WO2004024347A1 - Method of forming functional coating - Google Patents

Method of forming functional coating Download PDF

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Publication number
WO2004024347A1
WO2004024347A1 PCT/JP2003/011521 JP0311521W WO2004024347A1 WO 2004024347 A1 WO2004024347 A1 WO 2004024347A1 JP 0311521 W JP0311521 W JP 0311521W WO 2004024347 A1 WO2004024347 A1 WO 2004024347A1
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WO
WIPO (PCT)
Prior art keywords
film
functional
forming
glass
functional film
Prior art date
Application number
PCT/JP2003/011521
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French (fr)
Japanese (ja)
Inventor
Toyoyuki Teranishi
Original Assignee
Nippon Sheet Glass Co., Ltd.
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Publication date
Application filed by Nippon Sheet Glass Co., Ltd. filed Critical Nippon Sheet Glass Co., Ltd.
Priority to JP2004535918A priority Critical patent/JPWO2004024347A1/en
Publication of WO2004024347A1 publication Critical patent/WO2004024347A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/76—Hydrophobic and oleophobic coatings

Definitions

  • the present invention relates to a method for forming a functional film having anti-fogging property and water repellency on a surface of a base material such as a glass plate or a resin plate. This technique is effective, for example, for forming a functional coating on window glass for automobiles.
  • a technique for forming a functional film such as an antifogging property or a water repellent property on the surface of a base material such as a glass plate or a resin plate is conventionally known (for example, see Japanese Patent Application Laid-Open No. H10-194784).
  • a functional film such as an antifogging property or a water repellent property
  • a base material such as a glass plate or a resin plate
  • functional coatings various materials have been developed and used.
  • the former corresponds to a case where a car manufacturer attaches a glass formed with a water-repellent film to a car body
  • the latter corresponds to a case where a car user applies a water-repellent coating agent to the glass assembled to the car body to form a film. Is the case.
  • the method of forming a functional film on the surface of a substrate in advance is often applied only to a highly durable film because the functional film is often rubbed in the process of assembling the substrate to the final product.
  • the functional film on the surface may be easily peeled off, so that the functional film is transferred to another member (for example, a jig for handling) in the process of assembling the final product. This is there. Therefore, in order to solve such a transfer problem, a method of handling a glass article by interposing paper or cloth between an organic functional film and a holding jig has been proposed (see Japanese Unexamined Patent Publication (Kokai) No. 2002-139686). However, before and after the glass article handling step, a step of attaching paper or cloth and a step of removing the paper or cloth are required, which causes an increase in cost.
  • the method of forming a functional film on the surface of the base material after assembling the base material into the final product is difficult to control the environment when forming the film and the cleanness of the base material. Since the method is limited to a method that can be easily processed by general users, the resulting functional film has a drawback of poor durability.
  • An object of the present invention is to provide a functional film having excellent durability, which can prevent deterioration of the functional film and transfer of the functional film to other members in the process of assembling the base material to the final product.
  • An object of the present invention is to provide a method that can be formed on a substrate surface. Disclosure of the invention
  • a base film is previously formed on the substrate surface, and the base material with the base film is used as a final product. After assembling, a method of forming a functional film by forming a functional film by applying a functional coating agent on the base film is provided.
  • a protective layer of the base film is formed, and the protective layer of the base film is removed before applying the functional coating agent.
  • the base film is preferably a silicon-based film having a smooth or uneven surface.
  • the underlayer film is a silica-based film having an uneven shape on the surface by containing silica fine particles.
  • the functional film is preferably an organic functional film.
  • the organic functional film is preferably an antifogging film, a water repellent film, or a super water repellent film.
  • the substrate is preferably a transparent glass plate or a transparent resin plate.
  • FIG. 1 is a flowchart showing the working procedure of the method of the present invention.
  • EI 2 is a flowchart showing a modification of the working procedure of the method of the present invention.
  • a base film for improving the durability of the functional film is formed on the surface of the base material in advance. Then, the base material with the base film is assembled into a final product. Then, in the state of the final product, a functional coating is formed by applying a functional coating agent on the base film. In this way, in the final product assembling process, since the functional film has not yet been formed on the base material surface, there is no problem of deterioration of the functional film or transfer of the functional film to other members. . In addition, since a good base film is already formed on the base material in the state of being assembled into the final product, the functional coating with excellent durability can be easily applied by applying a functional coating agent. A film is obtained. The working procedure of the method of the present invention is shown in FIG.
  • the state of the base film in the state of the final product is determined.
  • the functional film may be formed by removing the protective layer and applying a functional coating agent on the base film. In this way, it is possible to prevent the surface of the base material from being stained or damaged after the formation of the base film and before the formation of the functional film.
  • FIG. 2 shows a modification of the working procedure of the method.
  • the substrate used in the present invention is typically glass, but may be ceramics, synthetic resin, metal or the like.
  • the base film is not particularly limited as long as it is a material having excellent adhesion to the substrate surface, high hardness of the base film itself, and excellent adhesion to the functional film formed thereon.
  • a silica-based film material is particularly preferred from the viewpoint of adhesion to the substrate.
  • the surface of the undercoating film may be smooth or uneven.
  • the functional coating is an anti-fog coating, a water-repellent coating, or a super water-repellent coating
  • the surface of the base coating may be uneven. This is preferred because the shape effect improves hydrophilicity (anti-fogging property) or water repellency.
  • the underlayer may be formed by any method according to the film material, such as a sol-gel method, an evaporation method, a sputtering method, and a CVD method, but the sol-gel method is preferred from the viewpoint of manufacturing cost.
  • a sol-gel method an evaporation method, a sputtering method, and a CVD method
  • the sol-gel method is preferred from the viewpoint of manufacturing cost.
  • flow coating, dip coating, force coating, spin coating, spray coating, no coating, roll coating, brush coating, dip coating It can be applied to the substrate surface by crush adsorption method.
  • fine particles of silica may be added to a coating solution used in the sol-gel method.
  • Examples of the functional film material in the present invention include an anti-fogging agent and a water repellent applied to a front glass for automobiles and the like. According to the present invention, since the base film already formed on the base material assembled into the final product has already been formed, the user simply applies a functional coating agent to the base material in the same manner as in the conventional case, thereby facilitating the operation. A functional film having excellent durability can be obtained.
  • a film that can be washed away with water or an organic solvent, a protective film, and the like can be used, but the present invention is not limited thereto.
  • a membrane that can be washed away with water or an organic solvent can be removed by rinsing with water or an organic solvent (eg, alcohol). If a protective film is used, it can be removed by peeling it off.
  • Hydrolysis-condensation polymerization solution of ethyl silicate (trade name: HAS-10, manufactured by Collcoat Co., Ltd.) 11.8 parts by weight, having a diameter of 10 to 20 nm and a length of 40 ⁇ 300 nm chain silica colloid (trade name: Snowtex 0 UP, manufactured by Nissan Chemical Industries, Ltd., solid content: 15% by weight) 13.3 parts by weight and 2 parts by weight
  • One propanol (74.9 parts by weight) was mixed at room temperature, diluted 3 times by weight with 2-propanol, and stirred at room temperature for 2 hours to obtain a coating solution for an uneven base film.
  • the glass plate that has been polished and cleaned with a cerium oxide-based abrasive, rinsed with pure water, and then dried is immersed in the coating solution for the underlayer film, and pulled up at a speed of 20 cm / min.
  • an uneven base film was applied to the glass plate.
  • the front glass for automobiles is used so that the uneven undercoat film is on the inside of the vehicle.
  • the glass was bent by placing it in a high-temperature furnace at a temperature of 600 or more.
  • the front glass with the uneven base film was assembled to the car body in a line-type automobile assembly process.
  • the front glass is soldered with a suction cup.
  • the glass is usually handled with the same suction cup. However, a part of the previous irregular underlayer was not transferred to the glass.
  • the surfactant is sodium 2-diethylhexylsulfosuccinate (trade name: Lapisol A-30, manufactured by Nippon Yushi Co., Ltd.) was applied by a spray coat method and dried sufficiently at room temperature. After drying, the surface was rubbed with a cotton cloth to remove excess surfactant, and a surfactant layer having a thickness of about 10 nm was formed to obtain an antifogging glass.
  • the anti-fog performance and durability of the obtained anti-fog glass were repeatedly evaluated by an anti-fog test.
  • the method of the repetitive anti-fogging test is as follows in accordance with JISS 400, keeping the outer surface of the glass at 25 ° C, the temperature of 43 ° C and the relative humidity of 95% on the inner surface of the car where the anti-fog film is formed. The humid air of RH was directly blown for 3 minutes, and the degree of cloudiness was visually observed. Then, while keeping the temperature of the outer surface of the vehicle at 25, the inner surface of the vehicle was dried for 2 minutes while directly blowing dry air at 25 ° C and a relative humidity of 10% RH.
  • Table 1 shows the antifogging results 30 seconds after the start of the humid air spraying in the first cycle and the 10th cycle. From these results, the anti-fog glass did not fog at all in the initial stage, and although the image was slightly distorted at the 10th cycle, no fogging occurred. However, it was confirmed that the durability was excellent.
  • Ethanol 98.44 4 parts by weight of chain silica colloid (trade name: Snowtex 0 UP, manufactured by Nissan Chemical Industries, Ltd., solid content 15% by weight) 1.1 3 parts by weight Tetrachlorosilane (trade name: LS-10, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.43 parts by weight was added with stirring, and the mixture was further stirred at room temperature for 2 hours. A cured coating liquid was obtained.
  • the above-mentioned room-temperature curing coating liquid for uneven base film is applied by flow coating to the interior surface of a front glass plate for automobiles that has been polished and cleaned with a cerium oxide abrasive, and then rinsed with pure water and dried. Then, the glass was dried at room temperature to obtain a front glass with a ground film under the unevenness.
  • Example 1 the front glass with the uneven undercoat film was assembled into an automobile, and then a surfactant was applied thereto.
  • the obtained anti-fog glass was subjected to anti-fog performance and durability performance.
  • Example 1 no fogging occurred at the initial stage, and slight image distortion was observed even at the 10th cycle, but no fogging occurred and extremely durability was achieved. It was confirmed that the performance was excellent.
  • part of the uneven base film was not transferred to other glass in the automobile assembly process.
  • Example 1 After the interior surface of the front glass for automobiles on which the uneven undercoat film formed in Example 1 was formed was thoroughly cleaned with a solvent, the above organosilane coating solution was applied to a cotton cloth, and excess adhesion was observed. The organosilane was wiped with a new cotton cloth to obtain an anti-fog glass.
  • the anti-fog glass obtained was evaluated for anti-fog performance and durability performance in the same manner as in Example 1. As a result, no fogging occurred at the initial stage, and slight image distortion was observed even at the 10th cycle. However, it was confirmed that fogging did not occur and the durability was extremely excellent.
  • Example 1 A surfactant was applied to the interior surface of normal front glass for automobiles in the same manner as in Example 1 to obtain an anti-fog glass.
  • the obtained antifogging glass was evaluated for antifogging performance and durability performance in the same manner as in Example 1. As a result, although no fogging occurred at the initial stage, fogging occurred at the 10th cycle, and the durability performance was improved. It was confirmed to be bad.
  • Example 1 Before assembling the front glass with a concavo-convex base film obtained in the same manner as in Example 1 into an automobile, a surfactant was applied in the same manner as in Example 1 to obtain an antifogging glass.
  • this anti-fog glass was assembled to a car in a line-type assembly process, it was confirmed that the surfactant was transferred to another glass via a suction cup.
  • the anti-fogging performance and the durability performance in the same manner as in Example 1 it was confirmed that the part was partially fogged in the first cycle, and that the anti-fogging performance was poor.
  • Example 2 After forming an uneven undercoat film on a glass plate in the same manner as in Example 1, in the same manner as in Example 1 except that the front glass was processed into an automotive front glass so that the film became the outer surface of the vehicle, the front glass with the uneven undercoat film was used in a line-type automobile assembly process. Assembled on the body. At this time, part of the uneven base film was not transferred to another glass in the automobile assembly process.
  • heptadecafluorodecyl trimethoxysilane (trade name: KBM-7803, manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 98 g of ethanol, and 0.1 N hydrochloric acid was further added. was added and stirred at 30 ° C. for 1 hour to obtain a water-repellent liquid.
  • the water repellency of the obtained water repellent glass was evaluated by the contact angle of water.
  • a contact angle meter (“CA-DT", manufactured by Kyowa Interface Science Co., Ltd.)
  • a water droplet having a mass of 2 mg was dropped on the surface of the glass plate, and the static contact angle was measured.
  • Table 2 shows the results of the initial water repellency. From these results, it was confirmed that the water-repellent glass was excellent in water-repellent performance.
  • the weather resistance of the obtained water-repellent glass was evaluated by an outdoor exposure test.
  • the outdoor exposure test involved parking the vehicle with the front glass facing south and exposing the water-repellent glass to direct sunlight and wind and rain.
  • the degree of deterioration of the water repellency of the water repellent glass after 6 months of the outdoor exposure test was measured by the contact angle.
  • the results are also shown in Table 2. From these results, it was confirmed that the water-repellent glass exhibited sufficient water-repellent performance even after 6 months of outdoor exposure and was extremely excellent in weather resistance. This was presumed to be due to the effect of the underlayer. (Example 5)
  • tetrachlorosilane (trade name: LS-10, manufactured by Shin-Etsu Chemical Co., Ltd.) with stirring, and further add room temperature. For 2 hours to obtain a room temperature curing coating liquid for a smooth underlayer.
  • the above-mentioned room-temperature hardening film for a smooth undercoating film is applied to the outer surface of a front glass plate for an automobile, which is polished and washed with a cerium oxide abrasive, rinsed with pure water, and dried.
  • the tinting solution was applied by a flow coating method and dried at room temperature to obtain a front glass with a smooth underlayer.
  • Example 4 the front glass with the smooth undercoating film is assembled into an automobile, and then a water-repellent treatment liquid is applied, and the obtained water-repellent glass is subjected to water repellency and weather resistance.
  • a water-repellent treatment liquid is applied, and the obtained water-repellent glass is subjected to water repellency and weather resistance.
  • the weather resistance was extremely excellent.
  • part of the smooth underlayer was not transferred to other glass during the automobile assembly process.
  • a water-repellent treatment liquid was applied to the outer surface of a normal vehicle front glass in the same manner as in Example 4 to obtain a water-repellent glass.
  • the obtained water-repellent glass was evaluated for water repellency and weather resistance in the same manner as in Example 4. As a result, although the initial water repellency was excellent, the water repellency after 6 months of outdoor exposure was 87 ° C. It was confirmed that the weatherability was poor.
  • the present invention is a method of forming a functional film by forming a base film on the surface of a base material in advance and applying a functional coating agent after assembling the final product. Therefore, there is no functional coating in the process of assembling the base material to the final product, so that the functional coating does not deteriorate and the functional coating does not transfer to other members.
  • a base film is already formed on the base material assembled into the final product, a functional film with excellent durability can be easily formed simply by applying a functional coating agent. You.
  • the undercoat film remains, so a good functional film can be restored by applying a functional coating agent again.

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  • General Chemical & Material Sciences (AREA)
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Abstract

A method of forming on a substrate surface a functional coating excelling in durability which can avoid the transfer of functional coating to other members and deterioration of functional coating at the step of fitting a substrate to a final product. A foundation film is provided on a substrate surface in advance. The substrate with the foundation film is fitted to a final product, and thereafter a functional coating agent is applied onto the foundation film to thereby form a functional coating. The foundation film is, for example, a silica coating having smooth or uneven surface. The uneven configuration can be realized by incorporation of silica fine particles. The functional coating is, for example, a functional coating of organic substance exhibiting antifogging or water-shedding/super-water-shedding properties. The substrate is a transparent glass plate, a transparent resin plate, etc.

Description

明 細 書 機能性皮膜の形成方法 技術分野  Description Method of forming functional film Technical field
本発明は、 ガラス板あるいは樹脂板などの基材表面に、 防曇性や撥水 性等の機能性皮膜を形成する方法に関する ものである。 この技術は、 例 えば自動車用の窓ガラスに機能性皮膜を形成するのに有効である。 背景技術  The present invention relates to a method for forming a functional film having anti-fogging property and water repellency on a surface of a base material such as a glass plate or a resin plate. This technique is effective, for example, for forming a functional coating on window glass for automobiles. Background art
ガラス板あるいは樹脂板な どの基材表面に、 防曇性や撥水性等の機能 性皮膜を形成する技術は従来公知である （例えば特開平 1 0— 1 9 4 7 8 4号公報参照） 。 機能性皮膜に関しては、 様々 な材料が開発され使用 されている。  A technique for forming a functional film such as an antifogging property or a water repellent property on the surface of a base material such as a glass plate or a resin plate is conventionally known (for example, see Japanese Patent Application Laid-Open No. H10-194784). For functional coatings, various materials have been developed and used.
このよ う な機能性皮膜を有する製品を製造する方法と しては、 先に基 材表面に機能性皮膜を形成しておいて、 その基材を最終製品に組み付け る方法と、 最終製品に基材を組み付けた後で、 基材表面に機能性皮膜を 形成する方法とがある。 例えば前者は、 自動車メ ーカーが撥水性皮膜を 形成したガラスを車体に組み付ける場合が相当 し、 後者は自動車ユーザ ―が車体に組み付けられているガラスに撥水性コーティ ング剤を塗布し て皮膜を形成する場合が相当する。  As a method of manufacturing a product having such a functional film, a method in which a functional film is first formed on a substrate surface, and the base material is assembled into a final product, After assembling the base material, there is a method of forming a functional film on the surface of the base material. For example, the former corresponds to a case where a car manufacturer attaches a glass formed with a water-repellent film to a car body, and the latter corresponds to a case where a car user applies a water-repellent coating agent to the glass assembled to the car body to form a film. Is the case.
予め基材表面に機能性皮膜を形成する方法は、 基材を最終製品に組み 付ける工程で機能性皮膜が擦られる こ とが多いため、 耐久性の高い皮膜 にしか適用でき ない。 また有機物機能性皮膜の場合には、 表面の機能性 皮膜が容易に剥ぎ取られる恐れがあるため、 最終製品に組み付ける工程 で他の部材 （例えばハン ドリ ング治具） に機能性皮膜が転写するこ とが ある。 そこで、 このよ う な転写の問題を解決するために、 有機物機能性 皮膜とハン ドリ ング治具の間に紙又は布などを介在させてガラス物品を 取り扱う方法が提案されている （特開 2 0 0 0 — 1 9 1 1 3 5号公報参 照） が、 ガラス物品取り扱い工程の前後に、 紙又は布を取り付ける工程 と、 取り 除く工程が必要とな り 、 コス ト上昇の要因と なる。 The method of forming a functional film on the surface of a substrate in advance is often applied only to a highly durable film because the functional film is often rubbed in the process of assembling the substrate to the final product. In the case of an organic functional film, the functional film on the surface may be easily peeled off, so that the functional film is transferred to another member (for example, a jig for handling) in the process of assembling the final product. This is is there. Therefore, in order to solve such a transfer problem, a method of handling a glass article by interposing paper or cloth between an organic functional film and a holding jig has been proposed (see Japanese Unexamined Patent Publication (Kokai) No. 2002-139686). However, before and after the glass article handling step, a step of attaching paper or cloth and a step of removing the paper or cloth are required, which causes an increase in cost.
最終製品に基材を組み付けた後で、 基材表面に機能性皮膜を形成する 方法は、 皮膜を成膜する時の環境や基材の清诤度を制御する こ とが困難 であ り 、 一般ユーザーが簡単に処理でき る程度の方法に限られるため、 得られる機能性皮膜は耐久性が乏しい欠点がある。  The method of forming a functional film on the surface of the base material after assembling the base material into the final product is difficult to control the environment when forming the film and the cleanness of the base material. Since the method is limited to a method that can be easily processed by general users, the resulting functional film has a drawback of poor durability.
本発明の目的は、 基材を最終製品に組み付ける工程で機能性皮膜の劣 化や、 他の部材への機能性皮膜の転写を防ぐこ とができ、 かつ耐久性に 優れた機能性皮膜を基材表面に形成できる方法を提供する こ とである。 発明の開示  An object of the present invention is to provide a functional film having excellent durability, which can prevent deterioration of the functional film and transfer of the functional film to other members in the process of assembling the base material to the final product. An object of the present invention is to provide a method that can be formed on a substrate surface. Disclosure of the invention
上記目的を達成するために、 本発明によれば、 基材表面に機能性皮膜 を形成する方法において、 基材表面に予め下地膜を形成 しておき、 この 下地膜付き基材を最終製品に組み付けた後に、 該下地膜上に機能性コ— ティ ング剤を塗布する こ と によ り機能性皮膜を形成する機能性皮膜の形 成方法が提供される。  In order to achieve the above object, according to the present invention, in a method for forming a functional film on a substrate surface, a base film is previously formed on the substrate surface, and the base material with the base film is used as a final product. After assembling, a method of forming a functional film by forming a functional film by applying a functional coating agent on the base film is provided.
前記基材表面に予め下地膜を形成した後に、下地膜の保護層を形成し、 前記機能性コーティ ング剤を塗布する前に、 前記下地膜の保護層を除去 する こ とが好ま しい。  It is preferable that after forming a base film on the surface of the base material in advance, a protective layer of the base film is formed, and the protective layer of the base film is removed before applying the functional coating agent.
下地膜は、 表面が平滑な又は凹凸形状を有する シ リ 力系皮膜である こ とが好ま しい。  The base film is preferably a silicon-based film having a smooth or uneven surface.
下地膜は、 シリ カ微粒子を含有するこ とで表面に凹凸形状が付与され ているシリ カ系皮膜である こ とが好ま しい。 機能性皮膜は、 有機物機能性皮膜である こ とが好ま しい。 It is preferable that the underlayer film is a silica-based film having an uneven shape on the surface by containing silica fine particles. The functional film is preferably an organic functional film.
有機物機能性皮膜は、 防曇性皮膜又は撥水性皮膜、 超撥水性皮膜であ る こ とが好ま しい。  The organic functional film is preferably an antifogging film, a water repellent film, or a super water repellent film.
基材は、 透明ガラス板又は透明樹脂板である こ とが好ま しい。 図面の簡単な説明  The substrate is preferably a transparent glass plate or a transparent resin plate. BRIEF DESCRIPTION OF THE FIGURES
図 1 は、 本発明方法の作業手順を示すフローチヤ一 トである。  FIG. 1 is a flowchart showing the working procedure of the method of the present invention.
EI 2 は、本発明方法の作業手順の変形例を示すフローチヤ一 ト である。 発明を実施するための最良の形態  EI 2 is a flowchart showing a modification of the working procedure of the method of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION
本発明では、 まず機能性皮膜の耐久性を向上させるための下地膜を予 め基材表面に形成してお く 。 そして、 この下地膜付き基材を最終製品に 組み付ける。 その後、 最終製品の状態で、 下地膜上に機能性コ一ティ ン グ剤を塗布する こ と によ つて機能性皮膜を形成する。このよ う にする と、 最終製品の組立工程では、 基材表面に未だ機能性皮膜が形成されていな いため、 機能性皮膜の劣化や他の部材へ機能性皮膜が転写する問題は生 じない。 また、 最終製品に組み付けられた状態の基材には既に良好な下 地膜が形成されているため、 機能性コ ーティ ング剤を塗布する こ と によ つて、 容易に耐久性に優れた機能性皮膜が得られる。 本発明方法の作業 手順を図 1 に示す。  In the present invention, first, a base film for improving the durability of the functional film is formed on the surface of the base material in advance. Then, the base material with the base film is assembled into a final product. Then, in the state of the final product, a functional coating is formed by applying a functional coating agent on the base film. In this way, in the final product assembling process, since the functional film has not yet been formed on the base material surface, there is no problem of deterioration of the functional film or transfer of the functional film to other members. . In addition, since a good base film is already formed on the base material in the state of being assembled into the final product, the functional coating with excellent durability can be easily applied by applying a functional coating agent. A film is obtained. The working procedure of the method of the present invention is shown in FIG.
また、 下地膜及び下地膜の保護層を予め基材表面に形成して、 この下 地膜及び下地膜の保護層付き基材を最終製品に組み付けた後に、 最終製 品の状態で、 下地膜の保護層を除去し、 下地膜の上に機能性コーティ ン グ剤を塗布する こ とによ つて機能性皮膜を形成しても よい。 このよ う に する と、 下地膜を形成後、 機能性皮膜を形成する までの間に基材の表面 が汚れた り傷が付いた りする こ と を防止する こ とができ る。 この本発明 方法の作業手順の変形例を図 2 に示す。 In addition, after forming the base film and the protective layer of the base film on the surface of the base material in advance, and assembling the base film and the base material with the protective layer of the base film into the final product, the state of the base film in the state of the final product is determined. The functional film may be formed by removing the protective layer and applying a functional coating agent on the base film. In this way, it is possible to prevent the surface of the base material from being stained or damaged after the formation of the base film and before the formation of the functional film. This invention FIG. 2 shows a modification of the working procedure of the method.
本発明で用いる基材と しては、 典型的にはガラスがあるが、 その他に もセラ ミ ッ クス、 合成樹脂、 あるいは金属等でも よい。  The substrate used in the present invention is typically glass, but may be ceramics, synthetic resin, metal or the like.
下地膜と しては、基材表面との密着性に優れ下地膜自体の硬度が高く 、 且つその上に形成する機能性皮膜との密着性に優れた材料であれば特に 制限はないが、 基材がガラスの場合には基材との密着性の観点から特に シリ カ系の膜材料が好ま しい。 この下地膜は、 その表面が平滑であって も よい し凹凸形状であつても構わないが、 例えば機能性皮膜が防曇性皮 膜や撥水性皮膜、 超撥水性皮膜の場合は、 凹凸形状にする と形状効果で 親水性 （防曇性） 又は撥水性が向上するため好ま しい。  The base film is not particularly limited as long as it is a material having excellent adhesion to the substrate surface, high hardness of the base film itself, and excellent adhesion to the functional film formed thereon. When the substrate is glass, a silica-based film material is particularly preferred from the viewpoint of adhesion to the substrate. The surface of the undercoating film may be smooth or uneven.For example, when the functional coating is an anti-fog coating, a water-repellent coating, or a super water-repellent coating, the surface of the base coating may be uneven. This is preferred because the shape effect improves hydrophilicity (anti-fogging property) or water repellency.
下地膜の形成方法は、 ゾルゲル法、 蒸着法、 スパッ タ リ ング法、 C V D法など膜材料に応じた任意の方法でよいが、 製造コス トの面からみる とゾルゲル法が好ま しい。 例えば、 フ ローコーティ ング、 ディ ッ プコー テ ィ ング、 力一テ ンコーテ ィ ング、 ス ピンコ ーテ ィ ング、 ス プレー コー ティ ング、 ノ ー コーテ ィ ング、 ロ ールコーテ ィ ング、 刷毛塗り コーティ ング、 浸潰吸着法などで基材表面に塗布でき る。 下地膜に凹凸形状を付 与する場合には、 例えばゾルゲル法で用いる コ ーティ ング液中にシリ 力 微粒子を添加しておけばよい。  The underlayer may be formed by any method according to the film material, such as a sol-gel method, an evaporation method, a sputtering method, and a CVD method, but the sol-gel method is preferred from the viewpoint of manufacturing cost. For example, flow coating, dip coating, force coating, spin coating, spray coating, no coating, roll coating, brush coating, dip coating It can be applied to the substrate surface by crush adsorption method. In the case where the base film is provided with a concavo-convex shape, for example, fine particles of silica may be added to a coating solution used in the sol-gel method.
本発明における機能性皮膜材料と しては、 例えば自動車用フ ロ ン ト ガ ラス等に適用する防曇剤や撥水剤などがある。 本発明では、 最終製品に 組み付けられた状態の基材には既に下地膜が形成されているため、 ユー ザ一が従来同様に基材に機能性コ一ティ ング剤を塗布するだけで、 容易 に耐久性の優れた機能性皮膜が得られる。  Examples of the functional film material in the present invention include an anti-fogging agent and a water repellent applied to a front glass for automobiles and the like. According to the present invention, since the base film already formed on the base material assembled into the final product has already been formed, the user simply applies a functional coating agent to the base material in the same manner as in the conventional case, thereby facilitating the operation. A functional film having excellent durability can be obtained.
下地膜の保護層 と しては、 例えば、 水又は有機溶剤にて洗い流すこ と が可能な膜、 保護フ ィ ルムな どを用いる こ とができ るが、 これに限る も のではない。 こ こで、 水又は有機溶剤にて洗い流すこ とが可能な膜を用 いる場合、 水、 有機溶剤 （例えばアルコール） にて洗い流すこ と に よ り 除去する こ とができ る。 また、 保護フ ィ ルム を用いる場合、 これを剥が すこ と によ り 除去する こ とができ る。 As the protective layer of the base film, for example, a film that can be washed away with water or an organic solvent, a protective film, and the like can be used, but the present invention is not limited thereto. Here, use a membrane that can be washed away with water or an organic solvent. Can be removed by rinsing with water or an organic solvent (eg, alcohol). If a protective film is used, it can be removed by peeling it off.
以下、 本発明の実施例と比較例について詳し く 説明する。  Hereinafter, examples and comparative examples of the present invention will be described in detail.
(実施例 1 )  (Example 1)
ェチルシ リ ケ一ト の加水分解縮重合液 （商品名 ： H A S— 1 0 、 コ ル コー ト株式会社製） 1 1 . 8重量部と、 直径が 1 0〜 2 0 nm で長さが 4 0〜 3 0 0 nm の鎖状シ リ カ コ ロ イ ド （商品名 ： ス ノ ーテ ッ クス 0 U P、 日産化学工業株式会社製、 固形分 1 5重量％) 1 3 . 3重量部と 2 一プロパノ ール 7 4 . 9重量部を室温で混合し、 これを 2—プロパノ ー ルで 3重量倍に希釈して、 室温で 2時間撹拌して凹凸下地膜用コ一ティ ング液を得た。  Hydrolysis-condensation polymerization solution of ethyl silicate (trade name: HAS-10, manufactured by Collcoat Co., Ltd.) 11.8 parts by weight, having a diameter of 10 to 20 nm and a length of 40 ~ 300 nm chain silica colloid (trade name: Snowtex 0 UP, manufactured by Nissan Chemical Industries, Ltd., solid content: 15% by weight) 13.3 parts by weight and 2 parts by weight One propanol (74.9 parts by weight) was mixed at room temperature, diluted 3 times by weight with 2-propanol, and stirred at room temperature for 2 hours to obtain a coating solution for an uneven base film. Was.
酸化セリ ゥム系研磨剤で表面研磨 · 洗浄し、 更に純水ですすいで乾燥 したガラス板を、 前記凹凸下地膜用コーティ ング液に浸潰し、 2 0 cm /分の速度で引 き上げる こ と によ り、ガラス板に凹凸下地膜を塗布した。 このガラス板を 1 0 0 でで 3 0分間乾燥させ、 更に 2 5 0 °Cで 3 0分間 乾燥させた後、 凹凸下地膜が車内面になる よ う に自動車用のフ ロ ン ト ガ ラス に加工し、 凹凸下地膜付き フ ロ ン ト ガラス を得た。 フ ロ ン ト ガラス への加工では、 ガラス を 6 0 0 で以上の高温炉に入れて曲げるため、 こ の温度を利用 して凹凸下地膜を焼成した。  The glass plate that has been polished and cleaned with a cerium oxide-based abrasive, rinsed with pure water, and then dried is immersed in the coating solution for the underlayer film, and pulled up at a speed of 20 cm / min. Thus, an uneven base film was applied to the glass plate. After drying this glass plate at 100 ° C. for 30 minutes and then at 250 ° C. for 30 minutes, the front glass for automobiles is used so that the uneven undercoat film is on the inside of the vehicle. To obtain a front glass with an uneven base film. In processing into front glass, the glass was bent by placing it in a high-temperature furnace at a temperature of 600 or more.
次に、 この凹凸下地膜付き フ ロ ン ト ガラスを、 ラ イ ン式の自動車組立 工程で車体に組み付けた。 ラィ ン式の自動車組立工程ではフ ロ ン ト ガラ スを吸盤でハン ドリ ングしてお り 、 上記凹凸下地膜付き フロ ン ト ガラス を組み付けた後は、 通常ガラスを同 じ吸盤でハン ドリ ングしたが、 通常 ガラスの方に前の凹凸下地膜の一部が転写する こ とはなかった。  Next, the front glass with the uneven base film was assembled to the car body in a line-type automobile assembly process. In the line type automobile assembly process, the front glass is soldered with a suction cup. After assembling the front glass with the uneven base film, the glass is usually handled with the same suction cup. However, a part of the previous irregular underlayer was not transferred to the glass.
その後、 上記凹凸下地膜が形成されている 自動車のフ ロ ン ト ガラスの 車内面を溶媒で綺麗に洗浄した後、 界面活性剤と して、 ジ 2—ェチルへ キシルスルホコハク酸ナ ト リ ウム （商品名 ： ラ ピゾ一ル A— 3 0、 日本 油脂株式会社製） の 0 . 0 5 %水溶液をスプレーコー ト法によ り 塗布し、 室温で充分乾燥させた。 乾燥後、 綿布を用いて表面を擦り余分な界面活 性剤を除去し、 約 1 0 nm の厚みの界面活性剤層を形成し、 防曇ガラス を得た。 After that, the front glass of the automobile on which the uneven underlayer is formed After the interior surface of the car is thoroughly cleaned with a solvent, the surfactant is sodium 2-diethylhexylsulfosuccinate (trade name: Lapisol A-30, manufactured by Nippon Yushi Co., Ltd.) Was applied by a spray coat method and dried sufficiently at room temperature. After drying, the surface was rubbed with a cotton cloth to remove excess surfactant, and a surfactant layer having a thickness of about 10 nm was formed to obtain an antifogging glass.
得られた防曇ガラスについて、 その防曇性能と耐久性能を、 繰り 返し 防曇試験で評価した。 繰り返し防曇試験の方法は、 J I S S 4 0 3 0 に従い、 ガラスの車外面を 2 5 °Cに保ち、 防曇膜が形成されている車 内面に、 温度 4 3 °C、 相対湿度 9 5 % R Hの高湿空気を直接吹き付けな がら 3分間保ち、 その曇り具合を目視で観察した。 その後、 車外面の温 度を 2 5 でに保ったま ま、 車内面に 2 5 °C、 相対湿度 1 0 % R Hの乾燥 空気を直接吹き付けながら' 2分間乾燥させた。 この高湿空気の吹き付け と乾燥空気の吹き付け操作を 1 サイ ク ルと し、 1 0サイ クルの繰り 返し を行い、 サイ ク ル毎の曇り具合を目視で観察した。 その 1 サイ クル目 と 1 0 サイ クル目の髙湿空気吹き付け開始から 3 0秒後の防曇性結果を、 表 1 に示す。 この結果から、 上記防曇ガラスは、 初期は全く曇 りが発生 せず、 また、 1 0サイ クル目でも若干の像の歪みが見られる も のの、 曇 り が発生する こ とはな く 、 非常に耐久性能に優れている こ とが確認され た。  The anti-fog performance and durability of the obtained anti-fog glass were repeatedly evaluated by an anti-fog test. The method of the repetitive anti-fogging test is as follows in accordance with JISS 400, keeping the outer surface of the glass at 25 ° C, the temperature of 43 ° C and the relative humidity of 95% on the inner surface of the car where the anti-fog film is formed. The humid air of RH was directly blown for 3 minutes, and the degree of cloudiness was visually observed. Then, while keeping the temperature of the outer surface of the vehicle at 25, the inner surface of the vehicle was dried for 2 minutes while directly blowing dry air at 25 ° C and a relative humidity of 10% RH. The operation of blowing the high-humidity air and the blowing of the dry air were defined as one cycle, and the cycle was repeated 10 cycles, and the degree of cloudiness for each cycle was visually observed. Table 1 shows the antifogging results 30 seconds after the start of the humid air spraying in the first cycle and the 10th cycle. From these results, the anti-fog glass did not fog at all in the initial stage, and although the image was slightly distorted at the 10th cycle, no fogging occurred. However, it was confirmed that the durability was excellent.
(実施例 2 ) '  (Example 2) ''
エタ ノール 9 8 . 4 4重量部に鎖状シリ カ コ ロイ ド （商品名 ： スノ ー テ ッ クス 0 U P、 日産化学工業株式会社製、 固形分 1 5重量％) 1 . 1 3重量部とテ ト ラク ロロシラ ン （商品名 ： L S— 1 0、 信越化学工業株 式会社製） 0 . 4 3重量部を撹拌しながら添加し、 更に室温で 2時間撹 拌して、 凹凸下地膜用常温硬化コーティ ング液を得た。 酸化セリ ゥム系研磨剤で表面研磨 · 洗浄 、 更に純水ですすいで乾燥 した自動車用フ ロ ン ト ガラス板の車内面に、 前記凹凸下地膜用常温硬化 コーティ ング液をフローコー ト法で塗布し、 常温で乾燥させて、 凹凸下 地膜付き フロ ン ト ガラスを得た。 Ethanol 98.44 4 parts by weight of chain silica colloid (trade name: Snowtex 0 UP, manufactured by Nissan Chemical Industries, Ltd., solid content 15% by weight) 1.1 3 parts by weight Tetrachlorosilane (trade name: LS-10, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.43 parts by weight was added with stirring, and the mixture was further stirred at room temperature for 2 hours. A cured coating liquid was obtained. The above-mentioned room-temperature curing coating liquid for uneven base film is applied by flow coating to the interior surface of a front glass plate for automobiles that has been polished and cleaned with a cerium oxide abrasive, and then rinsed with pure water and dried. Then, the glass was dried at room temperature to obtain a front glass with a ground film under the unevenness.
その後は、 実施例 1 と同様に、 この凹凸下地膜付き フ ロ ン ト ガラス を 自動車に組み付けた後、 界面活性剤を塗布し、 得られた防曇ガラス につ いて、 防曇性能と耐久性能を評価した。 その結果、 実施例 1 と同様に初 期は全く 曇り が発生せず、 また、 1 0 サイ クル目でも若干の像の歪みが 見られる ものの、 曇り が発生する こ と はな く 、 非常に耐久性能に優れて いる こ とが確認された。 また、 自動車組立工程で他のガラスに凹凸下地 膜の一部が転写する こ と も なかった。  After that, as in Example 1, the front glass with the uneven undercoat film was assembled into an automobile, and then a surfactant was applied thereto. The obtained anti-fog glass was subjected to anti-fog performance and durability performance. Was evaluated. As a result, as in Example 1, no fogging occurred at the initial stage, and slight image distortion was observed even at the 10th cycle, but no fogging occurred and extremely durability was achieved. It was confirmed that the performance was excellent. In addition, part of the uneven base film was not transferred to other glass in the automobile assembly process.
(実施例 3 )  (Example 3)
[メ ト キシ （ポリエチレンォキシ） プロ ピル] ト リ メ ト キシシラ ン （商 品名 ： S I M 6 4 9 2 . 7 、 チッ ソ株式会社製、 含有率 9 0 %、 分子量 4 6 0 〜 5 9 0 、 エチレンオキサイ ド単位 6 〜 9 ) l g をエタ ノ ール 9 8 g に溶解し 更に 0 . 1 Nの塩酸を 1 g添加し、 3 0 で 1 時間撹拌 して、 オルガノ シラ ン塗布液を得た。  [Methoxy (polyethyleneoxy) propyl] trimethoxysilane (trade name: SIM 6492.7, manufactured by Chisso Corporation, content: 90%, molecular weight 4600 to 5900) Ethylene oxide units 6 to 9) lg is dissolved in 98 g of ethanol, 1 g of 0.1 N hydrochloric acid is further added, and the mixture is stirred at 30 for 1 hour to give an organosilane coating solution. Obtained.
実施例 1 で作製した凹凸下地膜が形成されている 自動車用のフロ ン ト ガラスの車内面を溶媒で綺麗に洗浄した後、 上記オルガノ シラ ン塗布液 を綿布に取り塗り込み、 余分に付着したオルガノ シラ ンを新しい綿布で 拭き取り 、 防曇ガラスを得た。  After the interior surface of the front glass for automobiles on which the uneven undercoat film formed in Example 1 was formed was thoroughly cleaned with a solvent, the above organosilane coating solution was applied to a cotton cloth, and excess adhesion was observed. The organosilane was wiped with a new cotton cloth to obtain an anti-fog glass.
得られた防曇ガラスについて、 実施例 1 と同様に防曇性能と耐久性能 を評価した結果、 初期は全く曇り が発生せず、 また、 1 0サイ クル目で も若干の像の歪みが見られる ものの、 曇りが発生するこ とはな く 、 非常 に耐久性能に優れている こ とが確認された。  The anti-fog glass obtained was evaluated for anti-fog performance and durability performance in the same manner as in Example 1. As a result, no fogging occurred at the initial stage, and slight image distortion was observed even at the 10th cycle. However, it was confirmed that fogging did not occur and the durability was extremely excellent.
(比較例 1 ) 通常の自動車用フロ ン トガラスの車内面に、 実施例 1 と同様に界面活 性剤を塗布し、 防曇ガラスを得た。 得られた防曇ガラスについて、 実施 例 1 と同様に防曇性能と耐久性能を評価した結果、 初期は全く曇りが発 生しなかったものの、 1 0サイクル目では曇りが発生し、 耐久性能が悪 いこ とが確認された。 (Comparative Example 1) A surfactant was applied to the interior surface of normal front glass for automobiles in the same manner as in Example 1 to obtain an anti-fog glass. The obtained antifogging glass was evaluated for antifogging performance and durability performance in the same manner as in Example 1. As a result, although no fogging occurred at the initial stage, fogging occurred at the 10th cycle, and the durability performance was improved. It was confirmed to be bad.
(比較例 2 )  (Comparative Example 2)
実施例 1 と同様にして得られた凹凸下地膜付きフ ロ ン ト ガラスを、 自 動車に組み付ける前に、 実施例 1 と同様に界面活性剤を塗布して防曇ガ ラスを得た。 この防曇ガラスをラ イ ン式の組立工程で自動車に組み付け たと ころ、 吸盤を介して他のガラスに界面活性剤が転写している こ とが 確認された。 また、 実施例 1 と同様に防曇性能と耐久性能を評価した結 果、 1 サイ クル目で部分的に曇る ところが確認され、 防曇性能が悪いこ とが確認された。  Before assembling the front glass with a concavo-convex base film obtained in the same manner as in Example 1 into an automobile, a surfactant was applied in the same manner as in Example 1 to obtain an antifogging glass. When this anti-fog glass was assembled to a car in a line-type assembly process, it was confirmed that the surfactant was transferred to another glass via a suction cup. In addition, as a result of evaluating the anti-fogging performance and the durability performance in the same manner as in Example 1, it was confirmed that the part was partially fogged in the first cycle, and that the anti-fogging performance was poor.
表 1 table 1
Figure imgf000009_0001
繰り返し防曇試験： ◎ 全く曇りが発生しない
Figure imgf000009_0001
Repeated antifogging test: 曇 No fogging occurs
〇 曇りは発生しないが、若干の像の歪みが発生  し な い No fogging, but slight image distortion
X 曇りが発生  X Cloudy
(実施例 4 ) (Example 4)
実施例 1 と同様にしてガラス板に凹凸下地膜を形成した後、 凹凸下地 膜が車外面になる よ う に自動車用のフロ ン ト ガラスに加工した以外は、 実施例 1 と同様に して、 凹凸下地膜付き フロ ン ト ガラス を、 ラ イ ン式の 自動車組立工程で車体に組み付けた。 この際、 自動車組立工程で他のガ ラスに凹凸下地膜の一部が転写する こ とはなかつた。 After forming an uneven undercoat film on a glass plate in the same manner as in Example 1, In the same manner as in Example 1 except that the front glass was processed into an automotive front glass so that the film became the outer surface of the vehicle, the front glass with the uneven undercoat film was used in a line-type automobile assembly process. Assembled on the body. At this time, part of the uneven base film was not transferred to another glass in the automobile assembly process.
次に、 ヘプタデカ フルォロデシル ト リ メ ト キシシラ ン （商品名 ： K B M— 7 8 0 3 、 信越化学工業株式会社製） 1 g をエタノ ール 9 8 g に溶 解し、 更に 0 . 1 Nの塩酸を 1 g添加し、 3 0 °Cで 1 時間撹拌して、 撥 水処理液を得た。  Next, 1 g of heptadecafluorodecyl trimethoxysilane (trade name: KBM-7803, manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 98 g of ethanol, and 0.1 N hydrochloric acid was further added. Was added and stirred at 30 ° C. for 1 hour to obtain a water-repellent liquid.
上記作製した凹凸下地膜が形成されている 自動車のフ ロ ン ト ガラスの 車外面を溶媒で綺麗に洗浄した後、 上記撥水処理液を綿布に取り塗り込 み、 余分に付着した撥水処理液を新しい綿布で拭き取り 、 撥水性ガラス を得た。  After thoroughly cleaning the exterior surface of the front glass of the automobile with the uneven undercoat film prepared above with a solvent, apply the above-mentioned water-repellent treatment liquid to a cotton cloth and apply extra water-repellent treatment. The liquid was wiped off with a new cotton cloth to obtain a water-repellent glass.
得られた撥水性ガラスについて、 まずその撥水性能を水の接触角で評 価した。 接触角計 （ 「C A— D T」 、 協和界面科学株式会社製） を用い、 2 m gの質量の水滴をガラス板表面に滴下して、静的接触角を測定した。 なおこの接触角の値が大きいほど、 静的な撥水性が優れている こ と を表 している。 この初期撥水性能の結果を表 2 に示す。 この結果から、 上記 撥水性ガラスは、 撥水性能に優れる こ とが確認された。  First, the water repellency of the obtained water repellent glass was evaluated by the contact angle of water. Using a contact angle meter ("CA-DT", manufactured by Kyowa Interface Science Co., Ltd.), a water droplet having a mass of 2 mg was dropped on the surface of the glass plate, and the static contact angle was measured. The larger the value of the contact angle, the better the static water repellency. Table 2 shows the results of the initial water repellency. From these results, it was confirmed that the water-repellent glass was excellent in water-repellent performance.
次に、 得られた撥水性ガラスについて、 その膜の耐候性能を屋外曝露 試験で評価した。 屋外曝露試験の方法は、 フロ ン ト ガラスが南向き にな る よ う に自動車を駐車し、 撥水性ガラスを直射日光と風雨に曝した。 こ の屋外曝露試験 6 ヶ月経過後の撥水性ガラスについて、 撥水性能の劣化 具合を接触角で測定した。 その結果も表 2 に併せて示す。 この結果から、 上記撥水性ガラスは、 屋外曝露 6 ヶ月後でも充分な撥水性能を示してお り 、 非常に耐候性能に優れる こ とが確認された。 これは、 下地膜の効果 による ものと推定できた。 (実施例 5 ) Next, the weather resistance of the obtained water-repellent glass was evaluated by an outdoor exposure test. The outdoor exposure test involved parking the vehicle with the front glass facing south and exposing the water-repellent glass to direct sunlight and wind and rain. The degree of deterioration of the water repellency of the water repellent glass after 6 months of the outdoor exposure test was measured by the contact angle. The results are also shown in Table 2. From these results, it was confirmed that the water-repellent glass exhibited sufficient water-repellent performance even after 6 months of outdoor exposure and was extremely excellent in weather resistance. This was presumed to be due to the effect of the underlayer. (Example 5)
エタ ノ ール 9 9 . 5重量部にテ ト ラ ク ロ ロ シラ ン （商品名 ： L S — 1 0、 信越化学工業株式会社製） 0 . 5重量部を撹拌しながら添加し、 更 に室温で 2時間撹拌して、平滑下地膜用常温硬化コーティ ング液を得た。 酸化セ リ ウ ム系研磨剤で表面研磨 · 洗浄し、 さ ら に純水ですすいで乾 燥した自動車用フ ロ ン ト ガラス板の車外面に、 前記平滑下地膜用常温硬 ィ匕コ一ティ ング液をフ ローコー ト法で塗布し、 常温で乾燥させて、 平滑 下地膜付き フ ロ ン トガラスを得た。  To 99.5 parts by weight of ethanol, add 0.5 parts by weight of tetrachlorosilane (trade name: LS-10, manufactured by Shin-Etsu Chemical Co., Ltd.) with stirring, and further add room temperature. For 2 hours to obtain a room temperature curing coating liquid for a smooth underlayer. The above-mentioned room-temperature hardening film for a smooth undercoating film is applied to the outer surface of a front glass plate for an automobile, which is polished and washed with a cerium oxide abrasive, rinsed with pure water, and dried. The tinting solution was applied by a flow coating method and dried at room temperature to obtain a front glass with a smooth underlayer.
その後は、 実施例 4 と同様に、 この平滑下地膜付き フ ロ ン ト ガラスを 自動車に組み付けた後、 撥水処理液を塗布し、 得られた撥水性ガラス に ついて、 撥水性能と耐候性能を評価した。 その結果、 実施例 4 と同様に、 非常に耐候性能に優れている こ とが確認された。 また、 自動車組立工程 で他のガラス に平滑下地膜の一部が転写する こ と も なかった。  After that, as in Example 4, the front glass with the smooth undercoating film is assembled into an automobile, and then a water-repellent treatment liquid is applied, and the obtained water-repellent glass is subjected to water repellency and weather resistance. Was evaluated. As a result, as in Example 4, it was confirmed that the weather resistance was extremely excellent. In addition, part of the smooth underlayer was not transferred to other glass during the automobile assembly process.
(比較例 3 )  (Comparative Example 3)
通常の自動車用フロ ン ト ガラスの車外面に、 実施例 4 と同様に撥水処 理液を塗布し、 撥水性ガラスを得た。 得られた撥水性ガラスについて、 実施例 4 と同様に撥水性能と耐候性能を評価した結果、 初期撥水性は優 れたものの、 屋外曝露 6 ヶ月後の撥水性能は、 8 7度であ.り、 耐候久性 能が悪いこ とが確認された。  A water-repellent treatment liquid was applied to the outer surface of a normal vehicle front glass in the same manner as in Example 4 to obtain a water-repellent glass. The obtained water-repellent glass was evaluated for water repellency and weather resistance in the same manner as in Example 4. As a result, although the initial water repellency was excellent, the water repellency after 6 months of outdoor exposure was 87 ° C. It was confirmed that the weatherability was poor.
(比較例 4 )  (Comparative Example 4)
実施例 4 と同様にして得られた凹凸下地膜付き フ ロ ン ト ガラ スを、 自 動車に組み付ける前に、 実施例 4 と同様に撥水処理液を塗布して撥水性 ガラスを得た。 この撥水性ガラス をラ イ ン式の組立工程で自動車に組み 付けたと ころ、 吸盤を介して他のガラスに撥水膜が転写している こ とが 確認された。 表 2 Before assembling the front glass with an uneven undercoat film obtained in the same manner as in Example 4 into an automobile, a water-repellent treatment liquid was applied in the same manner as in Example 4 to obtain a water-repellent glass. When this water-repellent glass was assembled to a car in a line-type assembly process, it was confirmed that the water-repellent film had been transferred to another glass via a suction cup. Table 2
Figure imgf000012_0001
産業上の利用可能性
Figure imgf000012_0001
Industrial applicability
本発明は上記のよ う に、 基材表面.に予め下地膜を形成 しておいて、 最 終製品への組み付け後に機能性コーテ ィ ング剤を塗布して機能性皮膜を 形成する方法であるため、 基材を最終製品に組み付ける工程で機能性皮 膜が無く 、 そのため機能性皮膜が劣化した り 、 機能性皮膜が他の部材に 転写する こ とはない。 また、 最終製品に組み付けられた状態の基材には 既に下地膜が形成されているため、 単に機能性コ ーティ ング剤を塗布す るだけで耐久性に優れた機能性皮膜が容易に形成でき る。 また、 長期間 にわたる使用などによ つて機能性皮膜が失われて も、 下地膜は残つてい るために再度機能性コーティ ング剤を塗布するこ とで良好な機能性皮膜 を修復でき る。  As described above, the present invention is a method of forming a functional film by forming a base film on the surface of a base material in advance and applying a functional coating agent after assembling the final product. Therefore, there is no functional coating in the process of assembling the base material to the final product, so that the functional coating does not deteriorate and the functional coating does not transfer to other members. In addition, since a base film is already formed on the base material assembled into the final product, a functional film with excellent durability can be easily formed simply by applying a functional coating agent. You. In addition, even if the functional film is lost due to long-term use, the undercoat film remains, so a good functional film can be restored by applying a functional coating agent again.
また、 基材表面に予め下地膜を形成した後に、 下地膜の保護層を形成 し、 機能性コーティ ング剤を塗布する前に、 下地膜の保護層を除去する 場合は、 下地膜を形成後、 機能性皮膜を形成する までの間に基材の表面 が汚れた り傷が付いた りする こ と を防止する こ とができ る。  In addition, after forming a base film in advance on the surface of the base material, forming a protective layer of the base film, and removing the protective layer of the base film before applying the functional coating agent, after forming the base film, In addition, it is possible to prevent the surface of the substrate from being stained or damaged until the functional film is formed.

Claims

請 求 の 範 囲 The scope of the claims
1 . 基材表面に機能性皮膜を形成する方法において、 基材表面に予め 下地膜を形成しておき、 この下地膜付き基材を最終製品に組み付けた後 に、 該下地膜上に機能性コ一ティ ング剤を塗布する こ と に よ り 機能性皮 膜を形成する機能性皮膜の形成方法。 1. In the method of forming a functional film on the surface of a base material, a base film is previously formed on the surface of the base material, and after the base material with the base film is assembled into a final product, the functional film is formed on the base film. A method for forming a functional film that forms a functional film by applying a coating agent.
2 . 前記基'材表面に予め下地膜を形成した後に、 下地膜の保護層を 形成し、 前記機能性コ ーテ ィ ング剤を塗布する前に、 前記下地膜の保護 層を除去する請求の範囲第 1 項記載の機能性皮膜の形成方法。  2. After forming a base film on the surface of the base material in advance, forming a protective layer of the base film, and removing the protective layer of the base film before applying the functional coating agent. 3. The method for forming a functional film according to item 1, wherein
3 . 下地膜は、 表面が平滑な又は凹凸形状を有する シリ カ系皮膜であ る請求の範囲第 1 項記載の機能性皮膜の形成方法。 3. The method for forming a functional film according to claim 1, wherein the base film is a silica-based film having a smooth or uneven surface.
4 . 下地膜は、 シリ カ微粒子を含有するこ とで表面に凹凸形状が付与 されている シリ カ系皮膜である請求の範囲第 3項記載の機能性皮膜の形 成方法。  4. The method for forming a functional film according to claim 3, wherein the undercoat film is a silica-based film having an uneven surface formed by containing silica fine particles.
5 . 機能性皮膜は、 有機物機能性皮膜である請求の範囲第 1 項記載の 機能性皮膜の形成方法。  5. The method for forming a functional film according to claim 1, wherein the functional film is an organic functional film.
6 . 有機物機能性皮膜は、 防曇性皮膜又は撥水性皮膜、 超撥水性皮膜 である請求の範囲第 5項記載の機能性皮膜の形成方法。  6. The method for forming a functional film according to claim 5, wherein the organic functional film is an antifogging film, a water repellent film, or a super water repellent film.
7 . 基材は、 透明ガラス板又は透明樹脂板である請求の範囲第 1 項記 載の機能性皮膜の形成方法。  7. The method for forming a functional film according to claim 1, wherein the substrate is a transparent glass plate or a transparent resin plate.
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