TW200835757A

TW200835757A - Coating solution for formation of low refractive coating film, process for production thereof, and anti-reflection material

Info

Publication number: TW200835757A
Application number: TW096138271A
Authority: TW
Inventors: Yoshihiro Tani; Kenichi Motoyama
Original assignee: Nissan Chemical Ind Ltd
Priority date: 2006-10-12
Filing date: 2007-10-12
Publication date: 2008-09-01
Also published as: CN101522839A; KR20090064415A; CN101522839B; WO2008044742A1; KR101457234B1; JPWO2008044742A1; TWI437057B; JP5458575B2

Abstract

Disclosed is a coating solution for the coating film formation, which can be cured at a low temperature even on a substrate having a high water contact angle and enables to form a coating film having high light permeability, high hardness, excellent scratch resistance and a low refractivity. Also disclosed is a process for producing the coating solution. Further disclosed is an anti-reflection material prepared by using the coating film. Specifically disclosed is a coating solution for forming a low refractive coating film, which comprises (A) a polysiloxane having a silicon atom to which a fluorinated organic group is attached, (B) a long-chain amine compound having 9 to 20 carbon atoms, and c an organic solvent in which the polysiloxane (A) and the long-chain amine compound (B) are dissolved.

Description

200835757 九、發明說明【發明所屬之技術領域】本發明有關含有聚矽氧烷之低折射率被膜形成用塗佈液、其製造方法，從該塗佈液所形成之低折射率被膜、以及具有該被膜之防反射材料。【先前技術】在來周知，如於基材表面形成具有較該基材之折射率爲小的低折射率之被膜時，則從該被膜表面反射之光的反射率會降低之事實。並且顯示如此降低之光反射率之低折射率被膜，係被作爲防止光反射之膜所利用，而適用於種種基材表面。例如，專利文獻1中，揭示有將使作爲Mg (鎂）源之鎂鹽或烷氧基鎂化合物等，與作爲F (氟）源之氟化物鹽反應所生成之MgF2微粒的醇分散液，或爲提升薄膜強度而對此添加有四烷氧基矽烷之液作爲塗佈液，並將此塗佈於玻璃基材上，在溫度100至500 °C下施加熱處理後，於基材上形成能顯示低折射率之防反射膜之方法。又，專利文獻2中，揭示有將本身爲四烷氧基矽烷等的水解聚縮合物而平均分子量相異之2種以上與醇等的溶劑混合後作成塗佈液，當從該塗佈液形成被膜時實施上述混合時的混合比例，相對濕度的控制等手段以製作被膜之作法。被膜係在250 °C以上的溫度加熱即可製得，其能顯示1.21至1.40的折射率，具有存在50至200nm直徑之微坑 200835757 (micropit)或凹凸，並具有60至16 Onm厚度。被膜係形成於玻璃基板上而由此可製造低折射玻璃。又，專利文獻3中，揭示有由玻璃 '及經於其表面所形成之具有高折射率之下層膜、以及經再於其表面所形成之具有低折射率之上層膜所成之低折射率玻璃。上層膜之形成，係依將使CF3(CF2)2C2H4Si(OCH3)3等具有聚碳氟鏈之含氟聚矽氧化合物、及對此成爲5至90質量％的 Si(OCH3)4等的矽烷偶合劑，在醇溶劑中，於醋酸等觸媒存在之下在室溫進行水解後過濾所調製之共聚合物之液塗佈於上述下層膜上，並在溫度120至25 (TC加熱之方法所實施。又，專利文獻4中，揭示有將依特定比例含有以 Si(OR)4表示之矽化合物、及以CFdCFdnCHzCHzSKOR1、表示之矽化合物、及以R2CH2OH表示之醇、以及草酸之反應混合物在水的不存在下加熱爲溫度40至1 80 °C，藉以生成聚矽氧烷溶液之塗佈液。如將此塗佈液塗佈於基材表面，並在溫度8 0至45 0 °C之下進行熱硬化，則可形成具有 1.28至1.38的折射率及90至115度的對水接觸角（water contact angle)之被膜。專利文獻1:日本專利特開平05-1 05424號公報專利文獻2 :日本專利特開平06- 1 57076號公報專利文獻3:日本專利特開昭6 1 -0 1 0043號公報專利文獻4:日本專利特開平09-208898號公報 200835757 【發明內容】 [發明所欲解決之課題] 如上述之各種顯示裝置等所用之防止反射之膜，係近年來，在液晶或電漿（plasma )等顯示裝置的大型化、輕量化或薄型化之進展當中，爲此等所使用之防止反射之基材，特別是防止反射之薄膜，係爲輕量化或高透明化起見，有將薄膜厚度作成較薄之傾向，以致有因熱所受之損傷增大之問題。因此，更加盼望開發一種能藉由薄膜不受損傷之程度之低溫處理而製得防止反射之基材般之較低溫硬化之熱硬化式的被膜形成用塗佈液。然而，如上述之在來的低折射率被膜的硬化溫度並非足夠低溫者，故盼望再進一步降低硬化溫度。再者，上述各種顯示裝置等中所用之防止反射之薄膜，係於附有硬質覆膜（lard coat)之三乙醯纖維素薄膜或附有硬質覆膜之聚對苯二甲酸乙二醇酯等的薄膜基材表面，使用較該基材之折射率爲低的被膜之形成而製得者。此時，因硬質覆膜的材質、或有無施加親水化處理等的表面處理而形成低折射率被膜之基材薄膜表面的對水接觸角將會具有種種大小，惟在來，於對水接觸角高的基材薄膜上形成耐擦傷性大的高硬度的低折射率被膜之作法，有其困難。因而，本發明之目的在於提供一種即使於對水接觸角高的基材上仍能在較低溫度下充分硬化，而可形成具有高光透射性（高透明性）、高硬度的耐擦傷性優異的低折射 -6 - 200835757 率之被膜之低折射率被膜形成用塗佈液、其製造方法，再者，可從該低折射率被膜形成用塗佈液製得之被膜、以及使用該被膜之防反射材料。 [用以解決課題之手段] 本發明人等，爲達成上述目的而專心硏究之結果發現，由含有具有經結合含氟有機基之矽原子之聚矽氧烷（A )、及碳數9至20的長鏈胺化合物（B )、以及有機溶劑（ C )之塗佈液所得之被膜，即使於90度以上之對水接觸角高的基材上仍能在低溫度下硬化，而具有高光透射性、高硬度的耐擦傷性優異之低折射率之事實。本發明中，爲何從上述塗佈液所形成之被膜具有如上述之優異的特性之機構並不十分明瞭，惟如本發明之塗佈液中所含之聚矽氧烷（A )不具有含氟有機基時，則不能製得具有低折射率之被膜。又，碳數9至20的長鏈胺化合物（B)，係可於較低的溫度硬化，而賦予高硬度的耐擦傷性優異之被膜。但，如胺化合物（B )的碳數少於9時，有可能在90度以上的對水接觸角高的表面之薄膜基材上不能獲得充分的耐擦傷性之情形，又，如碳數在20以上時，有可能在90度以上的對水接觸角高的表面之薄膜基材上不能獲得充分的成膜性之情形，而都會發生不能達成本發明之目的之情形。因而，本發明係具有如下述特徵之要旨者。 (1 ) 一種低折射率被膜形成用塗佈液，其特徵爲： 200835757 由含有具有結合有含氟有機基之矽原子之聚矽氧烷（A) 、及碳數9至20的長鏈胺化合物（B )，而此等化合物經溶解於有機溶劑（C )中所成。 (2 )如上述（1 )所記載之塗佈液，其中聚矽氧烷（ A) ’係對其全矽原子，具有結合有含氟有機基之矽原子 5至40莫耳％者。 (3 )如上述（1 )或（2 )所記載之塗佈液，其中長鏈胺化合物（B )，係直鏈狀的脂肪族一級胺或二級胺、或者具有脂環構造之脂肪族胺。 (4 )如上述（1 )至（3 )之任一項所記載之塗佈液 ’其中有機溶劑（C )，係由選自碳數1至6的醇及碳數3至 1 〇的乙二醇型醚所成群之至少1種所成者。 (5 )如上述（1 )至（4 )之任一項所記載之塗佈液，其中聚矽氧烷（A )，如將其所有之矽原子的合計量換算爲二氧化矽時，含有0.1至1 5質量％，而長鏈胺化合物 (B )，則對聚矽氧烷（A )的矽原子的合計量之1莫耳，含有0.01至0.2莫耳。 (6 )如上述（1 )至（5 )之任一項所記載之塗佈液，其中再含有以式（1 )表示之矽化合物（D )。 [化1] R10[Technical Field] The present invention relates to a coating liquid for forming a low refractive index film containing polysiloxane, a method for producing the same, a low refractive index film formed from the coating liquid, and the like The antireflection material of the film. [Prior Art] It is known that when a film having a low refractive index smaller than the refractive index of the substrate is formed on the surface of the substrate, the reflectance of light reflected from the surface of the film is lowered. Further, the low refractive index film which exhibits such reduced light reflectance is used as a film for preventing light reflection, and is suitable for use on various substrate surfaces. For example, Patent Document 1 discloses an alcohol dispersion liquid of MgF 2 fine particles produced by reacting a magnesium salt or an alkoxy magnesium compound as a source of Mg (magnesium) with a fluoride salt as a source of F (fluorine). Or a solution of tetraalkoxy decane added as a coating liquid for improving the strength of the film, and this is applied onto a glass substrate, and after heat treatment at a temperature of 100 to 500 ° C, it is formed on the substrate. A method of displaying an antireflection film having a low refractive index. Further, Patent Document 2 discloses that a hydrolyzed polycondensate such as tetraalkoxy decane is used, and two or more kinds of average molecular weights are mixed with a solvent such as an alcohol to prepare a coating liquid, and the coating liquid is obtained from the coating liquid. When the film is formed, the mixing ratio at the time of the above mixing, the control of the relative humidity, and the like are carried out to produce a film. The film is obtained by heating at a temperature of 250 ° C or higher, which exhibits a refractive index of 1.21 to 1.40, has micropits of thicknesses of 50 to 200 nm, 200835757 (micropit) or irregularities, and has a thickness of 60 to 16 Onm. The film is formed on a glass substrate to thereby produce a low refractive glass. Further, Patent Document 3 discloses a low refractive index which is formed by a glass film and a film having a high refractive index formed on the surface thereof and a film having a low refractive index formed on the surface thereof. glass. The formation of the upper layer film is a fluorinated polyfluorene compound having a polyfluorocarbon chain such as CF3(CF2)2C2H4Si(OCH3)3, and a decane such as Si(OCH3)4 of 5 to 90% by mass. a coupling agent, which is hydrolyzed in an alcohol solvent in the presence of a catalyst such as acetic acid at room temperature, and then filtered to dissolve the prepared copolymer onto the underlying film at a temperature of 120 to 25 (TC heating method) Further, Patent Document 4 discloses that a reaction mixture containing an anthracene compound represented by Si(OR)4, an anthracene compound represented by CFdCFdnCHzCHzSKOR1, an alcohol represented by R2CH2OH, and oxalic acid in a specific ratio is disclosed. Heating in the absence of water to a temperature of 40 to 180 ° C, thereby forming a coating solution of a polyoxyalkylene solution. If the coating liquid is applied to the surface of the substrate at a temperature of 80 to 45 ° C Under the thermal hardening, a film having a refractive index of 1.28 to 1.38 and a water contact angle of 90 to 115 degrees can be formed. Patent Document 1: Japanese Patent Laid-Open Publication No. 05-1 05424 2: Japanese Patent Laid-Open No. Hei 06- 1 57076, Patent Document 3: [Problems to be Solved by the Invention] The antireflection used in various display devices and the like as described above is disclosed in Japanese Laid-Open Patent Publication No. Hei 09-208898. In recent years, in the progress of increasing the size, weight, and thickness of display devices such as liquid crystals and plasmas, the antireflection substrate used for this purpose, particularly the film for preventing reflection, For the sake of light weight or high transparency, there is a tendency to make the thickness of the film thinner, so that the damage due to heat is increased. Therefore, it is more desirable to develop a degree by which the film can be prevented from being damaged. A coating liquid for forming a film of a film which is formed by a low-temperature-hardening film which is less thermally hardened by a low-temperature treatment. However, since the hardening temperature of the low-refractive-index film as described above is not sufficiently low, it is expected to be further Further, the anti-reflection film used in the above various display devices and the like is attached to a tributyl cellulose film with a hard coat or The surface of the film substrate having a hard film-coated polyethylene terephthalate or the like is obtained by forming a film having a lower refractive index than the substrate. In this case, the material of the hard film is The water contact angle of the surface of the substrate film forming the low refractive index film by the surface treatment with or without the hydrophilization treatment or the like will have various sizes, but the abrasion resistance is formed on the substrate film having a high water contact angle. It is difficult to make a high-hardness low-refractive-index film, and it is therefore an object of the present invention to provide a film which can be sufficiently hardened at a relatively low temperature even on a substrate having a high water contact angle. A coating liquid for forming a low refractive index film having a high refractive index (high transparency) and a high hardness and having excellent scratch resistance, and having a low-resistance -6 - 200835757 film, and a method for producing the same, and further reducing the refractive index The film obtained by the coating liquid for forming a film, and an antireflection material using the film. [Means for Solving the Problem] The inventors of the present invention have found that the polysiloxane (A) having a ruthenium atom having a fluorine-containing organic group bonded thereto and the carbon number 9 are found as a result of intensive investigation. The film obtained by the coating solution of the long-chain amine compound (B) and the organic solvent (C) of 20 can be hardened at a low temperature even on a substrate having a high water contact angle of 90 or more. High light transmittance, high hardness, and low scratch resistance which is excellent in scratch resistance. In the present invention, it is not clear why the film formed from the above coating liquid has the excellent characteristics as described above, but the polysiloxane (A) contained in the coating liquid of the present invention does not have a In the case of a fluoroorganic group, a film having a low refractive index cannot be obtained. Further, the long-chain amine compound (B) having 9 to 20 carbon atoms is a film which can be cured at a relatively low temperature and which is excellent in abrasion resistance with high hardness. However, if the carbon number of the amine compound (B) is less than 9, it is possible that a sufficient scratch resistance cannot be obtained on a film substrate having a surface having a high water contact angle of 90 degrees or more, and, for example, a carbon number When it is 20 or more, there is a possibility that sufficient film formability cannot be obtained on a film substrate having a surface having a high water contact angle of 90 degrees or more, and the object of the present invention may not be achieved. Accordingly, the present invention has the gist of the features described below. (1) A coating liquid for forming a low refractive index film, characterized in that: 200835757 consists of a polyoxyalkylene (A) having a ruthenium atom having a fluorine-containing organic group bonded thereto, and a long-chain amine having a carbon number of 9 to 20. Compound (B), which is prepared by dissolving in an organic solvent (C). (2) The coating liquid according to the above (1), wherein the polyoxyalkylene (A) ' is a total ruthenium atom and has 5 to 40 mol% of a ruthenium atom to which a fluorine-containing organic group is bonded. (3) The coating liquid according to the above (1) or (2), wherein the long-chain amine compound (B) is a linear aliphatic primary or secondary amine or an aliphatic having an alicyclic structure. amine. (4) The coating liquid described in any one of the above (1) to (3) wherein the organic solvent (C) is selected from the group consisting of an alcohol having 1 to 6 carbon atoms and a carbon number of 3 to 1 Å. At least one of a group of glycol ethers is formed. (5) The coating liquid according to any one of (1) to (4), wherein, when the total amount of all of the ruthenium atoms is converted into cerium oxide, the polysiloxane (A) is contained. 0.1 to 15% by mass, and the long-chain amine compound (B) contains 0.01 to 0.2 mol of the total amount of the ruthenium atom of the polyoxyalkylene (A). (6) The coating liquid according to any one of the above (1) to (5), further comprising a hydrazine compound (D) represented by the formula (1). [Chemical 1] R10

(1) 200835757 (式中，R1、R2、R3以及R4分glj獨立表示氫原子或碳數1 至5的飽和烴基，η表示2以上的整數）。 (7 ) —種低折射率被膜，係使上述（1 )至（6 )之任一項所記載之塗佈液硬化後所製得者。 (8) —種防反射材料，係上述（7 )所記載之低折射率被膜經形成於具有更高折射率之基材表面上者。 (9 ) 一種低折射率被膜形成用塗佈液之製造方法，其特徵爲：含有將含有具有結合有含氟有機基之矽原子之烷氧基矽烷5至40莫耳％之烷氧基矽烷的濃度，如將該烷氧基砂院的含砂原子換算爲二氧化砂時，爲有機溶劑中4 至1 5質量％之溶液，在對上述烷氧基矽烷的全烷氧化物基的1莫耳爲〇·2至2莫耳的草酸的存在下進行縮聚合（ Condensation polymerization )以製得聚矽氧烷（a )的溶液之過程、及對所得之聚矽氧烷（A )的溶液，混合碳數 9至20的長鏈胺化合物（B )與有機溶劑（C )的混合溶液之過程。 [發明之效果] 如採用本發明，則可提供一種即使於對水接觸角高的基材上仍能在低的溫度下充分硬化，而具有高光透射性（高透明性）、高硬度的耐擦傷性優異的低折射率之被膜之被膜形成用塗佈液、其有效製造方法。又，如採用本發曰月 ’則可提供可從該塗佈液製得之局硬度的耐擦傷性優里的低折射率被膜，及使用該被膜之防反射材料。 -9- 200835757 [發明之最佳實施形態] 以下，就本發明內容再詳細加以說明° <聚砍氧垸（A) > 本發明之低折射率被膜形成用塗佈液（以下’簡稱被膜形成用塗佈液、或塗佈液）中所含有之主骨架中具有經結合含氟有機基之矽原子之聚矽氧烷（A )(以下，簡稱聚矽氧烷（A))，係具有與主骨架中的矽原子結合，並被氟原子取代之有機基（本發明中，簡稱含氟有機基）之聚矽氧烷’換言之，具有經被氟原子取代之有機支鏈結合於砂原子之部位之聚砂氧院。上述之含氟有機基而言，一部分或全部爲被氟取代之有機基’通常多爲一部分的氫原子爲被氟取代之烷基、或含有一部分的氫原子爲被氟原子取代之醚鍵聯（ether linkage )之烷基。含氟有機基所具有之氟原子的數目並不特別加以限定。如含氟有機基的碳數超過12時，則可能有對後述之有機溶劑（C )的溶解性不足之情形。因此，較佳爲碳數3至 12的有機基。更佳爲碳數3至1〇。含氟有機基而言，可例舉：三氟丙基、十三氟辛基、十七氟癸基、五氟苯丙基等，惟並不限定於此等。含氟有機基中，在末端具有全氟烷基、具該基上結合有烴伸院基之較佳爲3至〗5的基，係由於容易製得透明性 -10- 200835757 高的被膜之故很合適。其較佳具體例而言，可舉：三氟丙基、十三氟辛基、十七氟癸基等。聚矽氧烷（A)，可具有1種如上述之含氟有機基，亦可具有複數種。聚矽氧烷（A)，祇要是能在塗佈液中形成均質的溶液之狀態者並不加以特定。如上述之結合有含氟有機基之矽原子爲聚矽氧烷（A)的全矽原子中之5至40莫耳％時 ’由於容易製得對水接觸角90度以上之被膜，且容易製得均質的聚矽氧烷（A )的溶液之故較佳。再者，如結合有含氟有機基之矽原子爲聚矽氧烷（A)的全矽原子中之10 至4 0莫耳％時，由於能更降低反射率之故較佳。又，如結合有含氟有機基之矽原子爲聚矽氧烷（A)的全矽原子中之5至2 5莫耳％時，由於能更提高耐擦傷性之故較佳。如綜合上述理由時，則結合有含氟有機基之矽原子，特佳爲聚矽氧烷（A)的全矽原子中之10至25莫耳％。製造具有含氟有機基之聚矽氧烷（A)之方法並不特別限定。一般而言，如將具有上述之含氟有機基之烷氧矽烷、或該烷氧基矽烷與其他的烷氧基矽烷進行縮聚合即可製得，其中，如將具有含氟有機基之烷氧基矽烷與四烷氧基矽烷、以及需要時，前述以外之烷氧基矽烷（以下，簡稱其他烷氧基矽烷）進行縮聚合時，由於能製得穩定且均質的聚矽氧烷（A )的溶液之故很合適。具有上述含氟有機基之烷氧基矽烷而言，可舉：以下述式（2)表示之|完氧基砂院。式中’ R1爲含氟有機基、 R2爲碳數1至5的烴基。 200835757 [化a R^KOR^s (2) 此種烷氧基矽烷的較佳具體例而言，可舉：三氟丙基甲氧基矽烷、三氟丙基三乙氧基矽烷、十三氟辛基三甲氧基矽烷、十三氟辛基三乙氧基矽烷、十七氟癸基三甲氧基矽烷、十七氟癸基三甲氧基矽烷、十七氟癸基三乙氧基矽烷等。又，能與具有含氟有機基之烷氧基矽烷進行縮合之四烷氧基矽烷而言，可例舉··四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四異丙氧基矽烷、四丁氧基矽烷等。四烷氧基矽烷可以一種單獨使用，亦可倂用複數種使用。又，其他的烷氧基矽烷，係含氟有機基以外的有機基及/或氫原子經結合於矽原子之烷氧基矽烷。此種，其他的烷氧基矽烷的具體例，可舉爲如下。三甲氧基矽烷、三乙氧基矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、丙基三甲氧基矽烷、丙基三乙氧基矽烷、丁基三甲氧基矽烷、丁基三乙氧基矽烷、戊基三甲氧基矽烷、戊基三乙氧基矽烷、庚基三甲氧基矽烷、庚基三乙氧基矽烷、辛基三甲氧基矽烷、辛基三乙氧基矽烷、十二烷基三甲氧基矽烷、十二烷基三乙氧基矽烷、十六烷基三甲氧基矽烷、十六烷基三乙氧基矽烷、十五烷基三甲氧基矽烷、十五烷基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、乙烯基三甲氧基矽烷 -12- 200835757 、r -胺丙基三甲氧基矽烷、r 一胺丙基三乙氧基矽烷、 r -環氧丙氧基三甲氧基矽烷、r -環氧丙氧基三乙氧基矽烷、r -縮水甘油氧丙基三甲氧基矽烷、r -縮水甘油氧丙基三乙氧基矽烷等的三烷氧基矽烷、及二甲基二甲氧基矽烷、二甲基二乙氧基矽烷等的二烷氧基矽烷、以及三甲基甲氧基矽烷、三甲基乙氧基矽烷等的三烷基烷氧基矽烷等。其他的烷氧基矽烷，可以單獨一種使用，亦可倂用複數種。爲製造聚矽氧烷（a )所用之具有含氟有機基之烷氧基矽烷的使用量，祇要是聚矽氧烷（A)在有機溶劑（C )中爲均質的溶液狀態，且不影響本發明之效果，則並不加以限定。其中，如具有含氟有機基之烷氧基矽烷爲全烷氧基矽烷之5至40莫耳％時，則由於可容易製得對水接觸角90度以上之被膜，且容易製得均質的聚矽氧烷（A)的溶液之故較佳。又，如具有含氟有機基之烷氧基矽烷爲全烷氧基矽烷之10至40莫耳％時，則由於能更降低反射率之故較佳。又，如具有含氟有機基之烷氧基矽烷爲全烷氧基矽烷之5至2 5莫耳％時，則由於能更提高耐擦傷性之故較佳。如綜合上述理由時，則具有含氟有機基之烷氧基矽烷，特佳爲全烷氧基矽烷之10至25莫耳％。製造具有含氟有機基之聚矽氧烷（A)之方法而言，可例舉：將具有含氟有機基之烷氧基矽烷，及需要時，四 -13- 200835757 院氧基砂院、及其他的烷氧基砂院的有機溶液，在草酸之存在下加熱以進行縮聚合之方法。具體而言，預先在醇中添加草酸作成草酸的醇溶液之後，在加熱該溶液之狀態下，進行上述各種烷氧基矽烷之混合之方法。草酸的存在量，係對所使用之烷氧基矽烷所具有之全太兀_基的1旲耳’較佳爲作成0.2至2旲耳。上述加熱較佳爲可在〇至180 °C下進行，又在防止液的蒸發、揮發之下，較佳爲在具備有回流管之容器中之回流之下，實施數十分鐘至十數小時。如製造具有上述含氟有機基之聚矽氧烷（A)時，在使用複數種烷氧基矽烷之情形，則可將烷氧基矽烷作爲預先混合之混合物使用，亦可將複數種的烷氧基矽烷依序添加於反應系中。如進行烷氧基矽烷之縮聚合時，則將有機溶劑中之烷氧基矽烷的全矽原子換算爲氧化物之濃度（以下，簡稱 Si02 (二氧化矽）換算濃度）作成較佳爲20質量％以下，特佳爲4至1 5質量％的範圍後進行加熱較合適。如選擇此種濃度範圍，則可抑制凝膠（gel )的生成而製得均質的聚矽氧烷（A )之溶液。進行上述院氧基政院之聚縮合時所用之有機溶劑（以下，簡稱聚合溶劑）’祇要是能溶解烷氧基矽烷者則並不特別加以限定。一般而言’由於因烷氧基矽烷之聚縮合反應而產生醇之故，採用醇類或與醇類相溶性良好的有機溶劑。特別是，醇類、乙二醇類、或乙二醇醚類。此種聚合 -14- 200835757 溶劑之具體例而言，可舉：甲醇、乙醇、丙醇、正丁醇等的醇，乙二醇一甲基醚、乙二醇一乙基醚、二乙二醇一甲基醚、二乙醇一乙基醚等的乙二醇醚等。上述之有機溶劑可混合複數種使用。又，本發明中，具有含氟有機基之聚矽氧烷（A)，可將依上述之方法所得之溶液直接作爲聚矽氧烷（A )之溶液，需要時，亦可將依上述之方法所得之溶液加以濃縮，或添加溶劑以稀釋或以其他溶劑取代後，作爲聚矽氧烷 (A )之溶液。如以其他溶劑取代時，則其溶劑（以下，簡稱取代溶劑）可爲與聚縮合所用者相同溶劑，亦可爲其他溶劑。此種溶劑，祇要是聚矽氧烷（A)能均勻溶解者則並不特別限定，可任意選擇一種或複數種使用。上述取代溶劑之具體例而言，可舉：甲醇、乙醇、異丙醇、丁醇、雙丙酮醇等的醇類；丙酮、甲基乙基甲酮、甲基異丁基甲酮等的酮類；乙二醇、丙二醇、己二醇等的乙二醇類；甲基溶纖素、乙基溶纖素、丁基溶纖素、乙基卡必醇、丁基卡必醇、二乙二醇一甲基醚、丙二醇一甲基醚、丙二醇一丁基醚等的乙二醇醚；醋酸甲基酯、醋酸乙基酯、乳酸乙基酯等的酯類等。 <長鏈胺化合物（B ) > 本發明之塗佈液中所含有之碳數9至20的長鏈胺化合物（B )(以下，簡稱長鏈胺化合物（B ))，係碳數9至 -15- 200835757 20的一元胺化合物。長鏈胺化合物（B)，係脂肪族胺基較佳，而可具有脂環構造。如長鏈胺化合物（B )之碳數爲9以上時，則即使超過90度般之對水接觸角高的表面之薄膜基材上仍然容易獲得充分的成膜性。碳數較佳爲1 〇以上。另一方面，如碳數超過20時，將會發生難於對水接觸角高的表面之薄膜基材上獲得充分的塗佈性。其中，碳數較佳爲18以下。(1) 200835757 (wherein, R1, R2, R3 and R4 represent glj independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms, and η represents an integer of 2 or more). (7) A low-refractive-index film obtained by curing the coating liquid according to any one of the above (1) to (6). (8) An antireflection material obtained by forming the low refractive index film described in the above (7) on the surface of a substrate having a higher refractive index. (9) A method for producing a coating liquid for forming a low refractive index film, comprising: an alkoxy decane containing 5 to 40 mol% of an alkoxy decane having a ruthenium atom to which a fluorine-containing organic group is bonded The concentration of the alkoxy sands in the alkoxysilane is 4 to 15% by mass in the organic solvent, and the total alkoxide group of the alkoxydecane is 1 a process in which a molar is subjected to condensation polymerization in the presence of 2 to 2 moles of oxalic acid to prepare a solution of polyoxyalkylene (a), and a solution of the obtained polyoxane (A) A process of mixing a mixed solution of a long-chain amine compound (B) having a carbon number of 9 to 20 and an organic solvent (C). [Effects of the Invention] According to the present invention, it is possible to provide a high light transmittance (high transparency) and high hardness resistance even at a low temperature even on a substrate having a high water contact angle. A coating liquid for forming a film having a low refractive index which is excellent in scratch resistance, and an effective production method thereof. Further, if the present invention is used, it is possible to provide a low refractive index film which is excellent in scratch resistance which can be obtained from the coating liquid, and an antireflection material using the film. -9-200835757 [Best Embodiment of the Invention] Hereinafter, the content of the present invention will be described in detail. <Polyoxime (A) > Coating liquid for forming a low refractive index film of the present invention (hereinafter referred to as 'abbreviation' a polysiloxane (A) having a fluorene-containing atom bonded to a fluorine-containing organic group in the main skeleton contained in the coating liquid for coating film formation or the coating liquid) (hereinafter, simply referred to as polysiloxane (A)) a polyoxyalkylene having an organic group (in the present invention, abbreviated as a fluorine-containing organic group) bonded to a ruthenium atom in a main skeleton and substituted by a fluorine atom, in other words, having an organic branch substituted by a fluorine atom The sandstone of the sand atom. In the above fluorine-containing organic group, a part or all of the organic group substituted by fluorine 'usually a part of a hydrogen atom is an alkyl group substituted by fluorine, or a part of a hydrogen atom is an ether bond substituted by a fluorine atom. (ether linkage) alkyl group. The number of fluorine atoms which the fluorine-containing organic group has is not particularly limited. When the carbon number of the fluorine-containing organic group exceeds 12, the solubility in the organic solvent (C) to be described later may be insufficient. Therefore, an organic group having 3 to 12 carbon atoms is preferred. More preferably, the carbon number is 3 to 1 Torr. The fluorine-containing organic group may, for example, be a trifluoropropyl group, a tridecafluorooctyl group, a heptadecafluoroindenyl group or a pentafluorophenylpropyl group, but is not limited thereto. Among the fluorine-containing organic groups, a perfluoroalkyl group at the terminal end, preferably a group of 3 to 7.5 having a hydrocarbon-extended group bonded to the group, is easy to produce a transparent film having a high transparency of -10-200835757. So it is very suitable. Preferred examples thereof include a trifluoropropyl group, a tridecafluorooctyl group, and a heptadecafluoroindenyl group. The polyoxyalkylene (A) may have one of the above-mentioned fluorine-containing organic groups, and may have plural kinds. The polyoxyalkylene (A) is not particularly limited as long as it can form a homogeneous solution in the coating liquid. When the ruthenium atom to which the fluorine-containing organic group is bonded is 5 to 40 mol% of the total ruthenium atom of the polysiloxane (A), it is easy to obtain a film having a water contact angle of 90 degrees or more, and is easy. A solution of a homogeneous polyoxane (A) is preferred. Further, when the ruthenium atom to which the fluorine-containing organic group is bonded is 10 to 40 mol% of the total ruthenium atom of the polysiloxane (A), it is preferable because the reflectance can be further lowered. Further, when the ruthenium atom to which the fluorine-containing organic group is bonded is 5 to 25 mol% of the total ruthenium atom of the polysiloxane (A), it is preferable because the scratch resistance can be further improved. When the above reasons are combined, the ruthenium atom to which the fluorine-containing organic group is bonded is particularly preferably 10 to 25 mol% of the total ruthenium atom of the polysiloxane (A). The method of producing the polyfluorinated alkane (A) having a fluorine-containing organic group is not particularly limited. In general, the alkoxysilane having the above fluorine-containing organic group or the alkoxydecane is subjected to polycondensation polymerization with another alkoxydecane, wherein, for example, an alkane having a fluorine-containing organic group is obtained. When the oxoxane and the tetraalkoxy decane and, if necessary, the alkoxy decane other than the above (hereinafter abbreviated as other alkoxy decane) are subjected to polycondensation, a stable and homogeneous polyoxane (A) can be obtained. The solution is very suitable. The alkoxy decane having the above-mentioned fluorine-containing organic group is exemplified by the following formula (2). In the formula, R1 is a fluorine-containing organic group, and R2 is a hydrocarbon group having 1 to 5 carbon atoms. 200835757 [Chemical A R^KOR^s (2) Preferred examples of such alkoxydecane include trifluoropropylmethoxydecane, trifluoropropyltriethoxydecane, and thirteen. Fluoxenyltrimethoxydecane, tridecafluorooctyltriethoxydecane, heptadecafluorodecyltrimethoxydecane, heptadecafluorodecyltrimethoxydecane, heptadecafluorodecyltriethoxydecane, etc. . Further, the tetraalkoxy decane which can be condensed with the alkoxy decane having a fluorine-containing organic group may, for example, be tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane or tetraiso Propoxydecane, tetrabutoxydecane, and the like. The tetraalkoxydecane may be used singly or in combination of plural kinds. Further, the other alkoxydecane is an alkoxy decane in which an organic group other than the fluorine-containing organic group and/or a hydrogen atom is bonded to a ruthenium atom. Specific examples of such other alkoxydecanes are as follows. Trimethoxy decane, triethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, propyl trimethoxy decane, propyl Triethoxy decane, butyl trimethoxy decane, butyl triethoxy decane, pentyl trimethoxy decane, pentyl triethoxy decane, heptyl trimethoxy decane, heptyl triethoxy decane , Octyltrimethoxydecane, Octyltriethoxydecane, Dodecyltrimethoxydecane, Dodecyltriethoxydecane, Cetyltrimethoxydecane, Hexadecyltriethyl Oxydecane, pentadecyltrimethoxynonane, pentadecyltriethoxydecane,phenyltrimethoxydecane,phenyltriethoxydecane,vinyltrimethoxydecane-12-200835757,r -Aminopropyltrimethoxydecane, r-Aminopropyltriethoxydecane, r-glycidoxytrimethoxydecane, r-glycidoxytriethoxydecane, r-glycidoxy Trialkyloxydecane, such as propyltrimethoxydecane, r-glycidoxypropyltriethoxydecane, and dimethyl Dimethoxy-Silane, dimethyl diethoxy silane-dialkoxy like Silane, trimethyl methoxysilane and Silane, trimethyl ethoxy silane-like trialkyl alkoxy silane-like. The other alkoxydecane may be used singly or in combination of plural kinds. The amount of the alkoxysilane having a fluorine-containing organic group used for producing the polyoxyalkylene (a) is a homogeneous solution state in the organic solvent (C) as long as it is a polyoxyalkylene (A), and does not affect The effects of the present invention are not limited. Wherein, if the alkoxy decane having a fluorine-containing organic group is 5 to 40 mol% of the total alkoxy decane, since the film having a water contact angle of 90 degrees or more can be easily obtained, it is easy to obtain a homogeneous film. The solution of polyoxyalkylene (A) is preferred. Further, when the alkoxysilane having a fluorine-containing organic group is from 10 to 40 mol% of the peralkyloxydecane, it is preferable because the reflectance can be further lowered. Further, when the alkoxysilane having a fluorine-containing organic group is 5 to 25 mol% of the total alkoxysilane, it is preferable because the scratch resistance can be further improved. When the above reasons are combined, the alkoxy decane having a fluorine-containing organic group is particularly preferably 10 to 25 mol% of the total alkoxy decane. The method for producing a polyfluorinated alkane (A) having a fluorine-containing organic group may, for example, be an alkoxydecane having a fluorine-containing organic group, and, if necessary, a tetra-l-200835757 And other organic solutions of alkoxy sands, heated in the presence of oxalic acid to carry out condensation polymerization. Specifically, a method in which oxalic acid is added as an alcohol solution of oxalic acid to an alcohol and then the above alkoxysilane is mixed is carried out while heating the solution. The amount of oxalic acid present is preferably from 0.2 to 2 Å for the total 兀-base of the alkoxy decane used. The above heating is preferably carried out at a temperature of from 〇 to 180 ° C, and is preferably carried out for several tens of minutes to ten hours under reflux of a vessel having a reflux tube, in order to prevent evaporation and volatilization of the liquid. . For the production of the polyfluorinated alkane (A) having the above fluorine-containing organic group, in the case of using a plurality of alkoxysilanes, the alkoxydecane may be used as a premixed mixture, or a plurality of kinds of alkane may be used. Oxydecane is added sequentially to the reaction system. When the polycondensation of alkoxy decane is carried out, the total ruthenium atom of the alkoxy decane in the organic solvent is converted into an oxide concentration (hereinafter, abbreviated as SiO 2 equivalent concentration) to preferably be 20 mass. Below %, it is more preferable to carry out heating after particularly preferably in the range of 4 to 15% by mass. If such a concentration range is selected, a gel (gel) formation can be suppressed to obtain a homogeneous solution of polyoxane (A). The organic solvent (hereinafter referred to as a polymerization solvent) used in the above-mentioned polycondensation of the hospital is not particularly limited as long as it can dissolve the alkoxysilane. In general, since an alcohol is produced by a polycondensation reaction of an alkoxydecane, an alcohol or an organic solvent having good compatibility with an alcohol is used. In particular, alcohols, glycols, or glycol ethers. Specific examples of such a polymerization-14-200835757 solvent include alcohols such as methanol, ethanol, propanol and n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and diethylene glycol. A glycol ether such as alcohol monomethyl ether or diethanol monoethyl ether. The above organic solvents may be used in combination of plural kinds. Further, in the present invention, the polyfluorinated alkane having a fluorine-containing organic group (A) may be directly used as a solution of the polyoxane (A) as needed, or may be used as described above. The solution obtained by the method is concentrated, or a solvent is added to be diluted or substituted with another solvent to obtain a solution of polyoxane (A). When it is substituted with another solvent, the solvent (hereinafter, abbreviated as a solvent) may be the same solvent as that used for the polycondensation, or may be another solvent. Such a solvent is not particularly limited as long as it is uniformly dissolved by polyoxyalkylene (A), and one type or plural types can be used arbitrarily. Specific examples of the above-mentioned substitution solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and diacetone alcohol; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Ethylene glycols such as ethylene glycol, propylene glycol, and hexanediol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethylene glycol mono Glycol ether such as propyl ether, propylene glycol monomethyl ether or propylene glycol monobutyl ether; esters such as methyl acetate, ethyl acetate, ethyl lactate, and the like. <Long-chain amine compound (B) > The long-chain amine compound (B) having a carbon number of 9 to 20 contained in the coating liquid of the present invention (hereinafter, simply referred to as a long-chain amine compound (B)) is a carbon number 9 to -15- 200835757 20 monoamine compound. The long-chain amine compound (B) is preferably an aliphatic amine group and may have an alicyclic structure. When the carbon number of the long-chain amine compound (B) is 9 or more, sufficient film formability can be easily obtained even on a film substrate having a surface having a high water contact angle of more than 90 degrees. The carbon number is preferably 1 Å or more. On the other hand, when the carbon number exceeds 20, sufficient coating properties are hard to be obtained on a film substrate which is difficult to have a surface having a high water contact angle. Among them, the carbon number is preferably 18 or less.

長鏈胺化合物（B )，可爲一級胺、二級胺或三級胺之任一種。以下，將舉各別的具體例，惟並不限定於此等例。一級胺而言，可舉：CH3(CH2)8NH2、CH3(CH2)9NH2 、CH3(CH2)10NH2、CHHCHduNHr CH3(CH2)12NH2、 CH3(CH2)13NH2、CH3(CH2)i4NH2、ch3(ch2)15nh2、 CH3(CH2)16NH2、CH3(CH2)17NH2、CH3(CH2)18NH2、 ch3(ch2)19nh2 ' 等的直鏈狀胺；（ch3)2ch(ch2)6nh2、 CH3(CH2)6CH(CH3)NH2、CH3(CH2)8CH(CH3)NH2、 CH3(CH2)i〇CH(CH3)NH2 ' CH3(CH2)iiCH(CH3)NH2 ' CH3(CH2)16CH(CH3)NH2 等的分枝胺。二級胺而言，可舉：ch3(ch2)7nhch3、 ch3(ch2)8nhch3、ch3(ch2)9nhch3、ch3(ch2)10nhch3 ' CH3(CH2)nNHCH3 ' CH3(CH2)i2NHCH3 ' CH3(CH2)13NHCH3、CH3(CH2)14NHCH3、 CH3(CH2)15NHCH3、CH3(CH2)16NHCH3、 CH3(CH2)17NHCH3、CH3(CH2)18NHCH3、 -16- 200835757 CH3(CH2)6NHCH2CH3、CH3(CH2)7NHCH2CH3、 CH3(CH2)8NHCH2CH3、CH3(CH2)9NHCH2CH3、 CH3(CH2)i〇NHCH2CH3 ' CH3(CH2)i 1NHCH2CH3 ' CH3(CH2)12NHCH2CH3、CH3(CH2)13NHCH2CH3、 CH3(CH2)14NHCH2CH3、CH3(CH2)15NHCH2CH3、 CKCHOuNHCHsCH、、CH3(CH2)17NHCH2CH3、等。The long-chain amine compound (B) may be any of a primary amine, a secondary amine or a tertiary amine. Hereinafter, specific examples will be given, but are not limited to these examples. For the primary amine, CH3(CH2)8NH2, CH3(CH2)9NH2, CH3(CH2)10NH2, CHHCHduNHr CH3(CH2)12NH2, CH3(CH2)13NH2, CH3(CH2)i4NH2, ch3(ch2)15nh2 , a linear amine such as CH3(CH2)16NH2, CH3(CH2)17NH2, CH3(CH2)18NH2, ch3(ch2)19nh2'; (ch3)2ch(ch2)6nh2, CH3(CH2)6CH(CH3)NH2 And a branched amine such as CH3(CH2)8CH(CH3)NH2, CH3(CH2)i〇CH(CH3)NH2'CH3(CH2)iiCH(CH3)NH2'CH3(CH2)16CH(CH3)NH2. The secondary amines are: ch3(ch2)7nhch3, ch3(ch2)8nhch3, ch3(ch2)9nhch3, ch3(ch2)10nhch3'CH3(CH2)nNHCH3 'CH3(CH2)i2NHCH3 'CH3(CH2)13NHCH3 , CH3(CH2)14NHCH3, CH3(CH2)15NHCH3, CH3(CH2)16NHCH3, CH3(CH2)17NHCH3, CH3(CH2)18NHCH3, -16-200835757 CH3(CH2)6NHCH2CH3, CH3(CH2)7NHCH2CH3, CH3(CH2 8NHCH2CH3, CH3(CH2)9NHCH2CH3, CH3(CH2)i〇NHCH2CH3 'CH3(CH2)i 1NHCH2CH3 'CH3(CH2)12NHCH2CH3, CH3(CH2)13NHCH2CH3, CH3(CH2)14NHCH2CH3, CH3(CH2)15NHCH2CH3, CKCHOuNHCHsCH, , CH3(CH2)17NHCH2CH3, and the like.

三級胺而言，可舉：ch3(ch2)6n(ch3)2、 ch3(ch2)7n(ch3)2、ch3(ch2)8n(ch3)2、 CH3(CH2)9N(CH3)2、CH3(CH2)10N(CH3)2、 CH3(CH2)iiN(CH3)2 ' CH3(CH2)i2N(CH3)2 ' CH3(CH2)13N(CH3)2、CH3(CH2)14N(CH3)2、 CH3(CH2)15N(CH3)2、CH3(CH2)16N(CH3)2、 CH3(CH2)17N(CH3)2、CH3(CH2)4N(CH2CH3)2、 CH3(CH2)5N(CH2CH3)2、CH3(CH2)6N(CH2CH3)2、 CH3(CH2)7N(CH2CH3)2、CH3(CH2)8N(CH2CH3)2、 CH3(CH2)9N(CH2CH3)2、CH3(CH2)10N(CH2CH3)2、 CH3(CH2)11N(CH2CH3)2 ' CH3(CH2)12N(CH2CH3)2 ' ch3(ch2)13n(ch2ch3)2、CH3(CH2)14N(CH2CH3)2、 CH3(CH2)15N(CH2CH3)2、等。又，具有脂環構造之胺之具體例而言，可舉：從下述式（A-1 )至（A-7 )等的化合物。 -17- 200835757 [化3]The tertiary amines include: ch3(ch2)6n(ch3)2, ch3(ch2)7n(ch3)2, ch3(ch2)8n(ch3)2, CH3(CH2)9N(CH3)2, CH3 (CH2)10N(CH3)2, CH3(CH2)iiN(CH3)2 'CH3(CH2)i2N(CH3)2 'CH3(CH2)13N(CH3)2, CH3(CH2)14N(CH3)2, CH3 (CH2)15N(CH3)2, CH3(CH2)16N(CH3)2, CH3(CH2)17N(CH3)2, CH3(CH2)4N(CH2CH3)2, CH3(CH2)5N(CH2CH3)2, CH3 (CH2)6N(CH2CH3)2, CH3(CH2)7N(CH2CH3)2, CH3(CH2)8N(CH2CH3)2, CH3(CH2)9N(CH2CH3)2, CH3(CH2)10N(CH2CH3)2, CH3 (CH2)11N(CH2CH3)2 'CH3(CH2)12N(CH2CH3)2 'ch3(ch2)13n(ch2ch3)2, CH3(CH2)14N(CH2CH3)2, CH3(CH2)15N(CH2CH3)2, etc. . Further, specific examples of the amine having an alicyclic structure include compounds derived from the following formulas (A-1) to (A-7). -17- 200835757 [化3]

(Α·1)(Α·1)

(Α-2)(Α-2)

(Α-7) 長鏈胺化合物（Β )而言，爲提高在對水接觸角高的，例如未經巷化處理（Saponification )之親水化處理之表面的薄膜上硬化之被膜的耐擦傷性起見，較佳爲一級胺或二級胺。更佳爲一級胺。此等長鏈胺化合物（B )，可以鹽的形態使用，惟在此情形，塗佈液的穩定性可能會提升。又，直鏈狀的脂肪族胺，由於不致於引起急遽的凝膠 -18- 200835757 化之下而有促進被膜的硬化之效果之故很合適。再者，直鏈狀的烷基胺，容易在對水接觸角高的基材上獲得充分的成膜性。在此，具有含有不飽和烷基、或芳香族之烷基之胺化合物亦不致於急遽的凝膠化之下可獲得促進被膜的硬化之效果，惟此時由於被膜的折射率會增高之故，有防止反射之功能會降低之傾向。本發明之塗佈液中之長鏈胺化合物（B )的含量，係對聚矽氧烷（A)的全矽原子的合計量的1莫耳，長鏈胺化合物（B)較佳爲作成0.01至0.2莫耳，更佳爲0.03至〇·1 莫耳之方式爲宜。如長鏈胺化合物（Β)爲0.01莫耳以上時，由於容易在低溫下硬化之故很合適，相反地，如〇·2 莫耳以下時，則由於被膜透明且無不均性而容易獲得高的被膜硬度之故很合適。 <有機溶劑（C ) > 作爲本發明之塗佈液的主溶劑之有機溶劑（C ) ’祇要是能溶解矽原子上結合有含氟有機基之聚矽氧烷（Α) 、碳數9至20的長鏈胺化合物（Β)、及需要時所含有之下述矽化合物（D )、以及其他成分，則均可使用。有機溶劑（C )的具體例而言，可舉：甲醇、乙醇、異丙醇、丁醇、雙丙酮醇等的脂肪族類；環戊基醇、環己基醇等的脂環式醇；苄基醇、肉桂醇（cinnamie alcohGl )等的芳香族醇；丙酮、甲基乙基甲酮、甲基異丁基甲ffi -19- 200835757 等的酮類；乙二醇、丙二醇、己二醇等的乙二醇類；甲基溶纖素、乙基溶纖素、丁基溶纖素、乙基卡必醇、丁基卡必醇、二乙二醇一甲基醚、丙二醇一甲基醚、丙二醇一丁基醚等的乙二醇醚；醋酸甲基酯、醋酸乙基酯、乳酸乙基酯等的酯類等。此等可以單獨使用、或倂用複數種有機溶劑。其中，較佳爲使用選自碳數較佳爲1至6，更佳爲1至4 的醇及碳數較佳爲3至10，更佳爲3至7的醚所成群之至少1 種所成者。 <矽化合物（D ) > 本發明之低折射率被膜形成用塗佈液中，較佳爲再含有以下述式（1 )表示之矽化合物（D )。如此，可更提高被膜的耐擦傷性。 [化4](Α-7) Long-chain amine compound (Β), in order to improve the scratch resistance of a film hardened on a film having a high water contact angle, for example, a surface which is not subjected to a hydrophilization treatment of Saponification For example, a primary or secondary amine is preferred. More preferably, it is a primary amine. These long-chain amine compounds (B) can be used in the form of a salt, but in this case, the stability of the coating liquid may be increased. Further, the linear aliphatic amine is suitable for promoting the hardening effect of the film because it does not cause an imminent gel -18-200835757. Further, the linear alkylamine is easy to obtain sufficient film formability on a substrate having a high water contact angle. Here, the amine compound having an unsaturated alkyl group or an aromatic alkyl group can also obtain an effect of promoting hardening of the film without being subjected to rapid gelation, but at this time, since the refractive index of the film is increased, There is a tendency to prevent the reflection function from being lowered. The content of the long-chain amine compound (B) in the coating liquid of the present invention is preferably 1 mol of the total amount of the total ruthenium atom of the polysiloxane (A), and the long-chain amine compound (B) is preferably prepared. From 0.01 to 0.2 m, more preferably from 0.03 to 〇·1. When the long-chain amine compound (Β) is 0.01 mol or more, it is easy to be hardened at a low temperature, and conversely, when it is below 〇·2 mol, it is easily obtained because the film is transparent and has no unevenness. High film hardness is suitable. <Organic solvent (C) > The organic solvent (C) as the main solvent of the coating liquid of the present invention is as long as it is capable of dissolving a polyfluorinated organic group-containing polyfluorene oxide (Α) and a carbon number The long-chain amine compound (Β) of 9 to 20, and the following hydrazine compound (D) and other components contained as needed may be used. Specific examples of the organic solvent (C) include aliphatics such as methanol, ethanol, isopropanol, butanol, and diacetone alcohol; alicyclic alcohols such as cyclopentyl alcohol and cyclohexyl alcohol; and benzyl Aromatic alcohols such as aryl alcohol, cinnamie alcohGl; ketones such as acetone, methyl ethyl ketone, methyl isobutyl methyl ffi -19-200835757; and ethylene glycol, propylene glycol, hexanediol, etc. Glycols; methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol A glycol ether such as a methyl ether; an ester such as methyl acetate, ethyl acetate or ethyl lactate. These may be used alone or in combination with a plurality of organic solvents. Among them, it is preferred to use at least one selected from the group consisting of an alcohol having a carbon number of preferably 1 to 6, more preferably 1 to 4, and an ether having a carbon number of preferably 3 to 10, more preferably 3 to 7. The person who made it. <Antimony compound (D) > The coating liquid for forming a low refractive index film of the present invention preferably further contains an antimony compound (D) represented by the following formula (1). In this way, the scratch resistance of the film can be further improved. [Chemical 4]

式（1 )中，R 、R2、R3以及R4分別獨立表示氫原子或碳數1至5的飽和烴基，η袠示2以上，較佳爲2至50之整數。碳數1至5的飽和烴基的具體例而言，可舉：甲基、乙基、丙基、丁基等。矽化合物（D )，可爲以式（1 )表示之化合物經混 -20 - 200835757 合複數種者。此時，n較佳爲2以上之整數，更佳爲4以上之整數。製造i：述矽化合物（D )之方法並不特別限定，例如 ’可依將Η烷氧基矽烷在醇等的有機溶劑中進行水解縮合之方法製得。此時，水解可爲部分水解，亦可爲完全水解。在完全水解的情形，理論上，添加四烷氧基矽烷中的全烷氧化物基的0·5倍莫耳的水即可，通常，較佳爲添加較〇·5倍莫耳爲過剩量的水。另一方面，在部分水解的情形 ’則可爲0.5倍莫耳以下的水量，惟較佳爲〇.2至〇.5倍莫耳〇上述原料的四烷氧基矽烷的具體例而言，可舉：四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四丁氧基矽烷等，而可容易從市售品取得。爲製造上述矽化合物（D)之反應所用之水量，雖可依需要適當選擇，惟較佳爲四烷氧基矽烷中的全烷氧化物基之0.5至2.5倍莫耳。又，在反應時，通常爲促進水解· 縮合反應之目的，而使用鹽酸、硫酸、硝酸、醋酸、甲酸、草酸、磷酸、氫氟酸、馬來酸等的酸，氨等的鹼以及鹽酸、硫酸、硝酸等的金屬鹽等的觸媒。又，如加熱溶解有烷氧基矽烷之溶液，以更促進聚縮合之作法亦爲一般性的作法。此時，加熱溫度及加熱時間則可依需要適當選擇，可例舉：在室溫至1 〇〇 °C下加熱· 攪拌0.5至48小時，或在回流下加熱•攪拌0.5至48小時等方法。 -21 - 200835757 上述反應中，進行四烷氧基矽烷之聚縮合時所用之有機溶劑，祇要是能溶解四烷氧基矽烷者則並不特別加以限定。一般而言，由於因四烷氧基矽烷的聚縮合反應而生成醇之故，採用醇類或與醇類相溶性良好的有機溶劑。此種有機溶劑的具體例而言，可舉：甲醇、乙醇、丙 _ 醇、正丁醇等的醇、乙二醇一甲基醚、乙二醇一乙基醚、二乙二醇一甲基醚、二乙二醇一乙基醚等的乙二醇醚等。 Φ 上述的有機溶劑，可混合複數種使用。如此所得之矽化合物（D )的有機溶劑的溶液，係以 Si02換算濃度計，較佳爲作爲30質量％以下。如在此濃度範圍下選擇任意濃度，即可抑制凝膠的生成而製得均質的溶液。在此，矽化合物（D )而言，亦可採用市售品。可例舉：均爲柯爾可得公司製之矽酸甲酯51、矽酸甲酯53A、矽酸乙酯40、矽酸乙酯48、SS-C1等。 <其他成分> ~ 本發明之低折射率被膜形成用塗佈液中，在不影響本 ‘ 發明之效果之範圍內，尙可含有聚矽氧烷（A )、胺化合物（B ) '有機溶劑（C )以及矽化合物（D )以外之其他成分，例如，無機微粒、調平劑（love ling agent)表面活性劑、以及水等的介質。無機微粒而言，較佳爲矽氧微粒、鋁氧微粒、鈦氧微粒、氟化鎂微粒等的微粒，而特佳爲作成膠體（colloid ) -22- 200835757 溶液者。此種膠體溶液，係經無機微粒粉分散於分散介質 (dispersing medium )中者，亦可爲市售品的膠體溶液。本發明之塗佈液中，如含有無機微粒，即能賦予將形成之硬化被膜的表面形成或其他功能。無機微粒而言，其平均粒徑較佳爲0.001至0.2# m，更佳爲〇·〇〇1至o.iem。如無機微粒的平均粒徑在0.2/zm以上時，可能使用塗佈液所形成之硬化被膜的透明性會降低。無機微粒的分散介質而言，可例舉：水或有有機溶劑。膠體溶液而言，從塗佈液的穩定性來看，pH値或pKa ( (電解質電離常數倒數的對數）値較佳爲2至10，特佳爲3 至7。可用於上述膠體溶液的分散介質之有機溶劑而言，可例舉：甲醇、異丙醇、乙二醇、丁醇、乙二醇一丙基醚等的醇類；甲基乙基甲酮等的酮類；甲苯、二甲苯等的芳香族烴類；二甲基甲醯胺、二甲基乙醯胺、N —甲基吡咯院酮等的醯胺類；醋酸乙酯、醋酸丁酯、r -丁內酯等的酯類；四氫呋喃、1，4 一二Of烷等的醚類。其中，較佳爲醇類或酮類。此等有機溶劑，可以單獨或混合2種以上後作爲分散介質使用。又，上述調平劑及表面活性劑等，則可使用周知者，特別是市售品係容易取得之故很合適。 <被膜形成用塗佈液> 本發明之被膜形成用塗佈液，係含有聚矽氧烷（A ) -23- 200835757 、長鏈胺化合物（B )、以及需要時之矽化合物（D )或其他成分，並此等成分經溶解於有機溶劑（C )中之溶液。本發明中，祇要是能製得前述的塗佈液，則其調製方法並不加以限定。例如，可將上述各成分依序添加所使用之有機溶劑（C )中並加以混合。此時，各成分的添加順序並不特別限定。又，亦可混合經將各成分分別溶解於所使用之有機溶劑（C )中之溶液。特別是，如對長鏈胺化合物（B )與有機溶劑（C )的混合溶液，混合聚矽氧烷（a )的溶液時，由於能抑制析出物的發生之故很合適。其中，如聚矽氧烷（A)係作爲有機溶劑（C)的溶液而製得時，則由於可直接使用聚矽氧烷（A )的溶液之故很合適。如將聚砂氧烷（A )作爲有機溶劑（C )的溶液而製得時，如上所述，較佳爲將具有結合有含氟有機基之矽原子之烷氧基矽烷的有機溶劑（C )的溶液，對該烷氧基矽烷的烷氧化物基的1莫耳，較佳爲在〇·2至2莫耳的草酸的存在下述進行縮聚合而製得。又’本發明之塗佈液中，以其pH的調製爲目的，可預先對聚矽氧烷（A )混合酸。酸的量，係對聚矽氧烷（ A)的矽原子的1莫耳較佳爲〇·〇1至2·5莫耳，更佳爲〇.〗至 2莫耳爲合適。上述中所用之酸而言，可例舉：鹽酸、硝酸、硫酸、磷酸等的無機酸；甲酸、醋酸、蘋果酸等的一元羧酸類；草酸、檸檬酸、丙酸、號拍酸等的多元竣酸等的有機酸。此中，溶液狀態的酸雖可直接使用，惟較佳爲以聚合溶劑 -24- 200835757 稀釋後使用。此外之酸，係聚合溶劑中以適當濃度溶解後使用爲宜。本發明之塗佈液中，按將聚矽氧烷（A )所具有之矽原子換算爲二氧化矽計，較佳爲〇. 1至1 5質量％，更佳爲 0.5至10質量％之方式含有聚矽氧烷（A)，且按對聚矽氧烷（A)的矽原子的1莫耳爲0.01至0.2莫耳，較佳爲0.03 至〇·1莫耳之方式含有長鏈胺化合物（B)。又，如含有矽化合物（D )時，則按對聚矽氧烷（A )的矽原子的1莫耳較佳爲〇·〇3至0·55莫耳，更佳爲0.05至〇·45莫耳之方式含有矽化合物（D)爲宜。本發明中，被膜形成用塗佈液中的Si 02固體成分換算濃度，較佳爲0.1至15質量％，更佳爲0.5至10質量％爲宜。如Si02濃度在0.1質量％以下時，則難以1次塗佈即可得所需膜厚，相反地，如在1 5質量％以下時，則溶液的適用期（pot fife )更容易穩定。在此所稱之Si 02固體成分換算濃度，係指將塗佈液中的矽原子換算爲二氧化矽時之濃度之意。例如，塗佈液中僅含有聚矽氧烷（A )時，則表示將聚矽氧烷（A)的矽原子換算爲二氧化矽時之濃度之意，又，如塗佈液中含有聚矽氧烷（A )及矽化合物（D )時，則表示將聚矽氧烷（A )和矽化合物（D )的矽原子的合計量換算爲二氧化矽時之濃度之意。上述塗佈液，將按照需要，添加有機溶劑而將Si02固體成分換算濃度成爲上述範圍之方式調製’惟爲此所用之有機溶劑，則可採用製造聚矽氧烷（A)時用於烷氧基烷 -25- 200835757 的聚縮合之有機溶劑、或聚矽氧烷（A)的溶液的濃縮、或稀釋或取代爲其他有機溶劑時所用之有機溶劑。有機溶劑可任意選擇一種或複數種使用。以下，舉出本發明之低折射率被膜形成用塗佈液的具體例。 ’ [1]含有聚矽氧烷（a )及長鏈胺化合物（B )，而此等經溶解於有機溶劑（C )中之塗佈液。 φ [2]含有聚矽氧烷（A )及長鏈胺化合物（B )及矽化合物（D )，而此等經溶解於有機溶劑（C )中之塗佈液。 [3 ]上述[1]或[2]中，含有無機微粒之塗佈液。 [4]上述[1]或[2]或[3]中，含有調平劑或表面活性劑之塗佈液。 <被膜之形成> # 本發明之低折射率被膜形成用塗佈液，如塗佈於基材上並使其熱硬化即可製得所需要的被膜。塗佈方法，可採用公知或周知之方法。例如，可採用：浸漬塗佈（dip ^ coating )法、流涎塗佈（flow coating )法、噴霧塗佈（ spray coating)法、鑲條塗佈（bar coating)法、凹輕塗佈（gravure coating )法、輥式塗佈（r〇ll coatillg )法、刮板塗佈（blade coating )法、空氣刮刀（airknife coating ) 法等方法。基材而言’可舉：由塑膠、玻璃、陶瓷等所成之基材 -26- 200835757 。塑膠而言，可舉：聚碳酸酯、聚（甲基）丙烯酸酯、聚醚颯·、聚芳酯、聚胺酯、聚颯、聚醚、聚醚酮、聚甲基戊烯、聚烯烴、聚對苯二甲酸乙二醇酯、聚（甲基）丙烯腈、三乙醯基纖維素、二乙醯基纖維素、醋酸丁酸纖維素等的薄片或薄膜等。本發明中’即使採用對水接觸角高的基材，例如，未 Μ加巷化處理等之提筒親水性之處理之基材，亦即，具有對水接觸角例如9 0度以上般的高的表面之基材的情形，仍然能將高光透射性、耐擦傷性優異之折射率較佳爲以下般的低折射率被膜形成於基材表面。將形成於基材表面之被膜的厚度，雖可藉由塗膜的厚度加以調節’惟亦可藉由塗佈液的S i Ο 2換算濃度之調節而容易加以調節。經形成於基材上之塗膜，雖可在溫度2 0至1 5 0 °C下直接使其熱硬化，惟亦可在事先在溫度2 0至1 (3 0 °C下乾燥後，再使其熱硬化。此時，乾燥所需要之時間較佳爲丨〇秒鐘至6分鐘。熱硬化所需時間，雖可按照所需要的被膜特性而適當選擇，惟通常爲1小時至7天。如選擇低的硬化溫度時，延長硬化時間即容易製得具有充分的耐擦傷性之被膜。又，本發明之撥水性被膜形成用之塗佈液，即使在 1 50 °C以上之硬化溫度，仍然能製得耐擦傷性優異的被膜。此時，較佳爲配合基材的耐熱溫度以調整硬化溫度及硬化時間。 -27· 200835757 <防反射材料等之用途> 從本發明之塗佈液所形成之被膜，如上所述，由於具有折射率例如1.4以下般的低折射率之故，特別可適合作爲防反射材料的用途使用。 ^ 如將本發明之被膜使用爲防反射材料時，於具有較本發明之被膜爲高的折射率之基材上形成本發明之被膜，即 φ 可容易賦予防止光反射之能力。亦即，於具有較本發明之被膜爲高的折射率之塑膠薄膜或玻璃般的基材表面形成本發明之被膜，即可作爲防止反射之薄膜或防止反射之玻璃等的防反射基材。本發明之被膜，係於基材表面作爲單一的被膜形成時有效者，亦可作爲於形成具有高折射率之單數或複數的下層之被膜上形成有本發明之被膜之具有層合構造之防反射體亦有效。 • 本發明之被膜，係很適合使用於電視機、玻璃製的陰極射線管（Braum tube )、電腦的顯示器、具有玻璃表面之鏡子、玻璃製商品陳列櫥等需要光的反射防止之領域。 ’ 再者，本發明之被膜，係由於本身的對水接觸角爲9 〇度以上之故具有撥水性，又在容易擦拭指紋或油性墨水之防污性方面具有實用性，由於在溫度20至150 °C般之比較低溫下之硬化處理時可充分硬化之故，在防反射基材之製造過程中亦非常有利者。本發明之被膜，係亦具有上述之優點之故，特別是在 -28- 200835757 液晶、電漿（plasma)等的顯示裝置或顯示監視器（ display monitor)等的防止反射之薄膜有用者。【實施方式】 ~ [實施例] ^ 以下，將提示合成例及實施例與比較例，以具體說明本發明內容，惟本發明並不因下述合成例及實施例而加以 φ 限制其解釋之範圍。本實施例中之簡縮語，表示如下意義。 ETOS :四乙氧基矽烷、 FS-13:十三氟辛基三甲氧基矽烷 C S - 8 :辛基三乙氧基矽烷 MEA : —乙醇胺 HA :己基胺 LA :月桂基胺 φ SA :硬脂基胺 IPA :異丙醇 ’ cHexOH :環己醇 _ PGME :丙二醇一甲基醚以下，將提示下述合成例中之測定方法。 [殘留烷氧基矽烷單體測定法] 使用氣相色譜法（以下，簡稱GC )，、測定聚砂氧|完 (A )的溶液中之殘留烷氧基矽烷單體。 -29- 200835757 GC測定，係採用島津製作所公司製Shimadzu GC-14B ’依下述條件測定者。管柱：毛細管柱CPB卜W25- 1 00 (長度 2 5 m m、直徑〇_5 3mm、厚度 l/zm) 管柱溫度：從起始溫度50°C，按15°C /分鐘之速度升溫至到達溫度2 9 0 °C ( 3分鐘）。試樣注入法：1 // 1 (微升）、注射溫度：24 0 °C、檢測器溫度：290 °C、載氣（Carrier gas ):氮氣（流量30 ml/分鐘）、檢測方法：FID (火焰離子化檢測器）法。 [合成例1 ] 於具備有回流管之4 口反應燒瓶中置入甲醇57.26g，在攪拌下每次少量添加草酸18.01 g以調製草酸的甲醇溶液。接著，加熱該溶液，在回流下進行TEOS ( 17.71g )與 FS-13 ( 7.02g )的混合物之滴下。滴下後回流5小時，放冷至室溫以調製聚矽氧烷（A )的溶液（PF )。藉由GC而測定聚矽氧烷（A )的溶液（PF )之結果，並未測出烷氧基矽烷單體之存在。 [合成例2] 於具備有回流管之4 口反應燒瓶中置入乙醇47.3 6g及草酸〇.18g及純水10.80g，在攪拌下添加TEOS 41.66g以調製混合液。接著，加熱該溶液並回流3小時’然後放冷至室溫以調製聚矽氧烷的溶液（PS )。藉由GC而測定該聚 -30- 200835757 矽氧烷的溶液（p s )之結果，並未測出烷氧基矽烷單體之存在。 [合成例3] 於具備有回流管之4 口反應燒瓶中置入甲醇60.Ug，在攪拌下每次少量添加草酸1 8 _ 0 1 g以調製草酸的甲醇溶液。接著，加熱該溶液，在回流下進行TEOS ( 17.71g )與 C S - 8 ( 4 · 1 5 g )的混合物之滴下。滴下後回流5小時，於冷至室溫以調製聚矽氧烷（A )的溶液（PC )。藉由GC而測定該聚矽氧烷（A )的溶液（P C )之結果，並未測出烷氧基矽烷單體之存在。 [表1 ] 聚矽氧矽化合物(g) 草酸純水甲醇乙醇烷溶液 TEOS FS-13 CS (g) (g) (g) (g) 合成例1 PF 17·71 0.0850 mol 7.02 0.0150 mol 18.01 57.26 合成例2 PS 41.66 0.2000 mol 0.18 10.80 47.36 合成例3 PC 17.71 0.0850 mol 4.15 0.0150mol 0.18 60.13In the formula (1), R, R2, R3 and R4 each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms, and η 袠 represents 2 or more, preferably 2 to 50. Specific examples of the saturated hydrocarbon group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group and the like. The hydrazine compound (D) may be a compound of the formula (1) which is mixed with -20 - 200835757. In this case, n is preferably an integer of 2 or more, more preferably an integer of 4 or more. The method for producing the compound (D) is not particularly limited, and for example, it can be obtained by a method in which a decyloxydecane is hydrolyzed and condensed in an organic solvent such as an alcohol. At this time, the hydrolysis may be partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, it is sufficient to add 0.5 to 5 times of water of the peralkoxide group in the tetraalkoxy decane. Usually, it is preferable to add more than 5 times mole to the excess amount. Water. On the other hand, in the case of partial hydrolysis, the amount of water may be 0.5 times or less, but it is preferably 〇.2 to 〇.5 times the specific example of the tetraalkoxy decane of the above raw material. Examples thereof include tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, and tetrabutoxy decane, and can be easily obtained from commercially available products. The amount of water used for the reaction for producing the above hydrazine compound (D) can be appropriately selected as needed, and is preferably 0.5 to 2.5 times moles of the total alkoxide group in the tetraalkoxy decane. Further, in the reaction, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, phosphoric acid, hydrofluoric acid or maleic acid, an alkali such as ammonia, and hydrochloric acid are usually used for the purpose of promoting hydrolysis and condensation reaction. A catalyst such as a metal salt such as sulfuric acid or nitric acid. Further, it is also a general practice to heat a solution in which an alkoxysilane is dissolved to further promote polycondensation. In this case, the heating temperature and the heating time may be appropriately selected as needed, and may be, for example, heating and stirring at room temperature to 1 〇〇 ° C for 0.5 to 48 hours, or heating under reflux, stirring for 0.5 to 48 hours, and the like. . In the above reaction, the organic solvent used for the polycondensation of the tetraalkoxydecane is not particularly limited as long as it can dissolve the tetraalkoxydecane. In general, since an alcohol is formed by a polycondensation reaction of a tetraalkoxynonane, an alcohol or an organic solvent having good compatibility with an alcohol is used. Specific examples of such an organic solvent include alcohols such as methanol, ethanol, propanol and n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and diethylene glycol monomethyl. A glycol ether such as a base ether or diethylene glycol monoethyl ether. Φ The above organic solvents can be used in combination with a plurality of types. The solution of the organic solvent of the hydrazine compound (D) thus obtained is preferably 30% by mass or less based on the concentration in terms of SiO 2 . If any concentration is selected within this concentration range, gel formation can be inhibited to produce a homogeneous solution. Here, as the hydrazine compound (D), a commercially available product can also be used. For example, methyl decanoate 51, methyl decanoate 53A, ethyl decanoate 40, ethyl decanoate 48, SS-C1, etc., manufactured by Colgate Co., Ltd., may be mentioned. <Other components> ~ In the coating liquid for forming a low refractive index film of the present invention, the ruthenium may contain a polyoxane (A) or an amine compound (B) within a range that does not affect the effects of the present invention. The organic solvent (C) and other components other than the hydrazine compound (D), for example, inorganic fine particles, a bleaching agent surfactant, and a medium such as water. The inorganic fine particles are preferably fine particles of neodymium oxide particles, aluminum oxide particles, titania particles, magnesium fluoride particles, and the like, and particularly preferably a colloid -22-200835757 solution. Such a colloidal solution may be a colloidal solution of a commercially available product by dispersing the inorganic fine particle powder in a dispersion medium. In the coating liquid of the present invention, if it contains inorganic fine particles, it can impart a surface formation or other function to the formed hardened film. The inorganic fine particles preferably have an average particle diameter of 0.001 to 0.2 # m, more preferably 〇·〇〇1 to o.iem. When the average particle diameter of the inorganic fine particles is 0.2/zm or more, the transparency of the cured film formed by using the coating liquid may be lowered. The dispersion medium of the inorganic fine particles may, for example, be water or an organic solvent. In the case of the colloidal solution, pH 値 or pKa ((the logarithm of the reciprocal of the electrolyte ionization constant) 値 is preferably from 2 to 10, particularly preferably from 3 to 7. From the viewpoint of the stability of the coating liquid, it can be used for dispersion of the above colloidal solution. The organic solvent of the medium may, for example, be an alcohol such as methanol, isopropanol, ethylene glycol, butanol or ethylene glycol monopropyl ether; a ketone such as methyl ethyl ketone; toluene or An aromatic hydrocarbon such as toluene; an amide such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone; ethyl acetate, butyl acetate or r-butyrolactone; An ether; an ether such as tetrahydrofuran or 1,4-dioxane. Among them, an alcohol or a ketone is preferred. These organic solvents may be used singly or in combination of two or more kinds as a dispersion medium. A flattening agent, a surfactant, and the like can be used, and a commercially available product is particularly suitable. <The coating liquid for forming a film> The coating liquid for forming a film of the present invention contains a poly a siloxane (A) -23- 200835757, a long-chain amine compound (B), and a ruthenium compound (D) when needed or The component is a solution in which the components are dissolved in the organic solvent (C). In the present invention, the preparation method is not limited as long as the coating liquid can be obtained. For example, the above components may be used. The organic solvent (C) to be used is sequentially added and mixed. In this case, the order of addition of each component is not particularly limited. Alternatively, the components may be separately dissolved in the organic solvent (C) to be used. In particular, when a solution of a polyoxane (a) is mixed with a mixed solution of a long-chain amine compound (B) and an organic solvent (C), it is suitable because the occurrence of precipitates can be suppressed. For example, when polyoxyalkylene (A) is prepared as a solution of the organic solvent (C), it is suitable because a solution of polyoxyalkylene (A) can be used as it is. For example, polyoxalate (A) When it is prepared as a solution of the organic solvent (C), as described above, a solution of an organic solvent (C) having an alkoxysilane having a ruthenium atom to which a fluorine-containing organic group is bonded is preferably used. 1 mole of the alkoxy group of the decane, preferably at 〇·2 In the coating liquid of the present invention, the polyoxosiloxane (A) may be mixed with an acid in advance for the purpose of preparing the pH of the coating liquid of the present invention. The amount of 1 mole of the ruthenium atom of the polyoxyalkylene (A) is preferably 〇·〇1 to 2.5 moles, more preferably 〇. 2 to 2 moles. The acid used in the above. In particular, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; monocarboxylic acids such as formic acid, acetic acid, and malic acid; and organic acids such as oxalic acid, citric acid, propionic acid, and acenaphthic acid. In this case, the acid in the solution state may be used as it is, but it is preferably used after being diluted with the polymerization solvent -24-200835757. Further, the acid is preferably used after being dissolved in a polymerization solvent at an appropriate concentration. The coating liquid of the present invention is preferably 〇1 to 15% by mass, more preferably 0.5 to 10% by mass, based on the cerium atom of the polyoxyalkylene (A). The method comprises a polyoxyalkylene (A), and the long-chain amine is contained in an amount of 0.01 to 0.2 mol, preferably 0.03 to 〇·1 mol, per mole of the ruthenium atom of the polyoxyalkylene (A). Compound (B). Further, when the ruthenium compound (D) is contained, 1 mole of the ruthenium atom of the polyoxyalkylene (A) is preferably 〇·〇3 to 0.55 mol, more preferably 0.05 to 〇·45. The molar form of the compound (D) is preferred. In the present invention, the concentration of the Si 02 solid content in the coating liquid for forming a film is preferably from 0.1 to 15% by mass, more preferably from 0.5 to 10% by mass. When the SiO 2 concentration is 0.1% by mass or less, it is difficult to apply the film thickness once, and conversely, when it is 15% by mass or less, the pot life of the solution is more easily stabilized. The Si 02 solid content conversion concentration referred to herein means the concentration at which the ruthenium atom in the coating liquid is converted into cerium oxide. For example, when the coating liquid contains only polyoxyalkylene (A), it means the concentration of the germanium atom of polyoxyalkylene (A) in terms of cerium oxide, and if the coating liquid contains poly In the case of the oxime (A) and the ruthenium compound (D), the meaning of the concentration when the total amount of the ruthenium atoms of the polysiloxane (A) and the ruthenium compound (D) is converted into ruthenium dioxide is expressed. The above-mentioned coating liquid is prepared by adding an organic solvent as needed, and modulating the concentration of the SiO 2 solid content to the above range. The organic solvent used for this purpose can be used for the production of alkoxylate when the polyoxane (A) is produced. The organic solvent of the polycondensation organic solvent of the alkyl bromide-25-200835757 or the solution of the polyoxyalkylene (A) is concentrated, or diluted or substituted with other organic solvents. The organic solvent may be selected singly or in combination. Hereinafter, a specific example of the coating liquid for forming a low refractive index film of the present invention will be described. '[1] contains a polyoxane (a) and a long-chain amine compound (B), and the coating liquid dissolved in the organic solvent (C). Φ [2] contains a polysiloxane (A) and a long-chain amine compound (B) and a ruthenium compound (D), and these are dissolved in an organic solvent (C). [3] The above [1] or [2], which contains a coating liquid of inorganic fine particles. [4] The coating liquid containing a leveling agent or a surfactant in the above [1] or [2] or [3]. <Formation of Film Formation># The coating liquid for forming a low refractive index film of the present invention is applied to a substrate and thermally cured to obtain a desired film. The coating method can be carried out by a known or well-known method. For example, a dip coating method, a flow coating method, a spray coating method, a bar coating method, or a gravure coating method can be employed. Method, roll coating method, blade coating method, airknife coating method, and the like. For the substrate, a substrate made of plastic, glass, ceramics, etc. -26- 200835757 can be mentioned. For plastics, polycarbonate, poly(meth)acrylate, polyether oxime, polyarylate, polyurethane, polyfluorene, polyether, polyether ketone, polymethylpentene, polyolefin, poly A sheet or film of ethylene terephthalate, poly(meth)acrylonitrile, triethylenesulfonyl cellulose, diethyl acetyl cellulose, cellulose acetate butyrate or the like. In the present invention, even if a substrate having a high water contact angle is used, for example, a substrate which is treated with a hydrophilicity such as a stepping treatment, that is, a substrate having a water contact angle of, for example, 90 degrees or more In the case of a substrate having a high surface, it is still possible to form a low refractive index film having a high refractive index and scratch resistance which is preferably as follows. The thickness of the film formed on the surface of the substrate can be adjusted by the thickness of the coating film. However, it can be easily adjusted by adjusting the concentration of the coating liquid in terms of S i Ο 2 . The coating film formed on the substrate can be directly thermally cured at a temperature of 20 to 150 ° C, but it can also be dried at a temperature of 20 to 1 (at 30 ° C beforehand). It is thermally hardened. At this time, the time required for drying is preferably from 丨〇 second to 6 minutes. The time required for thermal hardening can be appropriately selected according to the desired characteristics of the film, but usually from 1 hour to 7 days. When a low hardening temperature is selected, it is easy to obtain a film having sufficient scratch resistance by prolonging the hardening time. Further, the coating liquid for forming a water-repellent film of the present invention has a hardening temperature of at least 150 ° C. Further, it is possible to obtain a film excellent in scratch resistance. In this case, it is preferable to adjust the curing temperature and the curing time in accordance with the heat resistance temperature of the substrate. -27·200835757 <Use of antireflection material, etc.> As described above, the film formed of the coating liquid has a low refractive index of, for example, 1.4 or less, and is particularly suitable for use as an antireflection material. ^ If the film of the present invention is used as an antireflection material At the time of having the invention The film of the present invention is formed on a substrate having a high refractive index, that is, φ can easily impart an ability to prevent light reflection, that is, a plastic film or glass-like base having a refractive index higher than that of the film of the present invention. The film of the present invention can be used as an antireflection substrate such as a film for preventing reflection or a glass for preventing reflection. The film of the present invention is effective when the surface of the substrate is formed as a single film, and can also be used as a film. It is also effective to form an antireflection body having a laminated structure in which a film of the present invention is formed on a film having a single layer or a plurality of lower layers having a high refractive index. • The film of the present invention is suitably used for a cathode made of a television or glass. A radiation tube (Braum tube), a display of a computer, a mirror with a glass surface, a glass display cabinet, and the like, which require reflection of light. 'Further, the film of the present invention has a water contact angle of 9 It has water repellency above the twist, and it has practicality in easily rubbing the antifouling property of fingerprint or oily ink, because it is at a temperature of 20 to 150 °C. It can be sufficiently hardened during the hardening treatment at a lower temperature, and is also very advantageous in the manufacturing process of the antireflection substrate. The film of the present invention also has the above advantages, especially in the liquid crystal of -28-200835757, A display device such as a plasma or a film for preventing reflection such as a display monitor is useful. [Embodiment] ~ [Examples] ^ Hereinafter, a synthesis example, an embodiment, and a comparative example will be presented. The present invention is not limited by the following synthesis examples and examples, and the scope of the explanation is not limited by the following synthesis examples and examples. The abbreviations in the present embodiment have the following meanings: ETOS: tetraethoxy decane, FS- 13: Tridecafluorooctyltrimethoxydecane CS-8: Octyltriethoxydecane MEA: -ethanolamine HA: hexylamine LA: laurylamine φ SA: stearylamine IPA: isopropanol 'cHexOH: Cyclohexanol _ PGME: propylene glycol monomethyl ether or less, the measurement method in the following synthesis examples will be suggested. [Measurement Method of Residual Alkoxydecane Monomer] The residual alkoxydecane monomer in the solution of polyoxalate|complete (A) was measured by gas chromatography (hereinafter abbreviated as GC). -29- 200835757 The GC measurement was carried out by using Shimadzu GC-14B's manufactured by Shimadzu Corporation. Column: Capillary column CPB Bu W25- 1 00 (length 2 5 mm, diameter 〇 _5 3 mm, thickness l / zm) Column temperature: from the initial temperature of 50 ° C, at a rate of 15 ° C / min to The temperature reached 2 90 ° C (3 minutes). Sample injection method: 1 // 1 (microliter), injection temperature: 24 0 °C, detector temperature: 290 °C, carrier gas: nitrogen (flow rate 30 ml/min), detection method: FID (Flame ionization detector) method. [Synthesis Example 1] 57.26 g of methanol was placed in a reaction flask equipped with a reflux tube, and 18.01 g of oxalic acid was added in a small amount with stirring to prepare a methanol solution of oxalic acid. Next, the solution was heated, and a mixture of TEOS (17.71 g) and FS-13 (7.02 g) was dropped under reflux. After the dropwise addition, the mixture was refluxed for 5 hours, and allowed to cool to room temperature to prepare a solution (PF) of polyoxane (A). As a result of measuring the solution (PF) of polyoxyalkylene (A) by GC, the presence of the alkoxydecane monomer was not detected. [Synthesis Example 2] Into a four-neck reaction flask equipped with a reflux tube, 47.3 g of ethanol, 18 g of oxalate and 10.80 g of pure water were placed, and 41.66 g of TEOS was added under stirring to prepare a mixed solution. Next, the solution was heated and refluxed for 3 hours' and then allowed to cool to room temperature to prepare a solution (PS) of polyoxyalkylene. As a result of measuring the solution (p s ) of the poly-30-200835757 oxane by GC, the presence of the alkoxydecane monomer was not detected. [Synthesis Example 3] 60. Ug of methanol was placed in a 4-neck reaction flask equipped with a reflux tube, and 1 8 _ 0 1 g of oxalic acid was added in a small amount with stirring to prepare a methanol solution of oxalic acid. Next, the solution was heated, and a mixture of TEOS (17.71 g) and C S - 8 (4 · 15 g) was dropped under reflux. After the dropwise addition, the mixture was refluxed for 5 hours, and cooled to room temperature to prepare a solution (PC) of polyoxane (A). As a result of measuring the solution (P C ) of the polyoxyalkylene (A) by GC, the presence of the alkoxydecane monomer was not detected. [Table 1] Polyoxonium compound (g) Oxalic acid pure water Methanol ethanolane solution TEOS FS-13 CS (g) (g) (g) (g) Synthesis Example 1 PF 17·71 0.0850 mol 7.02 0.0150 mol 18.01 57.26 Synthesis Example 2 PS 41.66 0.2000 mol 0.18 10.80 47.36 Synthesis Example 3 PC 17.71 0.0850 mol 4.15 0.0150 mol 0.18 60.13

[實施例1至4、比較例1至6] 按表2所示組成，混合上述合成例中所得之聚矽氧烷的溶液、胺化合物以及有機溶劑以調製被膜形成用塗佈液 (Q1 至 Q4)。又，在比較例中，按表2所示組成，調製塗佈液（T1 -31 - 200835757 至 Τ 6 )。就此等Q1至Q4及T1至T6或使用此等之塗膜，進行下列所示之評價。 [表2][Examples 1 to 4, and Comparative Examples 1 to 6] The solution of the polyoxoxane obtained in the above Synthesis Example, the amine compound, and the organic solvent were mixed in the composition shown in Table 2 to prepare a coating liquid for forming a film (Q1 to Q4). Further, in the comparative example, the coating liquid (T1 - 31 - 200835757 to Τ 6 ) was prepared according to the composition shown in Table 2. For the above Q1 to Q4 and T1 to T6 or using these coating films, the evaluations shown below are carried out. [Table 2]

塗佈液 PF (g) PS (g) PC (g) 胺化合物 (g) cHexOH (g) POME (g) IPA (g) 實施例1 Q1 16.67 LA 0.19 5.00 20.00 58.14 實施例2 Q2 16.67 SA 0.27 5.00 20.00 58.06 實施例3 Q3 15.00 0.83 LA 0.19 5.00 20.00 58.98 實施例4 Q4 15.00 0.83 SA 0.27 5.00 20.00 58.90 比較例1 T1 16.67 5.00 20.00 58.33 比較例2 T2 16.67 MEA 0.06 5.00 20.00 58.27 比較例3 T3 16.67 HA 0.10 5.00 20.00 58.23 比較例4 T4 15.00 0.83 MEA 0·06 5.00 20.00 59.11 比較例5 T5 15.00 0.83 HA 0.10 5.00 20.00 59.07 比較例6 T6 16.67 5.00 20.00 58.33 〈儲存穩定性〉將被膜形成用塗佈液在溫度25 °C下靜置1個月後，使用孔徑0.45 /z m、內徑18 // m、長度22mm的聚四氟乙烯過濾器（倉敷紡績公司製層析儀（chromatograph ) 1 3N )過 -32- 200835757 濾1 00 cc，能過濾者記成〇、發生塞孔者記成x。將此結果表示於表3。 <硬化膜評價> 將被膜形成用塗佈液（Q1至Q4及T1至T6 )，使用鑲條塗佈器（No.6 )塗佈於附有硬質覆膜之三乙醯基纖維素 (以下，簡稱HC-TAC )薄膜（薄膜厚度80/zm、硬質覆膜表面的對水接觸角爲83度、波長5 5 0nm時之反射率爲4.5 % )，以形成塗膜。在溫度23 °C下放置30秒鐘後，在潔淨烘箱中，在100 °C下乾燥5分鐘，接著，在溫度90 °C下使其硬化1 5小時。就所得之硬化被膜，進行對水接觸角、油性筆擦拭性、指紋擦拭性、密合性、反射率以及耐擦傷性。又，折射率係使用如下述方式所形成之硬化膜加以測定者。將所調製之塗佈液（Q 1至Q4及T 1至T6 )，於矽晶圓上實施旋轉塗佈（Spin coating )以形成塗膜，並在溫度23°C下放置30秒鐘後，在潔淨烘箱中，在l〇(TC下乾燥5 分鐘’接著，在溫度90 °C下使其硬化15小時，製得膜厚爲 100nm的硬化被膜。此等的評價方法係如下所述，而將評價結果示於表3 及表4。 [對水接觸角] 使用協和界面科學公司製的自動接觸角計CA-Z型，測定當滴下純水3微升時的接觸角。 -33- 200835757 又，實施例中所使用之HC-T AC薄膜的硬質覆膜表面的對水接觸角，亦係依此法所測定者。 [油性筆擦拭性] 將經於硬化被膜表面，使用Pentel (偏特爾）公司製油性筆所施加之墨水，使用旭化成公司製偏哥特M-3加以擦拭，並以目視判定其擦拭容易性。將墨水已完全擦拭者記成〇、其他者記成X。 [指紋擦拭性] 使指紋附著於硬化被膜表面，並使用旭化成公司製編哥特M-3加以擦拭，以目的判定其擦拭容易性。將指紋已完全擦拭者記成〇、其他者記成X。 [密合性] 於基材上的硬化被膜以1 mm間隔按方格式狀裁切1 00 處，將玻璃紙帶（cellophane tape )(日綳公司註冊商標，24mm寬）與硬化被膜強硬貼合後，劇急剝離玻璃紙帶並以目視確認硬化被膜有無剝離之情形。將未剝離者記成〇、發生剝離者記成X。 [反射率] 使用島津製作所公司製的分光光度計UV 3 100PC，使波長5 5 0nm的光以入射角5度入射於硬化被膜，以測定反 -34- 200835757 射率。 [耐擦傷性] 使用日本鋼絲棉（steel wool )公司製鋼絲棉#〇〇〇〇，以400g/cm2壓力摩擦硬化被膜1〇來回，並以目視判定硬化被膜表面的擦傷的傷痕情形。判定基準係如下所示。 A:無傷痕至5條、B:傷痕6至10條、C:傷痕11至20 條、D :傷痕2 1至3 0條、E :傷痕3 1條以上 [折射率] 使用溝尻光學公司製的橢圓對稱計（ellipsometer) DVA-36L以測定在波長633nm的光時之折射率。Coating Liquid PF (g) PS (g) PC (g) Amine Compound (g) cHexOH (g) POME (g) IPA (g) Example 1 Q1 16.67 LA 0.19 5.00 20.00 58.14 Example 2 Q2 16.67 SA 0.27 5.00 20.00 58.06 Example 3 Q3 15.00 0.83 LA 0.19 5.00 20.00 58.98 Example 4 Q4 15.00 0.83 SA 0.27 5.00 20.00 58.90 Comparative Example 1 T1 16.67 5.00 20.00 58.33 Comparative Example 2 T2 16.67 MEA 0.06 5.00 20.00 58.27 Comparative Example 3 T3 16.67 HA 0.10 5.00 20.00 58.23 Comparative Example 4 T4 15.00 0.83 MEA 0·06 5.00 20.00 59.11 Comparative Example 5 T5 15.00 0.83 HA 0.10 5.00 20.00 59.07 Comparative Example 6 T6 16.67 5.00 20.00 58.33 <Storage Stability> The coating liquid for forming a film at a temperature of 25 ° After standing for 1 month under C, a PTFE filter (chromatograph 1 3N) with a pore diameter of 0.45 /zm, an inner diameter of 18 // m, and a length of 22 mm was used -32- 200835757 Filter 1 00 cc, the filter can be recorded as 〇, and the hole is recorded as x. This result is shown in Table 3. <Evaluation of Cured Film> The coating liquid for coating film formation (Q1 to Q4 and T1 to T6) was applied to a triethyl sulfonated cellulose with a hard coating film using a strip coater (No. 6). (hereinafter, abbreviated as HC-TAC) film (film thickness: 80/zm, a water contact angle of the hard film surface of 83 degrees, and a reflectance of 4.5% at a wavelength of 550 nm) to form a coating film. After standing at a temperature of 23 ° C for 30 seconds, it was dried in a clean oven at 100 ° C for 5 minutes, and then hardened at a temperature of 90 ° C for 15 hours. The obtained cured film was subjected to a water contact angle, oil pen wiping property, fingerprint wiping property, adhesion, reflectance, and scratch resistance. Further, the refractive index was measured using a cured film formed as follows. The prepared coating liquids (Q 1 to Q4 and T 1 to T6 ) were subjected to spin coating on a ruthenium wafer to form a coating film, and after standing at a temperature of 23 ° C for 30 seconds, In a clean oven, it was dried at 10 °C for 5 minutes, and then hardened at a temperature of 90 ° C for 15 hours to obtain a cured film having a film thickness of 100 nm. These evaluation methods are as follows. The evaluation results are shown in Tables 3 and 4. [Water contact angle] The contact angle of 3 μl of pure water was measured using an automatic contact angle meter CA-Z manufactured by Kyowa Interface Science Co., Ltd. -33- 200835757 Further, the water contact angle of the surface of the hard film of the HC-T AC film used in the examples is also determined by the method. [Oil pen wiping property] The surface of the film is cured, and Pentel (Pentel) is used. The ink applied by the company's oil-based pen was wiped with Asahi Kasei Corporation's Gothic M-3, and the wiping easiness was visually judged. The ink was completely wiped and the others were recorded as X. [Fingerprint Wiping] The fingerprint is attached to the surface of the hardened film and is edited by Asahi Kasei Corporation. Special M-3 was wiped, and the wiping easiness was determined for the purpose. The fingerprint was completely wiped as 〇, and the others were recorded as X. [Adhesiveness] The cured film on the substrate was placed in a square format at 1 mm intervals. After cutting the cellophane tape (registered trademark of Nisshin Co., Ltd., 24 mm wide) and the hardened film, the cellophane tape was peeled off sharply and the cured film was visually confirmed to be peeled off. When the peeling was recorded as a flaw, the peeling was recorded as X. [Reflectance] Using a spectrophotometer UV 3 100PC manufactured by Shimadzu Corporation, light having a wavelength of 550 nm was incident on the cured film at an incident angle of 5 degrees to measure the opposite. -34- 200835757 Rate of attack. [Scratch resistance] Using steel wool #〇〇〇〇, made by steel wool company, rubbed and hardened the film with a pressure of 400 g/cm2, and visually judged the surface of the hardened film. The scratch marks are as follows: A: no damage to 5, B: 6 to 10 scars, C: 11 to 20 scars, D: scars 2 to 30, E: scars 3 One or more [refractive index] is made by Gully Optical Co., Ltd. Circularly symmetric meter (ellipsometer) DVA-36L to measure the refractive index at the wavelength of 633nm light.

[表3][table 3]

塗佈液儲存穩定性對水接觸角〇油性筆擦拭性指紋擦拭性實施例1 Q1 〇 >100 〇〇實施例2 02 〇 >100 〇〇實施例3 Q3 〇 >100 〇〇實施例4 04 〇 >100 〇〇比較例1 T1 〇 >100 〇〇比較例2 T2 〇 >100 〇〇比較例3 T3 〇 >100 〇〇比較例4 T4 〇 >100 〇〇比較例5 T5 〇 >100 〇〇座較例6 T6 〇 85 X X -35- 200835757 [表4]Coating solution storage stability to water contact angle oily pen wiping fingerprint wiping property Example 1 Q1 〇 > 100 〇〇 Example 2 02 〇 > 100 〇〇 Example 3 Q3 〇 > 100 〇〇 Example 4 04 〇 > 100 〇〇 Comparative Example 1 T1 〇 > 100 〇〇 Comparative Example 2 T2 〇 > 100 〇〇 Comparative Example 3 T3 〇 > 100 〇〇 Comparative Example 4 T4 〇 > 100 〇〇 Comparative Example 5 T5 〇>100 〇〇座比例6 T6 〇85 XX -35- 200835757 [Table 4]

塗佈液折射率反射率（％) 密合性耐擦傷性實施例1 Q1 1.385 1.6 〇 C 實施例2 Q2 1.3 85 1.6 〇 B 實施例3 Q3 1.390 1.7 〇 B 實施例4 Q4 1.390 1.7 〇 A 比較例1 T1 1.375 1.4 〇 E 比較例2 T2 1.380 1.5 〇 E 比較例3 T3 1.385 1.6 〇 E 比較例4 T4 1.380 1.5 〇 E 比較例5 T5 1.385 1.6 〇 D 比較例6 T6 1.440 2.6 〇 E 如表3及表4所示，實施例1至4中，在90 °C的硬化溫度之下，顯示耐擦傷性爲C以上的優異的特性、及對水接觸角爲1〇〇度以上的優異的特性。並且，塗佈液（Q 1至Q4 )的儲存穩定性亦良好，而在溫度23 °C下儲存6個月後亦穩定者。再者，實施例1至4中，顯示1，400以下的低折射率，及低折射率之特性。另一方面，在不具有長鏈胺化合物（B )的情形，或者使用碳數8以下的胺化合物時的塗佈液（T1至5)之比較例1至5，係在9 0 °C的硬化溫度之下，耐擦傷性爲D以下般之不十分良好者。又，如表3及表4所示，實施例1至4，係指紋擦拭性及油性筆擦拭性般之防污特性優異，且與基材的密合性高者〇又’在使用具有未經氟原子取代之有機基之聚矽氧烷 -36- 200835757 之塗佈液（Τ6 )，則對水接觸角成爲90度以下’ 性亦低，高反射率般的不十分良好者。 [產業上之利用可能性] 本發明之撥水性被膜形成用塗佈液，可提供穩定性優異，在溫度2 0 °C至1 5 0 °C般的低溫的熱充分硬化、且低折射率而耐擦傷性優異的被膜。適合使用爲防反射基材，特別是很適合使用爲顯的防反射薄膜。本件係將200 6年10月12日所提出申請之日本案2006-2792 1 9號的說明書、申請專利範圍以及部內容加以引用，而作爲本發明之說明書的揭示而防污特一種儲存處理即可因此，可示元件用專利申請摘要的全所採用者Coating liquid refractive index reflectance (%) Adhesive scratch resistance Example 1 Q1 1.385 1.6 〇C Example 2 Q2 1.3 85 1.6 〇B Example 3 Q3 1.390 1.7 〇B Example 4 Q4 1.390 1.7 〇A Comparison Example 1 T1 1.375 1.4 〇E Comparative Example 2 T2 1.380 1.5 〇E Comparative Example 3 T3 1.385 1.6 〇E Comparative Example 4 T4 1.380 1.5 〇E Comparative Example 5 T5 1.385 1.6 〇D Comparative Example 6 T6 1.440 2.6 〇E As Table 3 As shown in Table 4, in Examples 1 to 4, at a curing temperature of 90 ° C, excellent properties such as scratch resistance of C or more and excellent characteristics of water contact angle of 1 degree or more were exhibited. . Further, the coating liquids (Q 1 to Q4 ) were also excellent in storage stability, and were stable after storage for 6 months at a temperature of 23 °C. Further, in Examples 1 to 4, the low refractive index of 1,400 or less and the low refractive index were exhibited. On the other hand, in the case of not having the long-chain amine compound (B), or the coating liquids (T1 to 5) using the amine compound having a carbon number of 8 or less, Comparative Examples 1 to 5 are at 90 ° C. Under the hardening temperature, the scratch resistance is not as good as D or less. Further, as shown in Tables 3 and 4, Examples 1 to 4 are excellent in antifouling properties such as fingerprint wiping property and oil-based pen wiping property, and have high adhesion to a substrate, and have a The coating liquid (Τ6) of the polyoxyalkylene-36-200835757 having an organic group substituted with a fluorine atom has a low water contact angle of 90 degrees or less, and is not very excellent in high reflectance. [Industrial Applicability] The coating liquid for forming a water-repellent film of the present invention can provide excellent heat stability at a low temperature of 20 ° C to 150 ° C and a low refractive index. A film excellent in scratch resistance. It is suitable for use as an anti-reflective substrate, and is particularly suitable for use as an antireflective film. The present specification is incorporated by reference to the specification, the scope of the patent application, and the content of the Japanese Patent Application No. 2006-2792 No. 9 filed on Oct. 12, 2006, which is incorporated herein by reference. Therefore, the full use of the patent application summary for the component can be displayed.

-37--37-

Claims

200835757 十、申請專利範圍 1 · 一種低折射率被膜形成用塗佈液，其特徵爲：由含有具有結合有含氟有機基之矽原子之聚矽氧烷（A)、及碳數9至20的長鏈胺化合物（B )，而此等化合物經溶解於有機溶劑（C )中所成。 2 ·如申請專利範圍第1項之塗佈液，其中聚矽氧烷 (A)，係對其全矽原子，具有結合有含氟有機基之矽原子5至40莫耳％者。 3·如申請專利範圍第1項或第2項之塗佈液，其中長鏈胺化合物（B_)，係直鏈狀的脂肪族一級胺或二級胺，或者具有脂環構造之脂肪族胺。 4.如申請專利範圍第1項至第3項之任一項之塗佈液，其中有機溶劑（C)，係由選自碳數1至6的醇及碳數3至10的乙二醇型醚所成群之至少1種所成者。 5·如申請專利範圍第1項至第4項之任一項之塗佈液，其中聚矽氧烷（A )，如將其所有之矽原子的合計量換算爲二氧化矽時，含有0.1至15質量％，而長鏈胺化合物（B )，則對聚矽氧烷（A )的矽原子的合計量之1莫耳，含有0.01至0.2莫耳。 6.如申請專利範圍第1項至第5項之任一項之塗佈液，其中再含有以式（1 )表示之矽化合物（D ) ’ -38- 200835757 [化1] R1〇200835757 X. Patent Application No. 1 A coating liquid for forming a low refractive index film, characterized by comprising a polyoxyalkylene (A) having a ruthenium atom having a fluorine-containing organic group bonded thereto, and a carbon number of 9 to 20 The long-chain amine compound (B), which is prepared by dissolving in an organic solvent (C). 2. The coating liquid according to the first aspect of the invention, wherein the polyoxyalkylene (A) is a total ruthenium atom having 5 to 40 mol% of a ruthenium atom to which a fluorine-containing organic group is bonded. 3. The coating liquid according to claim 1 or 2, wherein the long-chain amine compound (B_) is a linear aliphatic primary or secondary amine or an aliphatic amine having an alicyclic structure. . 4. The coating liquid according to any one of claims 1 to 3, wherein the organic solvent (C) is an alcohol selected from carbon atoms 1 to 6 and ethylene glycol having a carbon number of 3 to 10. At least one of a group of ethers is formed. 5. The coating liquid according to any one of claims 1 to 4, wherein the polyoxyalkylene (A) contains 0.1 if the total amount of all of its ruthenium atoms is converted to cerium oxide. Up to 15% by mass, and the long-chain amine compound (B) contains 0.01 to 0.2 mol of the total amount of the ruthenium atom of the polyoxyalkylene (A). 6. The coating liquid according to any one of claims 1 to 5, further comprising an anthracene compound (D) of the formula (1) - 38-200835757 [Chemical Formula 1] R1〇

R4 (l) (式中，R1、R2、R3以及R4分別獨立表示氫原子或碳數 1至5的飽和烴基，n表示2以上的整數）。 7 · —種低折射率被膜，係使申請專利範圍第1項至第6項之任一項之塗佈液加熱硬化後所製得者。 8· —種防反射材料，係申請專利範圍第7項之低折射率被膜經形成於具有更高折射率之基材表面上者。 9· 一種低折射率被膜形成用塗佈液之製造方法，其特徵爲：含有將含有具有結合有含氟有機基之矽原子之烷氧基矽烷5至40莫耳％之烷氧基矽烷的濃度，如將該烷氧基矽烷的全矽原子換算爲二氧化矽時，爲有機溶劑中4 至1 5質量％之溶液，在對上述烷氧基矽烷的全烷氧化物基的1莫耳爲0.2至2莫耳的草酸的存在下進行縮聚合以製得聚矽氧烷（A )的溶液之過程、及對所得之聚矽氧烷 (A )的溶液，混合碳數9至20的長鏈胺化合物（8)與有機溶劑（C )的混合液之過程。 -39- 200835757 七明說單簡號符表為代圖件表元代之定圖指表 :案代圖本本表1 ，代^Ν Λ/ 定一二指 rv fv 無無八、本案若有化學式時，請揭示最能顯示發明特徵的化學式：無 -3-R4 (1) (wherein R1, R2, R3 and R4 each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms, and n represents an integer of 2 or more). (7) A low-refractive-index film obtained by heat-hardening a coating liquid according to any one of claims 1 to 6. 8. An anti-reflective material which is formed by forming a low refractive index film on the surface of a substrate having a higher refractive index. 9. A method for producing a coating liquid for forming a low refractive index film, comprising: alkoxy decane having 5 to 40 mol% of an alkoxy decane having a ruthenium atom to which a fluorine-containing organic group is bonded; The concentration, if the total ruthenium atom of the alkoxy decane is converted to ruthenium dioxide, is a solution of 4 to 15% by mass in the organic solvent, and 1 mole of the total alkoxide group of the alkoxydecane described above. a process of polycondensation in the presence of 0.2 to 2 moles of oxalic acid to prepare a solution of polyoxyalkylene (A), and a solution of the obtained polyoxane (A), having a carbon number of 9 to 20 A process of mixing a long chain amine compound (8) with an organic solvent (C). -39- 200835757 七明说单单单符表 is the map of the generation of the map. The map is represented by the map: the representative of the map, the table 1 , the generation ^ Ν 定 / fixed one or two fingers rv fv no eight, the case if there is a chemical formula When revealing the chemical formula that best shows the characteristics of the invention: no-3-