JPWO2010038648A1 - Coating composition, antifouling treatment method and antifouling substrate - Google Patents

Coating composition, antifouling treatment method and antifouling substrate Download PDF

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JPWO2010038648A1
JPWO2010038648A1 JP2010531816A JP2010531816A JPWO2010038648A1 JP WO2010038648 A1 JPWO2010038648 A1 JP WO2010038648A1 JP 2010531816 A JP2010531816 A JP 2010531816A JP 2010531816 A JP2010531816 A JP 2010531816A JP WO2010038648 A1 JPWO2010038648 A1 JP WO2010038648A1
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徹 葛山
徹 葛山
遠藤　俊哉
俊哉 遠藤
大樹 杉山
大樹 杉山
西村　剛
剛 西村
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株式会社ティー アンド ケー
株式会社ティー アンド ケー
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • C09D5/165—Macromolecular compounds containing hydrolysable groups
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04M—TELEPHONIC COMMUNICATION
    • H04M1/00—Substation equipment, e.g. for use by subscribers
    • H04M1/02—Constructional features of telephone sets
    • H04M1/17—Hygienic or sanitary devices on telephone equipment
    • 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
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
    • C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers

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  • Chemical & Material Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
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  • Health & Medical Sciences (AREA)
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  • Signal Processing (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Paints Or Removers (AREA)
  • Surface Treatment Of Glass (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

防汚性に優れ、透明であり、実用上十分な耐久性を持った防汚性被膜を、低コストで形成することができるコーティング用組成物、防汚処理方法および防汚性基材を提供する。ペルフルオロアルキレンエーテル基を分子主鎖内に含み、シリコン原子を含む加水分解性基を側鎖に含む式１で表される化合物を溶媒に溶解してなり、上記溶媒がフッ素化炭化水素およびフッ素化エーテルの少なくとも１つを含むフッ素系溶媒同士の混合溶媒であり、上記フッ素系溶媒は１気圧下での沸点が４０℃以上７０℃以下であり、混合されている上記フッ素系溶媒の沸点の最大値と最小値の差が２５℃以内である。Provided a coating composition, an antifouling treatment method and an antifouling substrate capable of forming an antifouling coating excellent in antifouling property, transparent and sufficiently durable for practical use at low cost. To do. A compound represented by Formula 1 containing a perfluoroalkylene ether group in the molecular main chain and a hydrolyzable group containing a silicon atom in the side chain is dissolved in a solvent, and the solvent is a fluorinated hydrocarbon or fluorinated compound. It is a mixed solvent of fluorine-based solvents containing at least one ether, and the fluorine-based solvent has a boiling point of 40 ° C. or more and 70 ° C. or less under 1 atm, and the maximum boiling point of the mixed fluorine-based solvent is The difference between the value and the minimum value is within 25 ° C.

Description

本発明は、コーティング用組成物、防汚処理方法および防汚性基材に関し、特に防汚性を付与できるコーティング用組成物、防汚処理方法および該方法で防汚処理された携帯電話に関する。   The present invention relates to a coating composition, an antifouling treatment method and an antifouling substrate, and more particularly to a coating composition capable of imparting antifouling properties, an antifouling treatment method and a mobile phone antifouling treated by the method.

携帯電話の表示面、液晶パネルやタッチパネルの表示面、メガネレンズなどは、人が使用することによって、皮脂、指紋、汗、化粧品などが付着する。そこで、汚れが付着しにくく、かつ汚れを拭き取りやすくするための表面処理として、防汚処理が施される場合がある。
防汚処理は、基材の表面に防汚性を有する物質を薄膜にコーティングするものである。薄膜の原料としては、フルオロアルキル樹脂あるいはシリコーン系樹脂を利用することが多いが、中でもペルフルオロポリエーテル基を含む化合物は、その表面エネルギーが小さく、またエーテル結合を含むために分子構造が柔軟であることから、優れた防汚性を発揮することが知られている。これを薄膜にコーティングする際には、基材と薄膜の密着性を確保するため、同化合物中に加水分解が可能な基を導入したものを原料とするのが一般的である。Sebum, fingerprints, sweat, cosmetics, and the like adhere to the display surface of a mobile phone, the display surface of a liquid crystal panel or touch panel, and eyeglass lenses when used by a person. Therefore, an antifouling treatment may be performed as a surface treatment for making it difficult for dirt to adhere and easily wiping off the dirt.
In the antifouling treatment, a thin film is coated on the surface of the substrate with a substance having antifouling properties. As the raw material for the thin film, a fluoroalkyl resin or a silicone-based resin is often used. Among them, a compound containing a perfluoropolyether group has a small surface energy and a flexible molecular structure because it contains an ether bond. Therefore, it is known to exhibit excellent antifouling properties. When coating this on a thin film, in order to ensure adhesion between the base material and the thin film, it is common to use a material in which a hydrolyzable group is introduced into the compound.

例えば特許第３４４９０７０号には、ペルフルオロポリエーテル変性シランを真空蒸着法により薄膜にコーティングする方法が提案されている。しかしながら、真空蒸着法では、高価な生産設備を必要とし、また生産性が低いため、生産コストが高くなる問題があった。また、真空蒸着法で薄膜化が可能な原料は、その分子量が約５０００以下のものに制限されるため、高機能な長鎖型の原料を利用できないという問題があった。   For example, Japanese Patent No. 3449070 proposes a method of coating perfluoropolyether-modified silane on a thin film by vacuum deposition. However, the vacuum deposition method has a problem in that an expensive production facility is required and productivity is low, resulting in high production costs. In addition, since the raw material that can be thinned by the vacuum deposition method is limited to those having a molecular weight of about 5000 or less, there is a problem that a highly functional long-chain type raw material cannot be used.

そこで、低コストで生産可能な、ディップ法、スプレー法などのウエットコーティング法が注目されている。
しかし、従来のウエットコーティング法では、目的の化合物を可溶溶媒に溶かして溶液化し、基材表面に塗布するが、目的の化合物が加水分解する基を含んでいるため、溶液を大気中に曝すと大気中の水分と化合物が反応して、溶液がゲル化したり、目的の化合物が粒子化したりする問題がある。
また、ディップ法においては、溶液が大気に曝される時間が長いため、溶液の変質が顕著であり、原料の利用効率、被膜の品質上の問題が発生し、結果的に生産コストが高くなってしまうという問題があった。またディップ法では、原理的に形成される被膜が分子１層しか堆積しないため、実用上十分な耐久性を持つ被膜を形成することが困難であった。Therefore, wet coating methods such as dip method and spray method, which can be produced at low cost, are attracting attention.
However, in the conventional wet coating method, the target compound is dissolved in a soluble solvent to form a solution and applied to the surface of the substrate. However, since the target compound contains a group that hydrolyzes, the solution is exposed to the atmosphere. There is a problem that water and compounds in the atmosphere react with each other, and the solution gels or the target compound particles.
In the dip method, since the solution is exposed to the atmosphere for a long time, the deterioration of the solution is remarkable, causing problems in the use efficiency of the raw material and the quality of the coating, resulting in an increase in production cost. There was a problem that. Further, in the dip method, since the film formed in principle deposits only one molecular layer, it was difficult to form a film having practically sufficient durability.

スプレー法は溶液が大気に曝される時間を短くすることができるので、溶液が変質することは避けられる。また生産性も高く、大面積化も容易であることから、大量生産に向いた工法であると言える。
しかしながら、スプレーノズルから噴射された液滴が基材表面に付着し、濡れ拡がり、溶媒が乾燥して目的の化合物が表面で薄膜化する過程で、原料高分子が粒子化して被膜が白濁する問題があった。
特許第３４４９０７０号 Since the spray method can shorten the time during which the solution is exposed to the atmosphere, the solution is prevented from being altered. In addition, it can be said that the method is suitable for mass production because of its high productivity and easy area enlargement.
However, the droplet sprayed from the spray nozzle adheres to the substrate surface, spreads wet, the solvent dries, and the target compound becomes a thin film on the surface. was there.
Japanese Patent No. 3449070

本発明は、上記問題を解決するためになされたもので、防汚性に優れ、透明であり、実用上十分な耐久性を持った防汚性被膜を、低コストで形成することができるコーティング用組成物、防汚処理方法および防汚性基材の提供を目的とする。   The present invention has been made to solve the above-mentioned problems, and is a coating capable of forming an antifouling film having excellent antifouling property, transparency, and practically sufficient durability at a low cost. An object is to provide a composition, an antifouling treatment method and an antifouling substrate.

本発明のコーティング用組成物は、ペルフルオロアルキレンエーテル基を分子主鎖内に含み、シリコン原子を含む加水分解性基を側鎖に含む化合物を溶媒に溶解した組成物であることを特徴とする。この組成物において、上記溶媒がフッ素化炭化水素およびフッ素化エーテルの少なくとも１つを含むフッ素系溶媒同士の混合溶媒であり、上記フッ素系溶媒は１気圧下での沸点が４０℃以上７０℃以下であり、混合されている上記フッ素系溶媒の沸点の最大値と最小値の差が２５℃以内であることを特徴とする。
特に上記化合物が下記式（１）で表される化合物であることを特徴とする。

Figure 2010038648
式中、Ｒｆは炭素数１〜１６の直鎖状または分岐状パーフルオロアルキル基、Ｙは水素原子または炭素数１〜３のアルキル基、Ｒ1はハロゲン原子、−ＯＲ3基、−ＯＣＯＲ3基、−ＯＣ（Ｒ3）＝Ｃ（Ｒ4）2基、−ＯＮ＝Ｃ（Ｒ3）2基、および−ＯＮ＝Ｃ（Ｒ5）2基から選ばれる少なくとも１つの基を表し、Ｒ3は脂肪族炭化水素基または芳香族炭化水素基を表し、Ｒ4は水素原子または炭素数１〜３のアルキル基を表し、Ｒ5は炭素数３〜６の２価の脂肪族炭化水素基を表し、ｑは１〜５０の整数、ｍは０〜２の整数、ｒは１〜１０の整数を表す。
また、式（１）で表される化合物を溶解するフッ素系溶媒が１,１,１,３,３−ペンタフルオロブタン、ペルフルオロヘキサン、１,１,１,２,２,３,３,４,５,５,５−ウンデカフルオロ−４−（トリフルオロメチル）ペンタン、または、メチルノナフルオロブチルエーテルであることを特徴とする。The coating composition of the present invention is a composition in which a compound containing a perfluoroalkylene ether group in a molecular main chain and a hydrolyzable group containing a silicon atom in a side chain is dissolved in a solvent. In this composition, the solvent is a mixed solvent of fluorine-based solvents containing at least one of a fluorinated hydrocarbon and a fluorinated ether, and the fluorine-based solvent has a boiling point of 40 ° C. or higher and 70 ° C. or lower at 1 atm. The difference between the maximum value and the minimum value of the boiling point of the mixed fluorine-based solvent is 25 ° C. or less.
In particular, the compound is a compound represented by the following formula (1).
Figure 2010038648
 In the formula, Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, Y is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 1 is a halogen atom, —OR 3 group, —OCOR 3 Represents at least one group selected from a group, —OC (R 3 ) ═C (R 4 ) 2 group, —ON═C (R 3 ) 2 group, and —ON═C (R 5 ) 2 group; 3 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R 4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 5 represents a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms. Q represents an integer of 1 to 50, m represents an integer of 0 to 2, and r represents an integer of 1 to 10.
Moreover, the fluorine-type solvent which melt | dissolves the compound represented by Formula (1) is 1,1,1,3,3-pentafluorobutane, perfluorohexane, 1,1,1,2,2,3,3,4. , 5,5,5-undecafluoro-4- (trifluoromethyl) pentane or methyl nonafluorobutyl ether.

本発明の防汚処理方法は、無機基材の表面、または無機もしくは有機基材に形成された無機表面膜の表面にコーティングを施すことにより、防汚処理を行なう防汚処理方法において、上記無機基材の表面または無機表面膜の表面へのコーティングが上記本発明のコーティング用組成物をスプレー法で塗布されたコーティングであることを特徴とする。
特に、上記無機表面膜は、ポリシラザン溶液をスプレー法で塗布することにより形成した無機表面膜であることを特徴する。The antifouling treatment method of the present invention is the above-mentioned inorganic antifouling treatment method in which antifouling treatment is performed by coating the surface of an inorganic substrate or the surface of an inorganic surface film formed on an inorganic or organic substrate. The coating on the surface of the substrate or the surface of the inorganic surface film is a coating in which the coating composition of the present invention is applied by a spray method.
In particular, the inorganic surface film is an inorganic surface film formed by applying a polysilazane solution by a spray method.

本発明の防汚性基材は、基材の表面、または基材に形成された無機表面膜の表面に防汚層を有する防汚性基材であって、上記防汚層が本発明の防汚処理方法により形成された防汚層であることを特徴とする。
特に、上記防汚性基材は、画像表示部を有し、該画像表示部の表面に上記防汚層が形成された携帯電話であることを特徴とする。The antifouling substrate of the present invention is an antifouling substrate having an antifouling layer on the surface of the substrate or the surface of the inorganic surface film formed on the substrate, the antifouling layer of the present invention It is an antifouling layer formed by an antifouling treatment method.
In particular, the antifouling base material is a mobile phone having an image display portion and having the antifouling layer formed on the surface of the image display portion.

本発明のコーティング用組成物は、式（１）で表される化合物を特定の構造および沸点を有する複数の混合溶媒を溶媒として用いるので、防汚性に優れ、透明であり、実用上十分な耐久性を持った被膜を、低コストで形成することが可能になった。   In the coating composition of the present invention, the compound represented by the formula (1) uses a plurality of mixed solvents having a specific structure and boiling point as a solvent. Therefore, the coating composition is excellent in antifouling property, transparent and practically sufficient. It has become possible to form a durable coating at low cost.

本発明の携帯電話の実施形態の一例を示す外観図である。It is an external view which shows an example of embodiment of the mobile telephone of this invention. 図１の断面ＡＡ’を示す概略図である。It is the schematic which shows the cross section AA 'of FIG.

本発明に使用できるペルフルオロアルキレンエーテル基を分子主鎖内に、シリコン原子を含む加水分解性基を側鎖に、それぞれ含む化合物は、コーティング用組成物の溶質となる化合物である。
上記ペルフルオロアルキレンエーテル基は、下記式（１−１）で表され、上記シリコン原子を含む加水分解性基は下記式（１−２）で表される。

Figure 2010038648
式（１−１）において、ｎは１〜５の整数を、式（１−２）において、ｍは０〜２の整数、Ｒ1は加水分解可能な基をそれぞれ表す。A compound containing a perfluoroalkylene ether group in the molecular main chain and a hydrolyzable group containing a silicon atom in a side chain, which can be used in the present invention, is a compound that becomes a solute of the coating composition.
The perfluoroalkylene ether group is represented by the following formula (1-1), and the hydrolyzable group containing a silicon atom is represented by the following formula (1-2).
Figure 2010038648
 In Formula (1-1), n represents an integer of 1 to 5, in Formula (1-2), m represents an integer of 0 to 2, and R 1 represents a hydrolyzable group.

ペルフルオロアルキレンエーテル基内におけるエーテル結合の頻度は特に限定されるものではなく、繰り返し単位として、−（ＯＣＦ2）−、−（ＯＣ2Ｆ4）−、−（ＯＣ3Ｆ6）−、−（ＯＣ4Ｆ8）−等が単独で、または複数組み合わされて形成されているペルフルオロアルキレンエーテル基が使用できる。また、ペルフルオロアルキレンエーテル基の一方の端部は、ｎが１以上のＣnＦ2n＋1−基であることが好ましい。Frequency of ether linkages in the perfluoroalkylene ether Motonai is not limited in particular, as a repeating unit, - (OCF 2) -, - (OC 2 F 4) -, - (OC 3 F 6) -, - ( A perfluoroalkylene ether group formed by singly or in combination of OC 4 F 8 )-and the like can be used. Moreover, it is preferable that one end part of the perfluoroalkylene ether group is a C n F 2n + 1 group having n of 1 or more.

側鎖に有するシリコン原子を含む加水分解性基としては、コーティングにおける塗膜形成時に水の作用により分解する基であればよく、上記式（１−２）で表される。
Ｒ1としては、例えばハロゲン原子、−ＯＲ3基、−ＯＣＯＲ3基、−ＯＣ（Ｒ3）＝Ｃ（Ｒ4）2基、−ＯＮ＝Ｃ（Ｒ3）2基、−ＯＮ＝Ｃ（Ｒ5）2基等が挙げられる。ここで、Ｒ3は脂肪族炭化水素基または芳香族炭化水素基を表し、Ｒ4は水素原子または炭素数１〜３のアルキル基を表し、Ｒ5は炭素数３〜６の２価の脂肪族炭化水素基を表す。
本発明において、好ましいＲ1としては、式（１）で表される化合物を溶質として用いた場合に、被膜の白濁発生をより抑えることができる塩素原子、−ＯＣＨ3基、−ＯＣ2Ｈ5基である。The hydrolyzable group containing a silicon atom in the side chain may be any group that can be decomposed by the action of water when a coating film is formed in the coating, and is represented by the above formula (1-2).
Examples of R 1 include a halogen atom, —OR 3 group, —OCOR 3 group, —OC (R 3 ) ═C (R 4 ) 2 group, —ON═C (R 3 ) 2 group, —ON═C ( R 5 ) 2 groups and the like. Here, R 3 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R 4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 5 represents a divalent fatty acid having 3 to 6 carbon atoms. Represents a group hydrocarbon group.
In the present invention, as preferred R 1 , when a compound represented by the formula (1) is used as a solute, a chlorine atom, —OCH 3 group, —OC 2 H 5 that can further suppress the occurrence of cloudiness in the coating film. It is a group.

上記本発明に使用できる化合物の好ましい例としては、式（１）で表される化合物が挙げられる。
Ｒｆとして表される炭素数１〜１６の直鎖状または分岐状ペルフルオロアルキル基としては、トリフルオロメチル基、ペルフルオロエチル基、ペルフルオロプロピル基、ペルフルオロブチル基、ペルフルオロペンチル基等が挙げられる。
Ｙとして表される炭素数１〜３のアルキル基としては、メチル基、エチル基、プロピル基が挙げられる。
ｑは１〜５０、好ましくは１８〜３０、より好ましくは２２〜２６の整数、ｍは０〜２、好ましくは０の整数、ｒは１〜１０、好ましくは１〜５の整数を表す。
式（１）で表されるフッ素化合物は市販のパーフルオロポリエーテルをシラン処理することによって得ることができる。その方法は、例えば、特開平１−２９４７０９号公報に開示されている。Preferable examples of the compound that can be used in the present invention include a compound represented by the formula (1).
Examples of the linear or branched perfluoroalkyl group having 1 to 16 carbon atoms represented by Rf include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluoropentyl group.
Examples of the alkyl group having 1 to 3 carbon atoms represented as Y include a methyl group, an ethyl group, and a propyl group.
q represents an integer of 1 to 50, preferably 18 to 30, more preferably 22 to 26, m represents an integer of 0 to 2, preferably 0, and r represents an integer of 1 to 10, preferably 1 to 5.
The fluorine compound represented by the formula (1) can be obtained by silane treatment of a commercially available perfluoropolyether. This method is disclosed, for example, in Japanese Patent Laid-Open No. 1-294709.

本発明で使用できる混合溶媒の成分を構成する、フッ素化炭化水素およびフッ素化エーテルの少なくとも１つを含むフッ素系溶媒は、１気圧下での沸点が４０℃以上７０℃以下である。また、混合溶媒中のフッ素系溶媒の沸点の最大値と最小値の差が２５℃以内、好ましくは２０℃以内である。
好ましい混合溶媒の構成は、１気圧下での沸点が４０℃以上７０℃以下のフッ素系溶媒１と、該溶媒１の沸点に対して２０℃以内の沸点差を有するフッ素系溶媒２との混合溶媒である。
上述の沸点条件を満たす２種類以上の溶媒を混合したコーティング剤をスプレーコーティングした場合には、膜厚のムラが抑制され、また透明な被膜が得られることが分かった。The fluorine-based solvent containing at least one of a fluorinated hydrocarbon and a fluorinated ether constituting the component of the mixed solvent that can be used in the present invention has a boiling point of 40 ° C. or higher and 70 ° C. or lower at 1 atm. Further, the difference between the maximum value and the minimum value of the boiling point of the fluorinated solvent in the mixed solvent is within 25 ° C, preferably within 20 ° C.
A preferred mixed solvent structure is a mixture of a fluorine-based solvent 1 having a boiling point of 40 ° C. or more and 70 ° C. or less under 1 atm and a fluorine-based solvent 2 having a boiling point difference within 20 ° C. with respect to the boiling point of the solvent 1. It is a solvent.
It was found that when the coating agent in which two or more kinds of solvents satisfying the above boiling point conditions were mixed by spray coating, unevenness in film thickness was suppressed and a transparent film was obtained.

混合溶媒ではなく、１種類の溶媒を使用したコーティング剤をスプレー法でコーティングすると、被膜が白濁しやすく、透明な薄膜を得る条件範囲（例えば、コーティング時の雰囲気の湿度と温度等）が著しく狭くなり、結果的に高コストなプロセスになってしまう。また、沸点の差が２５℃をこえる溶媒の組み合わせでは、被膜の膜厚均一性が損なわれ、目視で認識できるムラが発生してしまう。沸点が７０℃より高い溶媒を使用すると乾燥するまでの時間がかかり、逆に沸点が４０℃未満の低い溶媒を使用するとスプレーガンから噴射されたコーティング組成物の液滴が基材に到着する前にパウダー化し、透明な薄膜を得ることができない。そのメカニズムは明確ではないが、上記溶媒組成にすることで膜厚のムラを抑制して透明な被膜が得られる。   When a coating agent that uses one type of solvent instead of a mixed solvent is coated by the spray method, the coating tends to become cloudy, and the conditions for obtaining a transparent thin film (for example, the humidity and temperature of the atmosphere during coating) are extremely narrow. As a result, the process becomes expensive. In addition, in the case of a combination of solvents in which the difference in boiling points exceeds 25 ° C., the film thickness uniformity of the coating is impaired, and unevenness that can be recognized visually occurs. When a solvent having a boiling point higher than 70 ° C. is used, it takes time to dry, and conversely, when a solvent having a boiling point lower than 40 ° C. is used, before the droplets of the coating composition ejected from the spray gun arrive at the substrate. It is not possible to obtain a transparent thin film. Although the mechanism is not clear, by using the above solvent composition, a non-uniform film thickness can be suppressed and a transparent film can be obtained.

本発明で使用できる溶媒としては、環境破壊への影響、生産時の安全性、入手性などを考慮すると、１,１,１,３,３−ペンタフルオロブタン（沸点４０℃）、ペルフルオロヘキサン（沸点５６℃）、１,１,１,２,２,３,３,４,５,５,５−ウンデカフルオロ−４−（トリフルオロメチル）ペンタン（沸点５６℃）、メチルノナフルオロブチルエーテル（沸点６１℃）の中から２種類以上の溶剤を選んで混合したものが好適である。特に沸点の差が２０℃以内の２種類以上の溶剤を選んで混合したものが好適である。
また、混合溶媒の混合割合は、混合溶媒全体に対して、少なくとも１つの成分が１重量％以上、好ましくは２重量％以上混合されていることが好ましい。
なお、上記溶媒には濡れ性などの諸特性を調整する助剤を混合することができる。Solvents that can be used in the present invention include 1,1,1,3,3-pentafluorobutane (boiling point: 40 ° C.), perfluorohexane (boiling point: 40 ° C.) in consideration of environmental impact, safety during production, availability, and the like. (Boiling point 56 ° C.), 1,1,1,2,2,3,3,4,5,5,5-undecafluoro-4- (trifluoromethyl) pentane (boiling point 56 ° C.), methyl nonafluorobutyl ether ( A mixture of two or more solvents selected from a boiling point of 61 ° C. is preferable. In particular, a mixture obtained by selecting and mixing two or more solvents having a difference in boiling point of 20 ° C. or less is preferable.
The mixing ratio of the mixed solvent is such that at least one component is mixed by 1 wt% or more, preferably 2 wt% or more with respect to the entire mixed solvent.
In addition, the said solvent can be mixed with the adjuvant which adjusts various characteristics, such as wettability.

本発明のコーティング用組成物は、基材をコーティング用組成物に浸漬するディップ法、基材にコーティング用組成物を噴霧状に塗布するスプレー法、基材を回転させながらコーティング用組成物を滴下するスピンコート法などのウェットプロセス、コーティング用組成物の溶質を用いる真空蒸着法などのドライプロセスなど、公知の方法でコーティングすることで表面に防汚層を形成できる。
これらの中で、スプレー法で形成した防汚層は、他の方法よりも耐磨耗性に優れることが分かった。また、材料の利用効率、生産性の観点からも、スプレー法は他の方法よりも有利である。したがって、コーティング方法としてはスプレー法が最も好ましい。The coating composition of the present invention includes a dipping method in which a substrate is immersed in the coating composition, a spray method in which the coating composition is sprayed onto the substrate, and the coating composition is dropped while rotating the substrate. An antifouling layer can be formed on the surface by coating by a known method such as a wet process such as a spin coating method or a dry process such as a vacuum deposition method using a solute of a coating composition.
Among these, it was found that the antifouling layer formed by the spray method is more excellent in abrasion resistance than other methods. The spray method is more advantageous than other methods from the viewpoint of material utilization efficiency and productivity. Therefore, the spray method is most preferable as the coating method.

上記防汚層が形成される基材は、無機基材または有機基材を挙げることができる。
無機基材としては、ガラス、金属、セラミックスなどが挙げられる。これらの中で、透明もしくは半透明のガラス、セラミックスなどが好ましい。
有機基材としては、プラスチックス、ゴム、エラストマーなどが挙げられる。これらの中で、透明もしくは半透明のプラスチックスが好ましく、特にアクリル系樹脂、ポリカーボネート樹脂などが好ましい。
透明もしくは半透明の基材は、携帯電話、各種表示器などの表示部に用いられる場合が多く、防汚層の形成を特に必要とされる基材のためである。Examples of the substrate on which the antifouling layer is formed include an inorganic substrate or an organic substrate.
Examples of the inorganic substrate include glass, metal, and ceramics. Of these, transparent or translucent glass, ceramics and the like are preferable.
Examples of the organic substrate include plastics, rubber, and elastomer. Among these, transparent or translucent plastics are preferable, and acrylic resins and polycarbonate resins are particularly preferable.
A transparent or translucent base material is often used for a display unit such as a mobile phone or various displays, and is for a base material that particularly requires the formation of an antifouling layer.

基材の形状としてはフィルムまたはシートが好ましいが、特に限定されるものではなく、コーティング面が平面または滑らかな曲面であれば防汚層を形成する基材として使用できる。また、基材上にハードコーティング、反射防止コーティング、アンチグレアコーティングなど、他の表面処理があらかじめ施されていてもよい。   The shape of the substrate is preferably a film or a sheet, but is not particularly limited, and can be used as a substrate for forming an antifouling layer as long as the coating surface is a flat surface or a smooth curved surface. In addition, other surface treatments such as hard coating, antireflection coating, and antiglare coating may be performed on the substrate in advance.

無機基材または有機基材の表面に無機表面膜を設けることが好ましい。特に有機基材の表面には無機表面膜を設けることが好ましい。無機表面膜を設けることにより、防汚層の密着力が向上する。
無機表面膜としては、金属膜、半導体膜、酸化膜、窒化膜、酸窒化膜などから、製品の要求仕様に応じて選択することができる。無機表面膜の厚さは、防汚コーティング層の密着性が確保される必要最小限の厚さにすべきであり、０．０１〜１μｍの範囲、より好ましくは０．０５〜０．２μｍの範囲で形成するのが好ましい。ただし、防汚性以外の製品の要求仕様からこの範囲外の無機膜が必要な場合には、当然それに適合した膜厚としてもよい。It is preferable to provide an inorganic surface film on the surface of an inorganic substrate or an organic substrate. In particular, an inorganic surface film is preferably provided on the surface of the organic substrate. By providing the inorganic surface film, the adhesion of the antifouling layer is improved.
The inorganic surface film can be selected from a metal film, a semiconductor film, an oxide film, a nitride film, an oxynitride film, and the like according to the required specifications of the product. The thickness of the inorganic surface film should be the minimum necessary thickness to ensure the adhesion of the antifouling coating layer, and is in the range of 0.01 to 1 μm, more preferably 0.05 to 0.2 μm. It is preferable to form in a range. However, if an inorganic film outside this range is required based on the required specifications of the product other than the antifouling property, the film thickness may naturally be adapted to it.

基材の表面への無機表面膜の形成は、スプレー法、ゾルゲル法、スパッタリング法、ＣＶＤ法など公知の形成方法で成膜することができる。
式（１）で表される化合物の防汚層を形成する場合、ポリシラザン溶液を用いてスプレー法で塗布して乾燥した無機表面膜が実用上十分な耐摩耗性が得られることが分かった。また、生産コスト、生産性の観点からも、ポリシラザン溶液をスプレー法で塗布する無機表面膜形成方法は他の方法と同等もしくは優れていることから、無機表面膜はこの方法で形成するのが好ましい。The inorganic surface film can be formed on the surface of the base material by a known forming method such as a spray method, a sol-gel method, a sputtering method, or a CVD method.
When forming the antifouling layer of the compound represented by the formula (1), it was found that an inorganic surface film coated by a spray method using a polysilazane solution and dried can provide practically sufficient wear resistance. Also, from the viewpoint of production cost and productivity, the inorganic surface film forming method in which the polysilazane solution is applied by a spray method is equivalent to or superior to other methods, and therefore the inorganic surface film is preferably formed by this method. .

ポリシラザン溶液は、ＡＺエレクトロニックマテリアルズ社から市販されており、濃度、溶媒の種類などを基材の種類、膜厚、スプレー条件などに合わせて、希釈、濃縮を適宜行なえばよい。なお、ポリシラザン溶液をスプレー塗布する際に使用するキャリアガスは、極力水分を含まないガスが適しており、コストの観点から窒素ガスが最も適している。また、必要に応じて乾燥後のポリシラザン系無機膜を高湿度雰囲気中に放置すること、あるいは光または熱エネルギーを加えることにより、シリカへの転化を促進させてもよい。   The polysilazane solution is commercially available from AZ Electronic Materials, and the concentration and the type of solvent may be appropriately diluted and concentrated according to the type of substrate, film thickness, spray conditions, and the like. Note that the carrier gas used when spraying the polysilazane solution is a gas containing as little water as possible, and nitrogen gas is most suitable from the viewpoint of cost. Moreover, you may accelerate | stimulate the conversion to a silica by leaving the polysilazane type inorganic film after drying to stand in a high-humidity atmosphere as needed, or adding light or a thermal energy.

本発明の防汚性基材は、携帯電話の表示面、液晶パネルやタッチパネルの表示面、メガネレンズなど、皮脂、指紋、汗、化粧品などが付着しやすい基材の表面に上述した防汚処理が施されているものである。
以下、本発明のコーティング用組成物を用いて防汚層が形成された携帯電話の例について、図面を用いて説明する。
図１および図２は、携帯電話の一例を示す図である。
図１は携帯電話の全体を示し、通話等に使用する各種の操作キー１、電話に関する各種の情報（電話番号、電波状態、バッテリーの残量等）や画像表示部である画像表示装置２、マイク３、スピーカー４から構成されている。画像表示装置２は具体的には液晶ディスプレイ（ＬＣＤ）や有機エレクトロルミネッセンスディスプレイ（有機ＥＬディスプレイ）などが挙げられる。The antifouling substrate of the present invention is the antifouling treatment described above on the surface of a substrate to which sebum, fingerprints, sweat, cosmetics, etc. are likely to adhere, such as a display surface of a mobile phone, a display surface of a liquid crystal panel or a touch panel, and a spectacle lens. Is given.
Hereinafter, an example of a mobile phone in which an antifouling layer is formed using the coating composition of the present invention will be described with reference to the drawings.
1 and 2 are diagrams illustrating an example of a mobile phone.
FIG. 1 shows an entire mobile phone, various operation keys 1 used for a call, various information related to the telephone (telephone number, radio wave state, remaining battery level, etc.) and an image display device 2 which is an image display unit. It consists of a microphone 3 and a speaker 4. Specific examples of the image display device 2 include a liquid crystal display (LCD) and an organic electroluminescence display (organic EL display).

図２は図１の断面ＡＡ'を示す。画像表示装置２は携帯電話の筐体５の内部に設けられており、画像表示装置２の上には透過窓部材６が設けられている。透過窓部材６は一般的には光透過率の良い樹脂性であり、その材質はアクリル、ポリカーボネート等でできている。
本発明は、透過窓部材６に無機表面膜６ａおよび式（１）で表される化合物による防汚層６ｂを順に設けるものである。FIG. 2 shows a cross section AA ′ of FIG. The image display device 2 is provided inside a casing 5 of the mobile phone, and a transmission window member 6 is provided on the image display device 2. The transmission window member 6 is generally made of resin having a good light transmittance, and the material thereof is made of acrylic, polycarbonate, or the like.
In the present invention, the transparent window member 6 is provided with the inorganic surface film 6a and the antifouling layer 6b of the compound represented by the formula (1) in this order.

透明な無機表面膜６ａは、スパッタリング法によって透過窓部材６に形成される。無機表面膜６ａの材料としては、ポリシラザン系無機膜を利用できる。
また、表面の防汚層６ｂとしては、式（１）で表される化合物を溶質とするコーティング用組成物を用いてスプレー法で塗布・乾燥して形成できる。The transparent inorganic surface film 6a is formed on the transmission window member 6 by a sputtering method. As a material for the inorganic surface film 6a, a polysilazane-based inorganic film can be used.
Further, the antifouling layer 6b on the surface can be formed by applying and drying by a spray method using a coating composition having a compound represented by the formula (1) as a solute.

防汚処理理後の基材を以下の方法で評価した。評価項目とその方法を説明する。
（評価１）外観
評価サンプルを、暗室内で蛍光灯５００ルクス以上の照度の下、目視観察し、被膜の白濁、ムラの有無を判定した。
（評価２）皮脂付着性
評価サンプルを頬に押し当て、皮脂の付着状態を目視観察した。評価基準は、未処理の青板ガラスの付着状態を不良とし、これに比較して皮脂の付着が明らかに少ないものを良好とした。
（評価３）皮脂除去性
下記（評価４）の評価サンプルをセルロース製不織布（旭化成社製ベンコット）で軽く１０往復擦り、皮脂の残り方を目視観察した。評価基準は、皮脂がほとんど残らないものを良好、明らかに残るものを不良とした。
（評価４）耐摩耗性
コピー用紙（アスクル製スーパーホワイト）を９．８Ｎ／ｃｍ2の荷重でサンプルに押し当て、往復摺動させ、摺動部の水に対する接触角を測定し、接触角が９０°を下回るまでの摺動回数を測定した。試験は３回以上行ない、その平均値で評価した。なお、この試験方法で５万回程度の耐摩耗性があれば、実用上十分な耐摩耗性を有すると考えられる。
なお、以下の実施例、比較例に記載している膜厚は、評価サンプルと同時に形成したＳｉ（１００）基板上の被膜を、エリプソメーター（溝尻光学社製ＤＨＡ−ＦＲ）により測定した。また接触角は、評価サンプル表面の水に対する接触角を接触角計（協和界面科学社社製ＤＭ１００）により測定した。The base material after antifouling treatment was evaluated by the following method. The evaluation items and methods are described.
(Evaluation 1) Appearance An evaluation sample was visually observed in a dark room under an illuminance of 500 lux or more of fluorescent lamps, and the presence or absence of coating cloudiness or unevenness was determined.
(Evaluation 2) Sebum Adhesion The evaluation sample was pressed against the cheek, and the state of sebum adhesion was visually observed. As the evaluation criteria, the untreated soda sheet glass was considered to be poor in adhesion, and in comparison with this, the sebum was clearly less adhered.
(Evaluation 3) Sebum removability The evaluation sample shown below (Evaluation 4) was lightly rubbed 10 times with a cellulose nonwoven fabric (Bencot manufactured by Asahi Kasei Co., Ltd.), and the remaining sebum was visually observed. The evaluation criteria were good when almost no sebum remained, and poor when clearly remained.
(Evaluation 4) Abrasion resistance A copy paper (ASKUL Super White) was pressed against the sample with a load of 9.8 N / cm 2 and slid back and forth. The number of times of sliding until less than 90 ° was measured. The test was performed 3 times or more, and the average value was evaluated. If this test method has a wear resistance of about 50,000 times, it is considered that the wear resistance is practically sufficient.
In addition, the film thickness described in the following Examples and Comparative Examples was measured by using an ellipsometer (DHA-FR manufactured by Mizojiri Optical Co., Ltd.) on the film formed on the Si (100) substrate simultaneously with the evaluation sample. Moreover, the contact angle measured the contact angle with respect to the water of the evaluation sample surface with the contact angle meter (DM100 by Kyowa Interface Science Co., Ltd.).

実施例１
コーティング用組成物として、下記の式（２）で表される化合物１重量部を、ペルフルオロヘキサン（沸点５６℃）４重量部と１,１,１,３,３−ペンタフルオロブタン（沸点４０℃）１９５重量部との混合溶媒に溶解した組成物を準備した。このコーティング組成物をガラス基板（アズワン社製スライドガラスＳ１２２５）にスプレー法でコーティングして、５０℃で３０分間乾燥した。形成された防汚層の膜厚は８．４ｎｍ、接触角は１１６°だった。被膜の外観はムラがなく透明で、皮脂付着性、皮脂除去性とも良好だった。また耐摩耗性は９５，７６３回だった。結果を表１に示す。

Figure 2010038648
式（２）において、トリメトキシシランを側鎖に有する繰り返し単位の繰り返し数１−１０は、繰り返し数が１〜１０の混合物を表す。Example 1
As a coating composition, 1 part by weight of a compound represented by the following formula (2) is mixed with 4 parts by weight of perfluorohexane (boiling point 56 ° C.) and 1,1,1,3,3-pentafluorobutane (boiling point 40 ° C.). ) A composition dissolved in a mixed solvent with 195 parts by weight was prepared. This coating composition was coated on a glass substrate (Slide Glass S1225 manufactured by AS ONE) by a spray method and dried at 50 ° C. for 30 minutes. The formed antifouling layer had a film thickness of 8.4 nm and a contact angle of 116 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. The abrasion resistance was 95,763 times. The results are shown in Table 1.
Figure 2010038648
 In the formula (2), the repeating number 1-10 of the repeating unit having trimethoxysilane in the side chain represents a mixture having a repeating number of 1-10.

実施例２
コーティング用組成物として、上記式（２）で表される化合物１重量部を、ペルフルオロヘキサン（沸点５６℃）４重量部と１,１,１,２,２,３,３,４,５,５,５−ウンデカフルオロ−（トリフルオロメチル）ペンタン（沸点５６℃）１９５重量部との混合溶媒に溶解した組成物を準備した。このコーティング組成物をガラス基板（アズワン社製スライドガラスＳ１２２５）にスプレー法でコーティングして、５０℃で３０分間乾燥した。形成された防汚層の膜厚は９．２ｎｍ、接触角は１１５°だった。被膜の外観はムラがなく透明で、皮脂付着性、皮脂除去性とも良好だった。また耐摩耗性は８８，１４０回だった。結果を表１に示す。Example 2
As a coating composition, 1 part by weight of the compound represented by the above formula (2) is mixed with 4 parts by weight of perfluorohexane (boiling point 56 ° C.) and 1,1,1,2,2,3,3,4,5, A composition dissolved in a mixed solvent of 195 parts by weight of 5,5-undecafluoro- (trifluoromethyl) pentane (boiling point 56 ° C.) was prepared. This coating composition was coated on a glass substrate (Slide Glass S1225 manufactured by AS ONE) by a spray method and dried at 50 ° C. for 30 minutes. The formed antifouling layer had a thickness of 9.2 nm and a contact angle of 115 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. The abrasion resistance was 88,140 times. The results are shown in Table 1.

実施例３
コーティング用組成物として、上記式（２）で表される化合物１重量部を、ペルフルオロヘキサン（沸点５６℃）４重量部とメチルナノフルオロブチルエーテル（沸点６１℃）１９５重量部との混合溶媒に溶解した組成物を準備した。このコーティング組成物をガラス基板（アズワン社製スライドガラスＳ１２２５）にスプレー法でコーティングして、５０℃で３０分間乾燥した。形成された防汚層の膜厚は８．８ｎｍ、接触角は１１６°だった。被膜の外観はムラがなく透明で、皮脂付着性、皮脂除去性とも良好だった。また耐摩耗性は９２，５９８回だった。結果を表１に示す。Example 3
As a coating composition, 1 part by weight of the compound represented by the above formula (2) is dissolved in a mixed solvent of 4 parts by weight of perfluorohexane (boiling point 56 ° C.) and 195 parts by weight of methyl nanofluorobutyl ether (boiling point 61 ° C.). A prepared composition was prepared. This coating composition was coated on a glass substrate (Slide Glass S1225 manufactured by AS ONE) by a spray method and dried at 50 ° C. for 30 minutes. The formed antifouling layer had a film thickness of 8.8 nm and a contact angle of 116 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. The wear resistance was 92,598 times. The results are shown in Table 1.

実施例４
ハードコート付きアクリル基板（三菱レイヨン社製アクリライトＭＲ−２００）に、スプレー法でポリシラザン溶液（ＡＺエレクトロニックマテリアル社製アクアミカＮＬ１２０Ａ−０５）を塗布し、大気雰囲気に１昼夜放置してポリシラザン薄膜（膜厚９３ｎｍ）を形成した。その後、実施例２で使用したコーティング組成物を実施例２と同じ条件でスプレー法でコーティングした。防汚層の膜厚は８．５ｎｍ、接触角は１１７°だった。
被膜の外観はムラがなく透明で、皮脂付着性、皮脂除去性とも良好だった。また耐摩耗性は６６，０３１回だった。Example 4
A polysilazane solution (Aquamica NL120A-05 manufactured by AZ Electronic Materials Co., Ltd.) is applied to an acrylic substrate with hard coat (Acrylite MR-200 manufactured by Mitsubishi Rayon Co., Ltd.) by spraying, and left for a day and night in an air atmosphere to form a polysilazane thin film (film) A thickness of 93 nm) was formed. Thereafter, the coating composition used in Example 2 was coated by the spray method under the same conditions as in Example 2. The film thickness of the antifouling layer was 8.5 nm and the contact angle was 117 °.
The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. The abrasion resistance was 66,031 times.

比較例１
コーティング組成物として、上記式（２）で表される化合物１重量部を、ペルフルオロヘキサン（沸点５６℃）１９９重量部に溶解して準備した。このコーティング組成物をガラス基板（アズワン社製スライドガラスＳ１２２５）に実施例１と同じ条件でスプレー法でコーティングした。被膜の外観は、明らかに白濁していた。被膜の外観が不良であったため、皮脂付着性、皮脂除去性および耐摩耗性の評価を中止した。Comparative Example 1
As a coating composition, 1 part by weight of a compound represented by the above formula (2) was prepared by dissolving in 199 parts by weight of perfluorohexane (boiling point 56 ° C.). This coating composition was coated on a glass substrate (Azwan slide glass S1225) by the spray method under the same conditions as in Example 1. The appearance of the coating was clearly cloudy. Since the appearance of the film was poor, the evaluation of sebum adhesion, sebum removability and abrasion resistance was stopped.

比較例２
コーティング組成物として、上記式（２）で表される化合物１重量部を、ペルフルオロヘキサン（沸点５６℃）４重量部と旭硝子社製ＮｏｖｅｃＨＦＥ７２００（沸点７６℃）１９５重量部の混合溶媒に溶解して準備した。このコーティング組成物をガラス基板（アズワン社製スライドガラスＳ１２２５）に実施例１と同じ条件でスプレー法でコーティングした。被膜の外観は透明だったが、目視で認識できる円形の模様（ムラ）が発生した。被膜の外観が不良であったため、皮脂付着性、皮脂除去性および耐摩耗性の評価を中止した。Comparative Example 2
As a coating composition, 1 part by weight of a compound represented by the above formula (2) is dissolved in a mixed solvent of 4 parts by weight of perfluorohexane (boiling point 56 ° C.) and 195 parts by weight of Asahi Glass Novec HFE 7200 (boiling point 76 ° C.). Got ready. This coating composition was coated on a glass substrate (Azwan slide glass S1225) by the spray method under the same conditions as in Example 1. Although the appearance of the film was transparent, a circular pattern (unevenness) that could be recognized visually was generated. Since the appearance of the film was poor, the evaluation of sebum adhesion, sebum removability and abrasion resistance was stopped.

比較例３
コーティング組成物として、上記式（２）で表される化合物１重量部を、ペルフルオロヘキサン（沸点５６℃）４重量部と住友スリーエム社製フロリナートＦＣ−４０（沸点１５５℃）１９５重量部との混合溶媒に溶解して準備した。このコーティング組成物をガラス基板（アズワン社製スライドガラスＳ１２２５）に実施例１と同じ条件でスプレー法でコーティングした。被膜の外観は透明だったが、目視で認識できる不定形（アメーバ状）のムラが発生した。被膜の外観が不良であったため、皮脂付着性、皮脂除去性および耐摩耗性の評価を中止した。Comparative Example 3
As a coating composition, 1 part by weight of the compound represented by the above formula (2) is mixed with 4 parts by weight of perfluorohexane (boiling point 56 ° C.) and 195 parts by weight of Fluorinert FC-40 (boiling point 155 ° C.) manufactured by Sumitomo 3M Limited. Prepared by dissolving in a solvent. This coating composition was coated on a glass substrate (Azwan slide glass S1225) by the spray method under the same conditions as in Example 1. The appearance of the film was transparent, but irregular irregularities (amoeba-like) that could be recognized visually were generated. Since the appearance of the film was poor, the evaluation of sebum adhesion, sebum removability and abrasion resistance was stopped.

比較例４
実施例２で使用したコーティング組成物を、実施例４で使用したハードコート付きアクリル基板に直接スプレー法でコーティングした。防汚層の膜厚は９．９ｎｍ、接触角は１１６°だった。被膜の外観はムラがなく透明で、皮脂付着性、皮脂除去性とも良好だった。しかし、耐摩耗性は７，３７９回と低かった。Comparative Example 4
The coating composition used in Example 2 was coated directly on the hard-coated acrylic substrate used in Example 4 by a spray method. The film thickness of the antifouling layer was 9.9 nm, and the contact angle was 116 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. However, the wear resistance was as low as 7,379 times.

比較例５
実施例２で使用したコーティング組成物の溶質を、実施例２で使用したガラス基板に真空蒸着法で成膜した。真空蒸着の背景圧力は１０-3Ｐａ台とし、ガラス製坩堝に入れたコーティング組成物の溶質を室温から５００℃まで約３０分かけて昇温した。形成された被膜の膜厚は７．２ｎｍ、接触角は１１７°だった。被膜の外観はムラがなく透明で、皮脂付着性、皮脂除去性とも良好だった。しかし、耐摩耗性は４２，２１７回であり、実施例２と比較すると低かった。Comparative Example 5
The coating composition solute used in Example 2 was deposited on the glass substrate used in Example 2 by vacuum deposition. The background pressure of vacuum deposition was on the order of 10 −3 Pa, and the solute of the coating composition placed in a glass crucible was heated from room temperature to 500 ° C. over about 30 minutes. The formed film had a thickness of 7.2 nm and a contact angle of 117 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. However, the wear resistance was 42,217 times, which was lower than that of Example 2.

比較例６
実施例２で使用したコーティング組成物を、実施例２で使用したガラス基板にディップ法で成膜した。ディップは、室温で２４時間浸漬し、１０ｍｍ／秒程度の速さで引き上げた。形成された被膜の膜厚は５ｎｍ以下で、測定できなかった。また、接触角は１１７°だった。被膜の外観はムラがなく透明で、皮脂付着性、皮脂除去性とも良好だった。しかし、耐摩耗性は４，７０１回と低かった。Comparative Example 6
The coating composition used in Example 2 was formed into a film on the glass substrate used in Example 2 by the dip method. The dip was immersed for 24 hours at room temperature and pulled up at a speed of about 10 mm / second. The film thickness of the formed film was 5 nm or less and could not be measured. The contact angle was 117 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. However, the wear resistance was as low as 4,701 times.

比較例７
実施例４で使用したハードコート付きアクリル基板に、スパッタ法でＳｉＯ2薄膜（膜厚１０１ｎｍ）を形成した。スパッタはイオンビーム方式で行い、背景圧力を１０-3Ｐａ台とし、溶融石英ターゲットに７００ｅＶのＡｒイオンビームを照射した。その後、実施例２で使用したコーティング剤をスプレー法でコーティングした。防汚層の膜厚は８．９ｎｍ、接触角は１１５°だった。被膜の外観はムラがなく透明で、皮脂付着性、皮脂除去性とも良好だった。しかし、耐摩耗性は２０，５５８回と実施例４と比較すると低かった。Comparative Example 7
A SiO 2 thin film (film thickness: 101 nm) was formed on the acrylic substrate with hard coat used in Example 4 by sputtering. Sputtering was performed by an ion beam method, a background pressure was set to 10 −3 Pa, and a fused silica target was irradiated with a 700 eV Ar ion beam. Thereafter, the coating agent used in Example 2 was coated by a spray method. The film thickness of the antifouling layer was 8.9 nm and the contact angle was 115 °. The appearance of the coating was uniform and transparent, with good sebum adhesion and sebum removal properties. However, the wear resistance was 20,558 times, which was lower than that of Example 4.

各実施例と各比較例の結果を表１にまとめた。なお、表１において、溶媒Ａはペルフルオロヘキサン（沸点５６℃）を、溶媒Ｂは１,１,１,３,３−ペンタフルオロブタン（沸点４０℃）を、溶媒Ｃは１,１,１,２,２,３,３,４,５,５,５−ウンデカフルオロ-（トリフルオロメチル）ペンタン（沸点５６℃）を、溶媒Ｄはメチルナノフルオロブチルエーテル（沸点６１℃）を、溶媒Ｅは旭硝子社製ＮｏｖｅｃＨＦＥ７２００（沸点７６℃）を、溶媒Ｆは住友スリーエム社製フロリナートＦＣ−４０（沸点１５５℃）をそれぞれ表す。   The results of each Example and each Comparative Example are summarized in Table 1. In Table 1, solvent A is perfluorohexane (boiling point 56 ° C.), solvent B is 1,1,1,3,3-pentafluorobutane (boiling point 40 ° C.), and solvent C is 1,1,1, 2,2,3,3,4,5,5,5-undecafluoro- (trifluoromethyl) pentane (boiling point 56 ° C.), solvent D is methyl nanofluorobutyl ether (boiling point 61 ° C.), solvent E is Asahi Glass Co., Ltd. NovecHFE7200 (boiling point 76 ° C.), solvent F represents Sumitomo 3M Fluorinert FC-40 (boiling point 155 ° C.).

Figure 2010038648
Figure 2010038648

本発明のコーティング組成物および表面処理方法により、防汚性に優れ、透明であり、実用上十分な耐久性を持った防汚被膜を、低コストで形成することが可能となるので、携帯電話、表示装置等に利用できる。   According to the coating composition and the surface treatment method of the present invention, it is possible to form an antifouling film having excellent antifouling property, transparency, and practically sufficient durability at a low cost. It can be used for display devices.

１ 操作キー
２ 画像表示装置
３ マイク（送話口）
４ スピーカー（受話口）
５ 筐体
６ 透過窓部材
６ａ 無機表面膜
６ｂ 防汚層1 Operation key 2 Image display device 3 Microphone (speaker)
4 Speaker (Entrance)
5 Housing 6 Transmission window member 6a Inorganic surface film 6b Antifouling layer

Claims (10)

ペルフルオロアルキレンエーテル基を分子主鎖内に含み、シリコン原子を含む加水分解性基を側鎖に含む化合物を溶媒に溶解してなるコーティング用組成物であって、
前記溶媒がフッ素化炭化水素およびフッ素化エーテルの少なくとも１つを含むフッ素系溶媒同士の混合溶媒であり、前記フッ素系溶媒は１気圧下での沸点が４０℃以上７０℃以下であり、前記混合溶媒中の前記フッ素系溶媒の沸点の最大値と最小値の差が２５℃以内であることを特徴とするコーティング用組成物。A coating composition comprising a compound containing a perfluoroalkylene ether group in a molecular main chain and a hydrolyzable group containing a silicon atom in a side chain dissolved in a solvent,
The solvent is a mixed solvent of fluorine-based solvents including at least one of a fluorinated hydrocarbon and a fluorinated ether, and the fluorine-based solvent has a boiling point of 40 ° C. or more and 70 ° C. or less under 1 atm, and the mixture The coating composition, wherein the difference between the maximum value and the minimum value of the boiling point of the fluorinated solvent in the solvent is within 25 ° C. 前記ペルフルオロアルキレンエーテル基が下記式（１−１）で表され、前記シリコン原子を含む加水分解性基が下記式（１−２）で表されることを特徴とする請求項１記載のコーティング用組成物。
Figure 2010038648
 （式中、ｎは１〜５の整数、ｍは０〜２の整数、Ｒ1は加水分解可能な基を表す。）The said perfluoroalkylene ether group is represented by following formula (1-1), and the hydrolysable group containing the said silicon atom is represented by following formula (1-2), For coating of Claim 1 characterized by the above-mentioned. Composition.
Figure 2010038648
 (In the formula, n represents an integer of 1 to 5, m represents an integer of 0 to 2, and R 1 represents a hydrolyzable group.) 前記化合物が下記式（１）で表される化合物であることを特徴とする請求項２記載のコーティング用組成物。
Figure 2010038648
 （式中、Ｒｆは炭素数１〜１６の直鎖状または分岐状パーフルオロアルキル基、Ｙは水素原子または炭素数１〜３のアルキル基、Ｒ1はハロゲン原子、−ＯＲ3基、−ＯＣＯＲ3基、−ＯＣ（Ｒ3）＝Ｃ（Ｒ4）2基、−ＯＮ＝Ｃ（Ｒ3）2基、および−ＯＮ＝Ｃ（Ｒ5）2基から選ばれる少なくとも１つの基を表し、Ｒ3は脂肪族炭化水素基または芳香族炭化水素基を表し、Ｒ4は水素原子または炭素数１〜３のアルキル基を表し、Ｒ5は炭素数３〜６の２価の脂肪族炭化水素基を表し、ｑは１〜５０の整数、ｍは０〜２の整数、ｒは１〜１０の整数を表す。）The coating composition according to claim 2, wherein the compound is a compound represented by the following formula (1).
Figure 2010038648
 (In the formula, Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, Y is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 1 is a halogen atom, —OR 3 group, —OCOR; Represents at least one group selected from three groups, —OC (R 3 ) ═C (R 4 ) 2 groups, —ON═C (R 3 ) 2 groups, and —ON═C (R 5 ) 2 groups, R 3 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R 4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 5 represents a divalent aliphatic hydrocarbon having 3 to 6 carbon atoms. And q represents an integer of 1 to 50, m represents an integer of 0 to 2, and r represents an integer of 1 to 10.) 前記Ｒ1が塩素原子、−ＯＣＨ3基、および−ＯＣ2Ｈ5基から選ばれる少なくとも１つの基であることを特徴とする請求項３記載のコーティング用組成物。The coating composition according to claim 3, wherein R 1 is at least one group selected from a chlorine atom, —OCH 3 group, and —OC 2 H 5 group. 前記フッ素系溶媒が１,１,１,３,３−ペンタフルオロブタン、ペルフルオロヘキサン、１,１,１,２,２,３,３,４,５,５,５−ウンデカフルオロ−４−（トリフルオロメチル）ペンタン、または、メチルノナフルオロブチルエーテルであることを特徴とする請求項１記載のコーティング用組成物。   The fluorine-based solvent is 1,1,1,3,3-pentafluorobutane, perfluorohexane, 1,1,1,2,2,3,3,4,5,5,5-undecafluoro-4- The coating composition according to claim 1, which is (trifluoromethyl) pentane or methyl nonafluorobutyl ether. 前記混合溶媒が１,１,１,３,３−ペンタフルオロブタン、ペルフルオロヘキサン、１,１,１,２,２,３,３,４,５,５,５−ウンデカフルオロ−４−（トリフルオロメチル）ペンタン、および、メチルノナフルオロブチルエーテルから選ばれた２種類のフッ素系溶媒の混合溶媒であることを特徴とする請求項１記載のコーティング用組成物。   The mixed solvent is 1,1,1,3,3-pentafluorobutane, perfluorohexane, 1,1,1,2,2,3,3,4,5,5,5-undecafluoro-4- ( The coating composition according to claim 1, which is a mixed solvent of two kinds of fluorine-based solvents selected from (trifluoromethyl) pentane and methyl nonafluorobutyl ether. 無機基材の表面、または無機もしくは有機基材に形成された無機表面膜の表面にコーティングを施すことにより、防汚処理を行なう防汚処理方法において、
前記無機基材の表面または無機表面膜の表面へのコーティングが請求項１記載のコーティング用組成物をスプレー法で塗布されたコーティングであることを特徴とする防汚処理方法。In the antifouling treatment method for carrying out the antifouling treatment by coating the surface of the inorganic substrate or the surface of the inorganic surface film formed on the inorganic or organic substrate,
An antifouling treatment method, wherein the coating on the surface of the inorganic substrate or the surface of the inorganic surface film is a coating obtained by applying the coating composition according to claim 1 by a spray method. 前記無機表面膜は、ポリシラザン溶液をスプレー法で塗布することにより形成した無機表面膜であることを特徴する請求項７記載の防汚処理方法。   The antifouling treatment method according to claim 7, wherein the inorganic surface film is an inorganic surface film formed by applying a polysilazane solution by a spray method. 基材の表面、または基材に形成された無機表面膜の表面に防汚層を有する防汚性基材であって、
前記防汚層が請求項７記載の防汚処理方法により形成された防汚層であることを特徴とする防汚性基材。An antifouling substrate having an antifouling layer on the surface of the substrate or the surface of the inorganic surface film formed on the substrate,
The antifouling substrate, wherein the antifouling layer is an antifouling layer formed by the antifouling treatment method according to claim 7. 前記防汚性基材は、画像表示部を有し、該画像表示部の表面に請求項９記載の耐防汚層が形成された携帯電話であることを特徴とする防汚性基材。   The antifouling base material is a mobile phone having an image display part, and the antifouling layer according to claim 9 formed on the surface of the image display part.
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