JP2005345897A - Water-repellent composition, water-repellent thin film and thin film having water-repellent hydrophilic pattern - Google Patents

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

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JP2005345897A
JP2005345897A JP2004167292A JP2004167292A JP2005345897A JP 2005345897 A JP2005345897 A JP 2005345897A JP 2004167292 A JP2004167292 A JP 2004167292A JP 2004167292 A JP2004167292 A JP 2004167292A JP 2005345897 A JP2005345897 A JP 2005345897A
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water
repellent
thin film
compound
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Yutaka Furukawa
豊 古川
Takashi Okazoe
隆 岡添
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AGC Inc
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Asahi Glass Co Ltd
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Priority to PCT/JP2005/009479 priority 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

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

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-repellent composition with which a thin film having a water-repellent hydrophilic pattern can be easily formed by using light having relatively low energy. <P>SOLUTION: The water-repellent composition contains: a water-repellent compound (A) which is decomposed by an acid to decrease water repellency such as R<SP>f2</SP>OCOR<SP>3</SP>Si(R<SP>4</SP>)<SB>3-m</SB>X<SP>2</SP><SB>m</SB>, wherein R<SP>f2</SP>represents a monovalent polyfluoro alkyl group, R<SP>3</SP>represents an alkylene group, R<SP>4</SP>represents a methyl group, X represents a hydrolyzable group, and m represents an integer 1 to 3; and a compound (B) which is decomposed by light at ≥200 nm wavelength to generate an acid. A thin film formed by using the above composition has a water-repellent hydrophilic pattern formed by irradiation with light. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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.

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ニ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）の工程からなる。   Currently, as a method of manufacturing a fine device such as a semiconductor element, an integrated circuit, or an organic EL display device, a thin film of a functional material is formed on a substrate by vacuum deposition, sputtering, or the like, and the thin film is patterned by photolithography. Is used. Photolithography generally includes the following steps (1) to (3).

（１）パターニ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い、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ーは工程が複雑で、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く、設備が高価となる問題があった。   (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 has a complicated process and needs to be performed in a clean room, there is a problem that utilization efficiency of energy, material, etc. is low and equipment is expensive.

最近、基板上に、表面特性の異なるパターンを形成し、その表面特性の違い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２００ｎｍ未満の高エネルギー線が用いられるため、例えば酸化ケイ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。）。   Recently, a method has been proposed in which a pattern having different surface characteristics is formed on a substrate, and a micro device is manufactured using the difference in the surface characteristics. For example, a patterning method using ultraviolet rays is preferable in terms of manufacturing because a large-area substrate can be processed at once using a photomask. However, high energy rays of less than 200 nm have been mainly used as ultraviolet rays so far, for example, in the case of a silicon wafer substrate provided with a silicon oxide film, there has been a problem that the Si—O bond of the substrate is decomposed (patent) Reference 1 and Patent Reference 2).

特開平１１−３４４８０４号公報JP-A-11-344804 特開２０００−２８２２４０号公報JP 2000-282240 A

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、２００ｎｍ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ニングを形成できる撥水性組成物を提供することにある。   An object of the present invention is to eliminate the above-mentioned drawbacks of the prior art, and to provide a water-repellent composition capable of forming a water-repellent hydrophilic pattern on a substrate by irradiating with light of 200 nm or more. is there.

本発明は、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を提供する。
また本発明は、上記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を提供する。
また本発明は、上記撥水性薄膜に、パターンを有するフォトマスクを介して２００ｎｍ以上の光を照射し、次い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を提供する。 The present invention provides a water-repellent composition comprising Compound B that decomposes by irradiation with light of 200 nm or more and generates an acid, and Water-repellent compound A that decomposes by the acid generated from the compound and decreases water repellency.
Moreover, this invention provides the water-repellent thin film formed by apply | coating the said water-repellent composition on a board | substrate.
The present invention also provides a thin film having a water-repellent hydrophilic pattern formed by irradiating the water-repellent thin film with light of 200 nm or more through a photomask having a pattern, and then cleaning the surface of the thin film. To do.

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ー法に比較して、安価な装置を用い、少ない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。   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 relatively low energy of 200 nm or more, the water repellency on the surface of the thin film is lowered. By using this characteristic and irradiating light through a photomask having a pattern, a thin film having a water repellent hydrophilic pattern can be easily formed on the 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 with fewer steps by using an inexpensive apparatus as compared with the photolithography method.

本発明における撥水性化合物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、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、シリルエーテル基、シリルアミノ基等が好ましい。   The water repellent compound A in the present invention is decomposed by an acid and the water repellency is lowered. As the water repellent compound A, a compound having a fluorine-containing organic group, having a linking group capable of decomposing with an acid and releasing the fluorine-containing organic group is preferable. As the linking group, an ester group, a silyl ether group, a silylamino group and the like are preferable.

撥水性化合物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から選ばれる少なくとも１種の化合物および／または部分加水分解物であることが好ましい。
Ｒｆ１ＣＯＯＲ１Ｓｉ（Ｒ２）３−ｎＸ１ ｎ・・・式１
Ｒｆ２ＯＣＯＲ３Ｓｉ（Ｒ４）３−ｍＸ２ ｍ・・・式２
Ｒｆ３ＯＳｉ（Ｒ５）３−ｐＸ３ ｐ・・・式３
Ｒｆ４（Ｒ６）２ＳｉＯＲ７Ｓｉ（Ｒ８）３−ｑＸ４ ｑ・・・式４
ただし、式１〜４における記号は以下の意味を示す。
Ｒｆ１、Ｒｆ２、Ｒｆ３、Ｒｆ４：それぞれ独立して、１価含フッ素有機基。
Ｒ１、Ｒ３、Ｒ７：それぞれ独立して、２価有機基。
Ｒ２、Ｒ４、Ｒ５、Ｒ６、Ｒ８：それぞれ独立して、１価有機基。
Ｘ１、Ｘ２、Ｘ３、Ｘ４：それぞれ独立して、加水分解性基。
ｎ、ｍ、ｐ、ｑ：それぞれ独立して、１〜３の整数。 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 / or a partial hydrolyzate.
R f1 COOR 1 Si (R 2 ) 3-n X 1 n Formula 1
R f2 OCOR 3 Si (R 4 ) 3-m X 2 m ... Formula 2
R f3 OSi (R 5 ) 3-p X 3 p Formula 3
R f4 (R 6 ) 2 SiOR 7 Si (R 8 ) 3-q X 4 q Formula 4
However, the symbols in Formulas 1 to 4 have the following meanings.
R f1 , R f2 , R f3 , R f4 : each independently a monovalent fluorine-containing organic group.
R 1 , R 3 , R 7 : each independently a divalent organic group.
R 2 , R 4 , R 5 , R 6 , R 8 : each independently 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.

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。）において、Ｒｆ１としてはペルフルオ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オロアルキル基が好ましい。ペルフルオロアルキル基の炭素原子数としては１〜１６が好ましく、３〜１２がより好ましく、３〜８が最も好ましい。ペルフルオ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い。 In the compound represented by Formula 1 (hereinafter also referred to as Compound 1; the same applies to Formulas 2 to 4), R f1 is preferably a perfluoroalkyl group or a perfluoroalkyl group having an etheric oxygen atom. As a carbon atom number of a perfluoroalkyl group, 1-16 are preferable, 3-12 are more preferable, and 3-8 are the most preferable. The perfluoroalkyl group includes a linear structure, a branched structure, or a cyclic structure, and a linear structure is preferable. In the case of a branched structure, it is preferable that the branched portion is present at the terminal and the branched portion is a short chain having about 1 to 4 carbon atoms.

Ｒ１としては炭素原子数１〜１０のアルキレン基が好ましく、炭素原子数２〜５のアルキレン基がより好ましく、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、アセトキシ基、ケトオキシム基が好ましく、ハロゲン原子、アルコキシ基がより好ましく、Ｃｌ−、ＣＨ３Ｏ−、Ｃ２Ｈ５Ｏ−が最も好ましい。ｎは２〜３が好ましく、３がより好ましい。ｎが３であると撥水性組成物が基材への密着性に優れる。 R 1 is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 to 5 carbon atoms, and most preferably an alkylene group having 3 to 4 carbon atoms. 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 acetoxy group, or a ketoxime group, more preferably a halogen atom or an alkoxy group, and most preferably Cl—, CH 3 O—, or C 2 H 5 O—. n is preferably 2 to 3, and more preferably 3. When n is 3, the water repellent composition is excellent in adhesion to the substrate.

化合物１としては、以下の化合物等が挙げられる。
Ｆ（ＣＦ２）８ＣＯＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）８ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）７ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）６ＣＯＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）６ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３。
Ｆ（ＣＦ２）４ＣＯＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）４ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）３ＯＣＦ（ＣＦ３）ＣＯＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）３ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＯＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３。 Examples of compound 1 include the following compounds.
F (CF 2 ) 8 COO (CH 2 ) 4 Si (OCH 3 ) 3 , F (CF 2 ) 8 COO (CH 2 ) 3 Si (OCH 3 ) 3 , F (CF 2 ) 7 COO (CH 2 ) 3 Si (OCH 3 ) 3 , F (CF 2 ) 6 COO (CH 2 ) 4 Si (OCH 3 ) 3 , F (CF 2 ) 6 COO (CH 2 ) 3 Si (OCH 3 ) 3 .
F (CF 2 ) 4 COO (CH 2 ) 4 Si (OCH 3 ) 3 , F (CF 2 ) 4 COO (CH 2 ) 3 Si (OCH 3 ) 3 , F (CF 2 ) 3 OCF (CF 3 ) COO (CH 2) 4 Si (OCH 3) 3, F (CF 2) 3 OCF (CF 3) CF 2 OCF (CF 3) COO (CH 2) 4 Si (OCH 3) 3.

化合物１としては、Ｆ（ＣＦ２）８ＣＯＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３が好ましい。 As the compound 1, F (CF 2 ) 8 COO (CH 2 ) 4 Si (OCH 3 ) 3 is preferable.

化合物２、化合物３、化合物４において、Ｒｆ２、Ｒｆ３、Ｒｆ４は上記Ｒｆ１と同様の基が好ましく、Ｒ３、Ｒ７は前記Ｒ１と同様の基が好ましく、Ｒ４、Ｒ５、Ｒ６、Ｒ８は前記Ｒ２と同様の基が好ましく、Ｘ２、Ｘ３、Ｘ４は前記Ｘ１と同様の基が好ましく、ｍ、ｐ、ｑは前記ｎと同様の整数が好ましい。 In Compound 2, Compound 3, and Compound 4, R f2 , R f3 , and R f4 are preferably the same groups as R f1 above, and R 3 and R 7 are preferably the same groups as R 1 , 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, and m, p and q are preferably the same integers as n. .

化合物２としては、以下の化合物等が挙げられる。
Ｆ（ＣＦ２）８ＣＨ２ＣＨ２ＯＣＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）８ＣＨ２ＣＨ２ＯＣＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）８ＣＨ２ＯＣＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）７ＣＨ２ＯＣＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）６ＣＨ２ＣＨ２ＯＣＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）６ＣＨ２ＣＨ２ＯＣＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）４ＣＨ２ＣＨ２ＯＣＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）４ＣＨ２ＣＨ２ＯＣＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）３ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＨ２ＣＨ２ＯＣＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３。 Examples of the compound 2 include the following compounds.
F (CF 2 ) 8 CH 2 CH 2 OCO (CH 2 ) 4 Si (OCH 3 ) 3 , F (CF 2 ) 8 CH 2 CH 2 OCO (CH 2 ) 3 Si (OCH 3 ) 3 , F (CF 2 ) 8 CH 2 OCO (CH 2 ) 4 Si (OCH 3 ) 3 , F (CF 2 ) 7 CH 2 OCO (CH 2 ) 4 Si (OCH 3 ) 3 , F (CF 2 ) 6 CH 2 CH 2 OCO ( CH 2) 4 Si (OCH 3 ) 3, F (CF 2) 6 CH 2 CH 2 OCO (CH 2) 3 Si (OCH 3) 3, F (CF 2) 4 CH 2 CH 2 OCO (CH 2) 4 Si (OCH 3 ) 3 , F (CF 2 ) 4 CH 2 CH 2 OCO (CH 2 ) 3 Si (OCH 3 ) 3 , F (CF 2 ) 3 OCF (CF 3 ) CF 2 OCF 2 CF 2 CH 2 CH 2 OCO (C 2) 4 Si (OCH 3) 3.

化合物２としては、Ｆ（ＣＦ２）８ＣＨ２ＣＨ２ＯＣＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３が好ましい。 As the compound 2, F (CF 2 ) 8 CH 2 CH 2 OCO (CH 2 ) 4 Si (OCH 3 ) 3 is preferable.

化合物３としては以下の化合物等が挙げられる。
Ｆ（ＣＦ２）８ＣＨ２ＣＨ２ＯＳｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）７ＣＨ２ＯＳｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）６ＣＨ２ＣＨ２ＯＳｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）４ＣＨ２ＣＨ２ＯＳｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）３ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＨ２ＣＨ２ＯＳｉ（ＯＣＨ３）３。 Examples of the compound 3 include the following compounds.
F (CF 2) 8 CH 2 CH 2 OSi (OCH 3) 3, F (CF 2) 7 CH 2 OSi (OCH 3) 3, F (CF 2) 6 CH 2 CH 2 OSi (OCH 3) 3, F (CF 2) 4 CH 2 CH 2 OSi (OCH 3) 3, F (CF 2) 3 OCF (CF 3) CF 2 OCF 2 CF 2 CH 2 CH 2 OSi (OCH 3) 3.

化合物３としては、Ｃ８Ｆ１７ＣＨ２ＣＨ２ＯＳｉ（ＯＣＨ３）３が好ましい。 As the compound 3, C 8 F 17 CH 2 CH 2 OSi (OCH 3 ) 3 is preferable.

化合物４としては、以下の化合物が好ましく挙げられる。
Ｆ（ＣＦ２）８ＣＨ２ＣＨ２（ＣＨ３）２ＳｉＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）８ＣＨ２ＣＨ２ＣＨ２（ＣＨ３）２ＳｉＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）６ＣＨ２ＣＨ２（ＣＨ３）２ＳｉＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）６ＣＨ２ＣＨ２（ＣＨ３）２ＳｉＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）４ＣＨ２ＣＨ２（ＣＨ３）２ＳｉＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）４ＣＨ２ＣＨ２（ＣＨ３）２ＳｉＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）８ＣＨ２ＣＨ２（ＣＨ３）２ＳｉＯＣＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）８ＣＨ２ＣＨ２（ＣＨ３）２ＳｉＯＣＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、Ｆ（ＣＦ２）８ＣＨ２ＣＨ２（ＣＨ３）２ＳｉＯＮＨ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３。 As the compound 4, the following compounds are preferably exemplified.
F (CF 2) 8 CH 2 CH 2 (CH 3) 2 SiO (CH 2) 4 Si (OCH 3) 3, F (CF 2) 8 CH 2 CH 2 CH 2 (CH 3) 2 SiO (CH 2) 3 Si (OCH 3 ) 3 , F (CF 2 ) 6 CH 2 CH 2 (CH 3 ) 2 SiO (CH 2 ) 4 Si (OCH 3 ) 3 , F (CF 2 ) 6 CH 2 CH 2 (CH 3 ) 2 SiO (CH 2 ) 3 Si (OCH 3 ) 3 , F (CF 2 ) 4 CH 2 CH 2 (CH 3 ) 2 SiO (CH 2 ) 4 Si (OCH 3 ) 3 , F (CF 2 ) 4 CH 2 CH 2 (CH 3) 2 SiO (CH 2) 3 Si (OCH 3) 3, F (CF 2) 8 CH 2 CH 2 (CH 3) 2 SiOCO (CH 2) 4 Si (OCH 3) 3, F ( CF 2) 8 CH 2 CH (CH 3) 2 SiOCO (CH 2) 3 Si (OCH 3) 3, F (CF 2) 8 CH 2 CH 2 (CH 3) 2 SiONH (CH 2) 3 Si (OCH 3) 3.

化合物４としては、Ｆ（ＣＦ２）８ＣＨ２ＣＨ２（ＣＨ３）２ＳｉＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３が好ましい。 As the compound 4, F (CF 2 ) 8 CH 2 CH 2 (CH 3 ) 2 SiO (CH 2 ) 4 Si (OCH 3 ) 3 is preferable.

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（λｍａｘ）が２００ｎｍ以上のものが好ましく、２５０ｎｍ以上のものがより好ましく、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いて撥水性親水性パターンを有する薄膜を形成できる。 As compound B which decomposes | disassembles by light irradiation and generate | occur | produces an acid, that whose maximum absorption wavelength ((lambda) max ) is 200 nm or more is preferable, its 250 nm or more is more preferable, and its 300 nm or more is the most preferable. When the maximum absorption wavelength is within this range, a thin film having a water-repellent hydrophilic pattern can be formed using a simple device such as a high-pressure mercury lamp.

化合物Ｂとしては、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。   The compound B can be used without any particular limitation as long as it is a compound that generates an acid by being decomposed by light of 200 nm or more, that is, a photo acid generator (abbreviated as PAG for short). Specific examples of compound B include the following compounds.

Figure 2005345897
Figure 2005345897

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く、塩酸が好ましい。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−ＣＣｌ３から塩素ラジカルが発生し、化合物Ｂ中の水素原子を引き抜いて塩酸が発生すると考えられる。 The acid generated may be any acid that can decompose the water repellent compound A, and hydrochloric acid is preferred. The mechanism by which hydrochloric acid is generated is not necessarily clear, but it is considered that a chlorine radical is generated from -CCl 3 in compound B, and a hydrogen atom in compound B is withdrawn to generate hydrochloric acid.

撥水性組成物における撥水性化合物Ａと化合物Ｂの質量比は、９５／５〜９９．９９／０．０１が好ましく、９９／１〜９９．９／０．１がより好ましく、９９．８／０．２〜９９．５／０．５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。   The mass ratio of the water repellent compound A and the compound B in the water repellent composition is preferably 95/5 to 99.99 / 0.01, more preferably 99/1 to 99.9 / 0.1, and 99.8 / 0.2-99.5 / 0.5 is most preferred. Within this range, the water repellency of the surface of the water-repellent thin film is efficiently lowered by light irradiation.

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度以上が好ましく、１００度以上がより好ましい。前記薄膜は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く、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度以上が好ましく、５０度以上がより好ましく、７０度以上が最も好ましい。   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, and more preferably 100 degrees or more. The thin film preferably has a contact angle with water of 70 degrees or less after irradiation with light of 200 nm or more, more preferably 50 degrees or less, and most preferably 30 degrees or less. The difference in the contact angle of the thin film before and after irradiation with water is preferably 30 degrees or more, more preferably 50 degrees or more, and most preferably 70 degrees or more.

本発明の撥水性組成物は、有機溶剤を含むことが好ましい。
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く、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種を用いてもよく、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 water repellent composition of the present invention preferably contains an organic solvent.
The organic solvent is not particularly limited, and alcohols, ketones, aromatic hydrocarbons, and paraffinic hydrocarbons are preferable, and lower alcohols such as ethyl alcohol and 2-propyl alcohol or paraffinic hydrocarbons are more preferable. preferable. One organic solvent may be used, or two or more organic solvents may be mixed and used to adjust solubility and evaporation rate.

撥水性組成物において、撥水性化合物Ａと有機溶剤の質量比は１／１０００〜１／１０が好ましく、１／２００〜１／２０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。   In the water repellent composition, the mass ratio of the water repellent compound A and the organic solvent is preferably 1/1000 to 1/10, and more preferably 1/200 to 1/20. Within this range, a uniform thin film is formed and the water repellency is excellent.

本発明の撥水性薄膜の厚さは、特に限定されないが、０．５〜１００ｎｍが好ましく、１〜２０ｎｍがより好ましく、１〜５ｎｍ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。   The thickness of the water-repellent thin film of the present invention is not particularly limited, but is preferably 0.5 to 100 nm, more preferably 1 to 20 nm, and most preferably 1 to 5 nm. The thickness of the water repellent thin film is most preferably the thickness of a self-assembled film (also referred to as SMA). When in this range, a good water-repellent hydrophilic pattern can be obtained.

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く、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℃が好ましく、１０〜４０℃がより好ましい。時間としては、１〜６０分間が好ましく、５〜３０分間がより好ましい。   Examples of the method 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 and then dried in the air, in a nitrogen stream or the like. The drying is preferably performed at room temperature. When drying by heating, the heating temperature and time are set in consideration of the heat resistance of the substrate. As temperature, 0-80 degreeC is preferable and 10-40 degreeC is more preferable. As time, 1 to 60 minutes are preferable and 5 to 30 minutes are more preferable.

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 surface of the thin film.

照射する光の波長は２００〜８００ｎｍが好ましく、２５０〜６００ｎｍがより好ましく、３００〜４００ｎｍが最も好ましい。
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ー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しい。 The wavelength of the irradiated light is preferably 200 to 800 nm, more preferably 250 to 600 nm, and most preferably 300 to 400 nm.
The irradiation light is more preferably ultraviolet light. When the wavelength is within this range, the material constituting the substrate itself is not decomposed. Light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, xenon lamps, sodium lamps, nitrogen and other gas lasers, liquid lasers of organic dye solutions, and solid-state lasers containing rare earth ions in inorganic single crystals Etc. Further, as a light source other than the laser from which monochromatic light is obtained, light having a specific wavelength obtained by extracting a broadband line spectrum or continuous spectrum using an optical filter such as a bandpass filter or a cutoff filter may be used. Since a large area can be irradiated at a time, a high pressure mercury lamp or an ultrahigh pressure mercury lamp is preferable as the light source.

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、フォトマスクを介して光を照射する方法が好ましい。   Examples of the irradiation method include a method of irradiating light through a photomask having a predetermined pattern, a method using laser light, and the like. Since a large area can be irradiated at once, a method of irradiating light through a photomask is preferable.

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オロプロパン（以下、Ｒ−２２５と記す。）、ペルフルオロヘキサン等のペルフルオロカーボン類、（ペルフルオロブトキシ）メタン等のハイドロフルオロエーテル、デカフルオロペンタン等のハイドロフルオロカーボン等が挙げられる。   For cleaning the surface of the thin film after irradiation with light, it is preferable to use a solvent that dissolves the fluorine-containing organic group. Examples of the solvent include dichloropentafluoropropane (hereinafter referred to as R-225), perfluorocarbons such as perfluorohexane, hydrofluoroethers such as (perfluorobutoxy) methane, hydrofluorocarbons such as decafluoropentane, and the like.

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、光が照射されなかっ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。   In the water-repellent thin film of the present invention, the water-repellent portion of the water-irradiated portion decreases in water repellency, and the portion that is not irradiated with light maintains water-repellent property. The 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 then irradiating it once with light.

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 a 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 and releases a fluorine-containing organic group to form a hydroxyl group, a carboxyl group, a silanol group, an amino group, and the like, resulting in a decrease in water repellency. It is considered a thing.

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、プラスチック、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。   The substrate used in the present invention is not particularly limited, and preferred examples include glass, quartz glass, silicon wafer, plastic, and metal. Moreover, you may use the board | substrate with which the metal thin film was formed on these board | substrates.

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、酸化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。   EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these. In the examples, as 225, trade name AK-225 manufactured by Asahi Glass Co., Ltd. was used. Further, as the glass substrate, a 10 cm square 2 mm thick soda lime glass substrate was used, which was polished and washed with an abrasive containing cerium oxide fine particles, rinsed with pure water and air-dried. The contact angle with respect to water was determined as an average value of three contact angles measured by placing three droplets on the substrate using a sessile drop method.

［例１］
３００ｍＬのガラス製容器に、Ｆ（ＣＦ２）８ＣＯＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３の１質量部、２−プロパノールの１００質量部および０．１モル／Ｌ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（ＣＦ２）８ＣＯＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３に対して５モル％となる量の２−［２−（フラン−２−イル）ビニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン（以下、化合物ｂと記す。）を添加して撥水性組成物１を得た。 [Example 1]
In a 300 mL glass container, 1 part by mass of F (CF 2 ) 8 COO (CH 2 ) 4 Si (OCH 3 ) 3 , 100 parts by mass of 2-propanol, and 0.1 mol / L of hydrochloric acid at a concentration of 0.1 mol / L. 5 parts by mass was added, and a hydrolysis reaction was performed at room temperature for 12 hours to obtain a hydrolyzate 1. In the obtained hydrolyzate 1, 2- [2- (furan-2-yl) in an amount of 5 mol% with respect to the raw material F (CF 2 ) 8 COO (CH 2 ) 4 Si (OCH 3 ) 3 ) Vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine (hereinafter referred to as compound b) was added to obtain a water-repellent composition 1.

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であった。   2 mL of the obtained water-repellent composition 1 was dropped onto a glass substrate, spin-coated at 3000 rpm for 20 seconds, and then air-dried to prepare Sample 1-1. The formed thin film had a thickness of 3 nm.

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２００ｍＪ／ｃｍ２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。 The contact angle with respect to water of the obtained sample 1-1 was 105 degrees, and the contact angle with respect to water of the untreated glass substrate was 10 degrees or less. Sample 1-2 was produced by irradiating with ultraviolet rays using a high-pressure mercury lamp, washing with R-225, and air drying. When the irradiation amount was 200 mJ / cm 2, the contact angle of Sample 1-2 with water was 61 degrees.

［例２］
３００ｍＬのガラス製容器に、Ｆ（ＣＦ２）８Ｃ２Ｈ４ＯＣＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３の１質量部、２−プロパノールの１００質量部および０．１モル／Ｌ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２を得た。得られた加水分解物２に、原料のＦ（ＣＦ２）８Ｃ２Ｈ４ＯＣＯＣＨ２ＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）３に対して５モル％となる量の化合物ｂを添加して撥水性組成物２を得た。 [Example 2]
In a 300 mL glass container, 1 part by mass of F (CF 2 ) 8 C 2 H 4 OCO (CH 2 ) 4 Si (OCH 3 ) 3 , 100 parts by mass of 2-propanol and 0.1 mol / L hydrochloric acid Of 0.5 part by mass, and subjected to a hydrolysis reaction at room temperature for 12 hours to obtain a hydrolyzate 2. Compound b in an amount of 5 mol% with respect to the raw material F (CF 2 ) 8 C 2 H 4 OCOCH 2 CH 2 CH 2 CH 2 Si (OCH 3 ) 3 was added to the resulting hydrolyzate 2. Thus, a water repellent composition 2 was obtained.

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であった。   2 mL of the obtained water repellent composition 2 was dropped on a glass substrate, spin-coated at 3000 rpm for 20 seconds, and then air-dried to prepare Sample 2-1. The formed thin film had a thickness of 3 nm.

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。照射量が２００ｍＪ／ｃｍ２の場合の水に対する接触角は４２度であった。 The contact angle of the obtained sample 2-1 with respect to water was 104 degrees. Sample 2-2 was prepared by irradiating with ultraviolet rays using a high-pressure mercury lamp, washing with R-225, and air drying. When the irradiation amount was 200 mJ / cm 2 , the contact angle with water was 42 degrees.

［例３］
３００ｍＬのガラス製容器に、Ｆ（ＣＦ２）８Ｃ２Ｈ４ＯＳｉ（ＯＣＨ３）３の１質量部、２−プロパノールの１００質量部および０．１モル／Ｌ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（ＣＦ２）８Ｃ２Ｈ４ＯＳｉ（ＯＣＨ３）３に対して５モル％となる量の化合物ｂを添加して撥水性組成物３を得た。 [Example 3]
In a 300 mL glass container, 1 part by mass of F (CF 2 ) 8 C 2 H 4 OSi (OCH 3 ) 3 , 100 parts by mass of 2-propanol and 0.5 parts by mass of 0.1 mol / L hydrochloric acid And a hydrolysis reaction was performed at room temperature for 12 hours to obtain a hydrolyzate 3. Obtained resulting hydrolyzate 3, raw material F the (CF 2) 8 C 2 H 4 OSi (OCH 3) 3 was added compound b amount corresponding to 5 mol% with respect to the water repellent composition 3 It was.

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であった。   2 mL of the obtained water repellent composition 3 was dropped onto a glass substrate, spin-coated at 3000 rpm for 20 seconds, and then air-dried to prepare Sample 3-1. The thickness of the formed thin film was 2 nm.

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。照射量が２００ｍＪ／ｃｍ２の場合の水に対する接触角は２２度であった。 The contact angle of the obtained sample 3-1 with respect to water was 106 degrees. Sample 3-2 was produced by irradiating with ultraviolet rays using a high-pressure mercury lamp, washing with R-225, and air drying. The contact angle with respect to water when the irradiation amount was 200 mJ / cm 2 was 22 degrees.

［例４］
３００ｍＬのガラス製容器に、Ｆ（ＣＦ２）８ＣＨ２ＣＨ２（ＣＨ３）２ＳｉＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３の１質量部、２−プロパノールの１００質量部および０．１モル／Ｌ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（ＣＦ２）８ＣＨ２ＣＨ２（ＣＨ３）２ＳｉＯ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３に対して５モル％となる量の化合物ｂを添加して撥水性組成物４を得た。 [Example 4]
In a 300 mL glass container, 1 part by mass of F (CF 2 ) 8 CH 2 CH 2 (CH 3 ) 2 SiO (CH 2 ) 4 Si (OCH 3 ) 3 , 100 parts by mass of 2-propanol and 0.1 0.5 parts by mass of mol / L hydrochloric acid was added, and a hydrolysis reaction was performed at room temperature for 12 hours to obtain a hydrolyzate 4. The obtained hydrolyzate 4 was added to the raw material F (CF 2 ) 8 CH 2 CH 2 (CH 3 ) 2 SiO (CH 2 ) 4 Si (OCH 3 ) 3 in an amount of 5 mol% of compound b. Was added to obtain a water-repellent composition 4.

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であった。   2 mL of the obtained water-repellent composition 4 was dropped onto a glass substrate, spin-coated at 3000 rpm for 20 seconds, and then air-dried to prepare Sample 4-1. The formed thin film had a thickness of 3 nm.

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。照射量が７５０ｍＪ／ｃｍ２の場合の水に対する接触角は６０度であった。 The contact angle of the obtained Sample 4-1 with respect to water was 105 degrees. Sample 4-2 was prepared by irradiating with ultraviolet rays using a high-pressure mercury lamp, washing with R-225, and air drying. The contact angle with water when the irradiation amount was 750 mJ / cm 2 was 60 degrees.

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 the 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 ink jet printing, a clear pattern of the functional material is 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 (4)

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。   A water-repellent composition comprising Compound B that decomposes by irradiation with light of 200 nm or more and generates an acid, and Water-repellent compound A that decomposes by the acid generated from the compound and decreases water repellency. 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からなる群から選ばれる少なくとも１種の化合物および／またはその部分加水分解物である、請求項１に記載の撥水性組成物。
Ｒｆ１ＣＯＯＲ１Ｓｉ（Ｒ２）３−ｎＸ１ ｎ・・・式１
Ｒｆ２ＯＣＯＲ３Ｓｉ（Ｒ４）３−ｍＸ２ ｍ・・・式２
Ｒｆ３ＯＳｉ（Ｒ５）３−ｐＸ３ ｐ・・・式３
Ｒｆ４（Ｒ６）２ＳｉＯＲ７Ｓｉ（Ｒ８）３−ｑＸ４ ｑ・・・式４
ただし、式１〜４における記号は以下の意味を示す。
Ｒｆ１、Ｒｆ２、Ｒｆ３、Ｒｆ４：それぞれ独立して、１価含フッ素有機基。
Ｒ１、Ｒ３、Ｒ７：それぞれ独立して、２価有機基。
Ｒ２、Ｒ４、Ｒ５、Ｒ６、Ｒ８：それぞれ独立して、１価有機基。
Ｘ１、Ｘ２、Ｘ３、Ｘ４：それぞれ独立して、加水分解性基。
ｎ、ｍ、ｐ、ｑ：それぞれ独立して、１〜３の整数。 The water-repellent composition according to claim 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 / or a partial hydrolyzate thereof. Stuff.
R f1 COOR 1 Si (R 2 ) 3-n X 1 n Formula 1
R f2 OCOR 3 Si (R 4 ) 3-m X 2 m ... Formula 2
R f3 OSi (R 5 ) 3-p X 3 p Formula 3
R f4 (R 6 ) 2 SiOR 7 Si (R 8 ) 3-q X 4 q Formula 4
However, the symbols in Formulas 1 to 4 have the following meanings.
R f1 , R f2 , R f3 , R f4 : each independently a monovalent fluorine-containing organic group.
R 1 , R 3 , R 7 : each independently a divalent organic group.
R 2 , R 4 , R 5 , R 6 , R 8 : each independently 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. 請求項１または２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。   A water repellent thin film formed by applying the water repellent composition according to claim 1 or 2 onto a substrate. 請求項３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２００ｎｍ以上の光を照射し、次い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。
A thin film having a water-repellent hydrophilic pattern formed by irradiating the water-repellent thin film according to claim 3 with light of 200 nm or more through a photomask having a pattern and then cleaning the surface of the thin film.
JP2004167292A 2004-06-04 2004-06-04 Water-repellent composition, water-repellent thin film and thin film having water-repellent hydrophilic pattern Pending JP2005345897A (en)

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