WO2005119367A1 - Water-repellent composition, water-repellent thin film, and thin film with water-repellent/hydrophilic pattern - Google Patents

Water-repellent composition, water-repellent thin film, and thin film with water-repellent/hydrophilic pattern Download PDF

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Publication number
WO2005119367A1
WO2005119367A1 PCT/JP2005/009479 JP2005009479W WO2005119367A1 WO 2005119367 A1 WO2005119367 A1 WO 2005119367A1 JP 2005009479 W JP2005009479 W JP 2005009479W WO 2005119367 A1 WO2005119367 A1 WO 2005119367A1
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Prior art keywords
water
repellent
group
thin film
compound
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PCT/JP2005/009479
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French (fr)
Japanese (ja)
Inventor
Yutaka Furukawa
Takashi Okazoe
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Asahi Glass Company, Limited
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Publication of WO2005119367A1 publication Critical patent/WO2005119367A1/en

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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
    • 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
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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

Definitions

  • Water repellent composition Water repellent composition, water repellent thin film and thin film having water repellent hydrophilic pattern
  • the present invention relates to a water-repellent composition, a water-repellent thin film formed from the composition, and a thin film having a water-repellent hydrophilic pattern formed from the thin film.
  • a method for manufacturing a fine device such as a semiconductor element, an integrated circuit, and a device for an organic EL display
  • a thin film of a functional material is formed on a substrate by vacuum deposition, sputtering, or the like, and the thin film is subjected to photolithography.
  • Photolithography generally has the following process powers (1) to (3).
  • a thin film of a material to be patterned is formed on a substrate.
  • a photoresist film is formed on the thin film, exposed through a photomask having a predetermined pattern, and developed with an alkali developer to form a photoresist pattern.
  • Etching is performed using the photoresist pattern as a mask, and unnecessary portions are removed to obtain a thin film having a desired pattern shape. Since photolithography is a complicated process and must be performed in a clean room, there has been a problem that equipment with low utilization efficiency of energy and materials becomes expensive.
  • a method has been proposed in which a pattern having different surface characteristics is formed on a substrate, and a fine device is manufactured using the difference in surface characteristics.
  • a patterning method using ultraviolet light is preferable in terms of manufacturing because a large-area substrate can be processed at a time using a photomask.
  • a high energy energy line having a wavelength of less than 200 nm is mainly used as ultraviolet light, for example, in the case of a silicon wafer substrate provided with an oxide silicon film, it is decomposed to the Si—O bond of the substrate. There was a problem (see Patent Document 1 and Patent Document 2).
  • Patent Document 1 Japanese Patent Application Laid-Open No. 11-344804
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2000-282240
  • An object of the present invention is to eliminate the above-mentioned disadvantages of the prior art, and can form a water-repellent hydrophilic pattern Jung on a substrate by irradiating light having a wavelength of 200 ⁇ m or more. To provide things.
  • the present invention has the following gist.
  • a water-repellent composition comprising a compound B which decomposes by irradiation with light having a wavelength of 200 nm or more to generate an acid, and a water-repellent compound A which decomposes by the acid generated from the compound to reduce water repellency.
  • R i2 , R i3 , R M each independently represents a monovalent fluorinated organic group.
  • R 3 and R 7 each independently represent a divalent organic group.
  • R 2 , R 4 , R 5 , R 6 , R 8 each independently represents a monovalent organic group.
  • X 1 , X 2 , X 3 , X 4 each independently a hydrolyzable group.
  • n, m, p, q each independently, an integer of 1 to 3.
  • R n, R i2, R i3 , R M are each independently a pel full O b alkyl group having pel full O b alkyl group or E one ether oxygen atom, the (4 ) Aqueous composition.
  • the X 1 , X 2 , X 3 , and X 4 forces are each independently at least one hydrolyzable group selected from the group consisting of a halogen atom, an alkoxy group, an acetyloxy group, and a ketoxime group.
  • the water repellent composition according to any one of the above (4) to (6).
  • the contact angle with water of the water-repellent thin film before irradiation with light having a wavelength of 200 nm or more is 95 degrees or more, and the contact angle with water of the thin film after irradiation with light having a wavelength of 200 nm or more is 70 degrees or less.
  • the water repellent composition of the present invention can form a thin film having excellent water repellency on a substrate.
  • the thin film is irradiated with light having a wavelength of 200 nm or more, which is relatively low energy, the water repellency of the thin film surface is reduced.
  • a thin film having a water-repellent hydrophilic pattern can be easily formed on a substrate.
  • the water-repellent composition of the present invention it is possible to form a thin film having a water-repellent hydrophilic pattern in a small number of steps using an inexpensive apparatus as compared with a photolithography method.
  • the water repellent compound A in the present invention is decomposed by an acid to reduce water repellency.
  • a compound having a fluorinated organic group and having a bonding group that is decomposed by an acid to release the fluorinated organic group is preferable.
  • the bonding group an ester group, a silyl ether group, a silylamino group and the like are preferable.
  • the water repellent compound A is preferably at least one compound selected from the group consisting of fluorine-containing compounds represented by the following formulas 1 to 4 and Z or a partial hydrolyzate, .
  • R i2 , R i3 , R M each independently represents a monovalent fluorinated organic group.
  • R 3 and R 7 each independently represent a divalent organic group.
  • R 2 , R 4 , R 5 , R 6 , R 8 each independently represents a monovalent organic group.
  • X 1 , X 2 , X 3 , X 4 each independently a hydrolyzable group.
  • n, m, p, q each independently, an integer of 1 to 3.
  • R n is a perfluoroalkyl group or an etheric compound.
  • Perfluoroalkyl groups having an oxygen atom are preferred!
  • the number of carbon atoms in the perfluoroalkyl group is preferably 1 to 16, more preferably 3 to 12 force S, and most preferably 3 to 8 carbon atoms.
  • Examples of the perfluoroalkyl group include a linear structure, a branched structure and a cyclic structure, and a linear structure is preferable. In the case of a branched structure, it is preferable that the branched portion exists at the terminal and the branched portion is a short chain having about 1 to 4 carbon atoms.
  • R 1 an alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 2 to 5 carbon atoms is more preferable, and an alkylene group having 3 to 4 carbon atoms is more preferable.
  • R 2 is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
  • X 1 is preferably a halogen atom, an alkoxy group, an acetoxyl group, or a ketoxime group, more preferably a halogen atom or an alkoxy group.
  • n is preferably 2 to 3, and more preferably 3. If n is 3
  • the water-repellent composition has excellent adhesion to a substrate.
  • Examples of the compound 1 include the following compounds.
  • F (CF) COO (CH) Si (OCH) is preferable.
  • R i2, R i3, R M is the R n and signaling R 3 preferred the same groups
  • R 7 is the R 1 group similar to the preferred tool
  • R 5 , R 6 , and R 8 are preferably the same groups as R 2
  • X 4 are preferably the same groups as X 1 m
  • p, and q are the same The same integer as n is preferable.
  • Examples of the compound 2 include the following compounds.
  • F CF 2 CH 2 CH 2 OCO 2 (CH 2) 2 Si (OCH 2) is preferable.
  • Examples of the compound 3 include the following compounds.
  • the compound 4 is preferably F (CF 2) 2 CH 2 (CH 2) 2 SiO (CH 2) 2 Si (OCH 3).
  • Compound B which decomposes upon irradiation with light to generate an acid, has a maximum absorption wavelength ( ⁇ ) of 2 max.
  • a thin film having a water-repellent hydrophilic pattern can be formed using a simple device such as a high-pressure mercury lamp.
  • any compound that can be decomposed by light having a wavelength of 200 nm or more to generate an acid that is, a photoacid generator (abbreviated as PAG) can be used without particular limitation.
  • PAG photoacid generator
  • Specific examples of the compound B include the following compounds.
  • the generated acid is preferably hydrochloric acid as long as it is an acid capable of decomposing the water-repellent compound A.
  • hydrochloric acid is an acid capable of decomposing the water-repellent compound A.
  • the mass ratio of the water repellent compound AZ compound B in the water repellent composition is preferably from 95Z5 to 99.99 / 0.01 force S, more preferably from 99/1 to 99.9 / 0.1 force S. , 99.5 / 0.5 to 99.8 / 0.2 are most preferred. Within this range, the water repellency of the surface of the water-repellent thin film is reduced by light irradiation. Decreases efficiently.
  • the water-repellent thin film of the present invention is formed by applying a water-repellent composition on a substrate.
  • the contact angle of the water-repellent thin film with water is preferably 95 degrees or more, more preferably 100 degrees or more.
  • the thin film preferably has a contact angle with water of 70 ° or less, more preferably 50 ° or less, most preferably 30 ° or less.
  • the difference in contact angle of the thin film with water before and after light irradiation is preferably 30 degrees or more, more preferably 50 degrees or more, and most preferably 70 degrees or more.
  • the water-repellent composition of the present invention preferably contains an organic solvent.
  • the organic solvent is not particularly restricted but includes alcohols, ketones, aromatic hydrocarbons, lower alcohols such as ethyl alcohol and 2-propyl alcohol, which are preferred among paraffin hydrocarbons, and paraffin hydrocarbons. More preferred.
  • One organic solvent may be used, or two or more organic solvents may be used in combination to adjust solubility and evaporation rate.
  • the mass ratio of the water repellent compound AZ organic solvent is preferably 1Z1000 to 1Z10, more preferably 1Z200 to 1Z20. Within this range, a uniform thin film is formed and the water repellency is excellent.
  • the thickness of the water-repellent thin film of the present invention is not particularly limited, but is preferably from 0.5 to: LOOnm is more preferable 1 to 20 nm is more preferable l to 5 nm is most preferable.
  • the thickness of the water-repellent thin film is most preferably the thickness of a self-assembled film (also referred to as SMA). Within this range, a good water-repellent hydrophilic pattern can be obtained.
  • Examples of methods for applying the water-repellent composition include various known methods such as brush coating, flow coating, spin coating, dip coating, squeegee coating, spray coating, and hand coating.
  • the water repellent composition is applied to the surface, it is dried in the air, in a nitrogen stream, or the like.
  • the heating temperature and time are set in consideration of the heat resistance of the substrate.
  • the temperature is preferably from 0 to 80 ° C, more preferably from 10 to 40 ° C.
  • the time is preferably from 1 to 60 minutes, more preferably from 5 to 30 minutes.
  • the thin film having a water-repellent hydrophilic pattern of the present invention is formed by irradiating the water-repellent thin film with light and cleaning the thin film surface.
  • the wavelength of the light to be irradiated is preferably 200 to 800 mn force S, more preferably 250 to 600 mn force S, ⁇ 400nm is most preferred!
  • Irradiation light is more preferably ultraviolet light.
  • Light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, sodium lamps, gas lasers such as nitrogen, liquid lasers of organic dye solutions, and solid-state lasers containing rare earth ions in inorganic single crystals. And the like.
  • a light source other than a laser capable of obtaining monochromatic light light of a specific wavelength obtained by extracting a broadband line spectrum or continuous spectrum using an optical filter such as a band-pass filter or a cutoff filter may be used. Good. Since a large area can be irradiated at a time, a high-pressure mercury lamp or an ultra-high-pressure mercury lamp is preferred as a light source.
  • Examples of the irradiation method include a method of irradiating light through a photomask having a predetermined pattern, a method of using laser light, and the like. Because it can irradiate a large area at once
  • a method of irradiating light through a photomask is preferable.
  • a solvent that dissolves a fluorine-containing organic group examples include dichloropentafluoropropane (hereinafter referred to as R-225), perfluorocarbons such as perfluorohexane, hydrfluoroethers such as (perfluorobutoxy) methane, decafluoroether, and decahydrate.
  • R-225 dichloropentafluoropropane
  • perfluorocarbons such as perfluorohexane
  • hydrfluoroethers such as (perfluorobutoxy) methane
  • decafluoroether decahydrate
  • Fluorocapanone such as fluoropentane.
  • the portion irradiated with light has reduced water repellency, and the energized portion not irradiated with light maintains water repellency. Is formed.
  • a thin film having a hydrophilic and water-repellent pattern can be easily obtained by forming a thin film by applying a water-repellent composition and subsequently irradiating the light once.
  • the mechanism by which water repellency of the water repellent thin film is reduced by light irradiation is considered as follows.
  • the bonding group in the thin film formed from the fluorine-containing compound A is decomposed by an acid to release a fluorine-containing organic group and form a hydroxyl group, a carboxyl group, a silanol group, an amino group, and the like, so that the water repellency is reduced. It is thought to be.
  • the substrate used in the present invention is not particularly limited, and preferably includes glass, quartz glass, silicon wafer, plastic, metal and the like. In addition, a metal thin film is formed on these substrates. May be used.
  • AK-225 (trade name, manufactured by Asahi Glass Co., Ltd.) was used as R-225.
  • As the glass substrate a glass substrate was used in which the surface of a 10 cm square, 2 mm thick soda lime glass substrate was polished and cleaned with an abrasive containing cerium oxide fine particles, rinsed with pure water, and air-dried.
  • the contact angle with water was calculated as the average value of the measured contact angles at three points with three drops of water placed on the substrate using the static drop method.
  • the contact angle of the obtained sample 11 with water was 105 degrees, and the contact angle of the untreated glass substrate with water was 10 degrees or less.
  • Sample 12 was prepared by irradiating ultraviolet rays using a high-pressure mercury lamp, washing with R-225, and air-drying. When the irradiation amount was 200 miZcm 2, the contact angle to water of Sample 1-2 was 61 degrees.
  • the contact angle of the obtained Sample 2-1 with water was 104 degrees.
  • the sample was irradiated with ultraviolet rays using a high-pressure mercury lamp, washed with R-225, and air-dried to prepare Sample 2-2.
  • the irradiation power was 200 mJZcm 2
  • the contact angle with water was 42 degrees.
  • the contact angle of the obtained Sample 3-1 with water was 106 degrees.
  • the sample was irradiated with ultraviolet rays using a high-pressure mercury lamp, washed with R-225, and air-dried to prepare Sample 3-2.
  • the contact angle with water when the irradiation power was 200 mJZcm 2 was 22 degrees.
  • hydrolysis reaction was carried out at room temperature for 12 hours to obtain a hydrolyzate 4.
  • the obtained hydrolyzate 4 has 5 moles relative to the raw material F (CF) CHCH (CH) SiO (CH) Si (OCH).
  • the contact angle of the obtained sample 4-1 with water was 105 degrees.
  • High pressure mercury lamp The sample was irradiated with ultraviolet rays, washed with R-225, and air-dried to prepare Sample 4-2.
  • the irradiation power was S750 mjZcm 2
  • the contact angle with water was 60 degrees.
  • the thin film having a water-repellent hydrophilic pattern of the present invention can be used for forming a functional pattern. For example, by spraying a functional material onto the hydrophilic region of the thin film by inkjet printing, a clear pattern of the functional material can be easily formed.
  • a thin film having a water-repellent hydrophilic pattern has a use as a stamp for microcontact printing by including a functional ink in a hydrophilic region and transferring it to another substrate.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • Surface Treatment Of Glass (AREA)
  • Paints Or Removers (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Materials For Photolithography (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

A water-repellent composition from which a thin film having a water-repellent/hydrophilic pattern can be easily formed with the aid of a light having relatively low energy. The water-repellent composition comprises a water-repellent compound (A) which decomposes by the action of an acid to come to have reduced water repellency (e.g., Rf2OCOR3Si(R4)3-mX2m, wherein Rf2 is monovalent polyfluoroalkyl, R3 is alkylene, R4 is methyl, X is a hydrolyzable group, and m is an integer of 1-3) and a compound (B) which decomposes upon irradiation with a light having a wavelength of 200 nm or longer to generate an acid. A thin film formed from the composition is irradiated with a light to form a thin film having a water-repellent/hydrophilic pattern.

Description

明 細 書  Specification
撥水性組成物、撥水性薄膜および撥水性親水性パターンを有する薄膜 技術分野  Water repellent composition, water repellent thin film and thin film having water repellent hydrophilic pattern
[0001] 本発明は、撥水性組成物、該組成物から形成された撥水性薄膜、および該薄膜か ら形成された撥水性親水性パターンを有する薄膜に関する。  The present invention relates to a water-repellent composition, a water-repellent thin film formed from the composition, and a thin film having a water-repellent hydrophilic pattern formed from the thin film.
背景技術  Background art
[0002] 現在、半導体素子、集積回路、有機 ELディスプレイ用デバイス等の微細デバイス の製造方法としては、真空蒸着、スパッタリング等によって基板上に機能性材料の薄 膜を形成させ、該薄膜をフォトリソグラフィによってパターユングする方法が用いられ ている。フォトリソグラフィは、一般に以下の（1)〜（3)の工程力もなる。  [0002] At present, as a method for manufacturing a fine device such as a semiconductor element, an integrated circuit, and a device for an organic EL display, a thin film of a functional material is formed on a substrate by vacuum deposition, sputtering, or the like, and the thin film is subjected to photolithography. Is used to putter jungle. Photolithography generally has the following process powers (1) to (3).
[0003] (1)パターユングを行う材料の薄膜を基板上に形成する。（2)薄膜上にフォトレジス ト膜を形成し、所定のパターンを有するフォトマスクを介して露光し、アルカリ現像液 により現像して、フォトレジストパターンを形成する。 （3)フォトレジストパターンをマス クとしてエッチングを行 、、不要な部分を除去して所望のパターン形状を有する薄膜 を得る。フォトリソグラフィ一は工程が複雑で、クリーンルーム内で実施する必要があ ることから、エネルギー、材料等の利用効率が低ぐ設備が高価となる問題があった。  [0003] (1) A thin film of a material to be patterned is formed on a substrate. (2) A photoresist film is formed on the thin film, exposed through a photomask having a predetermined pattern, and developed with an alkali developer to form a photoresist pattern. (3) Etching is performed using the photoresist pattern as a mask, and unnecessary portions are removed to obtain a thin film having a desired pattern shape. Since photolithography is a complicated process and must be performed in a clean room, there has been a problem that equipment with low utilization efficiency of energy and materials becomes expensive.
[0004] 最近、基板上に、表面特性の異なるパターンを形成し、その表面特性の違 、を利 用して微細デバイスを作製する方法が提案されている。たとえば、紫外線を用いるパ ターニング方法は、フォトマスクを用いて大面積の基板を一度に処理することができ るため、製造面において好ましい。しかし、これまで紫外線として主に波長 200nm未 満の高工ネルギ一線が用いられるため、例えば酸ィ匕ケィ素膜を設けたシリコンウェハ 基板の場合には基板の Si— O結合まで分解してしまう問題があった (特許文献 1、特 許文献 2参照。）。  [0004] Recently, a method has been proposed in which a pattern having different surface characteristics is formed on a substrate, and a fine device is manufactured using the difference in surface characteristics. For example, a patterning method using ultraviolet light is preferable in terms of manufacturing because a large-area substrate can be processed at a time using a photomask. However, since a high energy energy line having a wavelength of less than 200 nm is mainly used as ultraviolet light, for example, in the case of a silicon wafer substrate provided with an oxide silicon film, it is decomposed to the Si—O bond of the substrate. There was a problem (see Patent Document 1 and Patent Document 2).
[0005] 特許文献 1：特開平 11 344804号公報 Patent Document 1: Japanese Patent Application Laid-Open No. 11-344804
特許文献 2：特開 2000 - 282240号公報  Patent Document 2: Japanese Patent Application Laid-Open No. 2000-282240
発明の開示  Disclosure of the invention
発明が解決しょうとする課題 [0006] 本発明の目的は、従来技術が有する前述の欠点を解消することにあり、波長 200η m以上の光を照射することにより、基板上に撥水性親水性パターユングを形成できる 撥水性組成物を提供することにある。 Problems the invention is trying to solve [0006] An object of the present invention is to eliminate the above-mentioned disadvantages of the prior art, and can form a water-repellent hydrophilic pattern Jung on a substrate by irradiating light having a wavelength of 200 ηm or more. To provide things.
課題を解決するための手段  Means for solving the problem
[0007] 本発明は、以下の要旨を有する。 [0007] The present invention has the following gist.
(1)波長 200nm以上の光の照射により分解して酸を発生する化合物 Bおよび該化 合物から発生した酸により分解して撥水性が低下する撥水性化合物 Aを含む撥水性 組成物。  (1) A water-repellent composition comprising a compound B which decomposes by irradiation with light having a wavelength of 200 nm or more to generate an acid, and a water-repellent compound A which decomposes by the acid generated from the compound to reduce water repellency.
(2)前記撥水性化合物 Aが、含フッ素有機基を有し、酸により分解して該含フッ素有 機基を放出する結合基を有する化合物である、上記（1)に記載の撥水性組成物。 (2) The water-repellent composition according to the above (1), wherein the water-repellent compound A is a compound having a fluorinated organic group and having a binding group which is decomposed by an acid to release the fluorinated organic group. object.
(3)前記含フッ素有機基を放出する結合基が、エステル基、シリルエーテル基、シリ ルァミノ基力もなる群力も選ばれる少なくとも 1種の結合基である、上記（2)に記載の 撥水性組成物。 (3) The water-repellent composition according to the above (2), wherein the bonding group releasing the fluorinated organic group is at least one bonding group selected from the group consisting of an ester group, a silyl ether group, and a silylamino group. object.
(4)前記撥水性化合物 Aが、下式 1〜4で表される含フッ素化合物力 なる群力 選 ばれる少なくとも 1種の化合物および Zまたはその部分加水分解物である、上記（1) 〜（3)の 、ずれかに記載の撥水性組成物。  (4) The above-mentioned (1) to (1), wherein the water-repellent compound A is at least one compound selected from the group consisting of fluorine-containing compounds represented by the following formulas 1 to 4 and Z or a partial hydrolyzate thereof. 3) The water repellent composition according to any one of the above.
^COOR'SKR2) X1 …式 1 ^ COOR'SKR 2 ) X 1 … Equation 1
Rf2OCOR3Si (R4) X2 …式 2 R f2 OCOR 3 Si (R 4 ) X 2 … Equation 2
3— m m  3—m m
Rf3OSi (R5) X3…式 3 R f3 OSi (R 5 ) X 3 … Equation 3
3-P P  3-P P
Rf4 (R6) SiOR7Si (R8) X4 · · ·式 4 R f4 (R 6) SiOR 7 Si (R 8) X 4 · · · Formula 4
2 3-q q  2 3-q q
ただし、式 1〜4における記号は以下の意味を示す。  However, the symbols in the formulas 1 to 4 have the following meanings.
Ri2、 Ri3、 RM:それぞれ独立して、 1価含フッ素有機基。R i2 , R i3 , R M : each independently represents a monovalent fluorinated organic group.
Figure imgf000003_0001
R3、 R7:それぞれ独立して、 2価有機基。
Figure imgf000003_0001
R 3 and R 7 each independently represent a divalent organic group.
R2、 R4、 R5、 R6、 R8 :それぞれ独立して、 1価有機基。 R 2 , R 4 , R 5 , R 6 , R 8 : each independently represents a monovalent organic group.
X1、 X2、 X3、 X4：それぞれ独立して、加水分解性基。 X 1 , X 2 , X 3 , X 4 : each independently a hydrolyzable group.
n、 m、 p、 q :それぞれ独立して、 1〜3の整数。  n, m, p, q: each independently, an integer of 1 to 3.
(5)前記 Rn、 Ri2、 Ri3、 RMが、それぞれ独立して、ペルフルォロアルキル基またはェ 一テル性の酸素原子を有するペルフルォロアルキル基である、上記 (4)に記載の撥 水性組成物。 (5) the R n, R i2, R i3 , R M are each independently a pel full O b alkyl group having pel full O b alkyl group or E one ether oxygen atom, the (4 ) Aqueous composition.
(6)前記 R R3、 R7が、それぞれ独立して、炭素原子数 1〜： LOのアルキレン基である 、上記 (4)または（5)に記載の撥水性組成物。 (6) The water repellent composition according to the above (4) or (5), wherein RR 3 and R 7 are each independently an alkylene group having 1 to carbon atoms: LO.
(7)前記 X1、 X2、 X3、 X4力 それぞれ独立して、ハロゲン原子、アルコキシ基、ァセト キシ基、及びケトォキシム基力 なる群力 選ばれる少なくとも 1種の加水分解性基で ある、上記 (4)〜（6)の 、ずれかに記載の撥水性組成物。 (7) The X 1 , X 2 , X 3 , and X 4 forces are each independently at least one hydrolyzable group selected from the group consisting of a halogen atom, an alkoxy group, an acetyloxy group, and a ketoxime group. The water repellent composition according to any one of the above (4) to (6).
(8)上記（1)〜（7)の ヽずれかに記載の撥水性組成物を基板上に塗布して形成され てなる撥水性薄膜。  (8) A water-repellent thin film formed by applying the water-repellent composition according to any one of the above (1) to (7) on a substrate.
(9)上記（8)に記載の撥水性薄膜に、パターンを有するフォトマスクを介して波長 20 Onm以上の光を照射し、次 ヽで該薄膜の表面を洗浄して形成されてなる撥水性親 水性パターンを有する薄膜。  (9) The water-repellent film formed by irradiating the water-repellent thin film according to (8) with light having a wavelength of 20 Onm or more through a photomask having a pattern, and then cleaning the surface of the thin film. A thin film having a hydrophilic pattern.
(10)波長 200nm以上の光を照射前の撥水性薄膜の水との接触角が 95度以上で あり、波長 200nm以上の光を照射後の該薄膜の水との接触角が 70度以下である、 上記 (8)に記載の撥水性薄膜または上記 (9)に記載の撥水性親水性パターンを有 する薄膜。  (10) The contact angle with water of the water-repellent thin film before irradiation with light having a wavelength of 200 nm or more is 95 degrees or more, and the contact angle with water of the thin film after irradiation with light having a wavelength of 200 nm or more is 70 degrees or less. A water-repellent thin film according to the above (8) or a thin film having a water-repellent hydrophilic pattern according to the above (9).
発明の効果  The invention's effect
[0008] 本発明の撥水性組成物は、基板上に撥水性に優れる薄膜を形成できる。該薄膜は 、比較的低エネルギーである波長 200nm以上の光を照射することにより、薄膜表面 の撥水性が低下する。この特性を用いて、パターンを有するフォトマスクを通して光を 照射することにより、基板上に容易に撥水性親水性パターンを有する薄膜を形成で きる。本発明の撥水性組成物を用いることにより、フォトリソグラフィ一法に比較して、 安価な装置を用い、少な 、工程で撥水性親水性パターンを有する薄膜を形成できる 発明を実施するための最良の形態  [0008] The water repellent composition of the present invention can form a thin film having excellent water repellency on a substrate. When the thin film is irradiated with light having a wavelength of 200 nm or more, which is relatively low energy, the water repellency of the thin film surface is reduced. By irradiating light through a photomask having a pattern using this characteristic, a thin film having a water-repellent hydrophilic pattern can be easily formed on a substrate. By using the water-repellent composition of the present invention, it is possible to form a thin film having a water-repellent hydrophilic pattern in a small number of steps using an inexpensive apparatus as compared with a photolithography method. Form
[0009] 本発明における撥水性ィ匕合物 Aは、酸により分解して撥水性が低下する。撥水性 化合物 Aとしては、含フッ素有機基を有し、酸により分解して該含フッ素有機基を放 出する結合基を有する化合物が好ましい。該結合基としては、エステル基、シリルェ 一テル基、シリルアミノ基等が好ましい。 [0010] 撥水性ィ匕合物 Aとしては、下式 1〜4で表される含フッ素化合物からなる群力 選ば れる少なくとも 1種の化合物および Zまたは部分加水分解物であることが好まし 、。 [0009] The water repellent compound A in the present invention is decomposed by an acid to reduce water repellency. As the water-repellent compound A, a compound having a fluorinated organic group and having a bonding group that is decomposed by an acid to release the fluorinated organic group is preferable. As the bonding group, an ester group, a silyl ether group, a silylamino group and the like are preferable. [0010] The water repellent compound A is preferably at least one compound selected from the group consisting of fluorine-containing compounds represented by the following formulas 1 to 4 and Z or a partial hydrolyzate, .
^COOR'SKR2) X1…式 1 ^ COOR'SKR 2 ) X 1 … Equation 1
Rf2OCOR3Si (R4) X2 …式 2 R f2 OCOR 3 Si (R 4 ) X 2 … Equation 2
3— m m  3—m m
Rf3OSi (R5) X3…式 3 R f3 OSi (R 5 ) X 3 … Equation 3
3-P P  3-P P
Rf4 (R6) SiOR7Si (R8) X4 · · ·式 4 R f4 (R 6) SiOR 7 Si (R 8) X 4 · · · Formula 4
2 3-q q  2 3-q q
ただし、式 1〜4における記号は以下の意味を示す。  However, the symbols in the formulas 1 to 4 have the following meanings.
Ri2、 Ri3、 RM:それぞれ独立して、 1価含フッ素有機基。R i2 , R i3 , R M : each independently represents a monovalent fluorinated organic group.
Figure imgf000005_0001
R3、 R7:それぞれ独立して、 2価有機基。
Figure imgf000005_0001
R 3 and R 7 each independently represent a divalent organic group.
R2、 R4、 R5、 R6、 R8 :それぞれ独立して、 1価有機基。 R 2 , R 4 , R 5 , R 6 , R 8 : each independently represents a monovalent organic group.
X1、 X2、 X3、 X4：それぞれ独立して、加水分解性基。 X 1 , X 2 , X 3 , X 4 : each independently a hydrolyzable group.
n、 m、 p、 q :それぞれ独立して、 1〜3の整数。  n, m, p, q: each independently, an integer of 1 to 3.
[0011] 式 1で表される化合物（以下、化合物 1とも記す。式 2〜4についても同様に記す。 ) にお!/、て、 Rnとしてはペルフルォロアルキル基またはエーテル性の酸素原子を有す るペルフルォロアルキル基が好まし!/、。ペルフルォロアルキル基の炭素原子数として は 1〜16が好ましぐ 3〜12力 Sより好ましく、 3〜8が最も好ましい。ペルフルォロアル キル基としては、直鎖構造、分岐構造または環状構造が挙げられるが、直鎖構造が 好ましい。分岐構造である場合には、分岐部分が末端に存在し、かつ分岐部分が炭 素数 1〜4程度の短鎖であるのが好まし 、。 [0011] In the compound represented by the formula 1 (hereinafter also referred to as compound 1; the same applies to formulas 2 to 4),! /, And R n is a perfluoroalkyl group or an etheric compound. Perfluoroalkyl groups having an oxygen atom are preferred! The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 16, more preferably 3 to 12 force S, and most preferably 3 to 8 carbon atoms. Examples of the perfluoroalkyl group include a linear structure, a branched structure and a cyclic structure, and a linear structure is preferable. In the case of a branched structure, it is preferable that the branched portion exists at the terminal and the branched portion is a short chain having about 1 to 4 carbon atoms.
[0012] R1としては炭素原子数 1〜10のアルキレン基が好ましぐ炭素原子数 2〜5のアル キレン基がより好ましぐ炭素原子数 3〜4のアルキレン基が最も好ましい。 R2は炭素 原子数 1〜 5のアルキル基が好ましく、炭素原子数 1〜 3のアルキル基がより好ましく 、メチル基が最も好ましい。 X1としては、ハロゲン原子、アルコキシ基、ァセトキシ基、 ケトォキシム基が好ましぐハロゲン原子、アルコキシ基がより好ましぐ C1一、 CH O As R 1 , an alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 2 to 5 carbon atoms is more preferable, and an alkylene group having 3 to 4 carbon atoms is more preferable. R 2 is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. X 1 is preferably a halogen atom, an alkoxy group, an acetoxyl group, or a ketoxime group, more preferably a halogen atom or an alkoxy group.
3 一、 C H O—が最も好ましい。 nは 2〜3が好ましぐ 3がより好ましい。 nが 3であると 3. C H O— is most preferred. n is preferably 2 to 3, and more preferably 3. If n is 3
2 5 twenty five
撥水性組成物が基材への密着性に優れる。  The water-repellent composition has excellent adhesion to a substrate.
[0013] 化合物 1としては、以下の化合物等が挙げられる。 [0013] Examples of the compound 1 include the following compounds.
F (CF ) COO (CH ) Si (OCH ) 、 F (CF ) COO (CH ) Si (OCH ) 、 F (CF ) COO (CH ) Si (OCH ) 、 F(CF ) COO(CH ) Si (OCH ) 、 F(CF ) COO(F (CF) COO (CH) Si (OCH), F (CF) COO (CH) Si (OCH), F (CF ) COO (CH) Si (OCH), F (CF) COO (CH) Si (OCH), F (CF) COO (
7 2 3 3 3 2 6 2 4 3 3 2 67 2 3 3 3 2 6 2 4 3 3 2 6
CH ) Si (OCH ) 。 CH) Si (OCH).
2 3 3 3  2 3 3 3
F(CF ) COO (CH ) Si (OCH ) 、 F(CF ) COO(CH ) Si (OCH ) 、 F(CF F (CF) COO (CH) Si (OCH), F (CF) COO (CH) Si (OCH), F (CF
2 4 2 4 3 3 2 4 2 3 3 3 22 4 2 4 3 3 2 4 2 3 3 3 2
) OCF(CF )COO(CH ) Si (OCH ) 、 F(CF ) OCF(CF )CF OCF(CF )C) OCF (CF) COO (CH) Si (OCH), F (CF) OCF (CF) CF OCF (CF) C
3 3 2 4 3 3 2 3 3 2 33 3 2 4 3 3 2 3 3 2 3
00(CH ) Si (OCH ) 。 00 (CH) Si (OCH).
2 4 3 3  2 4 3 3
[0014] 化合物 1としては、 F(CF ) COO (CH ) Si (OCH ) が好ましい。  [0014] As compound 1, F (CF) COO (CH) Si (OCH) is preferable.
2 8 2 4 3 3  2 8 2 4 3 3
[0015] 化合物 2、化合物 3、化合物 4において、 Ri2、 Ri3、 RMは上記 Rnと同様の基が好ま しぐ R3、 R7は前記 R1と同様の基が好ましぐ R4、 R5、 R6、 R8は前記 R2と同様の基が 好ましぐ X2、 X3、 X4は前記 X1と同様の基が好ましぐ m、 p、 qは前記 nと同様の整数 が好ましい。 [0015] Compound 2, Compound 3, in the compound 4, R i2, R i3, R M is the R n and signaling R 3 preferred the same groups, R 7 is the R 1 group similar to the preferred tool R 4 , R 5 , R 6 , and R 8 are preferably the same groups as R 2 , X 2 , X 3 , and X 4 are preferably the same groups as X 1 m, p, and q are the same The same integer as n is preferable.
[0016] 化合物 2としては、以下の化合物等が挙げられる。  [0016] Examples of the compound 2 include the following compounds.
F(CF ) CH CH OCO(CH ) Si (OCH ) 、 F(CF ) CH CH OCO (CH ) Si F (CF) CH CH OCO (CH) Si (OCH), F (CF) CH CH OCO (CH) Si
2 8 2 2 2 4 3 3 2 8 2 2 2 32 8 2 2 2 4 3 3 2 8 2 2 2 3
(OCH ) 、 F(CF ) CH OCO (CH ) Si (OCH ) 、 F(CF ) CH OCO(CH ) Si(OCH), F (CF) CH OCO (CH) Si (OCH), F (CF) CH OCO (CH) Si
3 3 2 8 2 2 4 3 3 2 7 2 2 43 3 2 8 2 2 4 3 3 2 7 2 2 4
(OCH ) 、 F(CF ) CH CH OCO (CH ) Si (OCH ) 、 F(CF ) CH CH OCO(OCH), F (CF) CH CH OCO (CH) Si (OCH), F (CF) CH CH OCO
3 3 2 6 2 2 2 4 3 3 2 6 2 23 3 2 6 2 2 2 4 3 3 2 6 2 2
(CH ) Si (OCH ) 、 F(CF ) CH CH OCO(CH ) Si (OCH ) 、 F(CF ) CH(CH) Si (OCH), F (CF) CH CH OCO (CH) Si (OCH), F (CF) CH
2 3 3 3 2 4 2 2 2 4 3 3 2 4 22 3 3 3 2 4 2 2 2 4 3 3 2 4 2
CH OCO (CH ) Si (OCH ) 、 F(CF ) OCF(CF )CF OCF CF CH CH OCCH OCO (CH) Si (OCH), F (CF) OCF (CF) CF OCF CF CH CH OC
2 2 3 3 3 2 3 3 2 2 2 2 22 2 3 3 3 2 3 3 2 2 2 2 2
0(CH ) Si (OCH ) 。 0 (CH) Si (OCH).
2 4 3 3  2 4 3 3
[0017] 化合物 2としては、 F(CF ) CH CH OCO (CH ) Si (OCH ) が好ましい。  As compound 2, F (CF 2) 2 CH 2 CH 2 OCO 2 (CH 2) 2 Si (OCH 2) is preferable.
2 8 2 2 2 4 3 3  2 8 2 2 2 4 3 3
[0018] 化合物 3としては以下の化合物等が挙げられる。 [0018] Examples of the compound 3 include the following compounds.
F(CF ) CH CH OSi(OCH ) 、 F(CF ) CH OSi(OCH ) 、 F(CF ) CH C F (CF) CH CH OSi (OCH), F (CF) CH OSi (OCH), F (CF) CH C
2 8 2 2 3 3 2 7 2 3 3 2 6 22 8 2 2 3 3 2 7 2 3 3 2 6 2
H OSi(OCH ) 、 F(CF ) CH CH OSi(OCH ) 、 F(CF ) OCF(CF )CF OCH OSi (OCH), F (CF) CH CH OSi (OCH), F (CF) OCF (CF) CF OC
2 3 3 2 4 2 2 3 3 2 3 3 22 3 3 2 4 2 2 3 3 2 3 3 2
F CF CH CH OSi(OCH ) 。 F CF CH CH OSi (OCH).
2 2 2 2 3 3  2 2 2 2 3 3
[0019] 化合物 3としては、 C F CH CH OSi(OCH ) が好ましい。  [0019] As compound 3, CFCHCHOSi (OCH) is preferable.
8 17 2 2 3 3  8 17 2 2 3 3
[0020] ィ匕合物 4としては、以下の化合物が好ましく挙げられる。 The following compounds are preferred examples of the compound 4.
F(CF ) CH CH (CH ) SiO (CH ) Si (OCH ) 、 F(CF ) CH CH CH (CH F (CF) CH CH (CH) SiO (CH) Si (OCH), F (CF) CH CH CH (CH
2 8 2 2 3 2 2 4 3 3 2 8 2 2 22 8 2 2 3 2 2 4 3 3 2 8 2 2 2
) SiO(CH ) Si (OCH ) 、 F(CF ) CH CH (CH ) SiO(CH ) Si (OCH ) 、) SiO (CH) Si (OCH), F (CF) CH CH (CH) SiO (CH) Si (OCH),
3 2 2 3 3 3 2 6 2 2 3 2 2 4 3 33 2 2 3 3 3 2 6 2 2 3 2 2 4 3 3
F(CF ) CH CH (CH ) SiO(CH ) Si (OCH ) 、 F(CF ) CH CH (CH ) SiF (CF) CH CH (CH) SiO (CH) Si (OCH), F (CF) CH CH (CH) Si
2 6 2 2 3 2 2 3 3 3 2 4 2 2 3 22 6 2 2 3 2 2 3 3 3 2 4 2 2 3 2
0(CH ) Si (OCH ) 、 F(CF ) CH CH (CH ) SiO(CH ) Si (OCH ) 、 F(CF0 (CH) Si (OCH), F (CF) CH CH (CH) SiO (CH) Si (OCH), F (CF
2 4 3 3 2 4 2 2 3 2 2 3 3 3 ) CH CH (CH ) SiOCO(CH ) Si(OCH ) 、 F(CF ) CH CH (CH ) SiOC2 4 3 3 2 4 2 2 3 2 2 3 3 3 ) CH CH (CH) SiOCO (CH) Si (OCH), F (CF) CH CH (CH) SiOC
2 8 2 2 3 2 2 4 3 3 2 8 2 2 3 22 8 2 2 3 2 2 4 3 3 2 8 2 2 3 2
0(CH ) Si(OCH ) 、 F(CF ) CH CH (CH ) SiONH(CH ) Si(OCH ) 。 0 (CH) Si (OCH), F (CF) CHCH (CH) SiONH (CH) Si (OCH).
2 3 3 3 2 8 2 2 3 2 2 3 3 3 2 3 3 3 2 8 2 2 3 2 2 3 3 3
[0021] 化合物 4としては、 F(CF ) CH CH (CH ) SiO(CH ) Si(OCH ) が好ましい。 The compound 4 is preferably F (CF 2) 2 CH 2 (CH 2) 2 SiO (CH 2) 2 Si (OCH 3).
2 8 2 2 3 2 2 4 3 3  2 8 2 2 3 2 2 4 3 3
[0022] 光の照射により分解して酸を発生する化合物 Bとしては、最大吸収波長（ λ )が 2 max [0022] Compound B, which decomposes upon irradiation with light to generate an acid, has a maximum absorption wavelength (λ) of 2 max.
OOnm以上のものが好ましぐ 250nm以上のものがより好ましぐ 300nm以上のもの が最も好ましい。最大吸収波長が該範囲であると、高圧水銀灯等の簡便な装置を用 V、て撥水性親水性パターンを有する薄膜を形成できる。 OOnm or more is preferred. 250nm or more is more preferred. 300nm or more is most preferred. When the maximum absorption wavelength is in the above range, a thin film having a water-repellent hydrophilic pattern can be formed using a simple device such as a high-pressure mercury lamp.
[0023] 化合物 Bとしては、波長 200nm以上の光により分解して酸を発生する化合物すな わち photo acid generator (略して PAGと記す。）であれば特に限定なく用いるこ とができる。化合物 Bの具体例としては、以下の化合物等が挙げられる。  As the compound B, any compound that can be decomposed by light having a wavelength of 200 nm or more to generate an acid, that is, a photoacid generator (abbreviated as PAG) can be used without particular limitation. Specific examples of the compound B include the following compounds.
[0024] [化 1] [0024] [Formula 1]
Figure imgf000008_0001
Figure imgf000008_0001
A max: 241 nm λ max: 328nm  A max: 241 nm λ max: 328 nm
Figure imgf000008_0002
Figure imgf000008_0002
λ max: 278nm OSO3CH3"  λ max: 278nm OSO3CH3 "
λ max: 252nm  λ max: 252nm
Figure imgf000008_0003
Figure imgf000008_0003
λ max: 395nm  λ max: 395nm
[0025] 発生する酸は撥水性化合物 Aを分解できる酸であればよぐ塩酸が好ま ヽ。塩酸 が発生する機構は必ずしも明確ではないが、化合物 Bにおける CC1から塩素ラジ [0025] The generated acid is preferably hydrochloric acid as long as it is an acid capable of decomposing the water-repellent compound A. Although the mechanism of the generation of hydrochloric acid is not always clear, the chlorine radical
3  Three
カルが発生し、化合物 B中の水素原子を引き抜 、て塩酸が発生すると考えられる。  It is considered that calcium is generated and hydrogen atoms in compound B are extracted, thereby generating hydrochloric acid.
[0026] 撥水性組成物における撥水性ィ匕合物 AZ化合物 Bの質量比は、 95Z5〜99. 99 /0. 01力 S好ましく、 99/1〜99. 9/0. 1力 Sより好ましく、 99. 5/0. 5〜99. 8/0 . 2が最も好ましい。該範囲であると、光の照射により撥水性薄膜の表面の撥水性が 効率よく低下する。 [0026] The mass ratio of the water repellent compound AZ compound B in the water repellent composition is preferably from 95Z5 to 99.99 / 0.01 force S, more preferably from 99/1 to 99.9 / 0.1 force S. , 99.5 / 0.5 to 99.8 / 0.2 are most preferred. Within this range, the water repellency of the surface of the water-repellent thin film is reduced by light irradiation. Decreases efficiently.
[0027] 本発明の撥水性薄膜は、撥水性組成物を基板上に塗布して形成されてなる。撥水 性薄膜の水との接触角は 95度以上が好ましぐ 100度以上がより好ましい。前記薄 膜は波長 200nm以上の光を照射後、水との接触角が 70度以下となることが好ましく 、 50度以下がより好ましぐ 30度以下が最も好ましい。光を照射する前後の薄膜の水 に対する接触角の差は 30度以上が好ましぐ 50度以上がより好ましぐ 70度以上が 最も好ましい。  [0027] The water-repellent thin film of the present invention is formed by applying a water-repellent composition on a substrate. The contact angle of the water-repellent thin film with water is preferably 95 degrees or more, more preferably 100 degrees or more. After irradiation of light having a wavelength of 200 nm or more, the thin film preferably has a contact angle with water of 70 ° or less, more preferably 50 ° or less, most preferably 30 ° or less. The difference in contact angle of the thin film with water before and after light irradiation is preferably 30 degrees or more, more preferably 50 degrees or more, and most preferably 70 degrees or more.
[0028] 本発明の撥水性組成物は、有機溶剤を含むことが好ま 、。  [0028] The water-repellent composition of the present invention preferably contains an organic solvent.
有機溶剤としては、特に限定されず、アルコール類、ケトン類、芳香族炭化水素類 、パラフィン系炭化水素類が好ましぐエチルアルコール、 2—プロピルアルコール等 の低級アルコール類またはパラフィン系炭化水素類がより好ましい。有機溶剤は、 1 種を用いてもよぐ 2種以上を混合して用いて、溶解性、蒸発速度を調節してもよい。  The organic solvent is not particularly restricted but includes alcohols, ketones, aromatic hydrocarbons, lower alcohols such as ethyl alcohol and 2-propyl alcohol, which are preferred among paraffin hydrocarbons, and paraffin hydrocarbons. More preferred. One organic solvent may be used, or two or more organic solvents may be used in combination to adjust solubility and evaporation rate.
[0029] 撥水性組成物において、撥水性ィ匕合物 AZ有機溶剤の質量比は 1Z1000〜1Z 10が好ましぐ 1Z200〜1Z20がより好ましい。該範囲であると、均一な薄膜が形成 され、撥水性に優れる。  [0029] In the water repellent composition, the mass ratio of the water repellent compound AZ organic solvent is preferably 1Z1000 to 1Z10, more preferably 1Z200 to 1Z20. Within this range, a uniform thin film is formed and the water repellency is excellent.
[0030] 本発明の撥水性薄膜の厚さは、特に限定されないが、 0. 5〜： LOOnmが好ましぐ 1 〜20nmがより好ましぐ l〜5nmが最も好ましい。撥水性薄膜の厚さは、自己組織 化膜 (SMAともいう。）の厚さが最も好ましい。該範囲にあると、良好な撥水性親水性 パターンが得られる。  [0030] The thickness of the water-repellent thin film of the present invention is not particularly limited, but is preferably from 0.5 to: LOOnm is more preferable 1 to 20 nm is more preferable l to 5 nm is most preferable. The thickness of the water-repellent thin film is most preferably the thickness of a self-assembled film (also referred to as SMA). Within this range, a good water-repellent hydrophilic pattern can be obtained.
[0031] 撥水性組成物を塗布する方法としては、はけ塗り、流し塗り、回転塗布、浸漬塗布、 スキージ塗布、スプレー塗布、手塗り等の各種公知の方法が挙げられる。撥水性組 成物は、表面に塗布した後、大気中、窒素気流中等で乾燥する。該乾燥は室温で行 うのが好ましぐ加熱によって乾燥する場合には、基材の耐熱性を加味して加熱の温 度、時間を設定する。温度としては、 0〜80°Cが好ましぐ 10〜40°Cがより好ましい。 時間としては、 1〜60分間が好ましぐ 5〜30分間がより好ましい。  [0031] Examples of methods for applying the water-repellent composition include various known methods such as brush coating, flow coating, spin coating, dip coating, squeegee coating, spray coating, and hand coating. After the water repellent composition is applied to the surface, it is dried in the air, in a nitrogen stream, or the like. When drying by heating, which is preferably performed at room temperature, the heating temperature and time are set in consideration of the heat resistance of the substrate. The temperature is preferably from 0 to 80 ° C, more preferably from 10 to 40 ° C. The time is preferably from 1 to 60 minutes, more preferably from 5 to 30 minutes.
[0032] 本発明の撥水性親水性パターンを有する薄膜は、前記撥水性薄膜に光を照射し、 薄膜表面を洗浄して形成されてなる。  The thin film having a water-repellent hydrophilic pattern of the present invention is formed by irradiating the water-repellent thin film with light and cleaning the thin film surface.
[0033] 照射する光の波長 ίま 200〜800mn力 S好ましく、 250〜600mn力 Sより好ましく、 300 〜400nmが最も好まし!、。 [0033] The wavelength of the light to be irradiated is preferably 200 to 800 mn force S, more preferably 250 to 600 mn force S, ~ 400nm is most preferred!
照射する光は紫外線がより好ましい。波長が該範囲にあると、基板を構成する材料自 体を分解しない。光の光源としては、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀 ランプ、キセノンランプ、ナトリウムランプ、窒素等の気体レーザー、有機色素溶液の 液体レーザー、無機単結晶に希土類イオンを含有させた固体レーザー等が挙げら れる。また、単色光が得られるレーザー以外の光源としては、広帯域の線スペクトル、 連続スペクトルをバンドパスフィルター、カットオフフィルタ一等の光学フィルターを使 用して取出した特定波長の光を使用してもよい。一度に大きな面積を照射することが できることから、光源としては高圧水銀ランプまたは超高圧水銀ランプが好ま 、。  Irradiation light is more preferably ultraviolet light. When the wavelength is in the above range, the material constituting the substrate does not decompose itself. Light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, sodium lamps, gas lasers such as nitrogen, liquid lasers of organic dye solutions, and solid-state lasers containing rare earth ions in inorganic single crystals. And the like. In addition, as a light source other than a laser capable of obtaining monochromatic light, light of a specific wavelength obtained by extracting a broadband line spectrum or continuous spectrum using an optical filter such as a band-pass filter or a cutoff filter may be used. Good. Since a large area can be irradiated at a time, a high-pressure mercury lamp or an ultra-high-pressure mercury lamp is preferred as a light source.
[0034] 照射方法としては、所定のパターンを有するフォトマスクを介して光を照射する方法 、レーザー光を用いる方法等が挙げられる。一度に大きな面積を照射できることから[0034] Examples of the irradiation method include a method of irradiating light through a photomask having a predetermined pattern, a method of using laser light, and the like. Because it can irradiate a large area at once
、フォトマスクを介して光を照射する方法が好ましい。 A method of irradiating light through a photomask is preferable.
[0035] 光を照射した後の薄膜表面の洗浄には、含フッ素有機基を溶解する溶剤を用いる ことが好ましい。溶剤としては、ジクロロペンタフルォロプロパン（以下、 R— 225と記 す。）、ペルフルォ口へキサン等のペルフルォロカーボン類、（ペルフルォロブトキシ） メタン等のハイド口フルォロエーテル、デカフルォロペンタン等のハイド口フルォロカ 一ボン等が挙げられる。 For cleaning the thin film surface after light irradiation, it is preferable to use a solvent that dissolves a fluorine-containing organic group. Examples of the solvent include dichloropentafluoropropane (hereinafter referred to as R-225), perfluorocarbons such as perfluorohexane, hydrfluoroethers such as (perfluorobutoxy) methane, decafluoroether, and decahydrate. Fluorocapanone such as fluoropentane.
[0036] 本発明の撥水性薄膜において、光を照射した部分は撥水性が低下し、光が照射さ れな力つた部分は撥水性を維持するので、光の照射により撥水性親水性パターンを 有する薄膜が形成される。本発明においては、撥水性組成物の塗布による薄膜形成 と、その後の一度の光の照射によって、親水性と撥水性のパターンを有する薄膜を 容易に得ることができる。  [0036] In the water-repellent thin film of the present invention, the portion irradiated with light has reduced water repellency, and the energized portion not irradiated with light maintains water repellency. Is formed. In the present invention, a thin film having a hydrophilic and water-repellent pattern can be easily obtained by forming a thin film by applying a water-repellent composition and subsequently irradiating the light once.
[0037] 本発明において、撥水性薄膜が光の照射により撥水性が低下する機構は次のよう に考えられる。含フッ素化合物 Aから形成された薄膜中の結合基は、酸により分解し 、含フッ素有機基を放出し、水酸基、カルボキシル基、シラノール基、アミノ基等が形 成されるため、撥水性が低下するものと考えられる。  In the present invention, the mechanism by which water repellency of the water repellent thin film is reduced by light irradiation is considered as follows. The bonding group in the thin film formed from the fluorine-containing compound A is decomposed by an acid to release a fluorine-containing organic group and form a hydroxyl group, a carboxyl group, a silanol group, an amino group, and the like, so that the water repellency is reduced. It is thought to be.
[0038] 本発明に用いる基板は特に限定されず、ガラス、石英ガラス、シリコンウェハ、ブラ スチック、金属等が好ましく挙げられる。また、これらの基板上に、金属薄膜が形成さ れた基板を用いてもよい。 [0038] The substrate used in the present invention is not particularly limited, and preferably includes glass, quartz glass, silicon wafer, plastic, metal and the like. In addition, a metal thin film is formed on these substrates. May be used.
実施例  Example
[0039] 以下に実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定され ない。実施例においては、 R— 225としては、旭硝子社製商品名 AK— 225を用いた 。また、ガラス基板としては、 10cm四方の厚さ 2mmソーダライム系ガラス基板の表面 を、酸ィ匕セリウム系微粒子を含む研磨剤で研磨洗浄し、純水ですすいで風乾したガ ラスを用いた。水に対する接触角は、静滴法を用い基板に水滴を 3ケ所乗せ、測定さ れた 3点の接触角の平均値として求めた。  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In the examples, AK-225 (trade name, manufactured by Asahi Glass Co., Ltd.) was used as R-225. As the glass substrate, a glass substrate was used in which the surface of a 10 cm square, 2 mm thick soda lime glass substrate was polished and cleaned with an abrasive containing cerium oxide fine particles, rinsed with pure water, and air-dried. The contact angle with water was calculated as the average value of the measured contact angles at three points with three drops of water placed on the substrate using the static drop method.
[0040] [例 1]  [0040] [Example 1]
300mLのガラス製容器に、 F (CF ) COO (CH ) Si(OCH ) の 1質量部、 2 プ  1 part by weight of F (CF) COO (CH) Si (OCH) in a 300 mL glass container
2 8 2 4 3 3  2 8 2 4 3 3
ロパノールの 100質量部および 0. 1モル ZL濃度の塩酸の 0. 5質量部を入れて、室 温で 12時間加水分解反応を行い加水分解物 1を得た。得られた加水分解物 1に、原 料の F (CF ) COO (CH ) Si(OCH ) に対して 5モル0 /0となる量の 2— [2— (フラ 100 parts by mass of lopanol and 0.5 parts by mass of hydrochloric acid having a concentration of 0.1 mol ZL were added, and a hydrolysis reaction was performed at room temperature for 12 hours to obtain hydrolyzate 1. To the resulting hydrolyzate 1, raw materials of F (CF) COO (CH) Si (OCH) is 5 mole 0/0 relative to the amount of 2- [2- (Hula
2 8 2 4 3 3  2 8 2 4 3 3
ン— 2—ィル）ビュル]— 4, 6 ビス（トリクロロメチル）—1, 3, 5 トリァジン（以下、化 合物 bと記す。）を添加して撥水性組成物 1を得た。  -2-yl) butyl]-4,6 bis (trichloromethyl) -1,3,5 triazine (hereinafter referred to as compound b) was added to obtain a water-repellent composition 1.
[0041] 得られた撥水性組成物 1の 2mLをガラス基板に滴下し、 3000回転で 20秒間スピ ンコートした後、風乾してサンプル 1—1を作製した。形成された薄膜の厚さは 3nmで めつに。 [0041] 2 mL of the obtained water repellent composition 1 was dropped on a glass substrate, spin-coated at 3000 rpm for 20 seconds, and then air-dried to prepare Sample 1-1. The thickness of the formed thin film is 3 nm.
[0042] 得られたサンプル 1 1の水に対する接触角は 105度であり、未処理のガラス基板 の水に対する接触角は 10度以下であった。高圧水銀ランプを用いて紫外線を照射 し R— 225で洗浄し風乾してサンプル 1 2を作製した。照射量が 200miZcm2の場 合のサンプル 1 - 2の水に対する接触角は 61度であった。 [0042] The contact angle of the obtained sample 11 with water was 105 degrees, and the contact angle of the untreated glass substrate with water was 10 degrees or less. Sample 12 was prepared by irradiating ultraviolet rays using a high-pressure mercury lamp, washing with R-225, and air-drying. When the irradiation amount was 200 miZcm 2, the contact angle to water of Sample 1-2 was 61 degrees.
[0043] [例 2]  [0043] [Example 2]
300mLのガラス製容器に、 F (CF ) C H OCO (CH ) Si (OCH ) の 1質量部、  In a 300 mL glass container, 1 part by mass of F (CF) CHOCO (CH) Si (OCH),
2 8 2 4 2 4 3 3  2 8 2 4 2 4 3 3
2 プロパノールの 100質量部および 0. 1モル ZLの塩酸の 0. 5質量部を入れて、 室温で 12時間加水分解反応を行 ヽ加水分解物 2を得た。得られた加水分解物 2に、 原料の F (CF ) C H OCOCH CH CH CH Si (OCH ) に対して 5モル0 /0となる 2 100 parts by mass of propanol and 0.5 part by mass of 0.1 mol ZL of hydrochloric acid were added, and a hydrolysis reaction was carried out at room temperature for 12 hours to obtain a hydrolyzate 2. To the resulting hydrolyzate 2, a 5 mole 0/0 of the raw material of F (CF) CH OCOCH CH CH CH Si (OCH)
2 8 2 4 2 2 2 2 3 3  2 8 2 4 2 2 2 2 3 3
量の化合物 bを添加して撥水性組成物 2を得た。 [0044] 得られた撥水性組成物 2の 2mLをガラス基板に滴下し、 3000回転で 20秒間スピ ンコートした後、風乾してサンプル 2—1を作製した。形成された薄膜の厚さは 3nmで めつに。 The amount of compound b was added to obtain water repellent composition 2. [0044] 2 mL of the obtained water-repellent composition 2 was dropped on a glass substrate, spin-coated at 3000 rpm for 20 seconds, and air-dried to prepare Sample 2-1. The thickness of the formed thin film is 3 nm.
[0045] 得られたサンプル 2—1の水に対する接触角は 104度であった。高圧水銀ランプを 用いて紫外線を照射し R— 225で洗浄し風乾してサンプル 2— 2を作製した。照射量 力 S200mjZcm2の場合の水に対する接触角は 42度であった。 [0045] The contact angle of the obtained Sample 2-1 with water was 104 degrees. The sample was irradiated with ultraviolet rays using a high-pressure mercury lamp, washed with R-225, and air-dried to prepare Sample 2-2. When the irradiation power was 200 mJZcm 2, the contact angle with water was 42 degrees.
[0046] [例 3]  [Example 3]
300mLのガラス製容器に、 F (CF ) C H OSi (OCH ) の 1質量部、 2—プロパノ  In a 300 mL glass container, 1 part by weight of F (CF) C H OSi (OCH), 2-propano
2 8 2 4 3 3  2 8 2 4 3 3
ールの 100質量部および 0. 1モル ZLの塩酸の 0. 5質量部を入れて、室温で 12時 間加水分解反応を行い加水分解物 3を得た。得られた加水分解物 3に、原料の F (C F ) C H OSi (OCH ) に対して 5モル0 /0となる量の化合物 bを添カ卩して撥水性組成Then, 100 parts by mass of the reaction mixture and 0.5 parts by mass of 0.1 mol ZL of hydrochloric acid were added, and a hydrolysis reaction was carried out at room temperature for 12 hours to obtain a hydrolyzate 3. To the resulting hydrolyzate 3, compound b amount of the raw material of F (CF) CH OSi (OCH ) is 5 mole 0/0 to添Ka卩water repellent composition
2 8 2 4 3 3 2 8 2 4 3 3
物 3を得た。  Obtained thing 3.
[0047] 得られた撥水性組成物 3の 2mLをガラス基板に滴下し、 3000回転で 20秒間スピ ンコートした後、風乾してサンプル 3—1を作製した。形成された薄膜の厚さは 2nmで めつに。  [0047] 2 mL of the obtained water-repellent composition 3 was dropped on a glass substrate, spin-coated at 3000 rpm for 20 seconds, and air-dried to prepare Sample 3-1. The thickness of the formed thin film is 2 nm.
[0048] 得られたサンプル 3—1の水に対する接触角は 106度であった。高圧水銀ランプを 用いて紫外線を照射し R— 225で洗浄し風乾してサンプル 3 - 2を作製した。照射量 力 S200mjZcm2の場合の水に対する接触角は 22度であった。 [0048] The contact angle of the obtained Sample 3-1 with water was 106 degrees. The sample was irradiated with ultraviolet rays using a high-pressure mercury lamp, washed with R-225, and air-dried to prepare Sample 3-2. The contact angle with water when the irradiation power was 200 mJZcm 2 was 22 degrees.
[0049] [例 4]  [0049] [Example 4]
300mLのガラス製容器に、 F (CF ) CH CH (CH ) SiO (CH ) Si (OCH ) の  In a 300 mL glass container, add F (CF) CH CH (CH) SiO (CH) Si (OCH)
2 8 2 2 3 2 2 4 3 3 2 8 2 2 3 2 2 4 3 3
1質量部、 2—プロパノールの 100質量部および 0. 1モル ZLの塩酸の 0. 5質量部 を入れて、室温で 12時間加水分解反応を行い、加水分解物 4を得た。得られた加水 分解物 4に、原料の F (CF ) CH CH (CH ) SiO (CH ) Si (OCH ) に対して 5モ One part by mass, 100 parts by mass of 2-propanol and 0.5 part by mass of 0.1 mol ZL of hydrochloric acid were added, and a hydrolysis reaction was carried out at room temperature for 12 hours to obtain a hydrolyzate 4. The obtained hydrolyzate 4 has 5 moles relative to the raw material F (CF) CHCH (CH) SiO (CH) Si (OCH).
2 8 2 2 3 2 2 4 3 3  2 8 2 2 3 2 2 4 3 3
ル％となる量の化合物 bを添加して撥水性組成物 4を得た。  % Of the compound b was added to obtain a water repellent composition 4.
[0050] 得られた撥水性組成物 4の 2mLをガラス基板に滴下し、 3000回転で 20秒間スピ ンコートした後、風乾してサンプル 4—1を作製した。形成された薄膜の厚さは 3nmで めつに。 [0050] 2 mL of the obtained water repellent composition 4 was dropped on a glass substrate, spin-coated at 3000 rpm for 20 seconds, and then air-dried to prepare Sample 4-1. The thickness of the formed thin film is 3 nm.
[0051] 得られたサンプル 4—1の水に対する接触角は 105度であった。高圧水銀ランプを 用いて紫外線を照射し R— 225で洗浄し風乾してサンプル 4— 2を作製した。照射量 力 S750mjZcm2の場合の水に対する接触角は 60度であった。 [0051] The contact angle of the obtained sample 4-1 with water was 105 degrees. High pressure mercury lamp The sample was irradiated with ultraviolet rays, washed with R-225, and air-dried to prepare Sample 4-2. When the irradiation power was S750 mjZcm 2, the contact angle with water was 60 degrees.
産業上の利用可能性 Industrial applicability
本発明の撥水性親水性パターンを有する薄膜は、機能性パターンの形成に使用 できる。たとえば、インクジェットプリンティングにより機能性材料を該薄膜の親水性領 域に噴射することにより、鮮明な機能性材料のパターンが容易に形成される。撥水性 親水性パターンを有する薄膜は、親水性領域に機能性インクを含ませ、別の基材に 転写することにより、マイクロコンタクトプリンティング用のスタンプとしての用途を有す る。  The thin film having a water-repellent hydrophilic pattern of the present invention can be used for forming a functional pattern. For example, by spraying a functional material onto the hydrophilic region of the thin film by inkjet printing, a clear pattern of the functional material can be easily formed. A thin film having a water-repellent hydrophilic pattern has a use as a stamp for microcontact printing by including a functional ink in a hydrophilic region and transferring it to another substrate.

Claims

請求の範囲 The scope of the claims
[1] 波長 200nm以上の光の照射により分解して酸を発生する化合物 Bおよび該化合 物から発生した酸により分解して撥水性が低下する撥水性化合物 Aを含む撥水性組 成物。  [1] A water-repellent composition comprising a compound B which decomposes by irradiation with light having a wavelength of 200 nm or more to generate an acid, and a water-repellent compound A which decomposes by the acid generated from the compound to reduce water repellency.
[2] 前記撥水性化合物 Αが、含フッ素有機基を有し、酸により分解して該含フッ素有機 基を放出する結合基を有する化合物である、請求項 1に記載の撥水性組成物。  [2] The water-repellent composition according to claim 1, wherein the water-repellent compound is a compound having a fluorinated organic group and having a binding group which is decomposed by an acid to release the fluorinated organic group.
[3] 前記含フッ素有機基を放出する結合基が、エステル基、シリルエーテル基、シリル アミノ基カもなる群力も選ばれる少なくとも 1種の結合基である、請求項 2に記載の撥 水性組成物。  [3] The water-repellent composition according to claim 2, wherein the binding group releasing the fluorinated organic group is at least one binding group selected from the group consisting of an ester group, a silyl ether group and a silylamino group. object.
[4] 前記撥水性化合物 Aが、下式 1〜4で表される含フッ素化合物力 なる群力 選ば れる少なくとも 1種の化合物および Zまたはその部分加水分解物である、請求項 1〜 3の 、ずれかに記載の撥水性組成物。  [4] The water-repellent compound A according to any one of claims 1 to 3, wherein the compound is at least one compound selected from the group consisting of fluorine compounds represented by the following formulas 1 to 4 and Z or a partial hydrolyzate thereof. And a water-repellent composition according to any one of claims 1 to 4.
^COOR'SKR2) X1 …式 1 ^ COOR'SKR 2 ) X 1 … Equation 1
Rf2OCOR3Si (R4) X2 …式 2 R f2 OCOR 3 Si (R 4 ) X 2 … Equation 2
3— m m  3—m m
Rf3OSi (R5) X3…式 3 R f3 OSi (R 5 ) X 3 … Equation 3
3-P P  3-P P
Rf4 (R6) SiOR7Si (R8) X4 · · ·式 4 R f4 (R 6) SiOR 7 Si (R 8) X 4 · · · Formula 4
2 3-q q  2 3-q q
ただし、式 1〜4における記号は以下の意味を示す。  However, the symbols in the formulas 1 to 4 have the following meanings.
Rf\ Ri2、 Ri3、 RM:それぞれ独立して、 1価含フッ素有機基。 R f \ R i2 , R i3 , R M : each independently represents a monovalent fluorinated organic group.
R\ R3、 R7:それぞれ独立して、 2価有機基。 R \ R 3, R 7: each independently a divalent organic group.
R2、 R4、 R5、 R6、 R8 :それぞれ独立して、 1価有機基。 R 2 , R 4 , R 5 , R 6 , R 8 : each independently represents a monovalent organic group.
X1、 X2、 X3、 X4：それぞれ独立して、加水分解性基。 X 1 , X 2 , X 3 , X 4 : each independently a hydrolyzable group.
n、 m、 p、 q :それぞれ独立して、 1〜3の整数。  n, m, p, q: each independently, an integer of 1 to 3.
[5] 前記 1、 Ri2、 Ri3、 RMが、それぞれ独立して、ペルフルォロアルキル基またはエー テル性の酸素原子を有するペルフルォロアルキル基である、請求項 4に記載の撥水 性組成物。 [5] The 1, R i2, R i3, R M are each independently a pel full O b alkyl group having pel full O b alkyl group or ether oxygen atom, according to claim 4 Water-repellent composition.
[6] 前記 、 R3、 R7が、それぞれ独立して、炭素原子数 1〜： L0のアルキレン基である、 請求項 4または 5に記載の撥水性組成物。 [6] The water-repellent composition according to claim 4, wherein R 3 and R 7 are each independently an alkylene group having 1 to L0 carbon atoms.
[7] 前記 X1、 X2、 X3、 X4が、それぞれ独立して、ハロゲン原子、アルコキシ基、ァセトキ シ基、及びケトォキシム基力 なる群力 選ばれる少なくとも 1種の加水分解性基であ る、請求項 4〜6の ヽずれかに記載の撥水性組成物。 [7] X 1 , X 2 , X 3 , and X 4 each independently represent a halogen atom, an alkoxy group, The water-repellent composition according to any one of claims 4 to 6, wherein the water-repellent composition is at least one hydrolyzable group selected from the group consisting of a siloxane group and a ketoxime group.
[8] 請求項 1〜7の ヽずれかに記載の撥水性組成物を基板上に塗布して形成されてな る撥水性薄膜。 [8] A water-repellent thin film formed by applying the water-repellent composition according to any one of claims 1 to 7 on a substrate.
[9] 請求項 8に記載の撥水性薄膜に、パターンを有するフォトマスクを介して波長 200η m以上の光を照射し、次 ヽで該薄膜の表面を洗浄して形成されてなる撥水性親水性 ノターンを有する薄膜。  [9] The water-repellent hydrophilic film formed by irradiating the water-repellent thin film according to claim 8 with light having a wavelength of 200 ηm or more through a photomask having a pattern, and then cleaning the surface of the thin film. A thin film with a no-turn.
[10] 波長 200nm以上の光を照射前の撥水性薄膜の水との接触角が 95度以上であり、 波長 200nm以上の光を照射後の該薄膜の水との接触角が 70度以下である、請求 項 8に記載の撥水性薄膜または請求項 9に記載の撥水性親水性パターンを有する 薄膜。  [10] When the contact angle with water of the water-repellent thin film before irradiation with light having a wavelength of 200 nm or more is 95 degrees or more, and the contact angle with water of the thin film after irradiation with light having a wavelength of 200 nm or more is 70 degrees or less. A water-repellent thin film according to claim 8, or a thin film having a water-repellent hydrophilic pattern according to claim 9.
PCT/JP2005/009479 2004-06-04 2005-05-24 Water-repellent composition, water-repellent thin film, and thin film with water-repellent/hydrophilic pattern WO2005119367A1 (en)

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