JP7259789B2 - Quality evaluation method and quality control method for thin film of hydrolyzable fluorine-containing organosilicon compound - Google Patents
Quality evaluation method and quality control method for thin film of hydrolyzable fluorine-containing organosilicon compound Download PDFInfo
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本発明は、加水分解性含フッ素有機ケイ素化合物の薄膜の品質評価方法及び品質管理方法に関する。 TECHNICAL FIELD The present invention relates to a quality evaluation method and a quality control method for thin films of hydrolyzable fluorine-containing organosilicon compounds.
含フッ素有機ケイ素化合物は、通常、分子中にパーフルオロオキシアルキレン単位の繰り返し構造（パーフルオロポリエーテル構造）と、アルコキシシリル基等の加水分解性シリル基等を２個以上有する加水分解性含フッ素有機ケイ素化合物であり、特許文献１～４等で開示されている。これらの加水分解性含フッ素有機ケイ素化合物は、金属、磁器、ガラス等の基材表面に塗布・硬化され、該基材表面に撥水撥油層（防汚コーティング薄膜層）を形成して、油脂汚れ、指紋汚れ、その他の汚れを防止する機能を基材に付加するために用いられている。最近では車載レンズ、車載ディスプレイ、携帯用電子機器端末ディスプレイの反射防止膜上に当該の化合物が汚れ防止の目的で使用されている。 Fluorine-containing organosilicon compounds usually have a repeating structure of perfluorooxyalkylene units (perfluoropolyether structure) and two or more hydrolyzable silyl groups such as alkoxysilyl groups in the molecule. It is an organosilicon compound and is disclosed in Patent Documents 1 to 4 and the like. These hydrolyzable fluorine-containing organosilicon compounds are coated and cured on the surface of a substrate such as metal, porcelain, glass, etc., to form a water- and oil-repellent layer (antifouling coating thin film layer) on the substrate surface, It is used to add anti-smudge, fingerprint smudge, and other anti-smudge features to substrates. Recently, the compounds are used for antifouling purposes on antireflection films of vehicle-mounted lenses, vehicle-mounted displays, and portable electronic device terminal displays.
このような用途において、防汚コーティング薄膜層の性能として、撥水撥油性の他に光学的特性や耐久性が重要視されている。この防汚コーティング薄膜層の光学的特性は通常、紫外線から近赤外線までの透過率、反射率や曇り度（ヘーズ）により判断される。また、防汚コーティング薄膜層の耐久性は種々の材料による摩耗に対する摩耗耐久性や、種々の薬品への曝露に対する耐薬品性により判断される。 In such applications, optical properties and durability, in addition to water and oil repellency, are considered important as the performance of the antifouling coating thin film layer. The optical properties of this antifouling coating thin film layer are usually determined by the transmittance, reflectance and haze of ultraviolet to near-infrared rays. Further, the durability of the antifouling coating thin film layer is judged by the wear resistance against abrasion by various materials and the chemical resistance against exposure to various chemicals.
防汚コーティング薄膜層の形成において、一般的には、防汚コーティング薄膜層の品質を前述の光透過率や曇り度、摩耗耐久性や耐薬品性により評価し、その形成状態を管理する。しかし、摩耗耐久性の評価には長時間を要するため、防汚コーティング薄膜評価の効率化の観点で、簡便かつ確実な品質評価方法の開発が望まれている。 In the formation of the antifouling coating thin film layer, generally, the quality of the antifouling coating thin film layer is evaluated by the aforementioned light transmittance, haze, wear durability and chemical resistance, and the state of formation thereof is controlled. However, since it takes a long time to evaluate wear resistance, it is desired to develop a simple and reliable quality evaluation method from the viewpoint of improving the efficiency of antifouling coating thin film evaluation.
したがって、本発明は撥水撥油性、光学的特性、耐久性を有する含フッ素有機ケイ素化合物、特には、加水分解性含フッ素有機ケイ素化合物の薄膜（防汚コーティング薄膜）の膜厚を品質指標とした該薄膜の品質を効率的に評価及び管理する方法を提供することを目的とする。 Therefore, in the present invention, the thickness of a thin film (antifouling coating thin film) of a fluorine-containing organosilicon compound, particularly a hydrolyzable fluorine-containing organosilicon compound, having water and oil repellency, optical properties, and durability, is used as a quality index. It is an object of the present invention to provide a method for efficiently evaluating and controlling the quality of the thin film.
本発明者は、上記目的を達成するため鋭意研究した結果、撥水撥油性、光学的特性、摩耗耐久性と防汚コーティング層の膜厚とは相関関係があり、防汚コーティング層の膜厚を品質指標として計測することにより、その品質を効率的に評価及び管理できることを見出し、本発明を完成した。 As a result of intensive research to achieve the above object, the present inventors have found that there is a correlation between water and oil repellency, optical properties, wear durability, and the thickness of the antifouling coating layer, and that the thickness of the antifouling coating layer As a quality index, the inventors found that the quality can be efficiently evaluated and managed, and completed the present invention.
すなわち本発明は、下記の含フッ素有機ケイ素化合物の薄膜の品質評価方法及び品質管理方法を提供するものである。 That is, the present invention provides the following quality evaluation method and quality control method for a thin film of a fluorine-containing organosilicon compound.
［１］
基材上に形成された加水分解性含フッ素有機ケイ素化合物の薄膜の膜厚を計測し、該膜厚が６ｎｍから１１ｎｍであるか否かを判断する工程を含む加水分解性含フッ素有機ケイ素化合物の薄膜の品質を評価する方法。
［２］
基材上に形成された加水分解性含フッ素有機ケイ素化合物の薄膜の膜厚の計測方法が分光反射率計測による方法、分光エリプソメトリー計測による方法、及び／又は蛍光エックス線計測による方法である［１］に記載の加水分解性含フッ素有機ケイ素化合物の薄膜の品質を評価する方法。
［３］
基材が、シリコン単結晶基材、ガラス基材、金属基材、樹脂基材、二酸化ケイ素膜が塗布されたシリコン単結晶基材、二酸化ケイ素膜が塗布されたガラス基材、二酸化ケイ素膜が塗布された金属基材、及び二酸化ケイ素膜が塗布された樹脂基材から選ばれる［１］又は［２］に記載の加水分解性含フッ素有機ケイ素化合物の薄膜の品質を評価する方法。
［４］
加水分解性含フッ素有機ケイ素化合物の薄膜の形成方法がスプレー塗工、インクジェット塗工、スピン塗工、浸漬塗工、又は真空蒸着塗工の手段であることを特徴とする［１］～［３］のいずれかに記載の加水分解性含フッ素有機ケイ素化合物の薄膜の品質を評価する方法。
［５］
［１］～［４］のいずれかに記載の加水分解性含フッ素有機ケイ素化合物の薄膜の品質を評価する方法により、得られた評価結果に基づき、該薄膜の膜厚を調整することを特徴とする加水分解性含フッ素有機ケイ素化合物の薄膜の品質を管理する方法。
[1]
A hydrolyzable fluorine-containing organosilicon compound comprising a step of measuring the film thickness of a thin film of a hydrolyzable fluorine-containing organosilicon compound formed on a substrate and determining whether the film thickness is between 6 nm and 11 nm. A method for evaluating the quality of thin films of
[2]
The method for measuring the film thickness of the hydrolyzable fluorine-containing organosilicon compound thin film formed on the substrate is a method by spectroscopic reflectance measurement, a method by spectroscopic ellipsometry measurement, and/or a method by fluorescent X-ray measurement [1 ]. A method for evaluating the quality of a thin film of a hydrolyzable fluorine-containing organosilicon compound.
[3]
The substrate is a silicon single crystal substrate, a glass substrate, a metal substrate, a resin substrate, a silicon single crystal substrate coated with a silicon dioxide film, a glass substrate coated with a silicon dioxide film, or a silicon dioxide film A method for evaluating the quality of a thin film of a hydrolyzable fluorine-containing organosilicon compound according to [1] or [2], which is selected from a coated metal substrate and a resin substrate coated with a silicon dioxide film.
[4]
[1] to [3], wherein the method for forming a thin film of a hydrolyzable fluorine-containing organosilicon compound is spray coating, inkjet coating, spin coating, dip coating, or vacuum deposition coating. ] A method for evaluating the quality of a thin film of a hydrolyzable fluorine-containing organosilicon compound according to any one of the above.
[5]
The film thickness of the thin film is adjusted based on the evaluation results obtained by the method for evaluating the quality of the thin film of the hydrolyzable fluorine-containing organosilicon compound according to any one of [1] to [4]. A method for controlling the quality of a thin film of a hydrolyzable fluorine-containing organosilicon compound.
本発明は、膜厚を制御することで高い撥水撥油性、高い透過率、低い曇り度、高い摩耗耐久性と耐薬品性を有する加水分解性含フッ素有機ケイ素化合物の薄膜（防汚コーティング薄膜）を均質な品質で効果的な形成に資するものである。 The present invention provides a thin film of a hydrolyzable fluorine-containing organosilicon compound (antifouling coating thin film) that has high water and oil repellency, high transmittance, low haze, high wear durability and chemical resistance by controlling the film thickness. ) with uniform quality and effective formation.
加水分解性含フッ素有機ケイ素化合物の薄膜の形成
特許文献１～４等で開示されている含フッ素有機ケイ素化合物、特には、分子中にパーフルオロオキシアルキレン単位の繰り返し構造（パーフルオロポリエーテル構造）と、アルコキシシリル基等の加水分解性シリル基等を２個以上有する加水分解性含フッ素有機ケイ素化合物を含むコーティング液を、平坦な基材の表面上にスプレー塗工、インクジェット塗工、スピン塗工、浸漬塗工、真空蒸着塗工等の手段で塗布することで、含フッ素有機ケイ素化合物の薄膜が得られる。基材表面の算術平均粗さは１．０ｎｍ未満、二乗平均平方根粗さは２．０ｎｍ未満であることが好ましく、基材の材質はシリコン単結晶、ガラス、金属、樹脂、二酸化ケイ素膜が塗布されたシリコン単結晶（二酸化ケイ素をあらかじめ蒸着、スパッタ、ＣＶＤ、熱酸化処理等により成膜した基材）、二酸化ケイ素膜が塗布されたガラス、二酸化ケイ素膜が塗布された金属、二酸化ケイ素膜が塗布された樹脂である。
Formation of thin film of hydrolyzable fluorine-containing organosilicon compound Fluorine-containing organosilicon compounds disclosed in Patent Documents 1 to 4, in particular, a repeating structure of perfluorooxyalkylene units in the molecule (perfluoropolyether structure) and a coating liquid containing a hydrolyzable fluorine-containing organosilicon compound having two or more hydrolyzable silyl groups such as an alkoxysilyl group is applied onto the surface of a flat substrate by spray coating, inkjet coating, or spin coating. A thin film of the fluorine-containing organosilicon compound can be obtained by coating by means of coating, dip coating, vacuum deposition coating, or the like. The arithmetic mean roughness of the substrate surface is preferably less than 1.0 nm, and the root mean square roughness is preferably less than 2.0 nm. The material of the substrate is silicon single crystal, glass, metal, resin, silicon dioxide film coated silicon single crystal (substrate on which silicon dioxide is deposited in advance by vapor deposition, sputtering, CVD, thermal oxidation treatment, etc.), glass coated with silicon dioxide film, metal coated with silicon dioxide film, silicon dioxide film It is a coated resin.
基材の表面上に塗布（製膜）した含フッ素有機ケイ素化合物は、大気雰囲気下で一定時間放置することで、例えば大気中の湿気（水分）により加水分解・縮合して硬化することにより基材と良好に接着する。放置条件は、２５℃、相対湿度５０％の大気下での１２時間放置や、１５０℃、１時間放置などである。 The fluorine-containing organosilicon compound coated (film-formed) on the surface of the base material is left in the atmosphere for a certain period of time, for example, by hydrolysis and condensation due to moisture (moisture) in the air, and hardening. Adheres well to wood. Leaving conditions include leaving for 12 hours in the atmosphere at 25° C. and relative humidity of 50%, and leaving at 150° C. for 1 hour.
加水分解性含フッ素有機ケイ素化合物の薄膜の膜厚の計測
加水分解性含フッ素有機ケイ素化合物の薄膜の膜厚は、分光反射率計測による方法、分光エリプソメトリー計測による方法、及び／又は蛍光エックス線計測による方法により計測できる。
Measurement of film thickness of hydrolyzable fluorine-containing organosilicon compound thin film The thickness of the hydrolyzable fluorine-containing organosilicon compound thin film is measured by spectral reflectance measurement, spectroscopic ellipsometry measurement, and/or fluorescent X-ray measurement. It can be measured by the method by
（分光反射率計測による膜厚計測方法）
加水分解性含フッ素有機ケイ素化合物の薄膜を製膜（塗布及び硬化）した基材の分光反射率スペクトルに見られる、空気－加水分解性含フッ素有機ケイ素化合物薄膜の境界面および加水分解性含フッ素有機ケイ素化合物薄膜－基材の境界面で生じる反射光の干渉に起因する反射率の周期的な増減から膜厚を求めることができる。すなわち、式（１）を満たす場合は反射率の周期的変化の極大値をとり、式（２）を満たす場合に反射率の周期的変化の極小値をとる。したがって、加水分解性含フッ素有機ケイ素化合物の薄膜の屈折率、極大値および極小値の波長と整数ｍから、加水分解性含フッ素有機ケイ素化合物の薄膜の膜厚を求めることができる。整数ｍと波長の逆数（波数）１／λには比例関係があるため、分光反射率スペクトルの各極大値および各極小値に対応する整数ｍを求めることができる。加水分解性含フッ素有機ケイ素化合物の薄膜の屈折率は従前の方法により求めることができる（例えば、特願２０１９－１４５８５６号を参照せよ。）。このような計測は分光反射率計測器により行うことができる。
ｄ＝２ｍλ／４ｎ （１）
ｄ＝（（２ｍ＋１）λ）／４ｎ （２）
ここで、ｄは加水分解性含フッ素有機ケイ素化合物の薄膜の膜厚、ｍは整数、λは波長、ｎは加水分解性含フッ素有機ケイ素化合物の薄膜の屈折率である。
(Thickness measurement method by spectral reflectance measurement)
Air-hydrolyzable fluorinated organosilicon compound thin film interface and hydrolyzable fluorinated organosilicon compound thin film observed in spectral reflectance spectra of substrates on which thin films of hydrolyzable fluorinated organosilicon compounds have been formed (coated and cured) The film thickness can be determined from the periodic increase and decrease in reflectance caused by the interference of reflected light occurring at the interface between the organosilicon compound thin film and the substrate. That is, when the formula (1) is satisfied, the maximum value of the periodic change in reflectance is obtained, and when the formula (2) is satisfied, the minimum value of the periodic change in the reflectance is obtained. Therefore, the film thickness of the hydrolyzable fluorine-containing organic silicon compound thin film can be determined from the refractive index of the thin film of the hydrolyzable fluorine-containing organic silicon compound, the wavelengths of the maximum and minimum values, and the integer m. Since there is a proportional relationship between the integer m and the reciprocal of the wavelength (wavenumber) 1/λ, the integer m corresponding to each maximum value and each minimum value of the spectral reflectance spectrum can be obtained. The refractive index of a thin film of a hydrolyzable fluorine-containing organosilicon compound can be determined by a conventional method (see, for example, Japanese Patent Application No. 2019-145856). Such measurements can be made with a spectral reflectance meter.
d=2mλ/4n (1)
d=((2m+1)λ)/4n (2)
Here, d is the film thickness of the hydrolyzable fluorine-containing organic silicon compound thin film, m is an integer, λ is the wavelength, and n is the refractive index of the hydrolyzable fluorine-containing organic silicon compound thin film.
（分光エリプソメトリー計測による膜厚計測方法）
加水分解性含フッ素有機ケイ素化合物の薄膜を製膜した基材に直線偏光を入射し、反射される楕円偏光の位相角Δと、楕円偏光の振幅強度比から求められる正接Ψの値を計測することで、当該薄膜の光学定数（屈折率ｎ、消衰係数κ）から、その膜厚を特定できる。加水分解性含フッ素有機ケイ素化合物の薄膜の光学定数は従前の方法により求めることができる（例えば、特願２０１９－１４５８５６号を参照せよ。）。このような計測はエリプソメーターにより行うことができる。
(Film thickness measurement method by spectroscopic ellipsometry measurement)
Linearly polarized light is incident on a substrate on which a thin film of a hydrolyzable fluorine-containing organosilicon compound is formed, and the tangent Ψ value obtained from the phase angle Δ of the reflected elliptically polarized light and the amplitude intensity ratio of the elliptically polarized light is measured. Thus, the film thickness can be specified from the optical constants (refractive index n, extinction coefficient κ) of the thin film. The optical constants of a thin film of a hydrolyzable fluorine-containing organosilicon compound can be obtained by conventional methods (see, for example, Japanese Patent Application No. 2019-145856). Such measurements can be made with an ellipsometer.
（蛍光エックス線計測による膜厚計測方法）
また、蛍光エックス線計測によっても、加水分解性含フッ素有機ケイ素化合物の薄膜の膜厚を計測することができる。すなわち、ＪＩＳ Ｈ ８５０１：１９９９に示されたのと同様の方法で計測可能である。その場合、原子間力顕微鏡や触針式段差計で得た膜厚とフッ素元素由来の蛍光エックス線強度との相関を表す校正式を事前に準備する必要がある。
(Thickness measurement method by fluorescent X-ray measurement)
The thickness of the thin film of the hydrolyzable fluorine-containing organosilicon compound can also be measured by fluorescent X-ray measurement. That is, it can be measured by a method similar to that shown in JIS H 8501:1999. In that case, it is necessary to prepare in advance a calibration formula that expresses the correlation between the film thickness obtained by an atomic force microscope or a stylus profilometer and the intensity of fluorescent X-rays derived from elemental fluorine.
本発明では、ガラス、樹脂、金属等の基材上への加水分解性含フッ素有機ケイ素化合物の薄膜の形成において、該薄膜の膜厚を上記方法で計測し、該膜厚が６～１１ｎｍであると判断することが好ましい。また、本発明において、加水分解性含フッ素有機ケイ素化合物の薄膜の膜厚は、６～１１ｎｍであることが好ましく、７～１１ｎｍであることがより好ましく、８～１１ｎｍであることが最も好ましい。 In the present invention, in forming a thin film of a hydrolyzable fluorine-containing organosilicon compound on a substrate such as glass, resin, metal, etc., the film thickness of the thin film is measured by the above method, and the film thickness is 6 to 11 nm. It is preferable to determine that In the present invention, the film thickness of the hydrolyzable fluorine-containing organosilicon compound is preferably 6 to 11 nm, more preferably 7 to 11 nm, and most preferably 8 to 11 nm.
加水分解性含フッ素有機ケイ素化合物の薄膜の品質評価
加水分解性含フッ素有機ケイ素化合物の薄膜の品質は撥水性、撥油性、光透過率、曇り度、摩耗耐久性等の諸計測値により評価できる。
Quality evaluation of hydrolyzable fluorine-containing organosilicon compound thin films The quality of hydrolyzable fluorine-containing organosilicon compound thin films can be evaluated by various measurement values such as water repellency, oil repellency, light transmittance, haze, and abrasion resistance. .
（撥水性）
加水分解性含フッ素有機ケイ素化合物の薄膜を製膜した基材表面の水接触角により撥水性を評価する。水接触角は接触角計測装置を用いて計測できる。
(water repellency)
Water repellency is evaluated from the water contact angle of the substrate surface on which a thin film of the hydrolyzable fluorine-containing organosilicon compound is formed. The water contact angle can be measured using a contact angle measuring device.
（撥油性）
加水分解性含フッ素有機ケイ素化合物の薄膜を製膜した基材表面のオレイン酸もしくはヘキサデカンの接触角により撥油性を評価する。オレイン酸もしくはヘキサデカンの接触角は接触角計測装置を用いて計測できる。
(oil repellency)
The oil repellency is evaluated from the contact angle of oleic acid or hexadecane on the surface of the substrate on which the thin film of the hydrolyzable fluorine-containing organosilicon compound is formed. The contact angle of oleic acid or hexadecane can be measured using a contact angle measuring device.
（光透過率）
加水分解性含フッ素有機ケイ素化合物の薄膜を製膜した基材の光透過率は分光光度計により計測できる。
(light transmittance)
The light transmittance of the substrate on which the thin film of the hydrolyzable fluorine-containing organosilicon compound is formed can be measured with a spectrophotometer.
（曇り度）
加水分解性含フッ素有機ケイ素化合物の薄膜を製膜した基材の曇り度はＪＩＳ Ｋ７３６１に準じた方法で、ヘーズメーターを使用して計測できる。
(cloudiness)
The haze of a substrate on which a thin film of a hydrolyzable fluorine-containing organosilicon compound has been formed can be measured using a haze meter according to JIS K7361.
（摩耗耐久性）
摩耗耐久性について、加水分解性含フッ素有機ケイ素化合物の薄膜を製膜した基材をスチールウールや消しゴムを用いて摩擦し、摩耗部分の水接触角を計測することにより摩耗耐久性を評価できる。
(wear resistance)
Abrasion resistance can be evaluated by rubbing a base material on which a thin film of a hydrolyzable fluorine-containing organosilicon compound is formed with steel wool or an eraser, and measuring the water contact angle of the abraded portion.
以下、実施例及び比較例を示して本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
［実施例１］
（コーティング液の調製）
下記式で表される化合物１をフッ素溶剤（３Ｍ社製ＮＯＶＥＣ７２００）に重量濃度が２０％になるように溶解し、コーティング液とした。
(Preparation of coating liquid)
Compound 1 represented by the following formula was dissolved in a fluorinated solvent (NOVEC7200 manufactured by 3M) to a weight concentration of 20% to prepare a coating solution.
（コーティング液の塗布）
抵抗加熱型真空蒸着装置（ＶＴＲ－３５０Ｍ、アルバック機工製）にＳｉＯ2が１０ｎｍの膜厚で成膜されているガラス基材をセットし、抵抗加熱部にコーティング液を４μＬ滴下し、減圧した。容器内圧力が３×１０-3Ｐａ以下にまで減圧されたら、抵抗加熱を開始した。抵抗加熱部から約２０ｃｍ離れた位置に設置された水晶振動子膜厚計における最大蒸発速度が１．０ｎｍ／秒になるように抵抗加熱に投入する電力を調整した。水晶振動子膜厚計における蒸発速度が０．１ｎｍ／秒まで減少してから１００秒間は抵抗加熱を継続した。装置冷却のため、５分間待機後、大気開放を行い、化合物１の塗膜を有する基材を得た。
(Application of coating liquid)
A glass substrate having a 10 nm-thickness SiO 2 film was set in a resistance heating type vacuum deposition apparatus (VTR-350M, manufactured by ULVAC KIKO), and 4 μL of the coating liquid was dropped on the resistance heating part and the pressure was reduced. When the pressure inside the container was reduced to 3×10 −3 Pa or less, resistance heating was started. The power applied to the resistance heating was adjusted so that the maximum evaporation rate in a crystal oscillator film thickness gauge installed at a position about 20 cm away from the resistance heating part was 1.0 nm/sec. Resistive heating was continued for 100 seconds after the evaporation rate in the crystal oscillator film thickness gauge had decreased to 0.1 nm/sec. After waiting for 5 minutes to cool the apparatus, the apparatus was opened to the atmosphere to obtain a base material having a coating film of Compound 1.
（塗膜の硬化）
化合物１の塗膜を有する基材を２５℃、相対湿度５０％の環境下で１２時間以上放置し、塗膜を硬化し、化合物１の薄膜を得た。
(Curing of coating film)
A base material having a coating film of Compound 1 was allowed to stand in an environment of 25° C. and a relative humidity of 50% for 12 hours or longer to cure the coating film, thereby obtaining a thin film of Compound 1.
（膜厚の計測）
蛍光エックス線計測装置（Ｐｒｉｍｉｎｉ、リガク製）を使用して化合物１の薄膜の膜厚を得た。
(Measurement of film thickness)
The film thickness of the thin film of Compound 1 was obtained using a fluorescent X-ray measuring device (Primini, manufactured by Rigaku).
（撥水性の評価）
化合物１の薄膜を製膜した基材の水接触角を接触角計測装置（ＤｒｏｐＭａｓｔｅｒＤＭ－７０１、協和界面科学製）を用いて計測した。水滴量２μＬで計測し、水接触角１１２度以上で◎（優）、１０６度以上１１２度未満で○（良）、１００度以上１０６度未満で△（可）、１００度未満で×（不可）と評価した。
(Evaluation of water repellency)
The water contact angle of the base material on which the thin film of Compound 1 was formed was measured using a contact angle measuring device (DropMaster DM-701, manufactured by Kyowa Interface Science). Measured with a water droplet volume of 2 μL, ◎ (excellent) at a water contact angle of 112 degrees or more, ○ (good) at 106 degrees or more and less than 112 degrees, △ (acceptable) at 100 degrees or more and less than 106 degrees, and × (improper) at less than 100 degrees. ).
（曇り度の評価）
化合物１の薄膜を製膜した基材の曇り度はヘーズメーター（ＮＤＨ５０００、日本電色工業製）を使用して計測した。曇り度０．２６未満で◎（優）、０．２６以上０．３６未満で○（良）、０．３６以上１．００未満で△（可）、１．００以上で×（不可）と評価した。
(Evaluation of cloudiness)
The haze of the substrate on which the thin film of compound 1 was formed was measured using a haze meter (NDH5000, manufactured by Nippon Denshoku Industries). Haze less than 0.26 ◎ (excellent), 0.26 or more and less than 0.36 ○ (good), 0.36 or more and less than 1.00 △ (acceptable), 1.00 or more x (improper) evaluated.
（スチールウール摩耗耐久性の評価）
スチールウール摩耗耐久性は往復摩耗試験機（Ｔｙｐｅ４０、新東科学製）を用いて、以下の条件で試験した。
擦り材：スチールウール（Ｂｏｎｓｔａｒ＃００００）
荷重：１ｋｇ
往復距離：４０ｍｍ
往復速度：６０往復毎分
総摩耗往復回数：２００００回
摩耗往復回数２５００回毎に摩耗部分の水接触角を計測した。水接触角１００度以上を保つ摩耗往復回数をスチールウール摩耗耐久性の指標とし、摩耗往復回数が２００００回で◎（優）、１５０００回以上２００００回未満で○（良）、１００００回以上１５０００回未満で△（可）、１００００回未満で×（不可）と評価した。
(Evaluation of Steel Wool Abrasion Durability)
Steel wool abrasion resistance was tested using a reciprocating abrasion tester (Type 40, manufactured by Shinto Kagaku) under the following conditions.
Rubbing material: steel wool (Bonstar #0000)
Load: 1kg
Round trip distance: 40mm
Reciprocating speed: 60 reciprocating motions per minute Total number of reciprocating wear times: 20,000 times The water contact angle of the worn portion was measured every 2,500 reciprocating times of wear. The number of abrasion reciprocations that maintains a water contact angle of 100 degrees or more is used as an index of steel wool abrasion durability. ◎ (excellent) when the number of abrasion reciprocations is 20,000 times, ○ (good) when 15,000 or more and less than 20,000 times, and 10,000 or more and 15,000 times. Less than 10,000 times was evaluated as Δ (acceptable), and less than 10,000 times was evaluated as × (impossible).
［実施例２、３、比較例１～３］
化合物１の膜厚を表１に示す膜厚にするために抵抗加熱型真空蒸着装置の抵抗加熱部へのコーティング液の滴下量をそれぞれ、実施例２では３μＬ、実施例３では２μＬ、比較例１では２０μＬ、比較例２では８μＬ、比較例３では１μＬに変更した以外は、実施例１と同様に化合物１の薄膜を形成し、膜厚を計測し、撥水性、曇り度、スチールウール摩耗耐久性を評価した。結果を表１に示す。
[Examples 2 and 3, Comparative Examples 1 to 3]
In order to make the film thickness of Compound 1 as shown in Table 1, the amount of the coating liquid dropped onto the resistance heating unit of the resistance heating vacuum deposition apparatus was 3 μL in Example 2, 2 μL in Example 3, and 2 μL in Comparative Example. A thin film of Compound 1 was formed in the same manner as in Example 1, except that the amount was changed to 20 μL in 1, 8 μL in Comparative Example 2, and 1 μL in Comparative Example 3, and the film thickness was measured, and the water repellency, haze, and steel wool abrasion were measured. Durability was evaluated. Table 1 shows the results.
表１に示されるように、膜厚が特定範囲内にある加水分解性含フッ素有機ケイ素化合物の薄膜（防汚コーティング薄膜）は、高い撥水性、低い曇り度、高い摩耗耐久性を有することが明らかとなった。したがって、加水分解性含フッ素有機ケイ素化合物の薄膜の膜厚を計測することにより、加水分解性含フッ素有機ケイ素化合物の薄膜（防汚コーティング薄膜）の諸品質を同時に評価できる。 As shown in Table 1, a thin film of a hydrolyzable fluorine-containing organosilicon compound (antifouling coating thin film) having a film thickness within a specific range has high water repellency, low haze, and high abrasion resistance. It became clear. Therefore, by measuring the film thickness of the hydrolyzable fluorine-containing organosilicon compound thin film, various qualities of the hydrolyzable fluorine-containing organosilicon compound thin film (antifouling coating thin film) can be evaluated at the same time.
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