TW201809100A - Composition - Google Patents

Abstract

To provide a composition that achieves both water and oil repellency for a coating and can also improve film formation properties. This coating composition includes: an organic silicon compound (a) having bonded, to a silicon atom, at least one trialkylsilyl group-containing molecular chain and at least one hydrolysable group; a metal alkoxide (b); and a flourine-containing organic silicon compound (f) having bonded, to a silicon atom, a fluorine-containing group and a hydrolysable group.

Description

組成物 Composition

本發明係關於用以形成可對各種基材賦予撥水性及撥油性之被膜的組成物。 The present invention relates to a composition for forming a film capable of imparting water repellency and oil repellency to various substrates.

於各種顯示裝置、光學元件、半導體元件、建築材料、汽車零件、奈米壓印技術等中，因於基材之表面附著液滴，而有產生基材之髒污或腐蝕、進而因為該髒污或腐蝕造成性能降低等問題的情況。因此，於此等領域中，要求基材表面之撥水性及撥油性良好。 In various display devices, optical elements, semiconductor elements, building materials, automobile parts, nano-imprint technology, etc., due to the droplets adhering to the surface of the substrate, the substrate is soiled or corroded, and because of the soiling Contamination or corrosion can cause problems such as reduced performance. Therefore, in these fields, the water repellency and oil repellency of the substrate surface are required to be good.

專利文獻1中，提出含有直鏈狀聚二甲基矽氧烷與氟烷基矽烷，且進一步含有溶劑與觸媒之組成物，作為塗佈於具有彎曲形狀之玻璃基材，且可生產滑水性玻璃物品之處理劑。 Patent Document 1 proposes a composition containing a linear polydimethylsiloxane and a fluoroalkylsilane, and further containing a solvent and a catalyst, as a composition for coating on a glass substrate having a curved shape, and producing slip Treatment agent for water-based glass articles.

[先前技術文獻] [Prior technical literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本特開2006-256951號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2006-256951

本發明者等人，得到了以上述專利文獻1記載之被膜，有撥油性、密著性或製膜性不充分的情況之見解。本發明係有鑑於前述實情而為者，其目的為提供可在兼顧被膜之撥水性與撥油性的同時，進而亦提高製膜性之組成物。 The present inventors have found that the film described in the aforementioned Patent Document 1 may have insufficient oil repellency, adhesion, or film-forming properties. The present invention has been made in view of the foregoing facts, and an object of the present invention is to provide a composition which can improve film forming properties while taking into account the water repellency and oil repellency of a film.

本發明者等人鑑於上述實情戮力探討的結果，發現若使用含有特定之有機矽化合物、金屬烷氧化物及含氟有機矽化合物的組成物時，可兼顧所得被膜之撥水性與撥油性，進而製膜性亦成為良好，而完成本發明。本發明包含以下之發明。 In view of the results of the above-mentioned factual investigation, the inventors have found that if a composition containing a specific organosilicon compound, a metal alkoxide, and a fluorine-containing organosilicon compound is used, the water repellency and oil repellency of the obtained film can be taken into consideration. Furthermore, the film forming property became favorable, and completed this invention. The present invention includes the following inventions.

[1]一種塗覆組成物，其含有：至少1個含有三烷基矽烷基之分子鏈與至少1個水解性基鍵結於矽原子之有機矽化合物(a)、金屬烷氧化物(b)及含氟基與水解性基鍵結於矽原子之含氟有機矽化合物(f)。 [1] A coating composition comprising: at least one molecular chain containing a trialkylsilyl group and at least one hydrolyzable group, an organic silicon compound (a) and a metal alkoxide (b ) And a fluorine-containing organosilicon compound (f) in which a fluorine-containing group and a hydrolyzable group are bonded to a silicon atom.

[2]如[1]之塗覆組成物，其中前述化合物(a)為式(I)表示之化合物； [2] The coating composition according to [1], wherein the aforementioned compound (a) is a compound represented by formula (I);

[式(I)中，R^a表示含有三烷基矽烷基之分子鏈，A^a1係 分別獨立地表示水解性基；Z^a1表示含有三烷基矽烷基之分子鏈、含有烴鏈之基、含有矽氧烷骨架之基或水解性基]。 [In formula (I), R ^a represents a molecular chain containing a trialkylsilyl group, and A ^a1 each independently represents a hydrolyzable group; Z ^a1 represents a molecular chain containing a trialkylsilyl group, a group containing a hydrocarbon chain, Contains a siloxane skeleton or a hydrolyzable group].

[3]如[1]或[2]之塗覆組成物，其中前述金屬烷氧化物(b)，為式(II)表示之化合物；【化2】M-(A ^b1 ) _k (II) [3] The coating composition according to [1] or [2], wherein the aforementioned metal alkoxide (b) is a compound represented by formula (II); [Chemical Formula 2] M- (A ^b1 ) _k (II)

[式(II)中，M表示可形成金屬烷氧化物之3價或4價的金屬原子；A^b1係分別獨立地表示碳數1~4之烷氧基；k，係因應M，表示3或4之整數]。 [In formula (II), M represents a trivalent or tetravalent metal atom capable of forming a metal alkoxide; A ^b1 represents an alkoxy group having 1 to 4 carbon atoms independently; k, which corresponds to M, represents 3 Or an integer of 4].

[4]如[1]~[3]中任一項之塗覆組成物，其中前述化合物(f)，為式(III-1)及(III-2)之任一者表示之化合物； [4] The coating composition according to any one of [1] to [3], wherein the aforementioned compound (f) is a compound represented by any one of formulae (III-1) and (III-2);

[式(III-1)中，R^f1，表示碳數1~8之含有氟化碳之基；A^f1係分別獨立地表示水解性基；Z^f1表示含有矽氧烷骨架之基、含有烴鏈之基或水解性基]；【化4】R ^f2 -Si(A ^f2 ) ₃ (III-2) [In formula (III-1), R ^f1 represents a fluorinated carbon-containing group having 1 to 8 carbon atoms; A ^f1 represents a hydrolyzable group independently; Z ^f1 represents a group containing a siloxane skeleton and a hydrocarbon Chain group or hydrolyzable group]; [Chemical Formula 4] R ^f2 -Si (A ^f2 ) ₃ (III-2)

[上述式(III-2)中，R^f2表示水解性矽烷寡聚物殘基。A^f2係分別獨立地表示水解性基、碳數1~12之含氟烷基或碳數1~4之烷基]。 [In the above formula (III-2), R ^f2 represents a hydrolyzable silane oligomer residue. A ^f2 each independently represents a hydrolyzable group, a fluorine-containing alkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 4 carbon atoms].

[5]如[1]~[4]中任一項之塗覆組成物，其中前述含氟有機矽化合物(f)與前述有機矽化合物(a)之含有率的比(含 氟有機矽化合物(f)/有機矽化合物(a))，以莫耳比計，為7/1以上、20/1以下。 [5] The coating composition according to any one of [1] to [4], wherein the ratio of the content ratio of the fluorine-containing organosilicon compound (f) to the organosilicon compound (a) (inclusive) The fluorine organosilicon compound (f) / organosilicon compound (a)) has a molar ratio of 7/1 or more and 20/1 or less.

[6]如[1]~[5]中任一項之塗覆組成物，其中前述金屬烷氧化物(b)與前述含氟有機矽化合物(f)之含有率的比(金屬烷氧化物(b)/含氟有機矽化合物(f))，以莫耳比計，為0.01以上、50以下。 [6] The coating composition according to any one of [1] to [5], wherein the ratio of the content ratio of the metal alkoxide (b) to the fluorine-containing organosilicon compound (f) (metal alkoxide (b) / Fluorine-containing organosilicon compound (f)) is 0.01 or more and 50 or less in molar ratio.

[7]一種被膜，其係由如[1]~[6]之塗覆組成物所形成。 [7] A coating film formed from the coating composition as described in [1] to [6].

本發明之組成物，由於含有特定之有機矽化合物、金屬烷氧化物及含氟有機矽化合物，故可兼顧所得被膜之撥水性、撥油性及密著性，進而製膜性亦成為良好。 Since the composition of the present invention contains a specific organosilicon compound, metal alkoxide, and fluorine-containing organosilicon compound, the water repellency, oil repellency, and adhesion of the obtained film can be taken into consideration, and the film-forming property also becomes good.

本發明之組成物(以下，有僅稱為「組成物」者)，含有：至少1個含有三烷基矽烷基之分子鏈與至少1個水解性基鍵結於矽原子之有機矽化合物(a)；金屬烷氧化物(b)；及含氟基與水解性基鍵結於矽原子之含氟有機矽化合物(f)。金屬烷氧化物(b)本身，相較於有機矽化合物或含氟有機矽化合物(f)而言，對撥水性及撥油性之貢獻雖少，但由本發明之組成物所形成之被膜，可能因為來自金屬烷氧化物(b)之結構係作為間隔件而發揮功能，故含有 三烷基矽烷基之分子鏈或含氟基之撥水性及撥油性受到強調，進而所得之被膜的均質性亦會提高。 The composition of the present invention (hereinafter, simply referred to as a "composition") contains at least one organic silicon compound having a trialkylsilyl-containing molecular chain and at least one hydrolyzable group bonded to a silicon atom ( a); metal alkoxide (b); and a fluorine-containing organosilicon compound (f) having a fluorine-containing group and a hydrolyzable group bonded to a silicon atom. The metal alkoxide (b) itself has less contribution to water repellency and oil repellency than the organosilicon compound or fluorine-containing organosilicon compound (f), but the film formed from the composition of the present invention may Since the structure derived from the metal alkoxide (b) functions as a spacer, it contains The molecular chain of trialkylsilyl groups or the water-repellent and oil-repellent properties of fluorine-containing groups are emphasized, and the homogeneity of the resulting film will also be improved.

前述有機矽化合物(a)，於1分子中，具有：鍵結於中心矽原子的至少1個含有三烷基矽烷基之分子鏈、與鍵結於中心矽原子的至少1個水解性基。作為有機矽化合物(a)，可列舉1個含有三烷基矽烷基之分子鏈與3個水解性基鍵結於中心矽原子的化合物；1個含有三烷基矽烷基之分子鏈、1個含有矽氧烷骨架之基與2個水解性基鍵結於中心矽原子的化合物；1個含有三烷基矽烷基之分子鏈、1個含有烴鏈之基與2個水解性基鍵結於中心矽原子的化合物等。 The organosilicon compound (a) has, in one molecule, at least one trialkylsilyl-containing molecular chain bonded to a central silicon atom, and at least one hydrolyzable group bonded to a central silicon atom. Examples of the organosilicon compound (a) include a molecular chain containing a trialkylsilyl group and three hydrolyzable groups bonded to a central silicon atom; a molecular chain containing a trialkylsilyl group; and A compound containing a siloxane skeleton group and two hydrolyzable groups bonded to a central silicon atom; a molecular chain containing a trialkylsilyl group, a base containing a hydrocarbon chain, and two hydrolyzable groups bonded to Compounds with central silicon atoms.

具體而言，有機矽化合物(a)，較佳為下述式(I)表示之化合物。 Specifically, the organosilicon compound (a) is preferably a compound represented by the following formula (I).

[式(I)中，R^a表示含有三烷基矽烷基之分子鏈，A^a1係分別獨立地表示水解性基。Z^a1表示含有三烷基矽烷基之分子鏈、含有烴鏈之基、含有矽氧烷骨架之基或水解性基]。 [In formula (I), R ^a represents a molecular chain containing a trialkylsilyl group, and A ^a1 each independently represents a hydrolyzable group. Z ^a1 represents a molecular chain containing a trialkylsilyl group, a group containing a hydrocarbon chain, a group containing a siloxane skeleton, or a hydrolyzable group].

前述含有三烷基矽烷基之分子鏈，為具有含有三烷基矽烷基之基鍵結於分子鏈末端之結構的1價基，藉由使含有三烷基矽烷基之基鍵結於分子鏈，會提高由本 發明之組成物所形成之被膜的撥水性及撥油性。又，藉由存在有含有三烷基矽烷基之分子鏈，會減低液滴(水滴、油滴等)與該被膜之間的摩擦，液滴變得容易移動。進一步地，藉由具有三烷基矽烷基，會提高化學耐久性及/或物理耐久性，而提高耐熱性、耐光性。即使含有三烷基矽烷基之基的烷基取代為氟烷基，亦同樣地可提高該被膜界面(表面)之撥水性及撥油性。 The aforementioned trialkylsilyl-containing molecular chain is a monovalent group having a structure in which a trialkylsilyl-containing group is bonded to the end of the molecular chain, and a trialkylsilyl-containing group is bonded to the molecular chain. Will improve by this The water repellency and oil repellency of the film formed by the composition of the invention. In addition, the existence of a molecular chain containing a trialkylsilyl group reduces friction between the liquid droplets (water droplets, oil droplets, and the like) and the film, and the liquid droplets easily move. Furthermore, by having a trialkylsilyl group, chemical durability and / or physical durability are improved, and heat resistance and light resistance are improved. Even if an alkyl group containing a trialkylsilyl group is substituted with a fluoroalkyl group, the water repellency and oil repellency of the interface (surface) of the film can be improved in the same manner.

前述含有三烷基矽烷基之基，為含有至少1個三烷基矽烷基之基，較佳為含有2個以上、更佳為含有3個三烷基矽烷基。含有三烷基矽烷基之基，較佳為式(s1)表示之基。 The trialkylsilyl group-containing group is a group containing at least one trialkylsilyl group, and preferably contains two or more, more preferably three trialkylsilyl groups. The group containing a trialkylsilyl group is preferably a group represented by formula (s1).

[式(s1)中，R^s1表示烴基或三烷基矽烷氧基，該烴基或三烷基矽烷氧基中所含有的氫原子，亦可被氟原子取代。惟，R^s1全部為烴基時，R^s1為烷基。*表示鍵結位置]。 [In the formula (s1), R ^s1 represents a hydrocarbon group or a trialkylsilyloxy group, and a hydrogen atom contained in the hydrocarbon group or the trialkylsilyloxy group may be substituted with a fluorine atom. However, when all of R ^s1 is a hydrocarbon group, R ^s1 is an alkyl group. * Indicates the bond position].

R^s1表示之烴基之碳數。較佳為1~4、更佳為1~3、又更佳為1~2。R^s1全部為烴基時，3個R^s1之合計碳數，較佳為9以下、更佳為6以下、又更佳為4以下。 The carbon number of the hydrocarbon group represented by R ^s1 . It is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2. When all of R ^s1 is a hydrocarbon group, the total carbon number of the three R ^s1 is preferably 9 or less, more preferably 6 or less, and even more preferably 4 or less.

R^s1表示之烴基，較佳為脂肪族烴基、更佳為烷基。該烷基可列舉甲基、乙基、丙基、丁基等。複數個R^s1可 相同亦可相異，較佳為相同。3個R^s1當中較佳至少1個為甲基、更佳至少2個為甲基、特佳3個R^s1全部為甲基。 The hydrocarbon group represented by R ^s1 is preferably an aliphatic hydrocarbon group, more preferably an alkyl group. Examples of the alkyl group include methyl, ethyl, propyl, and butyl. The plurality of R ^s1 may be the same or different, and are preferably the same. Among the three R ^s1 , at least one is preferably a methyl group, more preferably at least two are methyl, and particularly preferably all three R ^s1 are methyl.

又，R^s1表示之三烷基矽烷基及三烷基矽烷氧基中所含有的氫原子，亦可被氟原子取代。氟原子之取代數，當以碳原子數目為A時，較佳為1以上、更佳為3以上、且較佳為2×A+1以下。又，烷基中所含有的氫原子被氟原子取代時，被取代之烷基數目，可於相對於每1個矽原子為1~3個之範圍適當選擇。 The hydrogen atom contained in the trialkylsilyl group and the trialkylsilyloxy group represented by R ^s1 may be substituted with a fluorine atom. When the number of fluorine atoms is A, the number of carbon atoms is preferably 1 or more, more preferably 3 or more, and more preferably 2 × A + 1 or less. When a hydrogen atom contained in an alkyl group is substituted with a fluorine atom, the number of substituted alkyl groups can be appropriately selected within a range of 1 to 3 for each silicon atom.

R^s1全部為烴基(烷基)之基(三烷基矽烷基)，具體而言，可列舉下述式表示之基等。式中，*表示鍵結位置。 All of R ^s1 is a hydrocarbon group (alkyl) group (trialkylsilyl group). Specific examples include a group represented by the following formula. In the formula, * indicates a bonding position.

R^s1之至少1個可為三烷基矽烷氧基。前述三烷基矽烷氧基，可列舉氧原子鍵結於R^s1全部為烴基(烷 基)之基(三烷基矽烷基)的矽原子上之基。 At least one of R ^s1 may be a trialkylsilyloxy group. Examples of the trialkylsilyloxy group include a group in which an oxygen atom is bonded to a silicon atom in which all of R ^s1 is a hydrocarbon group (alkyl) group (trialkylsilyl group).

R^s1之至少1個為三烷基矽烷氧基之基，可列舉下述式表示之基。 At least one of R ^s1 is a trialkylsilyloxy group, and examples thereof include a group represented by the following formula.

含有三烷基矽烷基之分子鏈中，三烷基矽烷基，較佳係鍵結於分子鏈之末端(自由端側)、特別是鍵結於分子鏈之主鏈(最長直鏈)之末端(自由端側)。 Among the molecular chains containing a trialkylsilyl group, the trialkylsilyl group is preferably bonded to the end of the molecular chain (free end side), especially to the end of the main chain (longest straight chain) of the molecular chain. (Free end side).

三烷基矽烷基所鍵結之分子鏈，較佳為直鏈狀或分支鏈狀、更佳為直鏈狀。前述分子鏈，較佳為含有二烷基矽氧烷鏈、更佳為含有直鏈狀二烷基矽氧烷鏈。又，前述分子鏈亦可含有2價烴基。即使分子鏈之一部分為2價烴基，由於其餘部分為二烷基矽氧烷鏈，故所得之 被膜的化學耐久性及/或物理耐久性良好。 The molecular chain to which the trialkylsilyl group is bonded is preferably linear or branched, and more preferably linear. The molecular chain preferably contains a dialkylsiloxane chain, and more preferably contains a linear dialkylsiloxane chain. The molecular chain may contain a divalent hydrocarbon group. Even if one part of the molecular chain is a divalent hydrocarbon group, since the remaining part is a dialkylsiloxane chain, the obtained The coating has good chemical and / or physical durability.

前述分子鏈，較佳為式(s2)表示之基。 The molecular chain is preferably a group represented by formula (s2).

[式(s2)中，R^s2表示碳數1~4之烷基。Z^s1表示-O-或2價烴基，該2價烴基中所含有的-CH₂-，亦可取代為-O-。Y^s1表示單鍵或-Si(R^s2)₂-L^s1-。L^s1表示2價烴基，該2價烴基中所含有的-CH₂-，亦可取代為-O-。左側之*表示與中心矽原子之鍵結位置，右側之*表示與含有三烷基矽烷基之基的鍵結位置]。 [In the formula (s2), R ^s2 represents an alkyl group having 1 to 4 carbon atoms. Z ^s1 represents -O- or a divalent hydrocarbon group, and -CH ₂ -contained in the divalent hydrocarbon group may be substituted with -O-. Y ^s1 represents a single bond or -Si (R ^s2 ) ₂ -L ^s1- . L ^s1 represents a divalent hydrocarbon group, and -CH ₂ -contained in the divalent hydrocarbon group may be substituted with -O-. The * on the left indicates the bonding position with the central silicon atom, and the * on the right indicates the bonding position with a trialkylsilyl group].

前述R^s2表示之烷基之碳數，較佳為1~4、更佳為1~3、又更佳為1~2。R^s2表示之烷基，可列舉甲基、乙基、丙基、丁基等，較佳為甲基或乙基、特佳為甲基。 The carbon number of the alkyl group represented by the aforementioned R ^s2 is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2. Examples of the alkyl group represented by R ^s2 include a methyl group, an ethyl group, a propyl group, and a butyl group. A methyl group or an ethyl group is preferred, and a methyl group is particularly preferred.

n1較佳為1~100、更佳為1~80、又更佳為1~50、特佳為1~30。 n1 is preferably 1 to 100, more preferably 1 to 80, still more preferably 1 to 50, and particularly preferably 1 to 30.

Z^s1或L^s1表示之2價烴基之碳數，較佳為1~10、更佳為1~6、又更佳為1~4。前述2價烴基較佳為鏈狀，為鏈狀時，可為直鏈狀、分支鏈狀的任意者。 The carbon number of the divalent hydrocarbon group represented by Z ^s1 or L ^s1 is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The divalent hydrocarbon group is preferably a chain, and when it is a chain, it may be any of a straight chain and a branched chain.

又，前述2價烴基，較佳為2價之脂肪族烴基、更佳為烷二基。2價烴基可列舉亞甲基、伸乙基、伸丙基、伸丁基等。 The divalent hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, and more preferably an alkanediyl group. Examples of the divalent hydrocarbon group include methylene, ethylene, propyl, and butyl.

進一步地，前述2價烴基中所含有的一部分 之-CH₂-亦可取代為-O-。此時連續2個-CH₂-並不同時取代為-O-，且鄰接於Si原子之-CH₂-並不取代為-O-。2個以上之-CH₂-取代為-O-時，-O-與-O-之間的碳原子數，較佳為2~4、更佳為2~3。2價烴基之一部分取代為-O-之基，具體而言，可例示具有(聚)乙二醇單位之基、具有(聚)丙二醇單位之基等。 Furthermore, a part of -CH ₂ -contained in the divalent hydrocarbon group may be substituted with -O-. At this time, two consecutive -CH ₂ -are not substituted with -O- simultaneously, and -CH ₂ -adjacent to the Si atom is not substituted with -O-. When two or more -CH ₂ -are substituted with -O-, the number of carbon atoms between -O- and -O- is preferably 2 to 4, more preferably 2 to 3. Part of the divalent hydrocarbon group is substituted with Examples of the -O- group include a group having a (poly) ethylene glycol unit and a group having a (poly) propylene glycol unit.

前述式(s2)中，較佳為Z^s1為-O-，Y^s1為單鍵，亦即前述分子鏈僅由二烷基矽烷氧基之重複所構成。二烷基矽氧烷鏈僅由二烷基矽烷氧基之重複所構成時，所得被膜之化學耐久性及/或物理耐久性良好。 In the aforementioned formula (s2), it is preferable that Z ^s1 is -O- and Y ^s1 is a single bond, that is, the aforementioned molecular chain is constituted only by repetition of a dialkylsiloxy group. When the dialkylsilane chain is composed only of the dialkylsiloxy repeat, the obtained film has good chemical durability and / or physical durability.

含有三烷基矽烷基之分子鏈中所含有的分子鏈，可列舉下述式表示之分子鏈。式中，p1表示1~30之整數，*表示形成聚矽氧烷骨架之矽原子或三烷基矽烷基上所鍵結之鍵結位置。 Examples of the molecular chain contained in the trialkylsilyl-containing molecular chain include a molecular chain represented by the following formula. In the formula, p1 represents an integer from 1 to 30, and * represents a bonding position of a silicon atom or a trialkylsilyl group forming a polysiloxane skeleton.

又，構成含有三烷基矽烷基之分子鏈的原子之合計數，較佳為24以上、更佳為40以上、又更佳為50以上；較佳為1200以下、更佳為700以下、又更佳為250以下。 The total number of atoms constituting the molecular chain containing the trialkylsilyl group is preferably 24 or more, more preferably 40 or more, and still more preferably 50 or more; more preferably 1200 or less, more preferably 700 or less, and More preferably, it is 250 or less.

含有三烷基矽烷基之分子鏈，較佳為下述式(s1)表示之基。 The molecular chain containing a trialkylsilyl group is preferably a group represented by the following formula (s1).

[式(s1)中，R^s1、R^s2、Z^s1、Y^s1、n1係與上述相同意義。*表示與矽原子之鍵結位置]。 [In formula (s1), R ^s1 , R ^s2 , Z ^s1 , Y ^s1 , and n1 have the same meanings as described above. * Indicates the bonding position with silicon atom].

含有三烷基矽烷基之分子鏈，更佳為下述式(s1-1)表示之基、又更佳為下述式(s1-1-1)表示之基。 The molecular chain containing a trialkylsilyl group is more preferably a group represented by the following formula (s1-1), and still more preferably a group represented by the following formula (s1-1-1).

[式(s1-1)及(s1-1-1)中，R^s2、Y^s1、Z^s1、n1係與上述相同意義。R^s3表示碳數1~4之烷基。*表示與矽原子之鍵結位置]。 [In the formulae (s1-1) and (s1-1-1), R ^s2 , Y ^s1 , Z ^s1 , and n1 have the same meanings as described above. R ^s3 represents an alkyl group having 1 to 4 carbon atoms. * Indicates the bonding position with silicon atom].

又，含有三烷基矽烷基之分子鏈，亦佳為下述式(s1-2)表示之基、更佳為下述式(s1-2-1)表示之基。 The molecular chain containing a trialkylsilyl group is also preferably a group represented by the following formula (s1-2), and more preferably a group represented by the following formula (s1-2-1).

[式(s1-2)及式(s1-2-1)中，R^s2、R^s3、Y^s1、Z^s1、n1係與上述相同意義。*表示與矽原子之鍵結位置]。 [In formulas (s1-2) and (s1-2-1), R ^s2 , R ^s3 , Y ^s1 , Z ^s1 , and n1 have the same meanings as described above. * Indicates the bonding position with silicon atom].

R^s3表示之烷基，可列舉與作為R^s1表示之烴基所例示之烷基相同之基，該烷基之碳數較佳為1~3、更佳為1~2。又，*-Si(R^s3)₃中所含有的R^s3的合計之碳數，較佳為9以下、更佳為6以下、又更佳為4以下。 Examples of the alkyl group represented by R ^s3 include the same groups as those exemplified for the hydrocarbon group represented by R ^s1 . The number of carbon atoms of the alkyl group is preferably 1 to 3, and more preferably 1 to 2. The total carbon number of R ^s3 contained in * -Si (R ^s3 ) ₃ is preferably 9 or less, more preferably 6 or less, and even more preferably 4 or less.

進一步地，*-Si(R^s3)₃中所含有的R^s3當中，較佳至少1個為甲基、更佳2個以上之R^s3為甲基、特佳3個R^s3全部為甲基。 Further, among R ^s3 contained in * -Si (R ^s3 ) ₃ , it is preferred that at least one is methyl, more preferably two or more R ^s3 are methyl, and particularly preferred three R ^{s3 are} all methyl. .

含有三烷基矽烷基之分子鏈，可列舉式(s1-I)表示之基。下述式(s1-I-1)~(s1-I-50)，為式(s1-I)表示之基的具體例子，但不限定於此等。式(s1-I)表示之基中，其中所含有的複數個R^s20及複數個R^s10，可分別相同、亦可相異。 Examples of the molecular chain containing a trialkylsilyl group include a group represented by the formula (s1-I). The following formulae (s1-I-1) to (s1-I-50) are specific examples of the base represented by the formula (s1-I), but are not limited thereto. In the base represented by the formula (s1-I), the plural R ^s20 and plural R ^s10 contained therein may be the same or different, respectively.

有機矽化合物(a)中，鍵結於中心矽原子的含有三烷基矽烷基之分子鏈個數，較佳為1~3、更佳為1~2、特佳為1。 In the organosilicon compound (a), the number of trialkylsilyl-containing molecular chains bonded to the central silicon atom is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.

當鍵結於矽原子時，前述水解性基只要係藉由水解而賦予羥基(矽醇基)之基即可，較佳可列舉例如甲氧基、乙氧基、丙氧基、丁氧基等之碳數1~4之烷氧基；乙醯氧基；氯原子；異氰酸酯基等。其中尤以碳數1~4之 烷氧基為佳、碳數1~2之烷氧基更佳。 When bonded to a silicon atom, the hydrolyzable group may be a group that imparts a hydroxyl group (silanol group) by hydrolysis. Preferred examples include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Alkoxy groups having 1 to 4 carbon atoms; ethoxyl groups; chlorine atoms; isocyanate groups, etc. Among them, especially carbon number 1 ~ 4 Alkoxy is preferred, and alkoxy having 1 to 2 carbon atoms is more preferred.

有機矽化合物(a)中，鍵結於中心矽原子之水解性基的個數，係1~3、較佳為2~3。 In the organosilicon compound (a), the number of hydrolyzable groups bonded to the central silicon atom is 1 to 3, preferably 2 to 3.

以下，有將水解性基鍵結於矽原子之基稱為水解性矽基的情況。 Hereinafter, a group in which a hydrolyzable group is bonded to a silicon atom may be referred to as a hydrolyzable silicon group.

前述含有矽氧烷骨架之基，為含有矽氧烷單位(Si-O-)之1價基，只要係以較構成含有三烷基矽烷基之分子鏈的原子數更少數目之原子所構成者即可。藉此，含有矽氧烷骨架之基，成為相較於含有三烷基矽烷基之分子鏈而言長度更短、或立體伸展度(容積)更小之基。含有矽氧烷骨架之基中，亦可含有2價烴基。 The aforementioned group containing a siloxane skeleton is a monovalent group containing a siloxane unit (Si-O-), as long as it is composed of a smaller number of atoms than the number of atoms constituting a molecular chain containing a trialkylsilyl group. That's all. As a result, the group containing a siloxane skeleton becomes a group having a shorter length or a smaller three-dimensional extension (volume) than a molecular chain containing a trialkylsilyl group. The group containing a siloxane skeleton may contain a divalent hydrocarbon group.

含有矽氧烷骨架之基，較佳為下述式(s2)表示之基。 The group containing a siloxane skeleton is preferably a group represented by the following formula (s2).

[式(s2)中，R^s2係與上述相同意義。R^s5表示烴基或羥基，該烴基中所含有的-CH₂-，亦可取代為-O-，該烴基中所含有的氫原子，亦可被氟原子取代。Z^s2表示-O-或2價烴基，該2價烴基中所含有的-CH₂-，亦可取代為-O-。Y^s2表示單鍵或-Si(R^s2)₂-L^s2-。L^s2表示2價烴基，該2價烴基中所含有的-CH₂-，亦可取代為-O-。n2表示0~5之整數。*表示與矽原子之鍵結位置]。 [In formula (s2), R ^s2 has the same meaning as described above. R ^s5 represents a hydrocarbon group or a hydroxyl group, -CH ₂ -contained in the hydrocarbon group may be substituted with -O-, and a hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom. Z ^s2 represents -O- or a divalent hydrocarbon group, and -CH ₂ -contained in the divalent hydrocarbon group may be substituted with -O-. Y ^s2 represents a single bond or -Si (R ^s2 ) ₂ -L ^s2- . L ^s2 represents a divalent hydrocarbon group, and -CH ₂ -contained in the divalent hydrocarbon group may be substituted with -O-. n2 represents an integer from 0 to 5. * Indicates the bonding position with silicon atom].

R^s5表示之烴基，可列舉與R^s1表示之烴基相同之基，較佳為脂肪族烴基、更佳為烷基。碳數較佳為1~4、更佳為1~3、又更佳為1~2。 Examples of the hydrocarbon group represented by R ^s5 include the same groups as the hydrocarbon group represented by R ^s1 , and an aliphatic hydrocarbon group is more preferable, and an alkyl group is more preferable. The carbon number is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.

Z^s2或L^s2表示之2價烴基，可列舉與Z^s1表示之2價烴基相同之基，碳數較佳為1~10、更佳為1~6、又更佳為1~4。又，Z^s2或L^s2表示之2價烴基，較佳為2價之脂肪族烴基、更佳為直鏈狀或分支鏈狀之烷二基。 The divalent hydrocarbon group represented by Z ^s2 or L ^s2 includes the same groups as the divalent hydrocarbon group represented by Z ^s1 . The number of carbons is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The divalent hydrocarbon group represented by Z ^s2 or L ^s2 is preferably a divalent aliphatic hydrocarbon group, and more preferably a linear or branched alkanediyl group.

n2較佳為1~5、更佳為1~3。 n2 is preferably 1 to 5, and more preferably 1 to 3.

含有矽氧烷骨架之基，具體而言，可列舉下述式表示之基。 Specific examples of the group containing a siloxane skeleton include a group represented by the following formula.

前述含有烴鏈之基，為含有烴鏈之1價基，只要相較於含有三烷基矽烷基之分子鏈的構成分子鏈之原子數而言，烴鏈部分之碳數為更少者即可。又，較佳為相較於構成含有三烷基矽烷基之分子鏈的最長直鏈之原子數而言，烴鏈之最長直鏈之碳數為更少者。 The aforementioned hydrocarbon chain-containing group is a monovalent group containing a hydrocarbon chain, as long as the carbon number of the hydrocarbon chain portion is smaller than the number of atoms constituting the molecular chain of the molecular chain containing the trialkylsilyl group. can. Moreover, it is preferable that the longest straight chain carbon number of a hydrocarbon chain is smaller than the longest straight chain atom number which comprises the molecular chain containing a trialkylsilyl group.

含有烴鏈之基，亦可僅由烴基(烴鏈)構成，該烴鏈中所含有的-CH₂-亦可取代為-O-，較佳為僅由烴基(烴鏈)所構成。惟鄰接於Si原子之-CH₂-並不取代為-O-，又，連續 2個-CH₂-亦不同時取代為-O-。 The group containing a hydrocarbon chain may be composed only of a hydrocarbon group (hydrocarbon chain), and -CH ₂ -contained in the hydrocarbon chain may also be substituted with -O-, and preferably is composed of only a hydrocarbon group (hydrocarbon chain). However, -CH ₂ -adjacent to the Si atom is not substituted with -O-, and two consecutive -CH ₂ -are not substituted with -O- at the same time.

再者，烴鏈部分之碳數，於氧非取代型之含有烴鏈之基中意指構成烴基(烴鏈)之碳原子數目，於氧取代型之含有烴鏈之基中，意指將-O-讀取並計數為-CH₂-之碳原子數目。以下，若無特別指明，係以氧非取代型之含有烴鏈之基(亦即1價烴基)為例來說明含有烴鏈之基，但在所有的說明中，該-CH₂-當中之一部分均可取代為-O-。 In addition, the carbon number of the hydrocarbon chain portion means the number of carbon atoms constituting the hydrocarbon group (hydrocarbon chain) in the oxygen-non-substituted hydrocarbon chain-containing group, and the oxygen-substituted hydrocarbon chain-containing group, which means- O- is read and counted as the number of carbon atoms in -CH _2- . In the following, unless otherwise specified, the oxygen-containing non-substituted hydrocarbon chain-containing group (ie, a monovalent hydrocarbon group) is used as an example to describe the hydrocarbon chain-containing group. However, in all the descriptions, -CH _2- Some can be replaced with -O-.

前述含有烴鏈之基之碳數較佳為1~3、更佳為1。又，前述含有烴鏈之基(烴基的情況時)，可為分支鏈狀亦可為直鏈狀。前述含有烴鏈之基(烴基的情況時)，較佳為含有飽和或不飽和之脂肪族烴鏈之基、更佳為含有飽和脂肪族烴鏈之基。前述含有飽和脂肪族烴鏈之基，較佳為甲基、乙基、丙基等之烷基。 The carbon number of the aforementioned hydrocarbon chain-containing group is preferably 1 to 3, and more preferably 1. The aforementioned hydrocarbon chain-containing group (in the case of a hydrocarbon group) may be branched or linear. The group containing a hydrocarbon chain (in the case of a hydrocarbon group) is preferably a group containing a saturated or unsaturated aliphatic hydrocarbon chain, and more preferably a group containing a saturated aliphatic hydrocarbon chain. The aforementioned group containing a saturated aliphatic hydrocarbon chain is preferably an alkyl group such as methyl, ethyl, or propyl.

烴鏈中所含有的-CH₂-取代為-O-時，可例示具有(聚)乙二醇單位之基等。 When -CH ₂ -contained in the hydrocarbon chain is substituted with -O-, examples include a group having a (poly) ethylene glycol unit.

其中，有機矽化合物(a)，尤以下述式(I-1)表示之化合物為佳、式(I-1-1)表示之化合物為更佳。 Among these, the organosilicon compound (a) is particularly preferably a compound represented by the following formula (I-1), and more preferably a compound represented by the formula (I-1-1).

[式(I-1)及(I-1-1)中，A^a1、Z^a1、Z^s1、Y^s1、R^s2、R^s3、n1，係分別與上述相同意義]。 [In formulae (I-1) and (I-1-1), A ^a1 , Z ^a1 , Z ^s1 , Y ^s1 , R ^s2 , R ^s3 , and n1 have the same meanings as described above, respectively].

又，有機矽化合物(a)，亦可為式(I-2)表示之化合物、較佳可為式(I-2-1)表示之化合物。 The organosilicon compound (a) may be a compound represented by the formula (I-2), and preferably a compound represented by the formula (I-2-1).

[式(I-2)及式(I-2-1)中，A^a1、Z^a1、Z^s1、Y^s1、R^s2、R^s3、n2，係分別與上述相同意義]。 [In formulae (I-2) and (I-2-1), A ^a1 , Z ^a1 , Z ^s1 , Y ^s1 , R ^s2 , R ^s3 , and n2 have the same meanings as described above, respectively].

有機矽化合物(a)，具體而言，可列舉式(I-I) 表示之基。下述式(I-I-1)~(I-I-100)，為式(I-I)表示之基的具體例子，但不限定於此等。式(s1-I)表示之基中，其中所含有的複數個A^a10、複數個R^s20及複數個R^s10，可分別相同、亦可相異。 Specific examples of the organosilicon compound (a) include a group represented by formula (II). The following formulae (II-1) to (II-100) are specific examples of the group represented by formula (II), but are not limited thereto. In the base represented by formula (s1-I), the plurality of A ^a10 , the plurality of R ^s20, and the plurality of R ^s10 contained therein may be the same or different, respectively.

有機矽化合物(a)之合成方法的例子，可列舉如下之方法。作為第一方法，可藉由使鍵結有含有三烷基矽烷基之分子鏈與鹵素原子(較佳為氯原子)之化合物、與於矽原子上鍵結有水解性基3個以上(特別是4個)之化合物反應來製造。 Examples of the method for synthesizing the organosilicon compound (a) include the following methods. As a first method, a compound containing a trialkylsilyl group-containing molecular chain and a halogen atom (preferably a chlorine atom) is bonded, and three or more hydrolyzable groups are bonded to a silicon atom (particularly, It is made by reacting 4) compounds.

作為第二合成方法，可藉由使於二烷基矽氧烷鏈之兩末端鍵結有鹵素原子之化合物(以下稱「二鹵化二烷基矽氧烷」)、鍵結有參(三烷基矽烷氧基)矽烷基與M¹O-基(M¹ 表示鹼金屬)之化合物(以下稱「鹼金屬矽烷基氧化物」)及於矽原子上鍵結有水解性基4個之化合物反應來製造。此等化合物之反應順序並無限定，較佳為首先使二鹵化二烷基矽氧烷與鹼金屬矽烷基氧化物反應，接著，使於矽原子上鍵結有水解性基4個之化合物反應。 As a second synthesis method, a compound in which a halogen atom is bonded to both ends of the dialkylsiloxane chain (hereinafter referred to as "dihalogenated dialkylsiloxane"), and Silyloxy) silyl group reacts with a compound of M ¹ O- group (M ¹ represents an alkali metal) (hereinafter referred to as "alkali metal silyl oxide") and a compound having four hydrolyzable groups bonded to a silicon atom To make. The reaction order of these compounds is not limited. It is preferred to first react a dihalogenated dialkylsiloxane with an alkali metal silane oxide and then react a compound having 4 hydrolyzable groups bonded to a silicon atom .

前述鹵素原子可列舉氟原子、氯原子、溴原子、碘原子等，較佳為氯原子。又，前述鹼金屬較佳為鋰。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A chlorine atom is preferred. The alkali metal is preferably lithium.

鹼金屬矽烷基氧化物，例如，可藉由使烷基鹼金屬與鍵結有參(三烷基矽烷氧基)矽烷基與羥基之化合物反應來製造。有機鹼金屬化合物，可列舉n-丁基鋰、sec-丁基鋰、tert-丁基鋰等之烷基鋰，特佳為n-丁基鋰。 The alkali metal silyl oxide can be produced, for example, by reacting an alkyl alkali metal with a compound having a reference (trialkylsilyloxy) silyl group and a hydroxyl group. Examples of the organic alkali metal compound include alkyl lithium such as n-butyllithium, sec-butyllithium, and tert-butyllithium, and particularly preferred is n-butyllithium.

又，作為第三合成方法，有機矽化合物(a)，例如亦可藉由使鹼金屬矽烷基氧化物及環狀二甲基矽氧烷反應，接著，使於矽原子上鍵結有水解性基3個與鹵素原子(特別是氯原子)1個之化合物反應來製造。 In addition, as the third synthesis method, the organosilicon compound (a) may, for example, be reacted with an alkali metal silyl oxide and a cyclic dimethylsiloxane, and then hydrolyzable to a silicon atom. It is produced by reacting three compounds with one halogen atom (especially a chlorine atom).

又，作為第四合成法，有機矽化合物(a)，例如亦可藉由使鹼金屬矽烷基氧化物及環狀二甲基矽氧烷反應，得到末端具有羥基之二甲基矽氧烷，接著，使四烷氧基矽烷反應來製造。 In addition, as the fourth synthesis method, the organosilicon compound (a) can also be obtained by reacting an alkali metal silyl oxide and a cyclic dimethylsiloxane to obtain a dimethylsiloxane having a hydroxyl group at the terminal. Next, tetraalkoxysilane is made to react.

有機矽化合物(a)之含有率，於組成物100質量%中，較佳為0.01質量%以上、更佳為0.05質量%以上、又更佳為0.1質量%以上；較佳為10質量%以下、更佳為5質量%以下、又更佳為3質量%以下。 The content of the organosilicon compound (a) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more, and preferably 10% by mass or less, based on 100% by mass of the composition. It is more preferably 5 mass% or less, and still more preferably 3 mass% or less.

前述金屬烷氧化物(b)，為烷氧基鍵結於金屬 原子之化合物，由本發明之組成物所形成之被膜中，可形成具有間隔件功能之部位。其結果，可提高含有三烷基矽烷基之分子鏈或含氟基所致之撥水性及撥油性提高作用，進而製膜性亦成為良好。 The metal alkoxide (b) is an alkoxy group bonded to a metal The atomic compound can form a part having a function of a spacer in a film formed from the composition of the present invention. As a result, the water-repellent and oil-repellent properties of the trialkylsilyl group-containing molecular chain or the fluorine-containing group can be improved, and the film-forming property can also be improved.

前述金屬烷氧化物(b)，具體而言，較佳為式(II)表示之化合物。又，式(II)表示之化合物，亦可為其水解縮合物。此處，水解縮合物，意指各化合物(II)中所含有的全部或一部分之烷氧基藉由水解而縮合之化合物。 The metal alkoxide (b) is specifically preferably a compound represented by the formula (II). The compound represented by the formula (II) may be a hydrolyzed condensate thereof. Here, the hydrolyzed condensate means a compound in which all or a part of the alkoxy group contained in each compound (II) is condensed by hydrolysis.

【化22】M-(A ^b1 ) _k (II) [Chem. 22] M- (A ^b1 ) _k (II)

[式(II)中，M表示可形成金屬烷氧化物之3價或4價的金屬原子。A^b1係分別獨立地表示碳數1~4之烷氧基。k，因應M之價數，係表示3或4之整數]。 [In formula (II), M represents a trivalent or tetravalent metal atom capable of forming a metal alkoxide. A ^b1 each independently represents an alkoxy group having 1 to 4 carbon atoms. k, corresponding to the valence of M, is an integer of 3 or 4].

M為可與烷氧基鍵結而形成金屬烷氧化物的金屬原子，該金屬原子亦包含Si、Ge等之半金屬。M可列舉Al、Fe、In等之3價金屬；Hf、Si、Ti、Sn、Zr等之4價金屬等，較佳為Al等之3價金屬；Si、Ti、Sn、Zr等之4價金屬；更佳為Al、Si、Ti、Zr；特佳為Si。此等金屬之烷氧化物，容易液狀化。又，M為3價金屬時，k表示3，M為4價金屬時，k表示4。 M is a metal atom that can be bonded to an alkoxy group to form a metal alkoxide, and the metal atom also includes a semimetal such as Si or Ge. M may be a trivalent metal such as Al, Fe, In, etc .; a tetravalent metal such as Hf, Si, Ti, Sn, Zr, etc., preferably a trivalent metal such as Al; 4 of Si, Ti, Sn, Zr, etc. Valence metals; more preferably Al, Si, Ti, Zr; particularly preferred is Si. These metal alkoxides are easily liquefied. When M is a trivalent metal, k represents 3, and when M is a tetravalent metal, k represents 4.

A^b1表示之烷氧基，更佳為碳數1~2之烷氧基。 The alkoxy group represented by A ^b1 is more preferably an alkoxy group having 1 to 2 carbon atoms.

又，有機矽化合物(a)之水解性基與金屬烷氧化物(b) 之烷氧基，可相同亦可相異，較佳為相同，較佳係均為碳數1~4之烷氧基。 The hydrolyzable group of the organosilicon compound (a) and the metal alkoxide (b) The alkoxy groups may be the same or different, and are preferably the same, and are preferably alkoxy groups having 1 to 4 carbon atoms.

金屬烷氧化物(b)可列舉四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四丁氧基矽烷等之四烷氧基矽烷；三乙氧基鋁、三丙氧基鋁、三丁氧基鋁等之三烷氧基鋁；三乙氧基鐵等之三烷氧基鐵；三甲氧基銦、三乙氧基銦、三丙氧基銦、三丁氧基銦等之三烷氧基銦；四甲氧基鉿、四乙氧基鉿、四丙氧基鉿、四丁氧基鉿等之四烷氧基鉿；四甲氧基鈦、四乙氧基鈦、四丙氧基鈦、四丁氧基鈦等之四烷氧基鈦；四甲氧基錫、四乙氧基錫、四丙氧基錫、四丁氧基錫等之四烷氧基錫；四甲氧基鋯、四乙氧基鋯、四丙氧基鋯、四丁氧基鋯等之四烷氧基鋯等。 Examples of the metal alkoxide (b) include tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane; triethoxyaluminum and tripropoxy Trialkoxy aluminum such as aluminum, tributoxy aluminum; trialkoxy iron such as triethoxy iron; trimethoxy indium, triethoxy indium, tripropoxy indium, tributoxy indium Indium trialkoxy indium; tetramethoxyfluorene, tetraethoxyfluorene, tetrapropoxyfluorene, tetrabutoxyfluorene, and other tetraalkoxyfluorene; tetramethoxy titanium, tetraethoxy titanium , Tetraalkoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, etc .; tetramethoxy tin, tetraethoxy tin, tetrapropoxy tin, tetrabutoxy tin, etc. ; Tetraalkoxyzirconium, such as zirconium tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium, etc.

金屬烷氧化物(b)之含有率，於組成物100質量%中，較佳為0.01質量%以上、更佳為0.5質量%以上、又更佳為1.0質量%以上；較佳為20質量%以下、更佳為10質量%以下、又更佳為5質量%以下。 The content of the metal alkoxide (b) is preferably 0.01% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more, and more preferably 20% by mass, based on 100% by mass of the composition. The content is preferably 10% by mass or less, and more preferably 5% by mass or less.

本發明之組成物中，金屬烷氧化物(b)與有機矽化合物(a)之比(金屬烷氧化物(b)/有機矽化合物(a))，以莫耳基準計，較佳為1/10以上、更佳為1/1以上、又更佳為2/1以上；較佳為100/1以下、更佳為50/1以下、又更佳為30/1以下、又再更佳為25/1以下。 In the composition of the present invention, the ratio of the metal alkoxide (b) to the organosilicon compound (a) (metal alkoxide (b) / organosilicon compound (a)) is preferably 1 on a mole basis. / 10 or more, more preferably 1/1 or more, and even more preferably 2/1 or more; preferably 100/1 or less, more preferably 50/1 or less, still more preferably 30/1 or less, and even better It is 25/1 or less.

前述含氟有機矽化合物(f)，於1分子中，具有鍵結於中心矽原子的至少1個含氟基、與鍵結於中心矽原子的至少1個水解性基。藉由於組成物中含有含氟有機 矽化合物，所得之被膜的撥水性及撥油性容易提高。 The fluorine-containing organosilicon compound (f) has at least one fluorine-containing group bonded to a central silicon atom and at least one hydrolyzable group bonded to a central silicon atom in one molecule. Because the composition contains fluorine-containing organic Silicon compounds can easily improve the water repellency and oil repellency of the obtained film.

前述含氟基，為包含碳原子與氟原子鍵結之結構的基，可為可具有取代基之氟化烴基，亦可為氟化烴基所鍵結之矽原子與-O-交互配置之基(有稱為水解性矽烷寡聚物殘基者)。 The aforementioned fluorine-containing group is a group including a structure in which a carbon atom and a fluorine atom are bonded, and may be a fluorinated hydrocarbon group which may have a substituent, or a group in which a silicon atom bonded to a fluorinated hydrocarbon group and -O- are arranged alternately. (There are residues called hydrolyzable silane oligomers).

前述含氟有機矽化合物(f)，具體而言，較佳為下述式(III-1)或(III-2)之任一者表示之化合物。又，式(III-1)或(III-2)表示之化合物，亦可分別為其水解縮合物(化合物中所含有的水解性基藉由水解而縮合之基)。 The fluorine-containing organosilicon compound (f) is specifically preferably a compound represented by any one of the following formula (III-1) or (III-2). The compound represented by the formula (III-1) or (III-2) may be a hydrolyzed condensate (a group in which a hydrolyzable group contained in the compound is condensed by hydrolysis), respectively.

[式(III-1)中，R^f1，表示碳數1~8之含有氟化碳之基。A^f1係分別獨立地表示水解性基。Z^f1表示含有矽氧烷骨架之基、含有烴鏈之基或水解性基]。 [In formula (III-1), R ^f1 represents a carbon fluoride-containing group having 1 to 8 carbon atoms. A ^f1 represents each independently a hydrolyzable group. Z ^f1 represents a group containing a siloxane skeleton, a group containing a hydrocarbon chain, or a hydrolyzable group].

【化24】R ^f2 -Si(A ^f2 ) ₃ (III-2) [Chemical formula 24] R ^f2 -Si (A ^f2 ) ₃ (III-2)

[上述式(III-2)中，R^f2表示水解性矽烷寡聚物殘基。A^f2係分別獨立地表示水解性基、碳數1~12之含氟烷基或碳數1~4之烷基]。 [In the above formula (III-2), R ^f2 represents a hydrolyzable silane oligomer residue. A ^f2 each independently represents a hydrolyzable group, a fluorine-containing alkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 4 carbon atoms].

A^f1、A^f2及Z^f1表示之水解性基，可列舉與有機矽化合物(a)之水解性基相同之基，較佳為烷氧基或異氰酸酯基、更佳為碳數1~4之烷氧基、又更佳為碳數1~2之 烷氧基。 The hydrolyzable groups represented by A ^f1 , A ^f2 and Z ^f1 include the same groups as the hydrolyzable group of the organosilicon compound (a), preferably an alkoxy group or an isocyanate group, more preferably a carbon number of 1 to 4 The alkoxy group is more preferably an alkoxy group having 1 to 2 carbon atoms.

又，含氟有機矽化合物(f)與有機矽化合物(a)之水解性基可相同亦可相異，較佳為相同，較佳為均為碳數1~4之烷氧基。 In addition, the hydrolyzable groups of the fluorine-containing organosilicon compound (f) and the organosilicon compound (a) may be the same or different, and are preferably the same, and are preferably alkoxy groups having 1 to 4 carbon atoms.

Z^f1表示之含有矽氧烷骨架之基、含有烴鏈之基及R^f1表示之含有氟化碳之基的原子數，較佳為較有機化合物(a)中之分子鏈(較佳為連結三烷基矽烷基與水解性矽基的鏈狀或環狀之烴及/或鏈狀或環狀之二烷基矽氧烷)的原子數更少。又，Z^f1中之含有矽氧烷骨架之基、含有烴鏈之基或R^f1表示之含有氟化碳之基中所含有的最長直鏈之碳數，較佳為少於含有三烷基矽烷基之分子鏈的原子數。藉此，於由本發明之組成物所形成之被膜中，來自金屬烷氧化物(b)之結構可作為間隔件而作用。 The number of atoms of the group containing a siloxane skeleton represented by Z ^f1 , the group containing a hydrocarbon chain and the group containing a fluorocarbon represented by R ^f1 is preferably more than the molecular chain (preferably linked) in the organic compound (a) Trialkylsilyl and hydrolyzable silyl chain or cyclic hydrocarbons and / or chain or cyclic dialkylsiloxanes) have fewer atoms. The longest linear carbon number contained in the group containing a siloxane skeleton, the group containing a hydrocarbon chain, or the group containing a fluorinated carbon represented by R ^{f1 in} Z ^f1 is preferably less than that containing a trialkyl group. The number of atoms in the molecular chain of a silane group. Thereby, in the film formed from the composition of the present invention, the structure derived from the metal alkoxide (b) can function as a spacer.

Z^f1表示之含有矽氧烷骨架之基、含有烴鏈之基，可列舉與Z^a2表示之含有矽氧烷骨架之基、含有烴鏈之基分別相同之基。 Examples of the group containing a siloxane skeleton and a group containing a hydrocarbon chain represented by Z ^f1 include the same groups as the group containing a siloxane skeleton and a group containing a hydrocarbon chain represented by Z ^a2 .

R^f1表示之含有氟化碳之基，為含有氟原子鍵結於碳原子之結構的1價基，較佳為末端具有氟烷基之基、較佳為末端具有氟烷基(較佳為三氟甲基)之基。含有氟化碳之基，較佳為式(f1)表示之基。 The group containing a fluorinated carbon represented by R ^f1 is a monovalent group containing a structure in which a fluorine atom is bonded to a carbon atom, preferably a group having a fluoroalkyl group at the terminal, and preferably a fluoroalkyl group at the terminal (preferably Trifluoromethyl). The group containing a fluorinated carbon is preferably a group represented by formula (f1).

[上述式(f1)中，R^f3表示碳數1~20之含氟烷基。R^f4表示氟原子或碳數1~20之氟烷基。R^b4表示氫原子或碳數1~4之烷基。L表示-O-、-COO-、-OCO-、-NR^f5-、-NR^f5CO-、及-CONR^f5-之任一者。R^f5表示氫原子或碳數1~4之烷基或碳數1~4之含氟烷基。h1~h5為0以上100以下之整數，h1~h5之合計值為100以下。又，附有h1~h5而以括弧括起的各重複單位之順序，於式中為任意。*表示鍵結位置]。 [In the above formula (f1), R ^f3 represents a fluorine-containing alkyl group having 1 to 20 carbon atoms. R ^f4 represents a fluorine atom or a fluoroalkyl group having 1 to 20 carbon atoms. R ^b4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. L represents any one of -O-, -COO-, -OCO-, -NR ^f5- , -NR ^f5 CO-, and -CONR ^f5- . R ^f5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms. h1 to h5 are integers from 0 to 100, and the total value of h1 to h5 is 100 or less. The order of each repeating unit enclosed by parentheses with h1 to h5 is arbitrary in the formula. * Indicates the bond position].

R^f3或R^f4表示之含氟烷基之碳數，係1~20、較佳為1~12、更佳為1~10、又更佳為1~5。又，R^f3或R^f4表示之含氟烷基中的氟原子之取代數，當以該含氟烷基中所含有的碳原子數目為A時，係1以上、2A+1以下；較佳為2A+1、亦即該含氟烷基為全氟烷基。 The carbon number of the fluorine-containing alkyl group represented by R ^f3 or R ^f4 is 1 to 20, preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 5. The number of substitutions of fluorine atoms in the fluorine-containing alkyl group represented by R ^f3 or R ^f4 is 1 or more and 2A + 1 or less when the number of carbon atoms contained in the fluorine-containing alkyl group is A; It is 2A + 1, that is, the fluorine-containing alkyl group is a perfluoroalkyl group.

R^b4表示之烷基，可列舉與作為R^s1表示之烴基所例示的烷基為相同之基。 Examples of the alkyl group represented by R ^b4 include the same ones as those exemplified for the hydrocarbon group represented by R ^s1 .

L^f1較佳為-O-、-COO-、及-OCO-之任一者。 L ^{f1 is} preferably any one of -O-, -COO-, and -OCO-.

h1較佳為1~30、更佳為1~25、又更佳為1~10、特佳為1~5、最佳為1~2。h2較佳為0~15、更佳為0~10。h3較佳為0~5、更佳為0~2。h4較佳為0~4、更佳為0~2。h5較佳為0~4、更佳為0~2。h1~h5之合計值較佳為3以上、更佳為5以上；又，較佳為80以下、更佳為50以下、又更佳為20以下。 h1 is preferably from 1 to 30, more preferably from 1 to 25, still more preferably from 1 to 10, particularly preferably from 1 to 5, and most preferably from 1 to 2. h2 is preferably 0-15, and more preferably 0-10. h3 is preferably 0 to 5, more preferably 0 to 2. h4 is preferably 0 to 4, and more preferably 0 to 2. h5 is preferably 0 to 4, more preferably 0 to 2. The total value of h1 to h5 is preferably 3 or more, more preferably 5 or more; and more preferably 80 or less, more preferably 50 or less, and still more preferably 20 or less.

特別佳為R^f3為碳數1~5之全氟烷基，R^f4為氟原子或碳數1~5之全氟烷基，R^b4為氫原子，h3、h4及 h5均為0，h1為1~5，h2為0~5。 Particularly preferably, R ^f3 is a perfluoroalkyl group having 1 to 5 carbon atoms, R ^f4 is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, R ^b4 is a hydrogen atom, h3, h4, and h5 are all 0, h1 It is 1 ~ 5, h2 is 0 ~ 5.

前述含有氟化碳之基，可列舉例如下述式表示之基。式中，R^f3、R^b4係與上述相同意義，R^f3較佳為碳數1~12之全氟烷基，R^b4較佳為氫原子。又，r2為5~20、較佳為8~15。r3為1~7、較佳為2~6。r4為1~10、較佳為3~7。r5為1~6、較佳為2~4。 Examples of the carbon fluoride-containing group include a group represented by the following formula. In the formula, R ^f3 and R ^{b4 have} the same meanings as above, R ^{f3 is} preferably a perfluoroalkyl group having 1 to 12 carbon atoms, and R ^{b4 is} preferably a hydrogen atom. In addition, r2 is 5 to 20, preferably 8 to 15. r3 is 1 to 7, preferably 2 to 6. r4 is 1 to 10, preferably 3 to 7. r5 is 1 to 6, preferably 2 to 4.

式(f1-1)表示之基，可列舉下述式表示之基。 Examples of the base represented by the formula (f1-1) include the base represented by the following formula.

式(f1-2)表示之基，可列舉下述式表示之基。惟L^f2表示碳數5~20之烷二基。 Examples of the base represented by the formula (f1-2) include the base represented by the following formula. However, L ^f2 represents an alkanediyl group having 5 to 20 carbon atoms.

【化28】F ₃ C-O-L ^f2 -* F ₃ CF ₂ C-O-L ^f2 -* F ₃ C(F ₂ C) ₂ -O-L ^f2 -* F ₃ C(F ₂ C) ₃ -O-L ^f2 -* ^{_{3 -OL f2 * F 3 C (}} F 2 C) - - [Formula 28] ^{_{F 3 COL f2 - * F 3}} CF 2 COL f2 - * F 3 C (F 2 C) 2 -OL f2 *

式(f1-3)表示之基，可列舉下述式表示之基。惟L^f2表示碳數5~20之烷二基。 Examples of the base represented by the formula (f1-3) include the base represented by the following formula. However, L ^f2 represents an alkanediyl group having 5 to 20 carbon atoms.

式(f1-4)表示之基，可列舉下述式表示之基。惟L^f2表示碳數5~20之烷二基。 Examples of the base represented by the formula (f1-4) include the base represented by the following formula. However, L ^f2 represents an alkanediyl group having 5 to 20 carbon atoms.

式(f1-5)表示之基，可列舉下述式表示之基。惟L^f3表示碳數1~6之烷二基。 Examples of the group represented by the formula (f1-5) include a group represented by the following formula. However, L ^f3 represents an alkanediyl group having 1 to 6 carbon atoms.

【化31】F ₃ C-L ^f3 -* F ₃ CF ₂ C-L ^f3 -* F ₃ C(F ₂ C) ₂ -L ^f3 -* F ₃ C(F ₂ C) ₃ -L ^f3 -* F ₃ C(F ₂ C) ₄ -L ^f3 -* F ₃ C(F ₂ C) ₅ -L ^f3 -* F ₃ C(F ₂ C) ₆ -L ^f3 -* F ₃ C(F ₂ C) ₇ -L ^f3 -* [Chem. 31] F ₃ CL ^f3- * F ₃ CF ₂ CL ^f3- * F ₃ C (F ₂ C) ₂ -L ^f3- * F ₃ C (F ₂ C) ₃ -L ^f3- * F ₃ C ( F ₂ C) ₄ -L ^f3- * F ₃ C (F ₂ C) ₅ -L ^f3- * F ₃ C (F ₂ C) ₆ -L ^f3- * F ₃ C (F ₂ C) ₇ -L ^f3 -*

含有氟化碳之基，可為氟烷基芳基、氟烷基烯基、氟烷基炔基等。氟烷基芳基，可列舉(氟C_1-8烷基)苯基、(氟C_1-8烷基)萘基，氟烷基烯基，可列舉(氟C_1-17烷基)乙烯基，氟烷基炔基，可列舉(氟C_1-17烷基)乙炔基。 The fluorocarbon-containing group may be a fluoroalkylaryl group, a fluoroalkylalkenyl group, a fluoroalkylalkynyl group, or the like. Examples of the fluoroalkylaryl group include (fluoro C _1-8 alkyl) phenyl, (fluoro C _1-8 alkyl) naphthyl, and fluoroalkyl alkenyl, and (fluoro C _1-17 alkyl) ethylene Examples of the group include a fluoroalkylalkynyl group and a (fluoro C _1-17 alkyl) ethynyl group.

Z^f1較佳為含有矽氧烷骨架之基或水解性基、更佳為水解性基。 Z ^{f1 is} preferably a group containing a siloxane skeleton or a hydrolyzable group, and more preferably a hydrolyzable group.

式(III-2)中，R^f2表示之水解性矽烷寡聚物殘基，意指來自包含矽原子與鍵結於矽原子之水解性基的化合物(以下有稱為「水解性矽烷單體」者)之水解縮合物的1價基。水解性矽烷寡聚物殘基中所含有的矽原子數目，例如為3以上、較佳為5以上、更佳為7以上。水解性矽烷寡聚物殘基中所含有的矽原子數目，較佳為15以下、更佳為13以下、又更佳為10以下。 In the formula (III-2), the hydrolyzable silane oligomer residue represented by R ^f2 means a compound derived from a hydrolyzable group containing a silicon atom and a silicon atom (hereinafter referred to as a "hydrolyzable silane monomer"") Is the monovalent group of the hydrolyzed condensate. The number of silicon atoms contained in the hydrolyzable silane oligomer residue is, for example, 3 or more, preferably 5 or more, and more preferably 7 or more. The number of silicon atoms contained in the hydrolyzable silane oligomer residue is preferably 15 or less, more preferably 13 or less, and even more preferably 10 or less.

又，前述水解性矽烷寡聚物殘基具有烷氧基時，該烷氧基可列舉甲氧基、乙氧基、丙氧基、丁氧基等，較佳為甲氧基、乙氧基等。前述水解性矽烷寡聚物殘基，可具有此等烷氧基之1種或2種以上，較佳為具有1種。 When the residue of the hydrolyzable silane oligomer has an alkoxy group, examples of the alkoxy group include methoxy, ethoxy, propoxy, and butoxy, and methoxy and ethoxy are preferred. Wait. The hydrolyzable silane oligomer residue may have one or two or more of these alkoxy groups, and preferably one.

水解性矽烷寡聚物殘基，較佳為式(f2)表示之基。 The hydrolyzable silane oligomer residue is preferably a group represented by formula (f2).

[上述式(f2)中，A^f3係分別獨立地表示水解性基、碳數1~4之烷基或碳數1~4之含氟烷基。h6為0以上100以下之整數。*表示與Si之鍵結位置]。 [In the above formula (f2), A ^f3 each independently represents a hydrolyzable group, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms. h6 is an integer from 0 to 100. * Indicates the bonding position with Si].

A^f3表示之水解性基，可列舉甲氧基、乙氧基、丙氧基、丁氧基等之碳數1~4(較佳為1~2)之烷氧基；氫原子；氰基；烯丙基、異氰酸酯基；較佳為烷氧基；更佳為乙氧基、甲氧基、異氰酸酯基。h6較佳為0以上10以下、更佳為0以上7以下。 Examples of the hydrolyzable group represented by A ^f3 include alkoxy groups having 1 to 4 carbon atoms (preferably 1 to 2) such as methoxy, ethoxy, propoxy, and butoxy; hydrogen atoms; cyano Allyl and isocyanate groups; alkoxy groups are preferred; ethoxy, methoxy and isocyanate groups are more preferred. h6 is preferably 0 or more and 10 or less, and more preferably 0 or more and 7 or less.

A^f3較佳為水解性基或碳數1~4之含氟烷基，較佳A^f3當中至少一個為碳數1~4之含氟烷基。又，較佳A^f3當中至少一個為水解性基(特別是甲氧基、乙氧基)。 A ^{f3 is} preferably a hydrolyzable group or a fluorine-containing alkyl group having 1 to 4 carbon atoms, and at least one of A ^{f3 is} preferably a fluorine-containing alkyl group having 1 to 4 carbon atoms. Moreover, it is preferable that at least one of A ^f3 is a hydrolyzable group (especially a methoxy group and an ethoxy group).

水解性矽烷寡聚物殘基，可列舉例如下述式表示之基。 Examples of the hydrolyzable silane oligomer residue include a group represented by the following formula.

式(III-1)表示之化合物，可列舉例如下述式表示之化合物。式中，r1為1~15、較佳為1~12、更佳為1~6。 Examples of the compound represented by the formula (III-1) include compounds represented by the following formula. In the formula, r1 is 1 to 15, preferably 1 to 12, and more preferably 1 to 6.

式(III-1)表示之化合物，亦可列舉下述式表示 之化合物。 The compound represented by formula (III-1) may also be represented by the following formula Of compounds.

式中，r2為5~20、較佳為8~15。r3為1~7、較佳為2~6。r4為1~10、較佳為2~8、更佳為2~5。r5為1~5、較佳為2~4。r6為2~10、較佳為2~8。r7為2~10、較佳為3~7。 In the formula, r2 is 5-20, preferably 8-15. r3 is 1 to 7, preferably 2 to 6. r4 is 1 to 10, preferably 2 to 8, and more preferably 2 to 5. r5 is 1 to 5, preferably 2 to 4. r6 is 2 to 10, preferably 2 to 8. r7 is 2 to 10, preferably 3 to 7.

式(III-2)表示之化合物，可列舉下述式表示之化合物。 Examples of the compound represented by the formula (III-2) include compounds represented by the following formula.

含氟有機矽化合物(f)之含有率，於組成物100質量%中，較佳為0.01質量%以上、更佳為0.05質量%以上、又更佳為1質量%以上；較佳為20質量%以下、更佳為10質量%以下、又更佳為7質量%以下。 The content rate of the fluorine-containing organosilicon compound (f) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 1% by mass or more in 100% by mass of the composition; more preferably 20% by mass % Or less, more preferably 10% by mass or less, and even more preferably 7% by mass or less.

本發明之組成物中，含氟有機矽化合物(f)與有機矽化合物(a)之含有率的比(含氟有機矽化合物(f)/有機矽化合物(a))，以莫耳比計，較佳為1/1以上、更佳為7/1以上、又更佳為10/1以上；較佳為100/1以下、更佳為50/1以下、又更佳為25/1以下、又再更佳為20/1以下、特佳為15/1以下。 In the composition of the present invention, the ratio of the content ratio of the fluorine-containing organosilicon compound (f) to the organosilicon compound (a) (fluorinated organosilicon compound (f) / organosilicon compound (a)) is in mole ratio , Preferably 1/1 or more, more preferably 7/1 or more, and even more preferably 10/1 or more; preferably 100/1 or less, more preferably 50/1 or less, and even more preferably 25/1 or less It is more preferably 20/1 or less, and particularly preferably 15/1 or less.

本發明之組成物中，金屬烷氧化物(b)與含氟有機矽化合物(f)之含有率的比(金屬烷氧化物(b)/含氟有機矽化合物(f))，以莫耳比計，較佳為0.01以上、更佳為0.1以上、又更佳為0.2以上；較佳為50以下、更佳為10以下、又更佳為5以下。 In the composition of the present invention, the ratio of the content ratio of the metal alkoxide (b) to the fluorine-containing organosilicon compound (f) (metal alkoxide (b) / fluorine-containing organosilicon compound (f)) is in mole The ratio is preferably 0.01 or more, more preferably 0.1 or more, and still more preferably 0.2 or more; preferably 50 or less, more preferably 10 or less, and still more preferably 5 or less.

本發明之組成物，較佳為進一步含有溶劑(c)。溶劑(c)可列舉水；醇系溶劑、醚系溶劑、酮系溶劑、酯系溶劑、醯胺系溶劑等之親水性有機溶劑；芳香族烴系溶劑、飽和烴系溶劑等之疏水性有機溶劑。此等可單獨使用、亦可合併使用2種以上。 The composition of the present invention preferably further contains a solvent (c). Examples of the solvent (c) include water; hydrophilic organic solvents such as alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, and ammonium-based solvents; and hydrophobic organic solvents such as aromatic hydrocarbon solvents and saturated hydrocarbon solvents. Solvent. These can be used alone or in combination of two or more.

前述醇系溶劑，可列舉甲醇、乙醇、丙醇、異丙醇、 丁醇、乙二醇、丙二醇、二乙二醇等，前述醚系溶劑，可列舉二甲氧基乙烷、四氫呋喃、二噁烷等，酮系溶劑，可列舉丙酮、甲基乙基酮等，酯系溶劑，可列舉乙酸乙酯、乙酸丁酯等，醯胺系溶劑，可列舉二甲基甲醯胺等，芳香族烴系溶劑，可列舉苯、甲苯、二甲苯等，飽和烴系溶劑，可列舉己烷、環己烷等。 Examples of the alcohol-based solvent include methanol, ethanol, propanol, isopropanol, Butanol, ethylene glycol, propylene glycol, diethylene glycol, and the like. Examples of the ether-based solvent include dimethoxyethane, tetrahydrofuran, and dioxane. Ketone-based solvents include acetone, methyl ethyl ketone, and the like. Ester-based solvents include ethyl acetate, butyl acetate, and the like; ammonium-based solvents, including dimethylformamide, and the like; aromatic hydrocarbon-based solvents, including benzene, toluene, and xylene; and saturated hydrocarbon-based solvents. Examples of the solvent include hexane and cyclohexane.

其中尤以醇系溶劑、酮系溶劑為佳，亦可含有水。 Among these, an alcohol-based solvent and a ketone-based solvent are particularly preferable, and water may be contained.

含有水時，於溶劑(c)中，水之含有率較佳為0.1質量%以上、更佳為5質量%以上、又更佳為10質量%以上；較佳為90質量%以下、更佳為70質量%以下、又更佳為50質量%以下。 When water is contained, the content of water in the solvent (c) is preferably 0.1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more; preferably 90% by mass or less, more preferably It is 70% by mass or less, and more preferably 50% by mass or less.

相對於有機矽化合物(a)、金屬烷氧化物(b)及含氟有機矽化合物(f)之合計1質量份而言，溶劑(c)較佳為0.1質量份以上、更佳為5質量份以上、又更佳為10質量份以上、特佳為12質量份以上；較佳為100質量份以下、更佳為80質量份以下、又更佳為50質量份以下。溶劑(c)之量若為此範圍，則被膜之厚度控制為容易。 The solvent (c) is preferably 0.1 parts by mass or more, more preferably 5 parts by mass based on 1 part by mass of the total of the organosilicon compound (a), the metal alkoxide (b), and the fluorine-containing organosilicon compound (f). 10 parts by mass or more, and more preferably 12 parts by mass or more; particularly preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and still more preferably 50 parts by mass or less. When the amount of the solvent (c) is within this range, it is easy to control the thickness of the film.

本發明之組成物，亦可進一步含有觸媒(d)。觸媒(d)只要係可作為鍵結於矽原子之水解性基的水解觸媒作用者即可，可列舉例如酸性化合物；鹼性化合物；有機金屬化合物等。前述酸性化合物，可列舉鹽酸、硝酸等之無機酸；乙酸等之有機酸等。前述鹼性化合物，可列舉氨；胺等。前述有機金屬化合物，可列舉以Al、Fe、Zn、Sn等之金屬元素為中心金屬之有機金屬化合物，可 列舉鋁乙醯丙酮錯合物、鋁乙基乙醯乙酸錯合物等之有機鋁化合物；辛酸鐵等之有機鐵化合物；鋅乙醯丙酮單水合物、環烷酸鋅、辛酸鋅等之有機鋅化合物；二丁基錫二乙酸錯合物等之有機錫化合物等。 The composition of the present invention may further contain a catalyst (d). The catalyst (d) may be a hydrolytic catalyst capable of acting as a hydrolyzable group bonded to a silicon atom, and examples thereof include an acidic compound, a basic compound, and an organic metal compound. Examples of the acidic compound include inorganic acids such as hydrochloric acid and nitric acid; organic acids such as acetic acid and the like. Examples of the basic compound include ammonia and amines. Examples of the organometallic compound include an organometallic compound including a metal element such as Al, Fe, Zn, and Sn as a central metal. Examples of organoaluminum compounds such as aluminum acetoacetone complex and aluminum ethylacetate acetic acid complex; organic iron compounds such as iron octoate; organic compounds such as zinc acetoacetone monohydrate, zinc naphthenate, and zinc octoate Zinc compounds; organotin compounds such as dibutyltin diacetate complex and the like.

其中，作為觸媒(d)，尤以有機金屬化合物、酸性化合物為佳；有機鋁化合物、鹽酸為更佳。 Among them, the catalyst (d) is particularly preferably an organometallic compound or an acidic compound; an organoaluminum compound or hydrochloric acid is more preferred.

相對於有機矽化合物(a)、金屬烷氧化物(b)及含氟有機矽化合物(f)之合計100質量份而言，觸媒(d)較佳為0.0001質量份以上、更佳為0.0002質量份以上、又更佳為0.001質量份以上；較佳為20質量份以下、更佳為10質量份以下、又更佳為5質量份以下。 The catalyst (d) is preferably 0.0001 parts by mass or more, more preferably 0.0002, based on 100 parts by mass of the total of the organosilicon compound (a), the metal alkoxide (b), and the fluorine-containing organosilicon compound (f). At least 0.001 parts by mass, more preferably at least 0.001 parts by mass; more preferably at most 20 parts by mass, more preferably at most 10 parts by mass, and even more preferably at most 5 parts by mass.

又，使用酸性化合物作為觸媒時，相對於有機矽化合物(a)、金屬烷氧化物(b)及含氟有機矽化合物(f)之合計100質量份而言，觸媒(d)較佳為0.001質量份以上、更佳為0.005質量份以上、又更佳為0.01質量份以上；較佳為1質量份以下、更佳為0.5質量份以下。 When an acidic compound is used as the catalyst, the catalyst (d) is preferable to 100 parts by mass of the total of the organosilicon compound (a), the metal alkoxide (b), and the fluorine-containing organosilicon compound (f). It is 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and still more preferably 0.01 parts by mass or more; preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less.

進一步地，使用有機金屬化合物作為觸媒時，相對於有機矽化合物(a)、金屬烷氧化物(b)及含氟有機矽化合物(f)之合計100質量份而言，觸媒(d)較佳為0.0001質量份以上、更佳為0.0002質量份以上、又更佳為0.001質量份以上；較佳為0.1質量份以下、更佳為0.05質量份以下。 Furthermore, when an organometallic compound is used as the catalyst, the catalyst (d) is 100 parts by mass of a total of the organosilicon compound (a), the metal alkoxide (b), and the fluorine-containing organosilicon compound (f). Preferably it is 0.0001 mass part or more, More preferably, it is 0.0002 mass part or more, Still more preferably, it is 0.001 mass part or more; Preferably it is 0.1 mass part or less, More preferably, it is 0.05 mass part or less.

進一步地，本發明之組成物，在不阻礙本發明之效果的範圍內，亦可含有抗氧化劑、防鏽劑、紫外線吸收劑、光安定劑、防黴劑、抗菌劑、生物附著防止劑、 消臭劑、顏料、難燃劑、抗靜電劑等之各種添加劑。 Further, the composition of the present invention may contain antioxidants, rust inhibitors, ultraviolet absorbers, light stabilizers, antifungal agents, antibacterial agents, biological adhesion preventive agents, and the like, as long as the effects of the present invention are not hindered. Various additives such as deodorant, pigment, flame retardant, antistatic agent.

前述抗氧化劑，可列舉酚系抗氧化劑、硫系抗氧化劑、磷系抗氧化劑、受阻胺系抗氧化劑等。 Examples of the antioxidant include phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and hindered amine-based antioxidants.

前述酚系抗氧化劑，可列舉n-十八烷基-3-(4-羥基-3,5-二-t-丁基苯基)丙酸酯、2,6-二-t-丁基-4-甲基酚、2,2-硫-二伸乙基-雙-[3-(3,5-二-t-丁基-4-羥基苯基)丙酸酯]、三-乙二醇-雙-[3-(3-t-丁基-5-甲基-4-羥基苯基)丙酸酯]、3,9-雙[2-{3-(3-t-丁基-4-羥基-5-甲基苯基)丙醯氧基}-1,1-二甲基乙基]-2,4,8,10-四氧雜螺[5．5]十一烷、肆{3-(3,5-二-t-丁基-4-羥基苯基)-丙酸}季戊四醇酯、2-t-丁基-6-(3-t-丁基-2-羥基-5-甲基苄基)-4-甲基苯基丙烯酸酯、2-[1-(2-羥基-3,5-二-t-戊基苯基)乙基]-4,6-二-t-戊基苯基丙烯酸酯、1,3,5-三甲基-2,4,6-參(3,5-二-t-丁基-4-羥基苄基)苯、參(3,5-二-t-丁基-4-羥基苄基)異三聚氰酸酯、1,3,5-參(4-t-丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮、2,2’-亞甲基雙(6-t-丁基-4-甲基酚)、4,4’-亞丁基雙(6-t-丁基-3-甲基酚)、4,4’-硫代雙(6-t-丁基-3-甲基酚)等。 Examples of the phenol-based antioxidant include n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate and 2,6-di-t-butyl- 4-methylphenol, 2,2-thio-diethylethyl-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tri-ethylene glycol -Bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis [2- {3- (3-t-butyl-4 -Hydroxy-5-methylphenyl) propanyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, { 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionic acid} pentaerythritol ester, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5- Methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t- Amylphenyl acrylate, 1,3,5-trimethyl-2,4,6-ginseng (3,5-di-t-butyl-4-hydroxybenzyl) benzene, ginseng (3,5- Di-t-butyl-4-hydroxybenzyl) isotricyanate, 1,3,5-ginseng (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)- 1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 2,2'-methylenebis (6-t-butyl-4-methylphenol), 4,4'-butylenebis (6-t-butyl-3-methylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), and the like.

前述硫系抗氧化劑，可列舉3,3’-硫代二丙酸二-n-十二烷酯、3,3’-硫代二丙酸二-n-十四烷酯、3,3’-硫代二丙酸二-n-十八烷酯、肆(3-十二烷硫基丙酸)季戊四醇酯等。 Examples of the sulfur-based antioxidant include 3,3'-thiodipropionate di-n-dodecyl ester, 3,3'-thiodipropionate di-n-tetradecanyl ester, and 3,3 ' -Di-n-octadecyl thiodipropionate, pentaerythritol ester (3-dodecylthiopropionate), and the like.

前述磷系抗氧化劑，可列舉參(2,4-二-t-丁基苯基)亞磷酸酯、雙(2,4-二-t-丁基苯基)季戊四醇二亞磷酸 酯、雙(2,6-二-t-丁基-4-甲基苯基)季戊四醇二亞磷酸酯、雙(2,4-二-異丙苯基苯基)季戊四醇二亞磷酸酯、肆(2,4-二-t-丁基苯基)-4,4’-聯苯基二亞磷酸酯、雙-[2,4-二-t-丁基,(6-甲基)苯基]乙基亞磷酸酯等。 Examples of the phosphorus-based antioxidant include (2,4-di-t-butylphenyl) phosphite and bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite. Ester, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, (2,4-di-t-butylphenyl) -4,4'-biphenyldiphosphite, bis- [2,4-di-t-butyl, (6-methyl) phenyl ] Ethyl phosphite and the like.

前述受阻胺系抗氧化劑，可列舉癸二酸雙(2,2,6,6-四甲基-4-哌啶基)酯(熔點81~86℃)、甲基丙烯酸2,2,6,6-四甲基-4-哌啶酯(熔點58℃)、聚[{6-(1,1,3,3-四甲基丁基)胺基-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亞胺基}-1,6-六亞甲基{(2,2,6,6-四甲基-4-哌啶基)亞胺基}]等。 Examples of the hindered amine-based antioxidant include bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate (melting point: 81-86 ° C), and methacrylic acid 2,2,6, 6-tetramethyl-4-piperidinyl ester (melting point 58 ° C), poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2 , 4-diyl} {(2,2,6,6-tetramethyl-4-piperidinyl) imino} -1,6-hexamethylene {(2,2,6,6-tetramethylene Methyl-4-piperidinyl) imino}] and the like.

前述防鏽劑，可列舉三乙醇胺等之烷醇胺；四級銨鹽；烷硫醇；咪唑啉、咪唑、烷基咪唑啉衍生物、苯并咪唑、2-巰基苯并咪唑、苯并***等之唑類；偏釩酸鈉；檸檬酸鉍；酚衍生物；烷基胺或聚烯基胺等之脂肪族胺、芳香族胺、乙氧基化胺、氰基烷基胺、安息香酸環己胺、伸烷基二胺等之脂肪族二胺、芳香族二胺等之胺化合物；前述胺化合物與羧酸之醯胺；烷基酯；嘧啶；環烷酸；磺酸複合體；亞硝酸鈣、亞硝酸鈉、亞硝酸二環己胺等之亞硝酸鹽；多元醇、多酚等之多元醇化合物；鉬酸鈉、鎢酸鈉、膦酸鈉、鉻酸鈉、矽酸鈉等之雜多酸鹽；明膠；羧酸之聚合物；硝基化合物；甲醛；乙炔醇；脂肪族硫醇、芳香族硫醇、乙炔硫醇等之硫醇化合物；脂肪族硫醚、芳香族硫醚、乙炔硫醚等之硫醚化合物；亞碸、二苄基亞碸等之亞碸化合物；硫脲；胺或四級銨鹽與鹵素離子 之組合；烷基胺與碘化鉀之組合；單寧與磷酸鈉之組合；三乙醇胺與月桂基肌胺酸之組合；三乙醇胺與月桂基肌胺酸與苯并***之組合；烷基胺與苯并***與亞硝酸鈉與磷酸鈉之組合等。 Examples of the rust inhibitor include alkanolamines such as triethanolamine; quaternary ammonium salts; alkanethiols; imidazoline, imidazole, alkylimidazoline derivatives, benzimidazole, 2-mercaptobenzimidazole, and benzotriazole Azoles such as azoles; sodium metavanadate; bismuth citrate; phenol derivatives; aliphatic amines such as alkylamines or polyalkenylamines, aromatic amines, ethoxylated amines, cyanoalkylamines, benzoin Amine compounds such as aliphatic diamines and aromatic diamines such as cyclohexylamine and alkylenediamine; amines of the aforementioned amine compounds and carboxylic acids; alkyl esters; pyrimidines; naphthenic acids; sulfonic acid complexes ; Nitrite salts such as calcium nitrite, sodium nitrite, dicyclohexyl nitrite, etc .; Polyol compounds such as polyols, polyphenols, etc .; Sodium molybdate, sodium tungstate, sodium phosphonate, sodium chromate, silicic acid Heteropoly acid salts of sodium; gelatin; polymers of carboxylic acids; nitro compounds; formaldehyde; acetylene alcohols; thiol compounds such as aliphatic thiols, aromatic thiols, acetylene thiols; aliphatic thioethers, aromatics Sulfide compounds such as sulfide and acetylene sulfide; fluorene compounds such as fluorene, dibenzylidene; thiourea; amines or Ammonium salt with a halogen ion Combination of alkylamine and potassium iodide; combination of tannin and sodium phosphate; combination of triethanolamine and laurylsarcosine; combination of triethanolamine and laurylsarcosine and benzotriazole; alkylamine and A combination of benzotriazole and sodium nitrite and sodium phosphate.

前述紫外線吸收劑/光安定劑，可列舉例如2-(5-甲基-2-羥基苯基)苯并***、2-[2-羥基-3,5-雙(α,α-二甲基苄基)苯基]-2H-苯并***、2-(3-t-丁基-5-甲基-2-羥基苯基)-5-氯苯并***、2-(2’-羥基-5’-t-辛基苯基)苯并***、與甲基-3-[3-t-丁基-5-(2H-苯并***-2-基)-4-羥基苯基]丙酸酯-聚乙二醇(分子量約300)之縮合物、羥基苯基苯并***衍生物、2-(4,6-二苯基-1,3,5-三嗪-2-基)-5[(己基)氧基]-酚、2-乙氧基-2’-乙基-草酸二苯胺化物等。 Examples of the ultraviolet absorber / light stabilizer include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- [2-hydroxy-3,5-bis (α, α-dimethylformaldehyde). Benzyl) phenyl] -2H-benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2 ' -Hydroxy-5'-t-octylphenyl) benzotriazole, and methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxy Phenyl] propionate-polyethylene glycol (molecular weight of about 300) condensate, hydroxyphenylbenzotriazole derivative, 2- (4,6-diphenyl-1,3,5-triazine- 2-yl) -5 [(hexyl) oxy] -phenol, 2-ethoxy-2'-ethyl-oxalate diphenylamine, and the like.

前述防黴劑/抗菌劑，可列舉2-(4-噻唑基)苯并咪唑、山梨酸、1,2-苯并異噻唑啉-3酮、(2-吡啶硫基-1-氧化物)鈉、去氫乙酸、2-甲基-5-氯-4-異二氫噻唑酮錯合物、2,4,5,6-四氯鄰苯二甲腈、2-苯并咪唑胺基甲酸甲酯、1-(丁基胺甲醯基)-2-苯并咪唑胺基甲酸甲酯、單或二溴氰基乙醯胺類、1,2-二溴-2,4-二氰基丁烷、1,1-二溴-1-硝基丙醇及1,1-二溴-1-硝基-2-乙醯氧基丙烷等。 Examples of the antifungal agent / antibacterial agent include 2- (4-thiazolyl) benzimidazole, sorbic acid, 1,2-benzoisothiazolin-3one, and (2-pyridylthio-1-oxide). Sodium, dehydroacetic acid, 2-methyl-5-chloro-4-isodihydrothiazolone complex, 2,4,5,6-tetrachlorophthalonitrile, 2-benzimidazoleaminocarboxylic acid Methyl esters, methyl 1- (butylaminomethylamidino) -2-benzimidazolecarbamate, mono- or dibromocyanoacetamides, 1,2-dibromo-2,4-dicyano Butane, 1,1-dibromo-1-nitropropanol and 1,1-dibromo-1-nitro-2-ethoxypropane, etc.

前述生物附著防止劑，可列舉四甲基秋蘭姆二硫醚、雙(N,N-二甲基二硫代胺基甲酸)鋅、3-(3,4-二氯苯基)-1,1-二甲基脲、二氯-N-((二甲基胺基)磺醯基)氟-N-(p-甲苯基)甲烷亞磺醯胺、吡啶-三苯基硼烷、N,N-二甲基-N’-苯基-N’-(氟二氯甲硫基)磺醯胺、硫氰酸銅(I)(1)、氧 化銅(I)、四丁基秋蘭姆二硫醚、2,4,5,6-四氯間苯二甲腈、伸乙雙(二硫代胺基甲酸)鋅、2,3,5,6-四氯-4-(甲基磺醯基)吡啶、N-(2,4,6-三氯苯基)馬來醯亞胺、雙(2-吡啶硫醇-1-氧化物)鋅鹽、雙(2-吡啶硫醇-1-氧化物)銅鹽、2-甲硫基-4-t-丁基胺基-6-環丙基胺基-s-三嗪、4,5-二氯-2-n-辛基-4-異噻唑啉-3-酮、呋喃酮類、烷基吡啶化合物、蘆竹鹼系化合物、異腈化合物等。 Examples of the biological adhesion preventing agent include tetramethylthiuram disulfide, zinc bis (N, N-dimethyldithioaminoformate), and 3- (3,4-dichlorophenyl) -1. , 1-dimethylurea, dichloro-N-((dimethylamino) sulfofluorenyl) fluoro-N- (p-tolyl) methanesulfenamidine, pyridine-triphenylborane, N , N-dimethyl-N'-phenyl-N '-(fluorodichloromethylthio) sulfonamide, copper (I) (1) (1), oxygen Copper (I), tetrabutylthiuram disulfide, 2,4,5,6-tetrachloroisophthalonitrile, zinc ethylenebis (dithioaminoformate), 2,3,5 , 6-tetrachloro-4- (methylsulfonyl) pyridine, N- (2,4,6-trichlorophenyl) maleimide, bis (2-pyridinethiol-1-oxide) Zinc salt, bis (2-pyridinethiol-1-oxide) copper salt, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 4,5 -Dichloro-2-n-octyl-4-isothiazolin-3-one, furanones, alkylpyridine compounds, arachine compounds, isonitrile compounds, and the like.

前述消臭劑，可列舉乳酸、琥珀酸、蘋果酸、檸檬酸、馬來酸、丙二酸、乙二胺聚乙酸、烷-1,2-二羧酸、烯-1,2-二羧酸、環烷-1,2-二羧酸、環烯-1,2-二羧酸、萘磺酸等之有機酸類；十一碳烯酸鋅、2-乙基己酸鋅、蓖麻油酸鋅等之脂肪酸金屬類；氧化鐵、硫酸鐵、氧化鋅、硫酸鋅、氯化鋅、氧化銀、氧化銅、金屬(鐵、銅等)葉綠酸鈉、金屬(鐵、銅、鈷等)酞青素、金屬(鐵、銅、鈷等)四磺酸酞青素、二氧化鈦、可見光反應型二氧化鈦(氮摻雜型等)等之金屬化合物；α-、β-或γ-環糊精、其甲基衍生物、羥基丙基衍生物、葡萄糖苷基衍生物、麥芽糖苷基衍生物等之環糊精類；多孔甲基丙烯酸聚合物、多孔丙烯酸聚合物等之丙烯酸系聚合物；多孔二乙烯基苯聚合物、多孔苯乙烯-二乙烯基苯-乙烯基吡啶聚合物、多孔二乙烯基苯-乙烯基吡啶聚合物等之芳香族系聚合物；該等之共聚物及幾丁質、幾丁聚糖、活性碳、二氧化矽凝膠、活性氧化鋁、沸石、陶瓷等之多孔質體等。 Examples of the deodorant include lactic acid, succinic acid, malic acid, citric acid, maleic acid, malonic acid, ethylene diamine polyacetic acid, alkane-1,2-dicarboxylic acid, and ene-1,2-dicarboxylic acid. Organic acids such as acids, naphthene-1,2-dicarboxylic acid, cycloolefin-1,2-dicarboxylic acid, naphthalenesulfonic acid; zinc undecylenate, zinc 2-ethylhexanoate, ricinoleic acid Fatty acid metals such as zinc; iron oxide, iron sulfate, zinc oxide, zinc sulfate, zinc chloride, silver oxide, copper oxide, metal (iron, copper, etc.) sodium chlorophyll, metal (iron, copper, cobalt, etc.) Metal compounds such as phthalocyanin, metals (iron, copper, cobalt, etc.) tetrasulfophthalocyanin, titanium dioxide, visible light-reactive titanium dioxide (nitrogen-doped, etc.); α-, β-, or γ-cyclodextrin, Cyclodextrins such as methyl derivative, hydroxypropyl derivative, glucosyl derivative, maltosyl derivative, etc .; acrylic polymers such as porous methacrylic polymer, porous acrylic polymer; etc. Aromatic polymerization of vinylbenzene polymer, porous styrene-divinylbenzene-vinylpyridine polymer, porous divinylbenzene-vinylpyridine polymer, etc. ; And copolymers of such chitin, chitosan, activated carbon, silicon dioxide gel, activated alumina, zeolite, porous ceramics, etc. and the like.

前述顏料可列舉碳黑、氧化鈦、酞青素系顏 料、喹吖酮系顏料、異吲哚酮系顏料、苝或perinine系顏料、喹啉黃系顏料、二酮吡咯并吡咯系顏料、雙噁嗪系顏料、雙偶氮縮合系顏料或苯并咪唑酮系顏料等。 Examples of the pigment include carbon black, titanium oxide, and phthalocyanin-based pigments. Materials, quinacridone-based pigments, isoindolinone-based pigments, pyrene or perinine-based pigments, quinoline yellow-based pigments, diketopyrrolopyrrole-based pigments, dioxazine-based pigments, bisazo-condensation-based pigments, or benzo Imidazolone pigments and the like.

前述難燃劑可列舉十溴聯苯、三氧化銻、磷系難燃劑、氫氧化鋁等。 Examples of the flame retardant include decabromobiphenyl, antimony trioxide, phosphorus-based flame retardant, aluminum hydroxide, and the like.

前述抗靜電劑，可列舉4級銨鹽型之陽離子界面活性劑、甜菜鹼型之兩性界面活性劑、磷酸烷酯型之陰離子界面活性劑、1級胺鹽、2級胺鹽、3級胺鹽、4級胺鹽或吡啶衍生物等之陽離子界面活性劑、硫酸化油、皂、硫酸化酯油、硫酸化醯胺油、烯烴之硫酸化酯鹽類、脂肪醇硫酸酯鹽類、烷基硫酸酯鹽、脂肪酸乙基磺酸鹽、烷基萘磺酸鹽、烷基苯磺酸鹽、琥珀酸酯磺酸鹽或磷酸酯鹽等之陰離子界面活性劑、多元醇之部分脂肪酸酯、脂肪醇之環氧乙烷加成物、脂肪酸之環氧乙烷加成物、脂肪胺基或脂肪酸醯胺之環氧乙烷加成物、烷基酚之環氧乙烷加成物、多元醇之部分脂肪酸酯之環氧乙烷加成物或聚乙二醇等之非離子界面活性劑、羧酸衍生物或咪唑啉衍生物等之兩性界面活性劑等。 Examples of the antistatic agent include cationic surfactants of the 4th ammonium type, amphoteric surfactants of the betaine type, anionic surfactants of the alkyl phosphate type, primary amine salts, secondary amine salts, and tertiary amines. Cation surfactants such as salts, grade 4 amine salts or pyridine derivatives, sulfated oils, soaps, sulfated ester oils, sulfated ammonium oils, sulfated ester salts of olefins, fatty alcohol sulfate salts, alkanes Anionic surfactants such as sulfuric acid sulfate salts, fatty acid ethyl sulfonates, alkyl naphthalene sulfonates, alkyl benzene sulfonates, succinate sulfonates, or phosphate esters, and some fatty acid esters of polyols , Ethylene oxide adducts of fatty alcohols, ethylene oxide adducts of fatty acids, ethylene oxide adducts of fatty amine groups or fatty acid amidoamines, ethylene oxide adducts of alkylphenols, Partial fatty acid esters of polyols, ethylene oxide adducts, non-ionic surfactants such as polyethylene glycol, and amphoteric surfactants such as carboxylic acid derivatives or imidazoline derivatives.

又，作為添加劑，亦可進一步共存有潤滑劑、填充劑、可塑劑、核劑、抗黏著劑、發泡劑、乳化劑、光澤劑、結著劑等。 Further, as additives, a lubricant, a filler, a plasticizer, a core agent, an anti-adhesive agent, a foaming agent, an emulsifier, a gloss agent, a binding agent, and the like may be further coexisted.

含有此等添加劑時，添加劑之含量，於組成物中，通常係0.1~70質量%、較佳為0.1~50質量%、更佳為0.5~30質量%、又更佳為2~15質量%。 When these additives are contained, the content of the additives in the composition is usually 0.1 to 70% by mass, preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and even more preferably 2 to 15% by mass. .

又，有機矽化合物(a)、金屬烷氧化物(b)及含氟有機矽化合物(f)之合計(含有溶劑(c)時，係有機矽化合物(a)、金屬烷氧化物(b)、含氟有機矽化合物(f)與溶劑(c)之合計)的含量，於組成物中，通常係60質量%以上、較佳為75質量%以上、更佳為85質量%以上、又更佳為95質量%以上。 The total of the organosilicon compound (a), the metal alkoxide (b), and the fluorine-containing organosilicon compound (f) (when the solvent (c) is contained, the organic silicon compound (a) and the metal alkoxide (b) Content of fluorine-containing organosilicon compound (f) and solvent (c)) in the composition is usually 60% by mass or more, preferably 75% by mass or more, more preferably 85% by mass or more, and more It is preferably 95% by mass or more.

使有機矽化合物(a)、金屬烷氧化物(b)及含氟有機矽化合物(f)與基材接觸之方法，可列舉例如旋轉塗佈法、浸漬塗佈法、噴霧塗佈法、輥塗佈法、棒塗佈法、模具塗佈法等，較佳為旋轉塗佈法、噴霧塗佈法。若依照旋轉塗佈法、噴霧塗佈法，則被膜之厚度調整成為容易。 Examples of the method for bringing the organosilicon compound (a), metal alkoxide (b), and fluorine-containing organosilicon compound (f) into contact with the substrate include spin coating, dip coating, spray coating, and rolls. The coating method, bar coating method, die coating method, and the like are preferably a spin coating method or a spray coating method. According to the spin coating method and the spray coating method, it is easy to adjust the thickness of the film.

此時，組成物亦可依需要進一步預先稀釋。稀釋倍率，相對於稀釋前之組成物而言，例如係2~100倍、較佳為5~50倍。稀釋溶劑可適當使用作為溶劑(c)所例示之溶劑。 At this time, the composition may be further diluted in advance if necessary. The dilution ratio is, for example, 2 to 100 times, and preferably 5 to 50 times, relative to the composition before dilution. As the diluent solvent, those exemplified as the solvent (c) can be appropriately used.

藉由於使本發明之組成物與基材接觸之狀態下，靜置於空氣中，會攝入空氣中之水分，使水解性基水解，形成矽氧烷骨架，而形成被膜。靜置時，亦可於40~250℃保持。 When the composition of the present invention is brought into contact with a substrate and left standing in the air, water in the air is taken in, the hydrolyzable groups are hydrolyzed to form a siloxane skeleton, and a film is formed. When standing still, it can be kept at 40 ~ 250 ℃.

由上述組成物所形成之被膜亦包含於本發明之範圍中。該被膜中，包含來自有機矽化合物(a)、金屬烷氧化物(b)及含氟有機矽化合物(f)之結構。 A film formed from the above composition is also included in the scope of the present invention. The film includes a structure derived from an organic silicon compound (a), a metal alkoxide (b), and a fluorine-containing organic silicon compound (f).

水對本發明之被膜之初期接觸角θ₀₁，較佳為80°以上、更佳為90°以上、又更佳為100°以上；可為 140°以下、進而亦可為130°以下。 The initial contact angle θ _{01 of} water to the film of the present invention is preferably 80 ° or more, more preferably 90 ° or more, and even more preferably 100 ° or more; it may be 140 ° or less, and further 130 ° or less.

前述接觸角，意指使用液量3.0μL之水，藉由θ/2法所測定之值。 The aforementioned contact angle means a value measured by a θ / 2 method using water with a liquid amount of 3.0 μL.

油對本發明之被膜之初期接觸角θ₀₂，較佳為55°以上、更佳為60°以上、又更佳為65°以上；可為120°以下、進而亦可為110°以下。 The initial contact angle θ _{02 of the} oil on the film of the present invention is preferably 55 ° or more, more preferably 60 ° or more, and even more preferably 65 ° or more; it may be 120 ° or less, and further 110 ° or less.

前述接觸角，意指使用液量3.0μL之十六烷，藉由θ/2法所測定之值。 The aforementioned contact angle means a value measured by a θ / 2 method using hexadecane with a liquid amount of 3.0 μL.

本發明之被膜，當於70℃之離子交換水中浸漬12小時後之接觸角為θ _w2時，以下述式表示之接觸角變化率d_w2，較佳為-25%以上、更佳為-15%以上、又更佳為-12%以上；較佳為0%，但-1%以下、進而-5%以下亦被容許。 When the contact angle of the film of the present invention after immersion in ion-exchanged water at 70 ° C. for 12 hours is θ _w2 , the contact angle change rate d _w2 expressed by the following formula is preferably -25% or more, more preferably -15 % Or more, and more preferably -12% or more; preferably 0%, but -1% or less and further -5% or less are also allowed.

接觸角變化率d_w2(%)=(θ_w2-θ₀₁)/θ₀₁×100 Change rate of contact angle d _w2 (%) = (θ _w2 -θ ₀₁ ) / θ ₀₁ × 100

來自有機矽化合物(a)之結構(A)，係以式(IA)表示。 The structure (A) derived from the organosilicon compound (a) is represented by the formula (IA).

[式(IA)中，R^a表示含有三烷基矽烷基之分子鏈，Z^a1表示含有三烷基矽烷基之分子鏈、含有矽氧烷骨架之基、含有烴鏈之基或-O-基]。 [In formula (IA), R ^a represents a molecular chain containing a trialkylsilyl group, and Z ^a1 represents a molecular chain containing a trialkylsilyl group, a group containing a siloxane skeleton, a group containing a hydrocarbon chain, or -O- base].

式(IA)中，R^a、Z^a1之含有三烷基矽烷基之分 子鏈、Z^a1之含有矽氧烷骨架之基、含有烴鏈之基，可分別由作為含有三烷基矽烷基之分子鏈、含有矽氧烷骨架之基、含有烴鏈之基而於上述所說明的範圍中適當選擇。 In formula (IA), R ^a , Z ^a1 contains a trialkylsilyl-containing molecular chain, Z ^a1 contains a siloxane skeleton-containing group, and a hydrocarbon chain-containing group, respectively, and can be used as a trialkylsilyl-containing group. The molecular chain, the group containing a siloxane skeleton, and the group containing a hydrocarbon chain are appropriately selected from the ranges described above.

其中，式(IA)中，Z^a1尤以含有矽氧烷骨架之基或-O-基為佳、以-O-基為更佳。 Among them, in the formula (IA), Z ^{a1 is} particularly preferably a group containing a siloxane skeleton or -O- group, and more preferably -O- group.

結構(A)可列舉式(IA-I)表示之結構。下述式(IA-I-1)~(IA-I-50)，為式(IA-I)表示之結構之具體例子，但不限定於此等。式(IA-I)表示之結構中，其中所含有的複數個R^s20及複數個R^s10，可分別相同、亦可相異。 The structure (A) includes a structure represented by the formula (IA-I). The following formulae (IA-I-1) to (IA-I-50) are specific examples of the structure represented by the formula (IA-I), but are not limited thereto. In the structure represented by the formula (IA-I), the plurality of R ^s20 and the plurality of R ^s10 contained therein may be the same or different, respectively.

又，來自金屬烷氧化物(b)之結構(B)中，鍵結於金屬原子(惟金屬原子為矽原子時，係與含有三烷基矽烷基之分子鏈所鍵結之矽原子不同)之基(含有烴鏈之基、含有矽氧烷骨架之基、羥基等)，構成原子數係少於含有三烷基矽烷基之分子鏈，因此該結構(B)作為間隔件作用之結果，容易提高含有三烷基矽烷基之分子鏈所致之撥水特性提高作用。又，藉由含有金屬烷氧化物(b)，可得到耐溫水性高、實用耐久性優良之膜。 In addition, in the structure (B) derived from the metal alkoxide (b), the metal atom is bonded (when the metal atom is a silicon atom, it is different from a silicon atom bonded to a molecular chain containing a trialkylsilyl group) The base (base containing a hydrocarbon chain, base containing a siloxane skeleton, hydroxyl group, etc.) has a smaller number of atoms than a molecular chain containing a trialkylsilyl group. Therefore, the structure (B) functions as a spacer, It is easy to improve the water-repellent properties of the molecular chain containing trialkylsilyl groups. Further, by containing the metal alkoxide (b), a film having high temperature and water resistance and excellent practical durability can be obtained.

來自金屬烷氧化物(b)之結構(B)，係以式(IIB) 表示。 Structure (B) from metal alkoxide (b) is represented by formula (IIB) Means.

[式(IIB)中，M、k係與上述相同意義。R^b2表示羥基或-O-基]。 [In formula (IIB), M and k have the same meanings as described above. R ^b2 represents a hydroxyl group or -O- group].

作為結構(B)，當M為Si時，可列舉下述式表示之結構。 As structure (B), when M is Si, the structure represented by a following formula is mentioned.

來自含氟有機矽化合物(f)之結構(F)，係以式(IIIF-1)或(IIIF-2)表示。 The structure (F) derived from the fluorine-containing organosilicon compound (f) is represented by the formula (IIIF-1) or (IIIF-2).

[式(IIIF-1)及式(IIIF-2)中，R^f1、R^f2係與上述相同意義。Z^f2表示含有矽氧烷骨架之基、含有烴鏈之基、羥基或-O-基。A^f3表示碳數1~12之含氟烷基、碳數1~4之烷基、羥基或-O-基]。 [In formulae (IIIF-1) and (IIIF-2), R ^f1 and R ^{f2 have} the same meanings as described above. Z ^f2 represents a group containing a siloxane skeleton, a group containing a hydrocarbon chain, a hydroxyl group, or an -O- group. A ^f3 represents a fluorine-containing alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or an -O- group].

Z^f2表示之含有矽氧烷骨架之基或含有烴鏈之基，可列舉與Z^a2表示之含有矽氧烷骨架之基、含有烴鏈之基分別相同之基。 Examples of the group containing a siloxane skeleton or a group containing a hydrocarbon chain represented by Z ^f2 include the same groups as the group containing a siloxane skeleton and a group containing a hydrocarbon chain represented by Z ^a2 .

結構(F)可列舉下述式表示之結構。式中，r8為1~20之整數、較佳為1~10之整數。r9為1~10之整數、較佳為1~5之整數。r10為1~10之整數、較佳為1~5之整數。 The structure (F) includes a structure represented by the following formula. In the formula, r8 is an integer of 1-20, preferably an integer of 1-10. r9 is an integer of 1 to 10, preferably an integer of 1 to 5. r10 is an integer of 1 to 10, preferably an integer of 1 to 5.

由本發明之組成物所形成之被膜，為具有含有三烷基矽烷基之分子鏈及含氟基者，且為具有來自金屬烷氧化物(b)而可發揮作為間隔件之功能的部位者，因此在可兼顧撥水性及撥油性的同時，被膜表面之平滑性亦良好。 The film formed from the composition of the present invention is one having a molecular chain containing a trialkylsilyl group and a fluorine-containing group, and having a site derived from the metal alkoxide (b) and capable of functioning as a spacer, Therefore, the water repellency and oil repellency can be considered at the same time, and the smoothness of the surface of the film is also good.

於基材上形成有本發明之被膜的被膜處理基 材亦包含於本發明之範圍中。基材之形狀，可為平面、曲面之任意者，亦可為組合多數之面的三維結構。又，基材能夠以有機系材料、無機系材料之任意者構成，前述有機系材料可列舉丙烯酸樹脂、聚碳酸酯樹脂、聚酯樹脂、苯乙烯樹脂、丙烯酸-苯乙烯共聚合樹脂、纖維素樹脂、聚烯烴樹脂、聚乙烯醇等之熱可塑性樹脂；酚樹脂、脲樹脂、三聚氰胺樹脂、環氧樹脂、不飽和聚酯、聚矽氧樹脂、胺基甲酸酯樹脂等之熱硬化性樹脂等，無機系材料可列舉陶瓷；玻璃；鐵、矽、銅、鋅、鋁、等之金屬；含有前述金屬之合金等。 Film treatment base having the film of the present invention formed on a substrate Materials are also included in the scope of the present invention. The shape of the base material may be any one of a flat surface and a curved surface, or a three-dimensional structure combining a plurality of surfaces. The substrate may be formed of any of an organic material and an inorganic material. Examples of the organic material include acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, and cellulose. Thermoplastic resins such as resins, polyolefin resins, and polyvinyl alcohol; thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins, and urethane resins Examples of the inorganic material include ceramics; glass; metals such as iron, silicon, copper, zinc, aluminum, and the like; alloys containing the foregoing metals, and the like.

對前述基材，亦可預先施以易接著處理。易接著處理可列舉電暈處理、電漿處理、紫外線處理等之親水化處理。又，亦能夠使用樹脂、矽烷偶合劑、四烷氧基矽烷等進行底塗處理。 The aforementioned substrate may be previously subjected to easy adhesion treatment. Examples of the easy adhesion treatment include hydrophilization treatments such as corona treatment, plasma treatment, and ultraviolet treatment. In addition, a primer treatment can also be performed using a resin, a silane coupling agent, a tetraalkoxysilane, and the like.

作為底塗層，較佳為由含有可形成矽氧烷骨架之成分(P)(以下有稱為成分(P)者)的底塗層形成用組成物所形成之層。底塗層形成用組成物，較佳含有由下述式(Pa)表示之化合物(以下有稱為化合物(Pa)者)及/或其部分水解縮合物所構成之(P1)成分，作為成分(P)。 The undercoat layer is preferably a layer formed from a composition for forming an undercoat layer containing a component (P) capable of forming a siloxane skeleton (hereinafter referred to as a component (P)). The composition for forming an undercoat layer preferably contains a component (P1) composed of a compound represented by the following formula (Pa) (hereinafter referred to as a compound (Pa)) and / or a partially hydrolyzed condensate thereof as a component (P).

Si(X^P2)₄…(Pa) Si (X ^P2 ) ₄ … (Pa)

[式(Pa)中，X^P2表示鹵素原子、烷氧基或異氰酸酯基]。 [In the formula (Pa), X ^P2 represents a halogen atom, an alkoxy group, or an isocyanate group].

上述式(Pa)中，X^P2較佳為氯原子、碳原子數1~4之烷氧基或異氰酸酯基，4個X^P2較佳為相同。 In the formula (Pa), X ^{P2 is} preferably a chlorine atom, an alkoxy group or an isocyanate group having 1 to 4 carbon atoms, and the four X ^{P2 are} preferably the same.

化合物(Pa)，可使用1種或2種以上，較佳為Si(NCO)₄、Si(OCH₃)₄、Si(OC₂H₅)₄等。 The compound (Pa) can be used singly or in combination of two or more kinds, preferably Si (NCO) ₄ , Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ or the like.

底塗層形成用組成物中所含有的(P1)成分，亦可為化合物(Pa)之部分水解縮合物。化合物(Pa)之部分水解縮合物，可使用酸觸媒或鹼觸媒，藉由一般的水解縮合方法來製造。部分水解縮合物之縮合度(多聚化度)，較佳為生成物會溶解於溶劑之程度。作為(Pa)成分，可為化合物(Pa)、亦可為化合物(Pa)之部分水解縮合物、亦可為化合物(Pa)與其部分水解縮合物之混合物，例如含有未反應之化合物(Pa)的化合物(Pa)之部分水解縮合物。化合物(Pa)或其部分水解縮合物亦可使用市售品。 The (P1) component contained in the undercoat layer-forming composition may be a partially hydrolyzed condensate of the compound (Pa). The partially hydrolyzed condensate of the compound (Pa) can be produced by an ordinary hydrolysis and condensation method using an acid catalyst or an alkali catalyst. The degree of condensation (degree of multimerization) of the partially hydrolyzed condensate is preferably such that the product is soluble in the solvent. The component (Pa) may be a compound (Pa), a partially hydrolyzed condensate of the compound (Pa), or a mixture of the compound (Pa) and a partially hydrolyzed condensate thereof, for example, containing an unreacted compound (Pa) Partially hydrolyzed condensate of compound (Pa). The compound (Pa) or a partially hydrolyzed condensate thereof may be a commercially available product.

又，底塗層形成用組成物，亦可進一步含有由式(Pb)表示之化合物(以下，有稱為化合物(Pb)者)及/或其部分水解縮合物所構成之(P2)成分，作為成分(P)。 The composition for forming an undercoat layer may further contain a component (P2) composed of a compound represented by the formula (Pb) (hereinafter referred to as a compound (Pb)) and / or a partially hydrolyzed condensate thereof, As component (P).

(X^P3)₃Si-(CH₂)_p-Si(X^P3)₃…(Pb) (X ^P3 ) ₃ Si- (CH ₂ ) _p -Si (X ^P3 ) ₃ … (Pb)

[惟，式(Pb)中，X^P3係分別獨立地表示水解性基或羥基，p為1~8之整數]。 [However, in the formula (Pb), X ^P3 each independently represents a hydrolyzable group or a hydroxyl group, and p is an integer of 1 to 8].

式(Pb)中，X^P3表示之水解性基，可列舉與上述X^P2相同之基或原子。由化合物(Pb)之安定性與水解之容易度的平衡之觀點，X^P3較佳為烷氧基及異氰酸酯基、特佳為烷氧基。 Examples of the hydrolyzable group represented by X ^P3 in the formula (Pb) include the same groups or atoms as those of X ^P2 . From the viewpoint of the balance between the stability of the compound (Pb) and the ease of hydrolysis, X ^{P3 is} preferably an alkoxy group and an isocyanate group, and particularly preferably an alkoxy group.

烷氧基較佳為碳原子數1~4之烷氧基、更佳為甲氧基或乙氧基。化合物(Pb)中存在有複數個之X^P3可為相同之基亦可為相異之基，由獲得容易度的觀點，相同之基較 佳。 The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group. In the compound (Pb), a plurality of X ^P3 may be the same group or different groups. From the viewpoint of obtaining ease, the same group is preferred.

化合物(Pb)可使用1種或2種以上，可列舉(CH₃O)₃SiCH₂CH₂Si(OCH₃)₃、(OCN)₃SiCH₂CH₂Si(NCO)₃、Cl₃SiCH₂CH₂SiCl₃、(C₂H₅O)₃SiCH₂CH₂Si(OC₂H₅)₃、(CH₃O)₃SiCH₂CH₂CH₂CH₂CH₂CH₂Si(OCH₃)₃等。 The compound (Pb) may be used singly or in combination of two or more, and examples thereof include (CH ₃ O) ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₃ , (OCN) ₃ SiCH ₂ CH ₂ Si (NCO) ₃ , and Cl ₃ SiCH ₂ CH ₂ SiCl ₃ , (C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ , (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ Wait.

成分(P2)亦可為化合物(Pb)之部分水解縮合物。化合物(Pb)之部分水解縮合物，可由與在化合物(Pa)之部分水解縮合物製造中所說明者為相同之方法得到。部分水解縮合物之縮合度(多聚化度)，較佳為生成物會溶解於溶劑之程度。作為成分(P2)，可為化合物(Pb)、亦可為化合物(Pb)之部分水解縮合物、亦可為化合物(Pb)與其部分水解縮合物之混合物，例如含有未反應之化合物(Pb)的化合物(Pb)之部分水解縮合物。化合物(Pb)或其部分水解縮合物亦可使用市售品。 The component (P2) may also be a partially hydrolyzed condensate of the compound (Pb). The partially hydrolyzed condensate of the compound (Pb) can be obtained by the same method as described in the production of the partially hydrolyzed condensate of the compound (Pa). The degree of condensation (degree of multimerization) of the partially hydrolyzed condensate is preferably such that the product is soluble in the solvent. The component (P2) may be a compound (Pb), a partially hydrolyzed condensate of the compound (Pb), or a mixture of the compound (Pb) and a partially hydrolyzed condensate, such as containing an unreacted compound (Pb) Partially hydrolyzed condensate of compound (Pb). The compound (Pb) or a partially hydrolyzed condensate thereof may be a commercially available product.

又，於底塗層形成用組成物中，作為成分(P)，可含有化合物(Pb)與化合物(Pa)之共水解所得的共水解縮合物、亦可含有各種聚矽氮烷。 The composition for forming the undercoat layer may contain, as component (P), a co-hydrolyzed condensate obtained by co-hydrolysis of the compound (Pb) and the compound (Pa), and may also contain various polysilazane.

底塗層形成用組成物，通常，於作為層構成成分之固體成分以外，係考慮經濟性、作業性、所得底塗層之厚度控制容易度等，而含有有機溶劑。有機溶劑較佳為會溶解底塗層形成用組成物所含有之固體成分者，可列舉與組成物所用之溶劑(c)相同之溶劑。有機溶劑不限定為1種，亦可混合極性、蒸發速度等相異之2種以上的溶劑來使用。 The composition for forming an undercoat layer generally contains an organic solvent in consideration of economy, workability, ease of controlling the thickness of the obtained undercoat layer, and the like, in addition to the solid content as a constituent component of the layer. The organic solvent is preferably one that can dissolve the solid components contained in the composition for forming the undercoat layer, and examples thereof include the same solvent as the solvent (c) used in the composition. The organic solvent is not limited to one type, and two or more solvents having different polarities and evaporation rates may be mixed and used.

底塗層形成用組成物，當含有部分水解縮合物或部分水解共縮合物時，亦可含有為了製造此等而使用之溶劑。 When the composition for forming an undercoat layer contains a partially hydrolyzed condensate or a partially hydrolyzed cocondensate, it may contain a solvent used for the production thereof.

進一步地，底塗層形成用組成物中，即使為不含部分水解縮合物或部分水解共縮合物者，為了促進水解共縮合反應，亦較佳為預先摻合與於部分水解縮合之反應中一般所使用者為相同之酸觸媒等之觸媒。即使含有部分水解縮合物或部分水解共縮合物時，當組成物中未殘存有使用於該等之製造的觸媒的情況時，亦以摻合觸媒為佳。底塗層形成用組成物，亦可含有用以使上述含有成分進行水解縮合反應或水解共縮合反應之水。 Furthermore, even if the composition for forming the undercoat layer does not contain a partially hydrolyzed condensate or a partially hydrolyzed cocondensate, in order to promote the hydrolyzed co-condensation reaction, it is preferably blended in advance with the reaction of the partially hydrolyzed condensation Generally, the catalysts are the same acid catalysts. Even when a partially hydrolyzed condensate or a partially hydrolyzed co-condensate is contained, it is preferable to blend the catalyst when the catalyst used in the production does not remain in the composition. The composition for forming an undercoat layer may also contain water for subjecting the aforementioned contained components to a hydrolysis condensation reaction or a hydrolysis co-condensation reaction.

使用底塗層形成用組成物形成基底層之方法，可使用於有機矽烷化合物系之表面處理劑中公知之方法。例如，能夠以刷毛塗佈、流動塗佈、旋轉塗佈、浸漬塗佈、刮刀塗佈、噴霧塗佈、手塗佈等之方法，將基底層形成用組成物塗佈於基體表面，於大氣中或氮環境中依需要乾燥後硬化，藉以形成基底層。硬化之條件，係依所用之組成物之種類、濃度等而適當控制。再者，底塗層形成用組成物之硬化，亦可與組成物之硬化同時進行。 A method for forming a base layer using a composition for forming an undercoat layer can be a known method for use in an organosilane compound-based surface treatment agent. For example, the composition for forming a base layer can be applied to the surface of a substrate by methods such as bristle coating, flow coating, spin coating, dip coating, blade coating, spray coating, and hand coating, and can be applied to the atmosphere. In the middle or nitrogen environment, it is dried and hardened as needed to form a base layer. The hardening conditions are appropriately controlled depending on the type and concentration of the composition used. The curing of the composition for forming the undercoat layer may be performed simultaneously with the curing of the composition.

底塗層之厚度，只要係可對於其上所形成之被膜賦予耐濕性、密著性、基體對鹼等之障壁性之厚度，則無特殊限定。 The thickness of the undercoat layer is not particularly limited as long as it can impart moisture resistance, adhesion, and barrier properties of the substrate to alkali to the film formed thereon.

由本發明之組成物所形成之被膜，可兼顧撥水性及撥油性、密著性及製膜性，有用於作為觸控式面板顯示器等之顯示裝置、光學元件、半導體元件、建築材 料、汽車零件、奈米壓印技術等之基材。由本發明之組成物所形成之被膜，可適合使用作為電車、汽車、船舶、航空機等之輸送機器之機體、窗玻璃(前面玻璃、側邊玻璃、後面玻璃)、反射鏡、保險桿等之物品。又，亦可使用於建築物外壁、帳篷、太陽光發電模組、隔音板、水泥等之屋外用途。亦可使用於漁網、捕蟲網、水槽等。進一步地，亦可利用於廚房、浴室、洗面台、鏡子、廁所相關之各構件的物品、吊燈、磁磚等之陶瓷器、人工大理石、空調等之各種屋內設備。又，亦可使用作為工廠內之治具或內壁、配管等之防污處理。亦適合於護目鏡、眼鏡、安全帽、柏青哥、纖維、傘、遊具、足球等。進一步地，亦可使用作為食品用包材、化粧品用包材、瓶之內部等各種包材之附著防止劑。 The film formed from the composition of the present invention can have both water repellency and oil repellency, adhesion and film-forming properties, and is used as a display device, optical element, semiconductor element, and building material for a touch panel display, etc. Materials, automotive parts, nano-imprint technology, etc. The film formed from the composition of the present invention can be suitably used as a body of a transportation device such as a tram, automobile, ship, or aircraft, window glass (front glass, side glass, rear glass), reflector, bumper, etc. . In addition, it can also be used for outdoor applications such as building exterior walls, tents, solar power generation modules, sound insulation panels, and cement. Can also be used in fishing nets, insect nets, sinks, etc. Furthermore, it can also be used in various indoor equipment such as kitchens, bathrooms, washstands, mirrors, toilet-related items, ceramics such as chandeliers, tiles, artificial marble, and air conditioners. It can also be used as antifouling treatment for jigs, inner walls, and piping in factories. Also suitable for goggles, glasses, hard hats, pachinko, fiber, umbrella, recreational equipment, football, etc. Further, it can be used as an adhesion preventing agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and the inside of bottles.

[實施例] [Example]

以下，列舉實施例以更具體說明本發明，但本發明本不受下述實施例限制，當然亦可於可符合前述及後述要旨之範圍內適當加以變更來實施，該等均包含於本發明之技術範圍中。再者，以下只要無特別指明，「份」意指「質量份」、「%」意指「質量%」。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, and of course, it can be appropriately modified and implemented within a range that can meet the foregoing and later gist, and these are included in the present invention Technical range. In addition, unless otherwise specified, "part" means "mass part" and "%" means "mass%".

接觸角評估 Contact angle evaluation

使用協和界面科學公司製DM700，以液滴法(解析方法：θ/2法)測定被膜表面之水及十六烷之接觸角。水滴量 為3.0μL、油滴量為3.0μL。 Using DM700 manufactured by Kyowa Interface Science Co., the contact angle of water and hexadecane on the surface of the film was measured by a droplet method (analysis method: θ / 2 method). Water droplets It was 3.0 μL, and the amount of oil droplets was 3.0 μL.

於照度1000勒克斯之環境下目視觀察被膜，官能評估有無著色或異物(以下歸納記載為「髒污」)，如以下般評估製膜性。 The film was visually observed under an environment of an illuminance of 1000 lux, and the presence or absence of coloring or foreign matter was evaluated functionally (hereinafter collectively referred to as "dirty"), and the film forming property was evaluated as follows.

◎：全無髒污 ◎: No dirt at all

○：仔細觀察時可確認到髒污 ○: Dirt can be confirmed upon careful observation

△：可確認到膜的部分髒污 △: Part of the film was confirmed to be dirty

×：可確認到膜的全體髒污 ×: The whole film was confirmed to be dirty

溫水試驗 Warm water test

於70℃之離子交換水中浸漬被膜12小時，測定浸漬前後之水的接觸角。 The film was immersed in ion-exchanged water at 70 ° C. for 12 hours, and the contact angle of water before and after immersion was measured.

由試驗後之接觸角與變化率進行溫水試驗耐性之綜合評估。 The comprehensive evaluation of the resistance to warm water test is made from the contact angle and change rate after the test.

◎：接觸角為99°以上且接觸角之變化率為-10%以上 ◎: The contact angle is 99 ° or more and the change rate of the contact angle is -10% or more

○：接觸角為未達99°~90°以上、且接觸角變化率為-10%以上 ○: The contact angle is less than 99 ° to 90 °, and the contact angle change rate is -10% or more

×：接觸角為未達90°、或接觸角變化率未達-10% ×: The contact angle is less than 90 °, or the contact angle change rate is less than -10%

實施例1-1 Example 1-1

於三口燒瓶中裝入參(三甲基矽烷氧基)矽醇4.69g、四氫呋喃(THF)21.2g，進行攪拌。冷卻至-40℃，滴下n-BuLi己烷溶液(1.6mol/L)9.38mL。昇溫至0℃，滴下溶解於21g之THF的六甲基環三矽氧烷10.01g，攪拌17小 時。冷卻至-40℃，於反應液中依次添加THF、離子交換水、己烷，進行分液，分取有機層。以離子交換水洗淨，以無水硫酸鎂乾燥後減壓濃縮，得到無色透明之中間體1。 A three-necked flask was charged with 4.69 g of ginsyl (trimethylsilyloxy) silanol and 21.2 g of tetrahydrofuran (THF), and stirred. After cooling to -40 ° C, 9.38 mL of an n-BuLi hexane solution (1.6 mol / L) was dropped. The temperature was raised to 0 ° C, and 10.01 g of hexamethylcyclotrisiloxane dissolved in 21 g of THF was dropped, and stirred for 17 hours. Time. After cooling to -40 ° C, THF, ion-exchanged water, and hexane were sequentially added to the reaction solution to perform liquid separation, and the organic layer was separated. It was washed with ion-exchanged water, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain colorless and transparent Intermediate 1.

裝入9.47g之中間體1、四甲氧基矽烷(TMOS)8.97g、t-丁基胺151.2μL，一邊攪拌一邊於30℃進行5小時反應。於12hPa、140℃減壓濃縮，得到下述式表示之化合物1。由NMR光譜算出式中以括弧所括起的單位之平均重複數後，為8。 9.47 g of intermediate 1 and 8.97 g of tetramethoxysilane (TMOS) and 151.2 μL of t-butylamine were charged, and the reaction was performed at 30 ° C. for 5 hours while stirring. It was concentrated under reduced pressure at 12 hPa and 140 ° C to obtain Compound 1 represented by the following formula. The average number of repetitions of the units enclosed in parentheses in the formula was 8 from the NMR spectrum.

實施例1-2 Example 1-2

於四口燒瓶中裝入三甲基矽醇0.72g、THF 6.72mL，進行攪拌。冷卻至-40℃，滴下n-BuLi己烷溶液(1.6mol/L)5.00mL。昇溫至0℃，滴下溶解於16.43mL之THF的六甲基環三矽氧烷14.24g，昇溫至室溫攪拌17小時。冷卻至-40℃，滴下氯三乙氧基矽烷1.59g。添加己烷進行過濾。將濾液以13hPa、25℃濃縮，得到化合物2。 由NMR光譜算出式中以括弧所括起的單位之平均重複數後，為8。 A four-necked flask was charged with 0.72 g of trimethylsilanol and 6.72 mL of THF, and stirred. After cooling to -40 ° C, 5.00 mL of n-BuLi hexane solution (1.6 mol / L) was dropped. The temperature was raised to 0 ° C, and 14.24 g of hexamethylcyclotrisiloxane dissolved in 16.43 mL of THF was dropped, and the temperature was raised to room temperature and stirred for 17 hours. After cooling to -40 ° C, 1.59 g of chlorotriethoxysilane was dropped. Hexane was added and filtered. The filtrate was concentrated at 13 hPa and 25 ° C to obtain compound 2. The average number of repetitions of the units enclosed in parentheses in the formula was 8 from the NMR spectrum.

實施例2-1 Example 2-1

以表7所示組成比混合作為有機矽化合物(a)之化合物1、作為金屬烷氧化物(b)之四乙氧基矽烷(TEOS)、作為含氟有機矽化合物(f)之三乙氧基(1H,1H,2H,2H-九氟己基)矽烷(C₄F₉-C₂H₄-Si-(OC₂H₅)₃)、作為觸媒(d)之0.01M鹽酸、及作為溶劑(c)之甲基乙基酮(MEK)，攪拌24h得到塗佈液。於經鹼洗淨之玻璃基板(EAGLE XG、Corning公司)上使用所得之旋轉塗佈器(MIKASA公司製)，將所得之塗佈液以3000rpm、20s塗佈，於室溫靜置1日後，進一步於特定溫度硬化，得到被膜。 Compound 1 as an organosilicon compound (a), tetraethoxysilane (TEOS) as a metal alkoxide (b), and triethoxyl as a fluorine-containing organosilicon compound (f) are mixed in a composition ratio shown in Table 7. (1H, 1H, 2H, 2H-nonafluorohexyl) silane (C ₄ F ₉ -C ₂ H ₄ -Si- (OC ₂ H ₅ ) ₃ ), 0.01M hydrochloric acid as catalyst (d), and as Methyl ethyl ketone (MEK) in the solvent (c) was stirred for 24 h to obtain a coating solution. The obtained spin coater (manufactured by MIKASA) was used on an alkali-washed glass substrate (EAGLE XG, Corning), and the obtained coating solution was applied at 3000 rpm and 20 s, and left to stand at room temperature for 1 day. It is further hardened at a specific temperature to obtain a film.

實施例2-2~2-8、比較例1~4 Examples 2-2 to 2-8, Comparative Examples 1 to 4

以表9所示組成比混合，得到塗佈液後，進行與實施例2-1相同之操作得到被膜。對於所製作之被膜，評估接觸角(水或十六烷)及溫水試驗後之接觸角。 After mixing at the composition ratio shown in Table 9, to obtain a coating liquid, the same operation as in Example 2-1 was performed to obtain a film. For the produced film, the contact angle (water or hexadecane) and the contact angle after the warm water test were evaluated.

表中，比較化合物1，表示以下述式表示之化合物。式中，由NMR光譜算出以括弧所括起的單位之平均重複數後，為24。 In the table, Comparative Compound 1 represents a compound represented by the following formula. In the formula, the average number of repetitions of the units enclosed in parentheses was calculated from the NMR spectrum, and was 24.

於實施例所得到之組成物，被膜形成時之製 膜性優良，且所得之被膜，撥水性及撥油性、密著性及製膜性優良。另一方面，於比較例所得到之組成物，被膜形成時之製膜性均不良。進一步地，由比較例4之組成物所得之被膜，撥水性及撥油性不良，由比較例2及比較例4之組成物所得到之被膜，溫水試驗之結果，可知密著性不良。 The composition obtained in the examples was prepared at the time of film formation. The film is excellent, and the obtained film is excellent in water repellency and oil repellency, adhesion and film forming property. On the other hand, the compositions obtained in the comparative examples had poor film-forming properties during film formation. Furthermore, the film obtained from the composition of Comparative Example 4 had poor water repellency and oil repellency, and the film obtained from the composition of Comparative Example 2 and Comparative Example 4 had a poor water-tightness as a result of the warm water test.

[產業上之可利用性] [Industrial availability]

由本發明之組成物所形成之被膜，可兼顧撥水性及撥油性與製膜性，有用於作為觸控式面板顯示器等之顯示裝置、光學元件、半導體元件、建築材料、汽車零件、奈米壓印技術等之基材。又，由本發明之組成物所形成之被膜，可適合使用作為電車、汽車、船舶、航空機等之輸送機器之機體、窗玻璃(前面玻璃、側邊玻璃、後面玻璃)、反射鏡、保險桿等之物品。又，亦可使用於建築物外壁、帳篷、太陽光發電模組、隔音板、水泥等之屋外用途。亦可使用於漁網、捕蟲網、水槽等。進一步地，亦可利用於廚房、浴室、洗面台、鏡子、廁所相關之各構件的物品、吊燈、磁磚等之陶瓷器、人工大理石、空調等之各種屋內設備。又，亦可使用作為工廠內之治具或內壁、配管等之防污處理。亦適合於護目鏡、眼鏡、安全帽、柏青哥、纖維、傘、遊具、足球等。進一步地，亦可使用作為食品用包材、化粧品用包材、瓶之內部等各種包材之附著防止劑。 The film formed by the composition of the present invention can be compatible with water repellency, oil repellency, and film forming properties, and is used as a display device, optical element, semiconductor element, building material, automobile part, nanometer pressure for touch panel display and the like. Printing technology and other substrates. In addition, the film formed from the composition of the present invention can be suitably used as a body for transportation equipment such as trams, automobiles, ships, and aircraft, window glass (front glass, side glass, rear glass), reflectors, bumpers, and the like. Items. In addition, it can also be used for outdoor applications such as building exterior walls, tents, solar power generation modules, sound insulation panels, and cement. Can also be used in fishing nets, insect nets, sinks, etc. Furthermore, it can also be used in various indoor equipment such as kitchens, bathrooms, washstands, mirrors, toilet-related items, ceramics such as chandeliers, tiles, artificial marble, and air conditioners. It can also be used as antifouling treatment for jigs, inner walls, and piping in factories. Also suitable for goggles, glasses, hard hats, pachinko, fiber, umbrella, recreational equipment, football, etc. Further, it can be used as an adhesion preventing agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and the inside of bottles.

Claims (7)

一種組成物，其含有至少1個含有三烷基矽烷基之分子鏈與至少1個水解性基鍵結於矽原子之有機矽化合物(a)、金屬烷氧化物(b)及含氟基與水解性基鍵結於矽原子之含氟有機矽化合物(f)。 A composition containing an organic silicon compound (a), a metal alkoxide (b), and a fluorine-containing group containing at least one trialkylsilyl-containing molecular chain and at least one hydrolyzable group bonded to a silicon atom. The hydrolyzable group is a fluorine-containing organosilicon compound (f) bonded to a silicon atom. 如請求項1之組成物，其中前述有機矽化合物(a)，為式(I)表示之化合物； [式(I)中，R^a表示含有三烷基矽烷基之分子鏈，A^a1係分別獨立地表示水解性基；Z^a1表示含有三烷基矽烷基之分子鏈、含有烴鏈之基、含有矽氧烷骨架之基或水解性基]。 The composition of claim 1, wherein the aforementioned organosilicon compound (a) is a compound represented by formula (I); [In formula (I), R ^a represents a molecular chain containing a trialkylsilyl group, and A ^a1 each independently represents a hydrolyzable group; Z ^a1 represents a molecular chain containing a trialkylsilyl group, a group containing a hydrocarbon chain, Contains a siloxane skeleton or a hydrolyzable group]. 如請求項1或2之組成物，其中前述金屬烷氧化物(b)，為式(II)表示之化合物；【化2】M-(A ^b1 ) _k (II)[式(II)中，M表示可形成金屬烷氧化物之3價或4價的金屬原子；A^b1係分別獨立地表示碳數1~4之烷氧基；k係因應M之價數，而表示3或4之整數]。 For example, the composition of claim 1 or 2, wherein the aforementioned metal alkoxide (b) is a compound represented by formula (II); [Chem 2] M- (A ^b1 ) _k (II) [in formula (II), M represents a trivalent or tetravalent metal atom that can form a metal alkoxide; A ^b1 represents an alkoxy group having a carbon number of 1 to 4, respectively; k represents an integer of 3 or 4 in accordance with the valence of M ]. 如請求項1~3中任一項之組成物，其中前述含氟有機矽化合物(f)，為式(III-1)及(III-2)之任一者表示之化合物； [式(III-1)中，R^f1表示碳數1~8之含有氟化碳之基；A^f1係分別獨立地表示水解性基；Z^f1表示含有矽氧烷骨架之基、含有烴鏈之基或水解性基]；【化4】R ^f2 -Si(A ^f2 ) ₃ (III-2)[上述式(III-2)中，R^f2表示水解性矽烷寡聚物殘基；A^f2係分別獨立地表示水解性基、碳數1~12之含氟烷基或碳數1~4之烷基]。 The composition according to any one of claims 1 to 3, wherein the aforementioned fluorine-containing organosilicon compound (f) is a compound represented by any one of formulae (III-1) and (III-2); [In formula (III-1), R ^f1 represents a fluorinated carbon-containing group having 1 to 8 carbon atoms; A ^f1 represents a hydrolyzable group independently; Z ^f1 represents a group containing a siloxane skeleton and a hydrocarbon chain Or a hydrolyzable group]; [Chemical Formula 4] R ^f2 -Si (A ^f2 ) ₃ (III-2) [In the above formula (III-2), R ^f2 represents a hydrolyzable silane oligomer residue; A ^f2 Each independently represents a hydrolyzable group, a fluorine-containing alkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 4 carbon atoms]. 如請求項1~4中任一項之組成物，其中前述含氟有機矽化合物(f)與前述有機矽化合物(a)之含有率的比(含氟有機矽化合物(f)/有機矽化合物(a))，以莫耳比計，為7/1以上、20/1以下。 The composition according to any one of claims 1 to 4, wherein the ratio of the content ratio of the aforementioned fluorine-containing organosilicon compound (f) to the aforementioned organosilicon compound (a) (fluorinated organosilicon compound (f) / organosilicon compound) (a)) is 7/1 or more and 20/1 or less in molar ratio. 如請求項1~5中任一項之組成物，其中前述金屬烷氧化物(b)與前述含氟有機矽化合物(f)之含有率的比(金屬烷氧化物(b)/含氟有機矽化合物(f))，以莫耳比計，為0.01以上、50以下。 The composition according to any one of claims 1 to 5, wherein the ratio of the content ratio of the metal alkoxide (b) to the fluorine-containing organic silicon compound (f) (metal alkoxide (b) / fluorine-containing organic The silicon compound (f)) has a molar ratio of 0.01 or more and 50 or less. 一種被膜，其係由如請求項1~6之組成物所形成。 A coating is formed of a composition as claimed in claims 1 to 6.