液に、触媒として酢酸０．０３ｇを添加し、４０℃で２時間撹拌した。これにより、シリカゾル加水分解物Ｉを調製した。得られたシリカゾルゲルである加水分解物Ｉをエタノール、１－プロパノール、２－プロパノールの混合液（比率 ８５：１０：５）で５倍に希釈して、液組成物が得られた。加水分解物Ｉ（シリカゾルゲル）を作るための液組成を表１に、シリカゾルゲルと溶媒を含む液組成物を表２に、加水分解物Ｉ（シリカゾルゲル）の組成を表３にそれぞれ示す。
Next, examples of the present invention will be described in detail together with comparative examples.
<Example 1>
Tetramethoxysilane (TMOS) trimer to pentamer (manufactured by Mitsubishi Chemical Corporation, trade name: MKC Silicate MS51) 8.01 g as a silicon alkoxide, and an oligomer type methyl group-containing silane (manufactured by JNC, trade name: FM -4411), 0.09 g of a fluorine-containing silane represented by the formula (31), and γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-) as an epoxy group-containing silane. 403) To 0.81 g and 10.5 g of ethanol (EtOH) (boiling point 78.3° C.), 10.5 g of toluene was added as an organic solvent, and 0.006 g of ion-exchanged water was added to obtain a separable flask. A mixture was prepared by stirring at a temperature of 25° C. for 5 minutes. In addition, 0.03 g of acetic acid was added as a catalyst to this mixed solution, and the mixture was stirred at 40° C. for 2 hours. Silica sol hydrolyzate I was thus prepared. The resulting hydrolyzate I, which is silica sol-gel, was diluted 5-fold with a mixture of ethanol, 1-propanol and 2-propanol (ratio 85:10:5) to obtain a liquid composition. The liquid composition for making hydrolyzate I (silica sol-gel) is shown in Table 1, the liquid composition containing silica sol-gel and a solvent is shown in Table 2, and the composition of hydrolyzate I (silica sol-gel) is shown in Table 3.
＜実施例２～７及び比較例１～２＞
表１～表３に示すように、ケイ素アルコキシド、フッ素含有シラン、アルキレン基含有シラン、メチル基含有シラン、水、エタノール（ＥｔＯＨ）、トルエン、触媒を用い、実施例１と同様にして、実施例２～７及び比較例１～２の加水分解物II～IX及び液組成物を得た。
<Examples 2-7 and Comparative Examples 1-2>
As shown in Tables 1 to 3, silicon alkoxide, fluorine-containing silane, alkylene group-containing silane, methyl group-containing silane, water, ethanol (EtOH), toluene, and a catalyst were used in the same manner as in Example 1. Hydrolyzates II to IX and liquid compositions of 2 to 7 and Comparative Examples 1 to 2 were obtained.
＜比較試験及び評価＞
実施例１～７及び比較例１～２で得られた９種類の液組成物を、バーコーター（安田精機製作所製、型番No.３）を用いて、厚さ２ｍｍ、たて１５０ｍｍ、よこ７５ｍｍのＳＵＳ３０４基材上にそれぞれ乾燥後の厚さが０．５～１μｍとなるように塗布し、９種類の塗膜を形成した。ここで、先ずバーコーターによる塗布時の成膜性を評価した。続いてすべての塗膜を室温にて、２０時間乾燥して９種類の防汚性が付与された膜を得た。これらの膜について、膜表面の撥水性、撥油性、ｎ－ヘキサデカンの転落性、膜の基材への密着性、油性マジック汚れの拭き取り性、膜表面の粒の有無と粒のサイズ、膜の表面粗さ及び膜成分中のフッ素とケイ素と炭素の質量比を次の方法で測定して評価した。これらの結果を表４に示す。なお、表４では、ｎ－ヘキサデカンを単に「ＨＤ」と表記している。
<Comparative test and evaluation>
The nine types of liquid compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were coated using a bar coater (manufactured by Yasuda Seiki Seisakusho, Model No. 3) to a thickness of 2 mm, a length of 150 mm, and a width of 75 mm. SUS 304 base material was coated so that the thickness after drying was 0.5 to 1 μm to form 9 kinds of coating films. Here, first, the film-forming properties during coating with a bar coater were evaluated. Subsequently, all the coating films were dried at room temperature for 20 hours to obtain 9 types of antifouling films. Regarding these films, the water repellency and oil repellency of the film surface, the n-hexadecane falling property, the adhesion of the film to the base material, the wiping off of oil-based marker stains, the presence or absence of grains on the film surface and the size of the grains, The surface roughness and the mass ratio of fluorine, silicon and carbon in the film components were measured and evaluated by the following methods. These results are shown in Table 4. In Table 4, n-hexadecane is simply written as "HD".
(1) 成膜性
成膜性は、膜を目視にて評価した。膜全体に弾き、筋等の発生がなく、液組成物を均一に塗布できたものは「良好」とし、膜の一部に僅かに弾き、筋等が生じたものは「可」とし、膜全体に弾き、筋等が生じたものは「不良」とした。
(1) Film formability The film formability was evaluated by visual inspection of the film. If the liquid composition could be uniformly applied without repelling or streaks on the entire film, it was rated as "good", and if it was slightly repelled and streaks occurred on a part of the film, it was rated as "good". If the whole surface was repelled and streaks or the like were generated, it was evaluated as "defective".
(2) 膜表面の撥水性（接触角）
協和界面科学製ドロップマスターＤＭ－７００を用いて、シリンジに２２℃±１℃のイオン交換水を準備し、シリンジの針の先端から２μＬの液滴を飛び出した状態にする。次いで評価するＳＵＳ３０４基材上の防汚性膜をこの液滴に近づけて防汚性膜に液滴を付着させる。この付着した水の接触角を測定した。静止状態で水が膜表面に触れた１秒後の接触角をθ／２法により解析した値を水の接触角とし、膜表面の撥水性を評価した。
(2) Water repellency of film surface (contact angle)
Using Drop Master DM-700 manufactured by Kyowa Interface Science Co., Ltd., ion-exchanged water at 22° C.±1° C. is prepared in a syringe, and a droplet of 2 μL is ejected from the tip of the needle of the syringe. Next, the antifouling film on the SUS 304 substrate to be evaluated is brought close to the droplet so that the droplet adheres to the antifouling film. The contact angle of this adhering water was measured. The water repellency of the film surface was evaluated using the value obtained by analyzing the contact angle of water one second after the film surface was in a stationary state by the θ/2 method.
(3) 膜表面の撥油性（接触角）
協和界面科学製ドロップマスターＤＭ－７００を用いて、シリンジに２２℃±１℃のｎ－ヘキサデカンを準備し、シリンジの針の先端から２μＬの液滴を飛び出した状態にする。次いで評価するＳＵＳ３０４基材上の防汚性膜をこの液滴に近づけて防汚性膜に液滴を付着させる。この付着したｎ－ヘキサデカンの接触角を測定した。静止状態でｎ－ヘキサデカンが膜表面に触れた１秒後の接触角をθ／２法により解析した値をｎ－ヘキサデカンの接触角とし、膜表面の撥油性を評価した。膜の表面状態が凸凹になって荒れていると通常よりも高い値を示すため、接触角が高過ぎる場合には、成膜性が不良であるとの判断基準となる。
(3) Oil repellency of film surface (contact angle)
Using Drop Master DM-700 manufactured by Kyowa Interface Science Co., Ltd., n-hexadecane at 22° C.±1° C. is prepared in a syringe, and a droplet of 2 μL is ejected from the tip of the needle of the syringe. Next, the antifouling film on the SUS 304 substrate to be evaluated is brought close to the droplet so that the droplet adheres to the antifouling film. The contact angle of this adhering n-hexadecane was measured. The oil repellency of the film surface was evaluated using the contact angle of n-hexadecane, which was obtained by analyzing the contact angle of n-hexadecane one second after touching the film surface in a stationary state by the θ/2 method. If the surface condition of the film is uneven and rough, the value is higher than normal. Therefore, if the contact angle is too high, it becomes a criterion for determining that the film formability is poor.
(4) ｎ－ヘキサデカンの転落性試験
協和界面科学製ドロップマスターＤＭ－７００を用いて、シリンジに２５℃±１℃のｎ－ヘキサデカンを準備し、水平に置いたＳＵＳ３０４基材上にシリンジからｎ－ヘキサデカンを９μＬの液滴を滴下し、基材を２度／分の速度で傾斜させ、ｎ－ヘキサデカンの液滴が移動開始するときの基材の傾けた角度を測定した。(3)の接触角が低くてもこの転落角度が小さい方が防汚性が高いことを意味する。
(4) Falling property test of n-hexadecane Using Drop Master DM-700 manufactured by Kyowa Interface Science, n-hexadecane at 25 ° C ± 1 ° C was prepared in a syringe, and placed horizontally on a SUS 304 base material from the syringe. A droplet of 9 μL of n-hexadecane was dropped, the substrate was tilted at a speed of 2 degrees/minute, and the tilt angle of the substrate when the droplet of n-hexadecane started to move was measured. Even if the contact angle of (3) is low, the smaller the falling angle, the higher the antifouling property.
(5) 膜の基材への密着性
７５ｍｍ×１５０ｍｍ×厚さ２ｍｍのＳＵＳ３０４基材上に塗膜を形成した。塗膜の上に、セロファンテープを貼り付けた後、テープを剥がしたときに、塗膜がテープ側に全く付かなかった場合を密着性が「良好」であるとし、塗膜の大部分がテープ側に貼り付き、ＳＵＳ基材界面で塗膜が剥がれてしまった場合を密着性が「不良」であるとした。
(5) Adhesion of Film to Substrate A coating film was formed on a SUS304 substrate of 75 mm×150 mm×2 mm thickness. After sticking cellophane tape on the coating film, when the tape is peeled off, the adhesion is considered to be "good" if the coating film does not stick to the tape at all, and most of the coating film is covered by the tape. Adhesion was determined to be "bad" when the coating film was stuck to the side and peeled off at the interface of the SUS substrate.
(6) 油性マジック汚れの拭き取り性
塗膜の上に、油性マジック［寺西化学工業（株）製 マジックインキ（登録商標）ＮＯ．７００ゴクホソ（黒）］で長さ３ｃｍの直線を書き、３０分後に、ベンコット（旭化成社製）にて、書いた部分を擦った。擦った回数が１～２回で油性マジックが容易に拭き取れたものを「良好」とし、３回以上擦って油性マジックが拭き取れたものを「可」とし、何回擦っても拭き取れなかったもの、又は塗膜が剥離してしまったものを「不可」とした。
(6) Ability to wipe off oil-based marker stains On the coating film, apply an oil-based marker [Magic Ink (registered trademark) NO. 700 Gokuhoso (black)], and after 30 minutes, the written portion was rubbed with Bemcot (manufactured by Asahi Kasei Co., Ltd.). The number of times of rubbing was 1-2 times and the oil-based marker was easily wiped off, which was rated as "good"; Or, when the coating film was peeled off, it was evaluated as "failed".
(7) 膜表面の観察
走査型レーザー顕微鏡（ＬＥＸＴ ＯＬＳ４５００：オリンパス社製）にて、１００μｍ2当りの塗膜を観察し、塗膜１００μｍ2当り７０～５００個の粒が存在するか否か、また存在する場合には、粒の大きさ（平均粒径）を観察した。
(7) Observation of film surface The coating film per 100 μm 2 is observed with a scanning laser microscope (LEXT OLS 4500: manufactured by Olympus) to determine whether 70 to 500 grains are present per 100 μm 2 of the coating film. When present, the grain size (average grain size) was observed.
(8) 膜の表面粗さ
走査型レーザー顕微鏡（ＬＥＸＴ ＯＬＳ４５００：オリンパス社製）にて、塗膜面の凹凸を計測し、表面粗さとして二乗平均平方根高さＳｑ値を算出した。
(8) Surface Roughness of Film The unevenness of the coating film surface was measured with a scanning laser microscope (LEXT OLS4500: manufactured by Olympus Corporation), and the root mean square height Sq value was calculated as the surface roughness.
(9) 膜成分中のフッ素とケイ素と炭素の質量比
塗膜を走査型電子顕微鏡・エネルギー分散型Ｘ線分光装置（ＳＥＭ－ＥＤＸ、日立ハイテクノロジー社製、ＳＵ－１５００）により塗膜の元素分析を行い、フッ素とケイ素と炭素の質量比を求めた。
(9) Mass ratio of fluorine, silicon and carbon in film components An analysis was performed to determine the mass ratio of fluorine, silicon and carbon.
表４から明らかなように、比較例１の液組成物では、シリカゾルゲル中、メチル基成分が存在しないため、膜表面に粒が存在せず、表面粗さＳｑ値に関しても４２ｎｍと低く、表面の凹凸が少ないこと、並びに、Ｆ：Ｃ：Ｓｉの比率にて、Ｃ値が１３．８と低いことから、撥水性と滑り性がやや悪化するため、油性マジック汚れの拭き取り性は「可」であった。それ以外の評価項目については、成膜性、塗膜の撥水撥油性、ｎ－ヘキサデカンの転落角、膜の基材への密着性はすべて良好であった。 As is clear from Table 4, in the liquid composition of Comparative Example 1, since no methyl group component was present in the silica sol-gel, no particles were present on the film surface, and the surface roughness Sq value was as low as 42 nm. and the C value is as low as 13.8 at the ratio of F:C:Si, so the water repellency and slipperiness are slightly deteriorated, so the wiping off of oily marker stains is “acceptable”. Met. As for the other evaluation items, the film-forming property, the water and oil repellency of the coating film, the falling angle of n- hexadecane, and the adhesion of the film to the substrate were all good.
また比較例２の液組成物では、シリカゾルゲル中、メチル基成分が１１．２質量％と多過ぎたため、成膜性が「不可」であり、膜表面に粒が存在したが、粒のサイズが８．０μｍと大き過ぎた。また、粒子の数も６０個と少ないこと、表面粗さＳｑ値も１２０ｎｍと大き過ぎることから、油性マジック汚れの拭き取り性は「可」であった。塗膜の撥水撥油性は良好であったが、ｎ－ヘキサデカンの転落性がやや劣っていた。膜の基材への密着性は良好であった。 In addition, in the liquid composition of Comparative Example 2, the methyl group component in the silica sol-gel was too large at 11.2% by mass, so the film-forming property was "impossible", and grains were present on the film surface, but the size of the grains was too large at 8.0 μm. In addition, the number of particles was as small as 60, and the surface roughness Sq value was too large as 120 nm. The water and oil repellency of the coating film was good, but the n- hexadecane drop-off property was slightly inferior. Adhesion of the film to the substrate was good.
これに対して、表４から明らかなように、実施例１～７の液組成物では、成膜性、塗膜の撥水撥油性、ｎ－ヘキサデカンの転落角、膜の基材への密着性はすべて良好であった。また膜表面にはすべて粒が７０個～５００個の範囲内で存在し、その平均粒径は０．１μｍ～５．０μｍの範囲内にあった。また、Ｆ：Ｃ：Ｓｉの比率も、（０．５～８）：（１４～２１）：（７５～８５）の範囲内にあった。この結果、油性マジック汚れの拭き取り性は良好であった。 On the other hand, as is clear from Table 4, the liquid compositions of Examples 1 to 7 exhibited excellent film-forming properties, water and oil repellency of the coating film, n- hexadecane falling angle, and adhesion of the film to the substrate. All the properties were good. In addition, 70 to 500 grains were present on all the film surfaces, and the average grain size was within the range of 0.1 μm to 5.0 μm. The ratio of F:C:Si was also in the range of (0.5-8):(14-21):(75-85). As a result, the wiping-off property of oil-based marker stains was good.
本発明の防汚性膜形成用液組成物は、機械油を使用する工場、油が飛散する厨房、油蒸気が立ちこめるレンジフード、換気扇、冷蔵庫扉等において、油汚れを防止する分野及び事務機器等の汚れを防止する分野に用いられる。 The antifouling film-forming liquid composition of the present invention is used in the field and office equipment to prevent oil stains in factories using machine oil, kitchens where oil scatters, range hoods, ventilators, refrigerator doors, etc. where oil vapor is trapped. It is used in the field to prevent dirt such as
Claims (1)
前記シリカゾルゲルを１００質量％とするときに、前記シリカゾルゲルが下記の一般式（１－１）で示されるペルフルオロアミン構造のフッ素含有官能基成分又は下記の一般式（１－２）で示されるペルフルオロエーテル構造のフッ素含有官能基成分を０．５質量％～１０質量％と炭素数２～７のアルキレン基成分を０．５質量％～２０質量％とメチル基成分を０．２質量％～１０質量％含み、
前記アルキレン基成分は、２－ (３，４－エポキシシクロヘキシル)エチルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン 又は多官能エポキシシランであり、
前記メチル基成分は、メチルトリメトキシシランのモノマー、ジメチルトリエトキシシランのモノマー、ポリジメチルシロキサン化合物、メトキシ基含有メチル系シリコーンオリゴマーであり、
前記溶媒が、炭素数１～４のアルコール及び／又は前記アルコール以外の溶媒である防汚性膜形成用液組成物の乾燥物であって、
膜表面に平均粒径０．１μｍ～５．０μｍのシロキサン骨格の成分を含む粒が１００μｍ2当り７０個～５００個存在し、表面粗さＳｑが４５ｎｍ～９５ｎｍであって、膜成分中のフッ素（Ｆ）と炭素（Ｃ）とケイ素（Ｓｉ）の質量比が、Ｆ：Ｃ：Ｓｉ＝（０．５～８）：（１４～２１）：（７５～８５）であることを特徴とする防汚性膜。
。また、Ｒｆ １ は、炭素数１～６のペルフルオロアルキレン基であって、直鎖状又は分枝
状であってもよい。また上記式（１－１）中、Ｘ１は、炭素数２～１０の炭化水素基であ
って、エーテル結合、ＣＯ－ＮＨ結合、Ｏ－ＣＯ－ＮＨ結合及びスルホンアミド結合から
選択される１種以上の結合を含んでいてもよい。
。また、また上記式（１－２）中、Ｘ１は、炭素数２～１０の炭化水素基であって、エー
テル結合、ＣＯ－ＮＨ結合、Ｏ－ＣＯ－ＮＨ結合及びスルホンアミド結合から選択される
１種以上の結合を含んでいてもよい。 Contains a component mainly composed of silica sol-gel and a solvent,
When the silica sol-gel is 100% by mass, the silica sol-gel is a fluorine-containing functional group component of a perfluoroamine structure represented by the following general formula (1-1) or represented by the following general formula (1-2) 0.5% to 10% by mass of a fluorine-containing functional group component of a perfluoroether structure, 0.5% to 20% by mass of an alkylene group component having 2 to 7 carbon atoms, and 0.2% by mass or more of a methyl group component 10% by mass,
The alkylene group component includes 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxysilane. silane, 3-glycidoxypropyltriethoxysilane or a polyfunctional epoxysilane,
The methyl group component is a methyltrimethoxysilane monomer, a dimethyltriethoxysilane monomer, a polydimethylsiloxane compound, or a methoxy group-containing methyl-based silicone oligomer,
The solvent is an alcohol having 1 to 4 carbon atoms and/or a dried product of a liquid composition for forming an antifouling film in which the solvent is a solvent other than the alcohol,
70 to 500 particles per 100 μm 2 containing siloxane skeleton components with an average particle size of 0.1 μm to 5.0 μm are present on the film surface, the surface roughness Sq is 45 nm to 95 nm, and fluorine in the film components The mass ratio of (F), carbon (C) and silicon (Si) is F:C:Si=(0.5-8):(14-21):(75-85) Antifouling membrane.
. In addition, Rf 1 is a perfluoroalkylene group having 1 to 6 carbon atoms and is linear or branched.
may be in the form of Further, in the above formula (1-1), X1 is a hydrocarbon group having 2 to 10 carbon atoms.
from an ether bond, a CO-NH bond, an O-CO-NH bond and a sulfonamide bond
It may contain one or more selected bonds.
. Further, in the above formula (1-2), X1 is a hydrocarbon group having 2 to 10 carbon atoms,
selected from a ter bond, a CO-NH bond, an O-CO-NH bond and a sulfonamide bond
It may contain one or more bonds.
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