TW201942206A - Mixed composition - Google Patents

Abstract

The present invention addresses the problem of providing a mixed composition that is capable of realizing a film having excellent water repellency (in particular, droplet sliding properties), oil repellency, and sulfuric acid resistance. The present invention pertains to a mixed composition of an organosilicon compound (A) in which at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a silicon atom, a metal compound (B) represented by formula (b1), an acid (C) with a first dissociation pKa of 1 or higher, and water (D), wherein the amount of water (D) is more than 0 mass% to less than 2.20 mass%. Formula (b1): M(Rb10)r(Ab1)m-r.

Description

混合組成物Mixed composition

本發明是有關於一種有機矽化合物與金屬化合物的混合組成物。The invention relates to a mixed composition of an organic silicon compound and a metal compound.

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（nano-imprint）技術等中，因液滴（尤其是水滴）附著於基材的表面而水其自身或水中所含的離子或灰塵（dust）有時會污染基材。因此，於該些領域中，要求基材表面的撥水·撥油性良好。作為用於形成提高基材表面的撥水·撥油性的皮膜的組成物，已知有混合有有機矽化合物的組成物，專利文獻1中揭示有混合有具有特定結構的有機矽化合物的組成物。另外，專利文獻2中揭示有混合有三烷氧基矽烷化合物、無機填料、觸媒、矽氧烷寡聚物、水、以及有機溶媒的塗料組成物作為用於對輥（roller）、金屬模具、板、料槽（chute）、料斗（hopper）、或烹飪器具等賦予撥水·撥油性及非黏著性的塗料組成物。
[現有技術文獻]
[專利文獻]In various display devices, optical elements, semiconductor elements, building materials, automotive parts, nano-imprint technology, etc., water droplets (especially water droplets) adhere to the surface of the substrate and water itself or in water The contained ions or dust can sometimes contaminate the substrate. Therefore, in these fields, the water repellency and oil repellency of the surface of the substrate are required to be good. As a composition for forming a film for improving the water repellency and oil repellency of the surface of a substrate, a composition mixed with an organic silicon compound is known, and Patent Document 1 discloses a composition mixed with an organic silicon compound having a specific structure. . In addition, Patent Document 2 discloses a coating composition in which a trialkoxysilane compound, an inorganic filler, a catalyst, a siloxane oligomer, water, and an organic solvent are mixed as a roller, a metal mold, A coating composition that imparts water repellency, oil repellency, and non-adhesion to a plate, a chute, a hopper, or a cooking appliance.
[Prior Art Literature]
[Patent Literature]

[專利文獻1]日本專利特開2017-201008號公報
[專利文獻2]日本專利特開2016-33190號公報[Patent Document 1] Japanese Patent Laid-Open No. 2017-201008
[Patent Document 2] Japanese Patent Laid-Open No. 2016-33190

[發明所欲解決之課題]
關於所述領域中使用的皮膜，根據戶外等用途而存在暴露於紫外線或雨水等嚴酷的環境中的情況，而期望即便於暴露於嚴酷的環境中後亦可維持良好的性能。於在戶外欲長時間維持撥水·撥油性的情況下，根據研究結果而明瞭因空氣中的SO_x 或NO_x 與水分進行反應而生成的硫酸或硝酸會導致塗膜的劣化，因此，其中就實用穩定性的觀點而言，尤其重要的是對於作為劣化因子而影響大的硫酸具有耐性。然而，使用專利文獻1、專利文獻2中揭示的組成物而獲得的皮膜中，關於耐硫酸性仍殘留有研究餘地。[Problems to be Solved by the Invention]
The film used in the above-mentioned fields may be exposed to severe environments such as ultraviolet rays or rain depending on applications such as outdoor use, and it is desirable to maintain good performance even after being exposed to severe environments. In the case where it is necessary to maintain water repellency and oil repellency outdoors for a long time, it is clear from the research results that sulfuric acid or nitric acid generated by the reaction of SO _x or NO _x in the air with moisture can cause deterioration of the coating film. From the viewpoint of practical stability, it is particularly important to have resistance to sulfuric acid, which has a large influence as a degradation factor. However, in the film obtained by using the composition disclosed in Patent Documents 1 and 2, there is still room for research on sulfuric acid resistance.

本發明是著眼於所述般的情況而成者，目的在於提供一種可實現撥水性（尤其是水滴的滑落性）·撥油性、以及耐硫酸性優異的皮膜的組成物。
[解決課題之手段]The present invention has been made focusing on the above-mentioned circumstances, and an object of the present invention is to provide a composition that can achieve a film that is excellent in water repellency (especially the slipping property of water droplets), oil repellency, and sulfuric acid resistance.
[Means for solving problems]

本發明包含以下的發明。
[1] 一種混合組成物，其為有機矽化合物（A）、下述式（b1）所表示的金屬化合物（B）、第1解離時的pKa為1以上的酸（C）、以及水（D）的混合組成物，所述有機矽化合物（A）中，至少一個含有三烷基矽烷基的分子鏈、與至少一個水解性基鍵結於矽原子，並且所述水（D）的量超過0質量%且小於2.20質量%，

M(R^b10 )_r (A^b1 )_m-r （b1）

[式（b1）中，M表示Al、Fe、In、Ge、Hf、Si、Ti、Sn、Zr、或Ta，R^b10 表示含有矽氧烷骨架的基、含有烴鏈的基、或氫原子，r為0或1；多個A^b1 分別獨立地表示水解性基，m根據金屬原子M而為3～5的整數]。
[2] 如[1]所述的混合組成物，其中所述水（D）的量超過0質量%且小於1.79質量%。
[3] 如[1]或[2]所述的混合組成物，其進而包含溶劑（E），且所述溶劑（E）的量為10質量%以上。
[4] 如[3]所述的混合組成物，其中所述水（D）的質量相對於所述溶劑（E）的質量的比例（D/E）為50質量%以下。
[5] 如[1]至[4]中任一項所述的混合組成物，其中所述金屬化合物（B）相對於所述有機矽化合物（A）的莫耳比（B/A）為2～500。
[6] 如[1]至[5]中任一項所述的混合組成物，其中所述酸（C）的量為30質量%以下。
[7] 如[1]至[6]中任一項所述的混合組成物，其中所述組成物中，第1解離時的pKa小於1的酸的量小於2.0質量%（包含0質量%）。
[8] 如[1]至[7]中任一項所述的混合組成物，其中所述有機矽化合物（A）為下述式（a1）所表示的化合物，
[化1]

[式（a1）中，多個A^a1 分別獨立地表示水解性基，Z^a1 表示含有三烷基矽烷基的分子鏈、含有矽氧烷骨架的基、或含有烴鏈的基，x為0或1，R^a1 表示含有三烷基矽烷基的分子鏈；Z^a1 及R^a1 的該三烷基矽烷基中所含的氫原子可經取代為氟原子]。
[9] 如[8]所述的混合組成物，其中所述有機矽化合物（A）為下述式（a2）所表示的化合物，
[化2]

[所述式（a2）中，A^a1 、Z^a1 、x與所述A^a1 、Z^a1 、x為相同含義；Z^s1 表示-O-或二價烴基，該二價烴基中所含的-CH₂ -可經取代為-O-，多個R^s2 分別獨立地表示碳數1～10的烷基，n1為1以上的整數，Y^s1 表示單鍵或-Si(R^s2 )₂ -L^s1 -，該L^s1 表示二價烴基，該二價烴基中所含的-CH₂ -可經取代為-O-，多個R^s1 分別獨立地表示烴基或三烷基矽烷基氧基]。
[10] 如[9]所述的混合組成物，其中所述n1為1～60的整數。
[11] 如[1]至[10]中任一項所述的混合組成物，其中所述有機矽化合物（A）與所述金屬化合物（B）的量的合計（A+B）為0.40質量%以上。
[12] 如[1]至[11]中任一項所述的混合組成物，其中所述金屬化合物（B）為下述式（b2）所表示的化合物，

Si(OR^b11 )_y H_4-y （b2）

[所述式（b2）中，R^b11 表示碳數1～6的烷基，y為3或4]。
[發明的效果]The present invention includes the following inventions.
[1] A mixed composition comprising an organosilicon compound (A), a metal compound (B) represented by the following formula (b1), an acid (C) having a pKa of 1 or more during the first dissociation, and water ( D) A mixed composition in which at least one molecular chain containing a trialkylsilyl group and at least one hydrolyzable group are bonded to a silicon atom in the organosilicon compound (A), and the amount of the water (D) More than 0% by mass and less than 2.20% by mass,

M (R ^b10 ) _r (A ^b1 ) _mr (b1)

[In formula (b1), M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta, and R ^b10 represents a group containing a siloxane skeleton, a group containing a hydrocarbon chain, or a hydrogen atom. , R is 0 or 1; a plurality of A ^b1 each independently represent a hydrolyzable group, and m is an integer of 3 to 5 depending on the metal atom M].
[2] The mixed composition according to [1], wherein the amount of the water (D) exceeds 0% by mass and less than 1.79% by mass.
[3] The mixed composition according to [1] or [2], further comprising a solvent (E), and an amount of the solvent (E) is 10% by mass or more.
[4] The mixed composition according to [3], wherein a ratio (D / E) of the mass of the water (D) to the mass of the solvent (E) is 50% by mass or less.
[5] The mixed composition according to any one of [1] to [4], wherein the molar ratio (B / A) of the metal compound (B) to the organosilicon compound (A) is 2 to 500.
[6] The mixed composition according to any one of [1] to [5], wherein the amount of the acid (C) is 30% by mass or less.
[7] The mixed composition according to any one of [1] to [6], wherein in the composition, an amount of an acid having a pKa of less than 1 at the time of the first dissociation is less than 2.0% by mass (including 0% by mass) ).
[8] The mixed composition according to any one of [1] to [7], wherein the organosilicon compound (A) is a compound represented by the following formula (a1),
[Chemical 1]

[In formula (a1), a plurality of A ^a1 each independently represent a hydrolyzable group, Z ^a1 represents a molecular chain containing a trialkylsilyl group, a group containing a siloxane skeleton, or a group containing a hydrocarbon chain, and x is 0 Or 1, R ^a1 represents a molecular chain containing a trialkylsilyl group; a hydrogen atom contained in the trialkylsilyl group of Z ^a1 and R ^a1 may be substituted with a fluorine atom].
[9] The mixed composition according to [8], wherein the organosilicon compound (A) is a compound represented by the following formula (a2),
[Chemical 2]

[In the formula (a2), A ^a1 , Z ^a1 , and x have the same meaning as the A ^a1 , Z ^a1 , and x; Z ^s1 represents —O— or a divalent hydrocarbon group, and the divalent hydrocarbon group contains — CH ₂ -may be substituted by -O-, multiple R ^s2 each independently represent an alkyl group having 1 to 10 carbon atoms, n1 is an integer of 1 or more, and Y ^s1 represents a single bond or -Si (R ^s2 ) ₂ -L ^s1- , where L ^s1 represents a divalent hydrocarbon group, -CH ₂ -contained in the divalent hydrocarbon group may be substituted with -O-, and a plurality of R ^s1 each independently represent a hydrocarbon group or a trialkylsilyloxy group].
[10] The mixed composition according to [9], wherein n1 is an integer of 1 to 60.
[11] The mixed composition according to any one of [1] to [10], wherein the total (A + B) of the amounts of the organosilicon compound (A) and the metal compound (B) is 0.40 Above mass%.
[12] The mixed composition according to any one of [1] to [11], wherein the metal compound (B) is a compound represented by the following formula (b2),

Si (OR ^b11 ) _y H _4-y (b2)

[In the formula (b2), R ^b11 represents an alkyl group having 1 to 6 carbon atoms, and y is 3 or 4].
[Effect of the invention]

本發明的組成物使用第1解離時的pKa為1以上的酸（C）作為觸媒並且將組成物中的水的量抑制為小於規定量，因此，可將對基材塗佈該組成物而形成皮膜時的水解縮合反應控制為適當的狀態。結果，所形成的皮膜具有良好的撥水·撥油性以及耐硫酸性。The composition of the present invention uses an acid (C) having a pKa of 1 or more as a catalyst during the first dissociation and suppresses the amount of water in the composition to less than a predetermined amount. Therefore, the composition can be applied to a substrate On the other hand, the hydrolysis and condensation reaction at the time of film formation is controlled to an appropriate state. As a result, the formed film has good water and oil repellency and sulfuric acid resistance.

本發明的組成物為有機矽化合物（A）、下述式（b1）所表示的金屬化合物（B）、第1解離時的pKa為1以上的酸（C）、以及水（D）的混合組成物，所述有機矽化合物（A）中，至少一個含有三烷基矽烷基的分子鏈、與至少一個水解性基鍵結於矽原子（以下，存在將該矽原子稱為「中心矽原子」的情況），並且於如下方面具有特徵：所述水（D）的量超過0質量%且小於2.20質量%。

M(R^b10 )_r (A^b1 )_m-r （b1）

[式（b1）中，M表示Al、Fe、In、Ge、Hf、Si、Ti、Sn、Zr、或Ta，R^b10 表示含有矽氧烷骨架的基、含有烴鏈的基、或氫原子，r為0或1；多個A^b1 分別獨立地表示水解性基，m根據金屬原子M而為3～5的整數]The composition of the present invention is a mixture of an organosilicon compound (A), a metal compound (B) represented by the following formula (b1), an acid (C) having a pKa of 1 or more at the first dissociation, and water (D). Composition, in the organosilicon compound (A), at least one molecular chain containing a trialkylsilyl group and at least one hydrolyzable group are bonded to a silicon atom (hereinafter, this silicon atom is referred to as a "central silicon atom""), And is characterized in that the amount of the water (D) exceeds 0% by mass and less than 2.20% by mass.

M (R ^b10 ) _r (A ^b1 ) _mr (b1)

[In formula (b1), M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta, and R ^b10 represents a group containing a siloxane skeleton, a group containing a hydrocarbon chain, or a hydrogen atom. , R is 0 or 1; a plurality of A ^b1 each independently represent a hydrolyzable group, and m is an integer of 3 to 5 according to the metal atom M]

使用此種組成物並藉由所述水解性基的水解、及縮聚而形成的皮膜藉由所述三烷基矽烷基而成為具有撥水·撥油性的皮膜，尤其是水滴的滑落性變良好。A film formed by using such a composition and hydrolyzed and polycondensed by the hydrolyzable group becomes a water-repellent and oil-repellent film by the trialkylsilyl group, and in particular, the sliding property of water droplets is improved. .

另外，藉由使用第1解離時的pKa為1以上的酸（C）作為觸媒並且抑制組成物中混合的水量，可抑制鍵結於矽原子的水解性基進行水解、及縮聚的反應的局部進行而於平穩的條件下形成皮膜。結果，可形成良好的皮膜，該皮膜的耐硫酸性優異。另外，耐磨耗性亦優異。In addition, by using an acid (C) having a pKa of 1 or more as a catalyst during the first dissociation and suppressing the amount of water mixed in the composition, it is possible to suppress the hydrolysis and polycondensation reaction of the hydrolyzable group bonded to the silicon atom. The film is formed locally and under stable conditions. As a result, a good film can be formed, and this film is excellent in sulfuric acid resistance. In addition, abrasion resistance is also excellent.

以下，依次對有機矽化合物（A）、金屬化合物（B）、第1解離時的pKa為1以上的酸（C）、以及水（D）進行說明。有機矽化合物（A）、金屬化合物（B）於組成物中亦可為縮合物。Hereinafter, the organic silicon compound (A), the metal compound (B), the acid (C) having a pKa of 1 or more at the first dissociation, and water (D) will be described in this order. The organosilicon compound (A) and the metal compound (B) may be condensation products in the composition.

1. 有機矽化合物（A）
本發明的有機矽化合物（A）中，至少一個含有三烷基矽烷基的分子鏈、與至少一個水解性基鍵結於中心矽原子。Organic silicon compound (A)
In the organosilicon compound (A) of the present invention, at least one molecular chain containing a trialkylsilyl group and at least one hydrolyzable group are bonded to a central silicon atom.

所謂含有三烷基矽烷基的分子鏈，是指具有含有三烷基矽烷基的基鍵結於分子鏈的末端而成的結構的一價基，藉由含有三烷基矽烷基的基與分子鏈鍵結，而由本發明的組成物形成的皮膜的撥水·撥油性提高，尤其是水滴的滑落性提高。另外，藉由存在含有三烷基矽烷基的分子鏈，液滴（水滴等）與該皮膜之間的阻力減低，液滴變得容易移動。即便於將含有三烷基矽烷基的基的烷基取代為氟烷基的情況下，亦可同樣地提高該皮膜界面（表面）的撥水性（尤其是水滴的滑落性）·撥油性。另外，藉由三烷基矽烷基偏向存在於該皮膜表面，而防止硫酸於膜中擴散，可獲得具有高的耐硫酸性的膜。進而，亦防止溫水於膜中擴散，因此成為後述的耐溫水特性亦優異的膜。The molecular chain containing a trialkylsilyl group is a monovalent group having a structure in which a group containing a trialkylsilyl group is bonded to the end of the molecular chain. Chain bonding improves the water repellency and oil repellency of the film formed from the composition of the present invention, and in particular, the sliding property of water droplets is improved. In addition, by the existence of a molecular chain containing a trialkylsilyl group, the resistance between the droplet (water droplets, etc.) and the film is reduced, and the droplet becomes easy to move. That is, when the trialkylsilyl group-containing alkyl group is easily substituted with a fluoroalkyl group, the water repellency (especially the slipping property of water droplets) and oil repellency of the film interface (surface) can be similarly improved. In addition, the trialkylsilyl group is biased to exist on the surface of the film to prevent sulfuric acid from diffusing in the film, and a film having high sulfuric acid resistance can be obtained. Furthermore, since the warm water is also prevented from diffusing in the film, it becomes a film which is also excellent in hot water resistance characteristics described later.

於所述有機矽化合物（A）中，鍵結於中心矽原子的含有三烷基矽烷基的分子鏈的個數為1以上，較佳為3以下，更佳為2以下。鍵結於中心矽原子的含有三烷基矽烷基的分子鏈的個數特佳為1。In the organosilicon compound (A), the number of trialkylsilyl-containing molecular chains bonded to the central silicon atom is 1 or more, preferably 3 or less, and more preferably 2 or less. The number of trialkylsilyl-containing molecular chains bonded to the central silicon atom is particularly preferably 1.

所述水解性基為藉由水解而提供羥基的基（與矽原子鍵結而成為矽烷醇基的基），例如可較佳地列舉：甲氧基、乙氧基、丙氧基、丁氧基等碳數1～4的烷氧基；羥基；乙醯氧基；氯原子；異氰酸酯基等。該些中，較佳為碳數1～4的烷氧基，更佳為碳數1或2的烷氧基。The hydrolyzable group is a group that provides a hydroxyl group by hydrolysis (a group bonded to a silicon atom to become a silanol group), and examples thereof include methoxy, ethoxy, propoxy, and butoxy. Alkoxy groups having 1 to 4 carbon atoms such as a hydroxyl group; a hydroxyl group; an ethoxy group; a chlorine atom; an isocyanate group and the like. Among these, an alkoxy group having 1 to 4 carbon atoms is preferred, and an alkoxy group having 1 or 2 carbon atoms is more preferred.

於所述有機矽化合物（A）中，鍵結於中心矽原子的水解性基的個數為1以上，較佳為2以上，通常較佳為3以下。In the organosilicon compound (A), the number of hydrolyzable groups bonded to the central silicon atom is 1 or more, preferably 2 or more, and usually 3 or less.

對所述有機矽化合物（A）的中心矽原子，除了鍵結含有三烷基矽烷基的分子鏈、水解性基以外，亦可鍵結含有矽氧烷骨架的基（較佳為元素數比構成含有三烷基矽烷基的分子鏈的分子鏈的元素數少的含有矽氧烷骨架的基）、或含有烴鏈的基（較佳為碳數比構成含有三烷基矽烷基的分子鏈的分子鏈的元素數少的含有烴鏈的含有烴鏈的基）。The central silicon atom of the organosilicon compound (A) may be bonded to a group containing a trialkylsilyl group and a hydrolyzable group, or a group containing a siloxane skeleton (preferably an element number ratio). A trialkylsilyl group-containing molecular chain has a small number of elements and a siloxane skeleton-containing group) or a hydrocarbon chain-containing group (preferably, the carbon number ratio constitutes a trialkylsilyl-containing molecular chain). Hydrocarbon chain-containing group containing a small number of elements in the molecular chain).

本發明的組成物亦可將所述有機矽化合物（A）混合兩種以上。In the composition of the present invention, two or more of the organosilicon compounds (A) may be mixed.

所述有機矽化合物（A）具體而言較佳為下述式（a1）所表示的化合物。The organosilicon compound (A) is preferably a compound represented by the following formula (a1).

[化3]
[Chemical 3]

[式（a1）中，多個A^a1 分別獨立地表示水解性基，Z^a1 表示含有三烷基矽烷基的分子鏈、含有矽氧烷骨架的基、或含有烴鏈的基，x為0或1，R^a1 表示含有三烷基矽烷基的分子鏈；Z^a1 及R^a1 的該三烷基矽烷基中所含的氫原子可經取代為氟原子][In formula (a1), a plurality of A ^a1 each independently represent a hydrolyzable group, Z ^a1 represents a molecular chain containing a trialkylsilyl group, a group containing a siloxane skeleton, or a group containing a hydrocarbon chain, and x is 0 Or 1, R ^a1 represents a molecular chain containing a trialkylsilyl group; a hydrogen atom contained in the trialkylsilyl group of Z ^a1 and R ^a1 may be substituted with a fluorine atom]

所述式（a1）中，多個A^a1 分別獨立地為水解性基，只要為藉由水解而提供羥基的基（與矽原子鍵結而成為矽烷醇基的基）即可，例如可較佳地列舉：甲氧基、乙氧基、丙氧基、丁氧基等碳數1～4的烷氧基；羥基；乙醯氧基；氯原子；異氰酸酯基等。該些中，較佳為碳數1～4的烷氧基，更佳為碳數1或2的烷氧基。In the formula (a1), a plurality of A ^a1 are each independently a hydrolyzable group, as long as it is a group that provides a hydroxyl group (a group bonded to a silicon atom to become a silanol group) by hydrolysis, for example, Preferred examples are: alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, and butoxy; hydroxyl groups; ethoxyl groups; chlorine atoms; isocyanate groups and the like. Among these, an alkoxy group having 1 to 4 carbon atoms is preferred, and an alkoxy group having 1 or 2 carbon atoms is more preferred.

所述式（a1）中，R^a1 為含有三烷基矽烷基的分子鏈，如上所述，為具有含有三烷基矽烷基的基鍵結於分子鏈的末端而成的結構的一價基。所述含有三烷基矽烷基的基為包含至少一個三烷基矽烷基的基，較佳為包含兩個以上、進而佳為三個三烷基矽烷基的基。In the formula (a1), R ^a1 is a molecular chain containing a trialkylsilyl group, and as described above, it is a monovalent group having a structure in which a group containing a trialkylsilyl group is bonded to an end of the molecular chain. . The trialkylsilyl group-containing group is a group containing at least one trialkylsilyl group, preferably a group containing two or more, and more preferably three trialkylsilyl groups.

所述含有三烷基矽烷基的基較佳為下述式（s1）所表示的基。The trialkylsilyl group-containing group is preferably a group represented by the following formula (s1).

[化4]
[Chemical 4]

[所述式（s1）中，多個R^s1 分別獨立地表示烴基或三烷基矽烷基氧基，該烴基或三烷基矽烷基氧基中所含的氫原子可經取代為氟原子；*表示鍵結鍵][In the formula (s1), a plurality of R ^s1 each independently represent 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; * Indicates a key-bond key]

於所述R^s1 為烴基的情況下，其碳數較佳為1～4，更佳為1～3，進而佳為1或2。When R ^s1 is a hydrocarbon group, its carbon number is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

於所述R^s1 為烴基的情況下，較佳為脂肪族烴基，更佳為烷基。作為該烷基，可列舉：甲基、乙基、丙基、丁基等。When R ^s1 is a hydrocarbon group, an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

多個R^s1 可相同亦可不同，較佳為相同。於R^s1 全部為烴基的情況下，三個R^s1 的合計碳數較佳為9以下，更佳為6以下，進而佳為4以下。較佳為三個R^s1 中的至少一個為甲基，更佳為至少兩個為甲基，特佳為三個R^s1 全部為甲基。The plurality of R ^s1 may be the same or different, and are preferably the same. 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. Preferably, at least one of the three R ^s1 is a methyl group, more preferably at least two are a methyl group, and particularly preferably, all three of the R ^s1 are methyl groups.

作為所述R^s1 全部為烴基（烷基）的基（三烷基矽烷基），具體而言，可列舉下述式所表示的基等。式中，*表示鍵結鍵。Examples of the group (trialkylsilyl group) in which all of R ^s1 is a hydrocarbon group (alkyl group) include a group represented by the following formula and the like. In the formula, * represents a bond.

[化5]
[Chemical 5]

另外，於所述式（s1）的R^s1 為三烷基矽烷基氧基的情況下，R^s1 的至少一個較佳為三烷基矽烷基氧基。When R ^s1 of the formula (s1) is a trialkylsilyloxy group, at least one of R ^s1 is preferably a trialkylsilyloxy group.

作為所述三烷基矽烷基氧基，可列舉氧原子與R^s1 全部為烴基（烷基）的基（三烷基矽烷基）的矽原子鍵結的基。於所述式（s1）中，較佳為兩個以上的R^s1 為三烷基矽烷基氧基，進而佳為三個R^s1 為三烷基矽烷基氧基。Examples of the trialkylsilyloxy group include a group in which an oxygen atom is bonded to a silicon atom of a group (trialkylsilyl group) in which all of R ^s1 is a hydrocarbon group (alkyl group). In the formula (s1), preferably two or more R ^s1 are trialkylsilyloxy groups, and further preferably three R ^s1 are trialkylsilyloxy groups.

作為R^s1 的至少一個為三烷基矽烷基氧基的基，可列舉下述式所表示的基。Examples of the group in which at least one of R ^s1 is a trialkylsilyloxy group include a group represented by the following formula.

[化6]
[Chemical 6]

於所述含有三烷基矽烷基的分子鏈中，三烷基矽烷基較佳為鍵結於分子鏈的末端（自由端側）、尤其是分子鏈的主鏈（最長直鏈）的末端（自由端側）。Among the trialkylsilyl-containing molecular chains, the trialkylsilyl group is preferably bonded to the end (free end side) of the molecular chain, especially the end of the main chain (longest straight chain) of the molecular chain ( Free end side).

所述鍵結有三烷基矽烷基的分子鏈較佳為直鏈狀或分支鏈狀，更佳為直鏈狀。The molecular chain to which the trialkylsilyl group is bonded is preferably linear or branched, and more preferably linear.

所述鍵結有三烷基矽烷基的分子鏈較佳為包含二烷基矽氧烷鏈，更佳為包含直鏈狀二烷基矽氧烷鏈。另外，包含二烷基矽氧烷鏈的所述分子鏈亦可包含二價烴基。即便該分子鏈的一部分為二價烴基，因剩餘部分為二烷基矽氧烷鏈，因此所獲得的皮膜的化學·物理耐久性良好。The molecular chain to which the trialkylsilyl group is bonded preferably contains a dialkylsiloxane chain, and more preferably contains a linear dialkylsiloxane chain. In addition, the molecular chain including a dialkylsiloxane chain may also include a divalent hydrocarbon group. Even if a part of the molecular chain is a divalent hydrocarbon group, and the remaining part is a dialkylsiloxane chain, the obtained film has good chemical and physical durability.

所述鍵結有三烷基矽烷基的分子鏈較佳為下述式（s2）所表示的基。The molecular chain in which the trialkylsilyl group is bonded is preferably a group represented by the following formula (s2).

[化7]
[Chemical 7]

[式（s2）中，Z^s1 表示-O-或二價烴基，該二價烴基中所含的-CH₂ -可經取代為-O-，多個R^s2 分別獨立地表示碳數1～10的烷基，n1為1以上的整數，Y^s1 表示單鍵或-Si(R^s2 )₂ -L^s1 -，該L^s1 表示二價烴基，該二價烴基中所含的-CH₂ -可經取代為-O-；於所述式（s2）中，左側的*表示與中心矽原子的鍵結鍵，右側的*表示與含有三烷基矽烷基的基的鍵結鍵][In formula (s2), Z ^s1 represents -O- or a divalent hydrocarbon group, -CH ₂ -contained in the divalent hydrocarbon group may be substituted with -O-, and each of R ^s2 independently represents a carbon number of 1 to Alkyl group of 10, n1 is an integer of 1 or more, Y ^s1 represents a single bond or -Si (R ^s2 ) ₂ -L ^s1- , and L ^s1 represents a divalent hydrocarbon group, and -CH ₂ -contained in the divalent hydrocarbon group May be substituted with -O-; in the formula (s2), * on the left represents a bond with a central silicon atom, and * on the right represents a bond with a trialkylsilyl group]

所述R^s2 所表示的烷基的碳數較佳為1～4，更佳為1～3，進而佳為1或2。The carbon number of the alkyl group represented by the R ^s2 is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

n1較佳為1～100的整數，更佳為1～80的整數，進而佳為1～60的整數，進而更佳為1～50的整數，特佳為1～45的整數，最佳為1～30的整數。n1 is preferably an integer from 1 to 100, more preferably an integer from 1 to 80, even more preferably an integer from 1 to 60, even more preferably an integer from 1 to 50, particularly preferably an integer from 1 to 45, and most preferably An integer from 1 to 30.

Z^s1 或L^s1 所表示的二價烴基的碳數較佳為1～10，更佳為1～6，進而佳為1～4。所述二價烴基較佳為鏈狀，為鏈狀的情況下，可為直鏈狀、分支鏈狀的任一種。另外，所述二價烴基較佳為二價脂肪族烴基，較佳為烷二基。作為所述二價烴基，可列舉：亞甲基、伸乙基、伸丙基、伸丁基等。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 chain-shaped, and when it is chain-shaped, it may be either linear or branched. 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.

進而，所述二價烴基中所含的一部分-CH₂ -可經取代為-O-。該情況下，連續的兩個-CH₂ -不會同時經取代為-O-，與Si原子鄰接的-CH₂ -不會經取代為-O-。於兩個以上的-CH₂ -經取代為-O-的情況下，-O-與-O-間的碳數較佳為2～4，進而佳為2或3。作為所述二價烴基的一部分經取代為-O-而成的基，具體而言，可例示具有(聚)乙二醇單元的基、具有(聚)丙二醇單元的基等。Furthermore, a part of -CH ₂ -contained in the divalent hydrocarbon group may be substituted with -O-. In this case, two consecutive -CH ₂ -are not substituted with -O- at the same time, 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, and more preferably 2 or 3. Specific examples of the group in which a part of the divalent hydrocarbon group is substituted with -O- include a group having a (poly) ethylene glycol unit, a group having a (poly) propylene glycol unit, and the like.

於所述式（s2）中，較佳為：Z^s1 為-O-，Y^s1 為單鍵，即所述分子鏈僅包含二烷基矽烷基氧基的重覆。於二烷基矽氧烷鏈僅包含二烷基矽烷基氧基的重覆的情況下，所獲得的皮膜的化學·物理耐久性良好。In the formula (s2), it is preferable that Z ^s1 is -O-, and Y ^s1 is a single bond, that is, the molecular chain includes only a superposition of a dialkylsilyloxy group. In the case where the dialkylsilane chain contains only the overlap of the dialkylsilyloxy group, the obtained film has good chemical and physical durability.

作為所述含有三烷基矽烷基的分子鏈中所含的分子鏈，可列舉下述式所表示的分子鏈。下述式中，q1表示1以上的整數，*表示與中心矽原子或含有三烷基矽烷基的基鍵結的鍵結鍵。q1為與所述n1相同的數值範圍，較佳的範圍亦相同，例如可為1～60，亦可為1～30。Examples of the molecular chain contained in the trialkylsilyl-containing molecular chain include a molecular chain represented by the following formula. In the following formula, q1 represents an integer of 1 or more, and * represents a bonding bond to a central silicon atom or a group containing a trialkylsilyl group. q1 is the same numerical range as n1, and the preferred range is also the same. For example, q1 may be 1 to 60 or 1 to 30.

[化8]
[Chemical 8]

[化9]
[Chemical 9]

[化10]
[Chemical 10]

另外，構成含有三烷基矽烷基的分子鏈的元素的合計數較佳為24以上，更佳為40以上，進而佳為50以上。另外，較佳為5000以下，更佳為4000以下，進而佳為2000以下，進而更佳為1200以下，特佳為700以下，最佳為250以下。The total number of elements constituting the trialkylsilyl-containing molecular chain is preferably 24 or more, more preferably 40 or more, and even more preferably 50 or more. In addition, it is preferably 5,000 or less, more preferably 4,000 or less, even more preferably 2,000 or less, even more preferably 1200 or less, particularly preferably 700 or less, and most preferably 250 or less.

所述含有三烷基矽烷基的分子鏈較佳為下述式（s3）所表示的基。The molecular chain containing the trialkylsilyl group is preferably a group represented by the following formula (s3).

[化11]
[Chemical 11]

[式（s3）中，Z^s1 、R^s2 、n1、Y^s1 、R^s1 與所述Z^s1 、R^s2 、n1、Y^s1 、R^s1 為相同含義；*表示與中心矽原子的鍵結鍵][In formula (s3), Z ^s1 , R ^s2 , n1, Y ^s1 , R ^s1 and Z ^s1 , R ^s2 , n1, Y ^s1 , and R ^{s1 have} the same meanings; * indicates a bond to the central silicon atom ]

所述含有三烷基矽烷基的分子鏈較佳為下述式（s3-1）或下述式（s3-2）所表示的基，更佳為下述式（s3-2）所表示的基。The molecular chain containing the trialkylsilyl group is preferably a group represented by the following formula (s3-1) or (s3-2), and more preferably a group represented by the following formula (s3-2) base.

於所述含有三烷基矽烷基的分子鏈由下述式（s3-1）表示的情況下，更佳為下述式（s3-1-1）所表示的基。When the trialkylsilyl group-containing molecular chain is represented by the following formula (s3-1), a group represented by the following formula (s3-1-1) is more preferred.

[化12]
[Chemical 12]

[式（s3-1）及式（s3-1-1）中，Z^s1 、R^s2 、n1、Y^s1 與所述Z^s1 、R^s2 、n1、Y^s1 為相同含義；R^s3 表示碳數1～4的烷基；*表示與中心矽原子的鍵結鍵][In the formula (S3-1) and formula ^{(s3-1-1), Z s1, R} s2, n1, Y s1 and the ^{Z s1, R s2, n1,} Y s1 is the same meaning; R ^s3 is a C 1 to 4 alkyl groups; * represents a bond to a central silicon atom]

R^s3 所表示的烷基的碳數較佳為1~3，更佳為1或2。另外，式（s3-1）及式（s3-1-1）中，-Si(R^s3 )₃ 中所含的R^s3 的合計碳數較佳為9以下，更佳為6以下，進而佳為4以下。進而，-Si(R^s3 )₃ 中所含的R^s3 中，較佳為R^s3 的至少一個為甲基，更佳為兩個以上的R^s3 為甲基，特佳為三個R^s3 全部為甲基。The carbon number of the alkyl group represented by R ^s3 is preferably 1 to 3, and more preferably 1 or 2. In addition, in formulas (s3-1) and (s3-1-1), the total carbon number of R ^s3 contained in -Si (R ^s3 ) ₃ is preferably 9 or less, more preferably 6 or less, and further preferably It is 4 or less. Further, R ^s3 contained -Si (R ^s3) _3, the R ^s3 is preferably at least one of methyl group, more preferably two or more of R ^s3 is a methyl group, and particularly preferably all three R ^s3 Is methyl.

於所述含有三烷基矽烷基的分子鏈由下述式（s3-2）表示的情況下，更佳為下述式（s3-2-1）所表示的基。When the trialkylsilyl group-containing molecular chain is represented by the following formula (s3-2), a group represented by the following formula (s3-2-1) is more preferred.

[化13]
[Chemical 13]

[所述式（s3-2）及式（s3-2-1）中，Z^s1 、R^s2 、n1、Y^s1 與所述Z^s1 、R^s2 、n1、Y^s1 為相同含義；R^s4 表示碳數1～4的烷基；*表示與中心矽原子的鍵結鍵]In [the formula (S3-2) and formula ^{(s3-2-1), Z s1, R} s2, n1, Y s1 and the ^{Z s1, R s2, n1,} Y s1 is the same meaning; R ^s4 represents Alkyl group of 1 to 4 carbons; * represents a bond to a central silicon atom]

R^s4 所表示的烷基的碳數較佳為1～3，更佳為1或2。另外，式（s3-2）及式（s3-2-1）中，多個-Si(R^s4 )₃ 中所含的R^s4 的合計碳數分別較佳為9以下，更佳為6以下，進而佳為4以下。進而，多個-Si(R^s4 )₃ 中所含的R^s4 中，較佳為R^s4 的至少一個為甲基，更佳為兩個以上的R^s4 為甲基，特佳為三個R^s4 全部為甲基。The carbon number of the alkyl group represented by R ^s4 is preferably 1 to 3, and more preferably 1 or 2. In addition, in formula (s3-2) and formula (s3-2-1), the total carbon number of R ^s4 contained in a plurality of -Si (R ^s4 ) ₃ is preferably 9 or less, more preferably 6 or less. It is further preferably 4 or less. Further, a plurality of R contained in ^S4 -Si (R ^s4) ₃ in ^S4 is preferably at least one R is a methyl group, more preferably two or more of R ^S4 is methyl, particularly preferably three R ^{s4 is} all methyl.

作為所述含有三烷基矽烷基的分子鏈，具體而言，可列舉下述式（s3-I）所表示的基。Specific examples of the trialkylsilyl-containing molecular chain include a group represented by the following formula (s3-I).

[化14]
[Chemical 14]

[所述式（s3-I）中，*表示與中心矽原子的鍵結鍵][In the formula (s3-I), * represents a bond to a central silicon atom]

所述式（s3-I）中，Z^s10 、R^s20 、n10、Y^s10 、R^s10 較佳為下述表1、表2所示的組合。In the formula (s3-I), Z ^s10 , R ^s20 , n10, Y ^s10 , and R ^{s10 are} preferably combinations shown in Tables 1 and 2 below.

[表1]
[Table 1]

[表2]
[Table 2]

所述表1、表2中所示的n10較佳為1～30。另外，所述式（a1）中，Z^a1 表示含有三烷基矽烷基的分子鏈、含有矽氧烷骨架的基、或含有烴鏈的基。N10 shown in Tables 1 and 2 is preferably 1 to 30. In the formula (a1), Z ^a1 represents a molecular chain containing a trialkylsilyl group, a group containing a siloxane skeleton, or a group containing a hydrocarbon chain.

於Z^a1 為含有三烷基矽烷基的分子鏈的情況下，可列舉與所述R^a1 相同者。In the case where Z ^a1 is a molecular chain containing a trialkylsilyl group, the same as R ^a1 may be mentioned.

於Z^a1 為含有矽氧烷骨架的基的情況下，所述含有矽氧烷骨架的基為含有矽氧烷單元（Si-O-）的一價基，較佳為由數量比構成R^a1 的含有三烷基矽烷基的分子鏈的元素數少的元素構成。藉此，含有矽氧烷骨架的基成為較含有三烷基矽烷基的分子鏈而言長度短、或立體廣度（體積大小）小的基。含有矽氧烷骨架的基亦可包含二價烴基。In the case where Z ^a1 is a group containing a siloxane skeleton, the group containing a siloxane skeleton is a monovalent group containing a siloxane unit (Si-O-), and R ^{a1 is} preferably composed of a quantity ratio. Is composed of a small number of elements of the molecular chain of the trialkylsilyl group. Thereby, the group containing a siloxane skeleton becomes a group which is shorter in length than a molecular chain containing a trialkylsilyl group, or which has a small three-dimensional breadth (volume size). The group containing a siloxane skeleton may also include a divalent hydrocarbon group.

所述含有矽氧烷骨架的基較佳為下述式（s4）所表示的基。The group containing a siloxane skeleton is preferably a group represented by the following formula (s4).

[化15]
[Chemical 15]

[式（s4）中，Z^s1 、R^s2 、及Y^s1 與所述Z^s1 、R^s2 、及Y^s1 為相同含義；R^s5 表示烴基或羥基，該烴基中所含的-CH₂ -可經取代為-O-，該烴基中所含的氫原子可經取代為氟原子；n3表示0～5的整數；*表示與中心矽原子的鍵結鍵][In formula (s4), Z ^s1 , R ^s2 , and Y ^s1 have the same meanings as Z ^s1 , R ^s2 , and Y ^s1 ; R ^s5 represents a hydrocarbon group or a hydroxyl group, and -CH ₂ -in the hydrocarbon group may After being substituted with -O-, the hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom; n3 represents an integer of 0 to 5; * represents a bond with a central silicon atom]

作為R^s5 所表示的烴基，可列舉與R^s1 所表示的烴基相同的基，較佳為脂肪族烴基，更佳為烷基。Examples of the hydrocarbon group represented by R ^s5 include the same groups as the hydrocarbon group represented by R ^s1 , preferably an aliphatic hydrocarbon group, and more preferably an alkyl group.

R^s5 所表示的烴基的碳數較佳為1～4，更佳為1～3，進而佳為1或2。The carbon number of the hydrocarbon group represented by R ^s5 is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

n3較佳為1～5的整數，更佳為1～3的整數。n3 is preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.

所述含有矽氧烷骨架的基的元素數的合計較佳為600以下，更佳為500以下，進而佳為350以下，進而更佳為100以下，特佳為50以下，最佳為30以下，另外，較佳為10以上。另外，R^a1 的含有三烷基矽烷基的分子鏈與Z^a1 的含有矽氧烷骨架的基的元素數的差較佳為10以上，更佳為20以上，且較佳為1000以下，更佳為500以下，進而佳為200以下。The total number of elements of the group containing a siloxane skeleton is preferably 600 or less, more preferably 500 or less, even more preferably 350 or less, even more preferably 100 or less, particularly preferably 50 or less, and most preferably 30 or less. In addition, it is preferably 10 or more. In addition, the difference between the number of elements of the trialkylsilyl group-containing molecular chain of R ^{a1 and} the siloxane group-containing group of Z ^a1 is preferably 10 or more, more preferably 20 or more, and preferably 1,000 or less, more It is preferably 500 or less, and further preferably 200 or less.

作為所述含有矽氧烷骨架的基，具體而言，可列舉下述式所表示的基。Specific examples of the group containing a siloxane skeleton include a group represented by the following formula.

[化16]
[Chemical 16]

於Z^a1 為含有烴鏈的基的情況下，較佳為烴鏈部分的碳數比構成含有三烷基矽烷基的分子鏈的分子鏈的元素數少。另外，較佳為烴鏈的最長直鏈的碳數比構成含有三烷基矽烷基的分子鏈的最長直鏈的元素數少。含有烴鏈的基通常僅由烴基（烴鏈）構成，視需要亦可為該烴鏈的一部分亞甲基（-CH₂ -）經取代為氧原子而成的基。另外，與Si原子鄰接的亞甲基（-CH₂ -）不會經取代為氧原子，另外，連續的兩個亞甲基（-CH₂ -）亦不會同時經取代為氧原子。When Z ^a1 is a group containing a hydrocarbon chain, the number of carbon atoms in the hydrocarbon chain portion is preferably smaller than the number of elements constituting the molecular chain of the trialkylsilyl-containing molecular chain. In addition, it is preferable that the number of carbons of the longest straight chain of the hydrocarbon chain is smaller than the number of elements of the longest straight chain constituting the molecular chain containing a trialkylsilyl group. The group containing a hydrocarbon chain is usually only composed of a hydrocarbon group (hydrocarbon chain), and may be a group in which a part of the hydrocarbon chain is substituted by an methylene group (-CH _2- ) with an oxygen atom, if necessary. In addition, the methylene group (-CH _2- ) adjacent to the Si atom is not substituted with an oxygen atom, and two consecutive methylene groups (-CH _2- ) are not substituted with an oxygen atom at the same time.

再者，所謂烴鏈部分的碳數，於未經氧取代型的含有烴鏈的基的情況下，是指構成烴基（烴鏈）的碳原子的數量，於經氧取代型的含有烴鏈的基的情況下，是指將氧原子假定為亞甲基（-CH₂ -）並進行計數而得的碳原子的數量。The carbon number of the hydrocarbon chain part means the number of carbon atoms constituting the hydrocarbon group (hydrocarbon chain) in the case of a hydrocarbon chain-containing group which is not oxygen-substituted, and the oxygen-substituted hydrocarbon chain-containing group. In the case of a radical, it refers to the number of carbon atoms obtained by assuming that an oxygen atom is a methylene group (-CH _2- ) and counting.

以下，只要並無特別說明，則以未經氧取代型的含有烴鏈的基（即一價烴基）為例而對含有烴鏈的基進行說明，於任一說明中，均可將其亞甲基（-CH₂ -）中的一部分取代為氧原子。Hereinafter, unless otherwise specified, a hydrocarbon chain-containing group (ie, a monovalent hydrocarbon group) that is not oxygen-substituted is used as an example to describe a hydrocarbon chain-containing group. In any description, the Part of the methyl group (-CH _2- ) is substituted with an oxygen atom.

關於所述含有烴鏈的基，於其為烴基的情況下，碳數較佳為1以上且3以下，更佳為1。另外，所述含有烴鏈的基可為分支鏈亦可為直鏈。所述含有烴鏈的基較佳為飽和或不飽和的脂肪族含有烴鏈的基，更佳為飽和脂肪族含有烴鏈的基。作為所述飽和脂肪族含有烴鏈的基，更佳為飽和脂肪族烴基。飽和脂肪族烴基例如包含甲基、乙基、丙基等。Regarding the hydrocarbon chain-containing group, when it is a hydrocarbon group, the number of carbons is preferably 1 or more and 3 or less, and more preferably 1. The hydrocarbon chain-containing group may be a branched chain or a straight chain. The hydrocarbon chain-containing group is preferably a saturated or unsaturated aliphatic hydrocarbon chain-containing group, and more preferably a saturated aliphatic hydrocarbon chain-containing group. The saturated aliphatic hydrocarbon group-containing group is more preferably a saturated aliphatic hydrocarbon group. The saturated aliphatic hydrocarbon group includes, for example, a methyl group, an ethyl group, a propyl group, and the like.

於飽和脂肪族烴基的一部分亞甲基（-CH₂ -）經取代為氧原子的情況下，具體而言，可例示具有(聚)乙二醇單元的基等。When a part of the methylene group (-CH _2- ) of the saturated aliphatic hydrocarbon group is substituted with an oxygen atom, specifically, a group having a (poly) ethylene glycol unit and the like can be exemplified.

所述式（a1）中，x較佳為0。In the formula (a1), x is preferably 0.

所述有機矽化合物（A）較佳為下述式（a2）所表示的化合物。The organosilicon compound (A) is preferably a compound represented by the following formula (a2).

[化17]
[Chemical 17]

[式（a2）中，A^a1 、Z^a1 、x、Z^s1 、R^s2 、n1、Y^s1 、R^s1 分別與所述A^a1 、Z^a1 、x、Z^s1 、R^s2 、n1、Y^s1 、R^s1 為相同含義][In formula (a2), A ^a1 , Z ^a1 , x, Z ^s1 , R ^s2 , n1, Y ^s1 , R ^s1 and the A ^a1 , Z ^a1 , x, Z ^s1 , R ^s2 , n1, Y ^{s1, respectively} , R ^s1 has the same meaning]

於所述式（a2）中，所述n1較佳為1～60的整數。所述n1更佳為2以上的整數，進而佳為3以上的整數，且更佳為50以下的整數，進而佳為40以下的整數，特佳為30以下的整數，最佳為25以下的整數。In the formula (a2), the n1 is preferably an integer of 1 to 60. The n1 is more preferably an integer of 2 or more, further preferably an integer of 3 or more, and more preferably an integer of 50 or less, further preferably an integer of 40 or less, particularly preferably an integer of 30 or less, and most preferably 25 or less. Integer.

所述式（a2）所表示的有機矽化合物（A）較佳為下述式（a2-1）或下述式（a2-2）所表示的化合物，更佳為下述式（a2-2）所表示的化合物。The organosilicon compound (A) represented by the formula (a2) is preferably a compound represented by the following formula (a2-1) or the following formula (a2-2), and more preferably the following formula (a2-2) ).

於所述式（a2）所表示的有機矽化合物（A）由下述式（a2-1）表示的情況下，更佳為下述式（a2-1-1）所表示的化合物。When the organosilicon compound (A) represented by the formula (a2) is represented by the following formula (a2-1), the compound represented by the following formula (a2-1-1) is more preferred.

[化18]
[Chemical 18]

[式（a2-1）及式（a2-1-1）中，A^a1 、Z^s1 、R^s2 、n1、Y^s1 、R^s3 與所述A^a1 、Z^s1 、R^s2 、n1、Y^s1 、R^s3 為相同含義][In formula (a2-1) and formula (a2-1-1), A ^a1 , Z ^s1 , R ^s2 , n1, Y ^s1 , R ^s3 and the A ^a1 , Z ^s1 , R ^s2 , n1, Y ^s1 , R ^{s3 have} the same meaning]

於所述式（a2）所表示的有機矽化合物（A）由下述式（a2-2）表示的情況下，更佳為下述式（a2-2-1）所表示的化合物。When the organosilicon compound (A) represented by the formula (a2) is represented by the following formula (a2-2), the compound represented by the following formula (a2-2-1) is more preferred.

[化19]
[Chemical 19]

[式（a2-2）及式（a2-2-1）中，A^a1 、Z^s1 、R^s2 、n1、Y^s1 、R^s4 與所述A^a1 、Z^s1 、R^s2 、n1、Y^s1 、R^s4 為相同含義][In formula (a2-2) and formula (a2-2-1), A ^a1 , Z ^s1 , R ^s2 , n1, Y ^s1 , R ^s4 and the A ^a1 , Z ^s1 , R ^s2 , n1, Y ^s1 , R ^s4 has the same meaning]

所述式（a2）所表示的有機矽化合物（A）具體可列舉式（A-I）所表示的化合物。Specific examples of the organosilicon compound (A) represented by the formula (a2) include compounds represented by the formula (A-I).

[化20]
[Chemical 20]

於所述式（A-I）中，A^a10 、Z^s10 、R^s20 、n10、Y^s10 、R^s10 較佳為下述表3-1、表3-2、表4-1、表4-2中所示的組合。In the formula (AI), A ^a10 , Z ^s10 , R ^s20 , n10, Y ^s10 , and R ^{s10 are} preferably as shown in Tables 3-1, 3-2, 4-1, and 4-2 below. The combination shown.

[表3-1]
[Table 3-1]

[表3-2]
[Table 3-2]

[表4-1]
[Table 4-1]

[表4-2]
[Table 4-2]

所述表3-1、表3-2、表4-1、表4-2中所示的n10較佳為1～30。The n10 shown in Tables 3-1, 3-2, 4-1, and 4-2 is preferably 1 to 30.

所述式（A-I）中，更佳為（A-I-26）所表示的化合物。即，作為所述式（a2）所表示的有機矽化合物（A），較佳為下述式（a3）所表示的化合物。In the formula (A-I), a compound represented by (A-I-26) is more preferable. That is, as the organosilicon compound (A) represented by the formula (a2), a compound represented by the following formula (a3) is preferred.

[化21]
[Chemical 21]

[式（a3）中，n2為1～60的整數][In formula (a3), n2 is an integer of 1 to 60]

所述n2更佳為2以上的整數，進而佳為3以上的整數，且更佳為50以下的整數，進而佳為40以下的整數，特佳為30以下的整數，最佳為25以下的整數。The n2 is more preferably an integer of 2 or more, further preferably an integer of 3 or more, and more preferably an integer of 50 or less, further preferably an integer of 40 or less, particularly preferably an integer of 30 or less, and most preferably 25 or less. Integer.

於組成物100質量%中，所述有機矽化合物（A）的量較佳為0.1質量%以上，更佳為0.2質量%以上，進而佳為0.3質量%以上，且較佳為2質量%以下，更佳為1質量%以下，進而佳為0.8質量%以下。所述有機矽化合物（A）的量可根據組成物的製備時的調配量或組成物的分析結果來算出。再者，於本說明書中，質量比或莫耳比可與所述同樣地根據組成物的製備時的調配量或組成物的分析結果來算出。The amount of the organosilicon compound (A) in 100% by mass of the composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, and preferably 2% by mass or less. It is more preferably 1% by mass or less, and further preferably 0.8% by mass or less. The amount of the organosilicon compound (A) can be calculated from the compounded amount during preparation of the composition or the analysis result of the composition. In addition, in this specification, a mass ratio or a molar ratio can be calculated from the compounding quantity at the time of preparation of a composition, or the analysis result of a composition similarly to the above.

作為所述有機矽化合物（A）的合成方法，可列舉日本專利特開2017-201009號公報中記載的方法。Examples of the method for synthesizing the organosilicon compound (A) include a method described in Japanese Patent Laid-Open No. 2017-201009.

2. 金屬化合物（B）
本發明的組成物為混合有下述式（b1）所表示的金屬化合物（B）的組成物。

M(R^b10 )_r (A^b1 )_m-r （b1）

[式（b1）中，M表示Al、Fe、In、Ge、Hf、Si、Ti、Sn、Zr、或Ta，R^b10 表示含有矽氧烷骨架的基、含有烴鏈的基、或氫原子，r為0或1；多個A^b1 分別獨立地表示水解性基，m根據金屬原子M而為3～5的整數]2. Metal compounds (B)
The composition of the present invention is a composition in which a metal compound (B) represented by the following formula (b1) is mixed.

M (R ^b10 ) _r (A ^b1 ) _mr (b1)

[In formula (b1), M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta, and R ^b10 represents a group containing a siloxane skeleton, a group containing a hydrocarbon chain, or a hydrogen atom. , R is 0 or 1; a plurality of A ^b1 each independently represent a hydrolyzable group, and m is an integer of 3 to 5 according to the metal atom M]

如所述式（b1）所表示般，所述金屬化合物（B）為至少一個水解性基A^b1 鍵結於金屬原子M的化合物。再者，於本說明書中，所謂「金屬」，是以亦包含Si或Ge等半金屬的含義來使用。As represented by the formula (b1), the metal compound (B) is a compound in which at least one hydrolyzable group A ^{b1 is} bonded to a metal atom M. In addition, in this specification, "metal" is used in the meaning which also includes a semimetal, such as Si or Ge.

如上所述，認為由本發明的組成物獲得的皮膜藉由源自有機矽化合物（A）的三烷基矽烷基而撥水·撥水功能提高，並且此種未鍵結含有三烷基矽烷基的分子鏈的金屬元素M於皮膜中作為間隔物（spacer）發揮功能。As described above, it is considered that the film obtained from the composition of the present invention improves the water repellency and water repellency function of the trialkylsilyl group derived from the organic silicon compound (A), and such unbonded trialkylsilyl group is contained. The metal element M of the molecular chain functions as a spacer in the membrane.

M較佳為Al、Si、Ti、Sn、Zr，更佳為Al、Si、Ti、Zr，進而佳為Si。M is preferably Al, Si, Ti, Sn, Zr, more preferably Al, Si, Ti, Zr, and even more preferably Si.

R^b10 為於至少一部分中具有含有矽氧烷骨架的基的基、或為於至少一部分中具有烴鏈的基、或表示氫原子。R ^b10 is a group having a siloxane group-containing group in at least a part, a group having a hydrocarbon chain in at least a part, or a hydrogen atom.

A^b1 所表示的水解性基、及R^b10 所表示的含有矽氧烷骨架的基、含有烴鏈的基可自所述有機矽化合物（A）中說明的水解性基、含有矽氧烷骨架的基、以及含有烴鏈的基中適宜選擇，較佳的範圍亦相同。The hydrolyzable group represented by A ^b1 and the siloxane group-containing group represented by R ^b10 and the hydrocarbon chain-containing group may be selected from the hydrolyzable group described above and the siloxane-containing group described in the organosilicon compound (A). The group and the group containing a hydrocarbon chain are suitably selected, and a preferable range is also the same.

M於金屬原子M為Al、Fe、In等三價金屬的情況下為3，於金屬原子M為Ge、Hf、Si、Ti、Sn、Zr等四價金屬的情況下為4，於金屬原子M為Ta等五價金屬的情況下為5。M is 3 when the metal atom M is a trivalent metal such as Al, Fe, and In, and 4 when the metal atom M is a tetravalent metal such as Ge, Hf, Si, Ti, Sn, Zr, etc. It is 5 when M is a pentavalent metal such as Ta.

本發明的組成物亦可為將金屬化合物（B）混合兩種以上而成的組成物。The composition of the present invention may be a composition obtained by mixing two or more metal compounds (B).

作為所述金屬化合物（B），可列舉：r=0、即僅水解性基A^b1 鍵結於金屬原子M的金屬化合物B1；或r=1、即含有矽氧烷骨架的基、含有烴鏈的基、或氫原子中的一個、與水解性基A^b1 中的兩個以上鍵結於金屬原子M的金屬化合物B2。Examples of the metal compound (B) include: r = 0, that is, a metal compound B1 in which only a hydrolyzable group A ^{b1 is} bonded to a metal atom M; or r = 1, that is, a group containing a siloxane skeleton, and a hydrocarbon One of a group of a chain or a hydrogen atom, and a metal compound B2 having two or more of the hydrolyzable groups A ^b1 bonded to a metal atom M.

（金屬化合物B1）
作為僅水解性基A^b1 鍵結於金屬原子M的金屬化合物B1，具體而言，可列舉：三乙氧基鋁、三丙氧基鋁、三丁氧基鋁等三烷氧基鋁；三乙氧基鐵等三烷氧基鐵；三甲氧基銦、三乙氧基銦、三丙氧基銦、三丁氧基銦等三烷氧基銦；四甲氧基鍺、四乙氧基鍺、四丙氧基鍺、四丁氧基鍺等四烷氧基鍺；四甲氧基鉿、四乙氧基鉿、四丙氧基鉿、四丁氧基鉿等四烷氧基鉿；四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四丁氧基矽烷等四烷氧基矽烷；四甲氧基鈦、四乙氧基鈦、四丙氧基鈦、四丁氧基鈦等四烷氧基鈦；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、四丁氧基鋯等四烷氧基鋯；五甲氧基鉭、五乙氧基鉭、五丙氧基鉭、五丁氧基鉭等五烷氧基鉭等。(Metal compound B1)
Specific examples of the metal compound B1 in which only the hydrolyzable group A ^{b1 is} bonded to the metal atom M include trialkoxy aluminum such as triethoxyaluminum, tripropoxyaluminum, and tributoxyaluminum; three Trialkoxy iron such as iron ethoxylate; Trialkoxy indium such as trimethoxy indium, triethoxy indium, tripropoxy indium, tributoxy indium; tetramethoxy germanium, tetraethoxy Tetraalkoxygermanium, such as germanium, tetrapropoxygermanium, and tetrabutoxygermanium; tetramethoxyfluorene, tetraethoxyfluorene, tetrapropoxyfluorene, and tetrabutoxyfluorene; Tetramethoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane; tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutyl Tetraalkoxy titanium such as titanium oxytitanium; Tetraalkoxy tin such as tetramethoxytin, tetraethoxy tin, tetrapropoxytin, tetrabutoxytin; tetramethoxyzirconium, tetraethoxy Tetraalkoxy zirconium such as zirconium, tetrapropoxy zirconium, tetrabutoxy zirconium; pentamethoxy tantalum, pentaethoxy tantalum, pentapropoxy tantalum, pentabutoxy tantalum, etc. .

（金屬化合物B2）
含有矽氧烷骨架的基、含有烴鏈的基、或氫原子中的一個、與水解性基A^b1 中的兩個以上鍵結於金屬原子M的金屬化合物B2較佳為金屬原子M為四價金屬（Ge、Hf、Si、Ti、Sn、Zr等），作為金屬原子M為Si時的具體例，可列舉：三甲基矽烷基氧基三甲氧基矽烷、三甲基矽烷基氧基三乙氧基矽烷、三甲基矽烷基氧基三丙氧基矽烷等三甲基矽烷基氧基三烷氧基矽烷；甲基三甲氧基矽烷、乙基三甲氧基矽烷、甲基三乙氧基矽烷、乙基三乙氧基矽烷、甲基三丙氧基矽烷等烷基三烷氧基矽烷；乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷等烯基三烷氧基矽烷；三甲氧基矽烷、三乙氧基矽烷、三丙氧基矽烷等三烷氧基矽烷；二甲氧基甲基矽烷、二乙氧基甲基矽烷等二烷氧基烷基矽烷等。(Metal compound B2)
One of a group containing a siloxane skeleton, a group containing a hydrocarbon chain, or a hydrogen atom, and a metal compound B2 that is bonded to two or more of the hydrolyzable groups A ^b1 to a metal atom M, preferably the metal atom M is four Examples of valent metals (Ge, Hf, Si, Ti, Sn, Zr, etc.) as specific examples when the metal atom M is Si include trimethylsilyloxytrimethoxysilane, trimethylsilyloxy Trimethylsilyloxytrialkoxysilanes such as triethoxysilane, trimethylsilyloxytripropoxysilane; methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethyl Alkyltrialkoxysilanes such as oxysilane, ethyltriethoxysilane, methyltripropoxysilane; alkenyltrialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, etc. ; Trialkoxysilanes such as trimethoxysilane, triethoxysilane, and tripropoxysilane; dialkoxyalkylsilanes such as dimethoxymethylsilane, diethoxymethylsilane; and the like.

作為所述金屬化合物（B），具體而言，較佳為下述式（b2）所表示的化合物。

Si(OR^b11 )_y H_4-y （b2）

[式（b2）中，R^b11 表示碳數1～6的烷基，y為3或4]As the metal compound (B), specifically, a compound represented by the following formula (b2) is preferred.

Si (OR ^b11 ) _y H _4-y (b2)

[In formula (b2), R ^b11 represents an alkyl group having 1 to 6 carbon atoms, and y is 3 or 4]

R^b11 所表示的烷基的碳數較佳為1～4，更佳為1～3，進而佳為1或2。The carbon number of the alkyl group represented by R ^b11 is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

作為R^b11 所表示的烷基，可列舉：甲基、乙基、丙基、丁基、戊基、己基等。Examples of the alkyl group represented by R ^b11 include methyl, ethyl, propyl, butyl, pentyl, and hexyl.

於組成物100質量%中，所述金屬化合物（B）的量較佳為0.1質量%以上，更佳為0.5質量%以上，進而佳為0.8質量%以上，且較佳為2.5質量%以下，更佳為2質量%以下，進而佳為1.5質量%以下。In 100% by mass of the composition, the amount of the metal compound (B) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, and preferably 2.5% by mass or less, It is more preferably 2% by mass or less, and still more preferably 1.5% by mass or less.

於組成物100質量%中，所述有機矽化合物（A）與所述金屬化合物（B）的量的合計（A+B）較佳為0.40質量%以上，更佳為0.8質量%以上，進而佳為1質量%以上，且較佳為2.5質量%以下，更佳為2質量%以下，進而佳為1.8質量%以下。The total (A + B) of the amount of the organosilicon compound (A) and the metal compound (B) in 100% by mass of the composition is preferably 0.40% by mass or more, more preferably 0.8% by mass or more, and furthermore It is preferably 1% by mass or more, more preferably 2.5% by mass or less, more preferably 2% by mass or less, and still more preferably 1.8% by mass or less.

所述金屬化合物（B）相對於所述有機矽化合物（A）的莫耳比（B/A）較佳為2～500。所述莫耳比（B/A）更佳為8以上，進而佳為10以上，特佳為15以上，最佳為20以上，且更佳為200以下，進而佳為100以下，特佳為50以下。The molar ratio (B / A) of the metal compound (B) to the organosilicon compound (A) is preferably 2 to 500. The molar ratio (B / A) is more preferably 8 or more, further preferably 10 or more, particularly preferably 15 or more, most preferably 20 or more, and more preferably 200 or less, further preferably 100 or less, and particularly preferably 50 or less.

3. 第1解離時的pKa為1以上的酸（C）
本發明的組成物需要使作為鍵結於矽原子的水解性基的水解觸媒而發揮作用的觸媒與所述有機矽化合物（A）及金屬化合物（B）一起共存，本發明的組成物於如下方面具有特徵：使用第1解離時的pKa為1以上的酸（C）（以下，有時簡稱為「酸（C）」）作為所述觸媒。作為觸媒，使用所述酸（C）而如後述般抑制組成物中混合的水量，藉此可平穩地進行皮膜形成時的反應，可形成良好的皮膜。所述pKa為酸解離常數，所述酸（C）的第1解離時的pKa較佳為1.5以上，更佳為2.5以上，進而佳為3.5以上。所述酸（C）的第1解離時的pKa的上限並無特別限定，例如較佳為10以下，更佳為8以下，進而佳為6以下。3. Acid (C) with a pKa of 1 or more during the first dissociation
The composition of the present invention needs to coexist with the organic silicon compound (A) and the metal compound (B) as a catalyst that functions as a hydrolysis catalyst that is a hydrolyzable group bonded to a silicon atom. The composition of the present invention The catalyst is characterized in that an acid (C) (hereinafter, sometimes simply referred to as “acid (C)”) having a pKa of 1 or more at the time of the first dissociation is used as the catalyst. As the catalyst, the amount of water mixed in the composition is suppressed as described later by using the acid (C), whereby the reaction during film formation can be performed smoothly, and a good film can be formed. The pKa is an acid dissociation constant, and the pKa during the first dissociation of the acid (C) is preferably 1.5 or more, more preferably 2.5 or more, and even more preferably 3.5 or more. The upper limit of the pKa during the first dissociation of the acid (C) is not particularly limited, and is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.

作為所述酸（C），可為無機酸亦可為有機酸，具體而言，可列舉：馬來酸（pKa=1.92）、磷酸（pKa=2.12）、甲酸（pKa=3.75）、苯甲酸（pKa=4.2）、苯基乙酸（pKa=4.31）、乙酸（pKa=4.76）、丁酸（pKa=4.83）、2-甲基丙酸（pKa=4.84）、丙酸（pKa=4.87）、2,2-二甲基丙酸（pKa=5.03）等。所述酸（C）可僅混合一種，亦可將兩種以上組合混合。作為所述酸（C），較佳為有機酸，更佳為馬來酸、甲酸、乙酸。The acid (C) may be either an inorganic acid or an organic acid. Specific examples include maleic acid (pKa = 1.92), phosphoric acid (pKa = 2.12), formic acid (pKa = 3.75), and benzoic acid. (PKa = 4.2), phenylacetic acid (pKa = 4.31), acetic acid (pKa = 4.76), butyric acid (pKa = 4.83), 2-methylpropionic acid (pKa = 4.84), propionic acid (pKa = 4.87), 2,2-dimethylpropionic acid (pKa = 5.03), etc. The acid (C) may be mixed with only one kind, or may be mixed with two or more kinds. The acid (C) is preferably an organic acid, and more preferably maleic acid, formic acid, or acetic acid.

於組成物100質量%中，所述酸（C）的量較佳為30質量%以下，更佳為10質量%以下，進而佳為1質量%以下，特佳為0.1質量%以下。所述酸（C）的量的下限通常超過0質量%，較佳為0.001質量%以上，更佳為0.0015質量%以上。The amount of the acid (C) in 100% by mass of the composition is preferably 30% by mass or less, more preferably 10% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. The lower limit of the amount of the acid (C) generally exceeds 0% by mass, preferably 0.001% by mass or more, and more preferably 0.0015% by mass or more.

本發明的組成物亦可混合第1解離時的pKa小於1的酸作為觸媒，該第1解離時的pKa小於1的酸的量較佳為小於2.0質量%，更佳為1.5質量%以下，進而佳為1質量%以下，進而更佳為0.5質量%以下，特佳為0.1質量%以下，最佳為0質量%。The composition of the present invention can also be mixed with an acid having a pKa of less than 1 during the first dissociation as a catalyst, and the amount of the acid having a pKa of less than 1 during the first dissociation is preferably less than 2.0% by mass, more preferably 1.5% by mass or less It is further preferably 1% by mass or less, further preferably 0.5% by mass or less, particularly preferably 0.1% by mass or less, and most preferably 0% by mass.

作為所述第1解離時的pKa小於1的酸，例如可列舉硝酸（pKa=-1.5）、鹽酸（pKa=-8）等。Examples of the acid having a pKa during the first dissociation of less than 1 include nitric acid (pKa = -1.5) and hydrochloric acid (pKa = -8).

4. 水（D）
本發明的組成物混合有水（D），藉此可使水解性基水解。4. Water (D)
The composition of the present invention is mixed with water (D), whereby the hydrolyzable group can be hydrolyzed.

本發明中，將所述組成物中混合的所述水（D）的量設為超過0質量%且小於2.20質量%。藉由將所述水的量設為小於2.20質量%，可平穩地進行皮膜形成時的反應，可形成良好的皮膜。於組成物100質量%中，所述水（D）的量較佳為2.0質量%以下，更佳為小於1.79質量%，進而佳為1.0質量%以下，特佳為0.5質量%以下，且較佳為0.005質量%以上，更佳為0.01質量%以上，進而佳為0.015質量%以上。In the present invention, the amount of the water (D) mixed in the composition is set to exceed 0% by mass and less than 2.20% by mass. By setting the amount of the water to be less than 2.20% by mass, the reaction during film formation can be smoothly performed, and a good film can be formed. In 100% by mass of the composition, the amount of the water (D) is preferably 2.0% by mass or less, more preferably less than 1.79% by mass, still more preferably 1.0% by mass or less, particularly preferably 0.5% by mass or less, and more It is preferably 0.005 mass% or more, more preferably 0.01 mass% or more, and still more preferably 0.015 mass% or more.

所述水（D）相對於所述有機矽化合物（A）與所述金屬化合物（B）的合計（A+B）的莫耳比[D/（A+B）]較佳為0.1～10。所述莫耳比[D/（A+B）]更佳為0.15以上，進而佳為0.2以上，且更佳為8以下，進而佳為5以下。The molar ratio [D / (A + B)] of the water (D) to the total (A + B) of the organic silicon compound (A) and the metal compound (B) is preferably 0.1 to 10 . The molar ratio [D / (A + B)] is more preferably 0.15 or more, even more preferably 0.2 or more, more preferably 8 or less, and even more preferably 5 or less.

5. 溶劑（E）
本發明的組成物進而亦可混合溶劑（E）。所述溶劑（E）是指水以外的溶劑，例如，可列舉醇系溶媒、醚系溶媒、酮系溶媒、酯系溶媒、醯胺系溶媒等。作為所述醇系溶媒，例如可列舉：甲醇、乙醇、丙醇、丁醇、乙二醇、丙二醇、二乙二醇等。作為所述醚系溶媒，例如可列舉：二甲氧基乙烷、四氫呋喃、二噁烷等。作為所述酮系溶媒，例如可列舉：丙酮、甲基乙基酮（2-丁酮）等。作為所述酯系溶媒，例如可列舉：乙酸乙酯、乙酸丁酯等。作為所述醯胺系溶媒，例如可列舉二甲基甲醯胺等。該些中，較佳為醇系溶媒或醚系溶媒，更佳為醇系溶媒。5. Solvent (E)
The composition of the present invention may further be mixed with a solvent (E). The solvent (E) refers to a solvent other than water, and examples thereof include alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, and amidine-based solvents. Examples of the alcohol-based solvent include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, and diethylene glycol. Examples of the ether-based solvent include dimethoxyethane, tetrahydrofuran, and dioxane. Examples of the ketone-based solvent include acetone and methyl ethyl ketone (2-butanone). Examples of the ester-based solvent include ethyl acetate and butyl acetate. Examples of the amidine-based solvent include dimethylformamide. Among these, an alcohol-based solvent or an ether-based solvent is preferable, and an alcohol-based solvent is more preferable.

組成物100質量%中，所述溶劑（E）的量較佳為10質量%以上，更佳為50質量%以上，進而佳為90質量%以上，特佳為95質量%以上，且較佳為98.5質量%以下，更佳為98.4質量%以下，進而佳為98.3質量%以下。In 100% by mass of the composition, the amount of the solvent (E) is preferably 10% by mass or more, more preferably 50% by mass or more, still more preferably 90% by mass or more, particularly preferably 95% by mass or more, and more preferably It is 98.5 mass% or less, more preferably 98.4 mass% or less, and still more preferably 98.3 mass% or less.

本發明的組成物中，所述水（D）的質量相對於所述溶劑（E）的質量的比例（D/E）較佳為50質量%以下，更佳為10質量%以下，進而佳為5質量%以下，特佳為1質量%以下。In the composition of the present invention, the ratio (D / E) of the mass of the water (D) to the mass of the solvent (E) is preferably 50% by mass or less, more preferably 10% by mass or less, and further preferably It is 5 mass% or less, and particularly preferably 1 mass% or less.

本發明的組成物於不會阻礙本發明的效果的範圍內例如亦可使抗氧化劑、防鏽劑、紫外線吸收劑、光穩定劑、防黴劑、抗菌劑、生物附著防止劑、除臭劑、顏料、阻燃劑、抗靜電劑等各種添加劑共存。The composition of the present invention can also make, for example, antioxidants, rust inhibitors, ultraviolet absorbers, light stabilizers, mildew inhibitors, antibacterial agents, biological adhesion preventive agents, and deodorants within a range that does not inhibit the effects of the invention , Pigments, flame retardants, antistatic agents and other additives coexist.

對本發明的組成物進行硬化，藉此可獲得膜。By curing the composition of the present invention, a film can be obtained.

對本發明的組成物進行硬化而成的膜通常形成於基材上。A film obtained by curing the composition of the present invention is usually formed on a substrate.

作為使本發明的組成物與基材接觸的方法，例如可列舉：將組成物塗佈於基材的方法。具體而言，可列舉：旋塗法、浸塗法、噴塗法、輥塗法、棒塗法、手工塗佈（使液體滲入至布等中並塗抹於基材的方法）、沖流（使用吸液管等將液體直接施加至基材並進行塗佈的方法）、噴霧（使用噴霧而對基材進行塗佈的方法）等。尤其，就作業性的觀點而言，較佳為旋塗法、噴塗法、手工塗佈、沖流、噴霧，更佳為旋塗法、手工塗佈、噴霧，進而佳為旋塗法。Examples of a method for bringing the composition of the present invention into contact with a substrate include a method of applying the composition to a substrate. Specific examples include spin coating method, dip coating method, spray coating method, roll coating method, bar coating method, manual coating method (a method in which a liquid is impregnated into a cloth or the like and applied to a substrate), and a flow method (using A method such as a pipette that applies a liquid directly to a substrate and applies the coating), a spray (a method of applying the substrate with a spray), and the like. In particular, from the viewpoint of workability, a spin coating method, a spray coating method, a manual coating, a jet flow, and a spray are preferred, a spin coating method, a manual coating, and a spray coating are more preferred, and a spin coating method is more preferred.

於使本發明的組成物與基材接觸的狀態下，在空氣中、常溫下靜置（例如，10小時～48小時）、或者加熱（例如，300℃以下）1小時～10小時左右，藉此促進水解性基的水解、及縮聚，從而可於基材上形成皮膜。In a state where the composition of the present invention is in contact with a substrate, it is left to stand in the air at normal temperature (for example, 10 hours to 48 hours) or heated (for example, 300 ° C or lower) for about 1 to 10 hours. This promotes hydrolysis and polycondensation of the hydrolyzable group, so that a film can be formed on the substrate.

皮膜的膜厚例如可為0.5 nm～100 nm左右。The film thickness of the film may be, for example, about 0.5 nm to 100 nm.

接觸本發明的組成物的基材並無特別限定，基材的形狀可為平面、曲面的任一種，亦可為將多個面組合而成的三維結構。The base material contacting the composition of the present invention is not particularly limited, and the shape of the base material may be any of a flat surface and a curved surface, or a three-dimensional structure in which a plurality of surfaces are combined.

另外，基材的材質亦無限定，可由有機系材料、無機系材料的任一種構成。作為所述有機系材料，例如可列舉：丙烯酸樹脂、聚碳酸酯樹脂、聚酯樹脂、苯乙烯樹脂、丙烯酸-苯乙烯共聚樹脂、纖維素樹脂、聚烯烴樹脂等熱塑性樹脂；酚樹脂、脲樹脂、三聚氰胺樹脂、環氧樹脂、不飽和聚酯、矽酮樹脂、胺基甲酸酯樹脂等熱硬化性樹脂等。作為所述無機系材料，例如可列舉：陶瓷；玻璃；鐵、矽、銅、鋅、鋁等金屬；包含所述金屬的合金等。In addition, the material of the substrate is not limited, and may be composed of any of an organic material and an inorganic material. Examples of the organic material include thermoplastic resins such as acrylic resins, polycarbonate resins, polyester resins, styrene resins, acrylic-styrene copolymer resins, cellulose resins, and polyolefin resins; phenol resins and urea resins. , Thermosetting resins such as melamine resin, epoxy resin, unsaturated polyester, silicone resin, and urethane resin. Examples of the inorganic material include ceramics; glass; metals such as iron, silicon, copper, zinc, and aluminum; alloys including the metals; and the like.

亦可對所述基材預先實施易接著處理。作為所述易接著處理，例如可列舉：電暈處理、電漿處理、紫外線處理等親水化處理。另外，亦可實施利用樹脂、矽烷偶合劑、四烷氧基矽烷等的底塗處理，亦可對基材預先塗佈聚矽氮烷等玻璃皮膜。The substrate may be subjected to easy adhesion treatment in advance. Examples of the easy adhesion treatment include a hydrophilization treatment such as a corona treatment, a plasma treatment, and an ultraviolet treatment. In addition, a primer treatment using a resin, a silane coupling agent, a tetraalkoxysilane, or the like may be performed, and a glass film such as polysilazane may be applied to the substrate in advance.

對本發明的組成物進行硬化而成的膜具有撥水性或液滴的滑落速度大的特徵。此處，撥水性或滑落速度的測定例如可使用水滴或其他各種液體等的液滴來測定。A film obtained by curing the composition of the present invention is characterized in that it has a high water repellency or a large drop rate of droplets. Here, the measurement of water repellency or slippage speed can be measured using, for example, water droplets or droplets of various other liquids.

對本發明的組成物進行硬化而成的膜上的液滴（具體而言，水滴）的接觸角較佳為95°以上，更佳為100°以上，進而佳為103°以上。該接觸角可依照後述的實施例的測定法來確定。The contact angle of liquid droplets (specifically, water droplets) on a film obtained by curing the composition of the present invention is preferably 95 ° or more, more preferably 100 ° or more, and even more preferably 103 ° or more. This contact angle can be determined in accordance with the measurement method of the examples described later.

對本發明的組成物進行硬化而成的膜上的液滴（具體而言，水滴）的滑落速度較佳為20 mm/秒以上，更佳為25 mm/秒以上，進而佳為30 mm/秒以上，特佳為45 mm/秒以上。該滑落速度可依照後述的實施例的測定法來確定。The sliding speed of the droplets (specifically, water droplets) on the film obtained by curing the composition of the present invention is preferably 20 mm / second or more, more preferably 25 mm / second or more, and even more preferably 30 mm / second. Above, particularly preferred is 45 mm / second or more. This slipping speed can be determined in accordance with the measurement method of the examples described later.

對本發明的組成物進行硬化而成的膜顯示出較佳為2000次以上、更佳為3000次以上、進而佳為5000次以上、特佳為8000次以上的耐磨耗性。該耐磨耗性可依照後述的實施例的測定法來確定。The film obtained by curing the composition of the present invention exhibits abrasion resistance of preferably 2,000 or more, more preferably 3,000 or more, even more preferably 5,000 or more, and particularly preferably 8,000 or more. The abrasion resistance can be determined in accordance with the measurement method of the examples described later.

對本發明的組成物進行硬化而成的膜具有良好的撥油性，例如，即便用油性記號筆（permanent marker）於皮膜表面畫圓亦可利用通常的紙或布來輕輕擦拭而容易地擦除記號筆痕跡。The film obtained by curing the composition of the present invention has good oil-repellency. For example, even if an oil-based marker (permanent marker) is used to draw a circle on the surface of the film, it can be easily wiped with ordinary paper or cloth to lightly wipe it. Marker marks.

對本發明的組成物進行硬化而成的膜顯示出良好的耐硫酸性，例如於對皮膜表面滴加硫酸後，即便用油性記號筆於滴加有硫酸的部位畫圓，亦可擦除記號筆痕跡。該耐硫酸性可依照後述的實施例的測定法來確定。The film obtained by curing the composition of the present invention exhibits good sulfuric acid resistance. For example, after adding sulfuric acid to the surface of a film, even if an oily marker is used to draw a circle on the portion where sulfuric acid is added, the marker can be erased. trace. This sulfuric acid resistance can be determined in accordance with the measurement method of the examples described later.

對本發明的組成物進行硬化而成的膜期望即便於溫水試驗後撥水性及液滴（例如，水滴）的滑落性亦良好。即，對本發明的組成物進行硬化而成的膜根據用途而有時會暴露於與溫水等接觸等嚴酷的環境中，而推崇即便於暴露於此種環境中後亦可維持良好的性能（以下，有時稱為耐溫水特性）。It is desirable that a film formed by curing the composition of the present invention has good water repellency and dropability of liquid droplets (for example, water droplets) even after a warm water test. That is, the film obtained by curing the composition of the present invention may be exposed to harsh environments such as contact with warm water depending on the application, and it is respected that good performance can be maintained even after exposure to such an environment ( Hereinafter, it is sometimes referred to as hot water resistance).

耐溫水特性可基於溫水試驗後的膜上的液滴（例如，水滴）的接觸角及滑落速度來評價。具體而言，關於對本發明的組成物進行硬化而成的膜，溫水試驗後的膜上的液滴（具體而言，水滴）的接觸角較佳為90°以上，更佳為95°以上，進而佳為101°以上。該溫水試驗後的液滴（具體而言，水滴）的接觸角可依照後述的實施例的測定法來確定。另外，關於對本發明的組成物進行硬化而成的膜，溫水試驗後的膜上的液滴（具體而言，水滴）的滑落速度較佳為10 mm/秒以上，更佳為20 mm/秒以上，進而佳為50 mm/秒以上。該溫水試驗後的滑落速度可依照後述的實施例的測定法來確定。
[實施例]The hot water resistance characteristics can be evaluated based on the contact angle and the sliding speed of liquid droplets (for example, water droplets) on the film after the warm water test. Specifically, regarding a film obtained by curing the composition of the present invention, the contact angle of droplets (specifically, water droplets) on the film after the warm water test is preferably 90 ° or more, and more preferably 95 ° or more It is more preferably 101 ° or more. The contact angle of the liquid droplets (specifically, water droplets) after the warm water test can be determined in accordance with the measurement method of the examples described later. In addition, as for the film obtained by curing the composition of the present invention, the drop rate of liquid droplets (specifically, water droplets) on the film after the warm water test is preferably 10 mm / sec or more, and more preferably 20 mm / More than seconds, and more preferably 50 mm / second or more. The slipping speed after the warm water test can be determined in accordance with the measurement method of the examples described later.
[Example]

以下，列舉實施例對本發明更具體地進行說明。本發明不受以下實施例的限制，亦可於適合於所述或後述的主旨的範圍內施加變更來實施，並且該些均包含於本發明的技術範圍內。Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples, and can be implemented by applying changes within the scope suitable for the gist described or described below, and these are all included in the technical scope of the present invention.

[實施例1]
（塗佈液的製作）
使所述表3-2中所示的（A-I-26）中n10的平均為24的化合物（以下，表述為化合物（1））0.22 g、四乙氧基矽烷0.53 g溶解於異丙醇1.6 g中，並於室溫下攪拌10分鐘。對所獲得的溶液滴加甲酸0.87 mg及水後，於65℃下攪拌7小時，獲得試樣溶液1。利用異丙醇44.52 g對所獲得的試樣溶液1進行稀釋，製作塗佈溶液1。塗佈溶液1中的各化合物的比例（質量%）如表1中所記載般（對於其他實施例及比較例而言，亦相同）。
（皮膜的製作）
使用旋塗機（三笠（MIKASA）公司製造）將所述塗佈溶液1塗佈於藉由大氣壓電漿處理而使表面活化的玻璃基板5×5 cm² （益格（EAGLE）XG，康寧（Corning）公司）的表面。塗佈條件是設為轉數3000 rpm、20秒。塗佈後，進行200℃、3小時的熱處理並加以硬化，藉此於玻璃基板上形成皮膜，並利用後述的測定方法來進行皮膜的評價。[Example 1]
(Preparation of coating solution)
In (AI-26) shown in Table 3-2, 0.22 g of a compound (hereinafter referred to as compound (1)) having an average n10 of 24 was dissolved in isopropanol 1.6. g and stir for 10 minutes at room temperature. After 0.87 mg of formic acid and water were added dropwise to the obtained solution, the solution was stirred at 65 ° C for 7 hours to obtain a sample solution 1. The obtained sample solution 1 was diluted with 44.52 g of isopropyl alcohol to prepare a coating solution 1. The ratio (% by mass) of each compound in the coating solution 1 is as described in Table 1 (the same applies to other examples and comparative examples).
(Production of film)
A spin coater (manufactured by MIKASA) was used to apply the coating solution 1 to a glass substrate 5 × 5 cm ² (EAGLE XG, Corning ( Corning). The coating conditions were set to 3000 rpm and 20 seconds. After coating, a film was formed on the glass substrate by heat treatment at 200 ° C. for 3 hours and curing, and the film was evaluated by a measurement method described later.

[實施例2]
於所述實施例1中，除了代替甲酸而使用乙酸0.87 mg的方面、與將攪拌時間設為4小時的方面以外，與所述實施例1同樣地製作塗佈溶液2。
除了使用所獲得的塗佈溶液2以外，與所述實施例1同樣地於玻璃基板上形成皮膜，並利用後述的測定方法來進行皮膜的評價。[Example 2]
In Example 1, a coating solution 2 was prepared in the same manner as in Example 1 except that 0.87 mg of acetic acid was used instead of formic acid, and that the stirring time was set to 4 hours.
A film was formed on the glass substrate in the same manner as in Example 1 except that the obtained coating solution 2 was used, and the film was evaluated by a measurement method described later.

[實施例3]
使所述化合物（1）0.17 g、三乙氧基矽烷0.32 g溶解於異丙醇1.33 g中，並於室溫下攪拌10分鐘。對所獲得的溶液滴加馬來酸1.6 mg及水後，於65℃下攪拌6小時，獲得試樣溶液3。利用異丙醇29.68 g對所獲得的試樣溶液3進行稀釋，製作塗佈溶液3。
除了使用所獲得的塗佈溶液3以外，與所述實施例1同樣地於玻璃基板上形成皮膜，並利用後述的測定方法來進行皮膜的評價。[Example 3]
0.17 g of the compound (1) and 0.32 g of triethoxysilane were dissolved in 1.33 g of isopropanol, and the mixture was stirred at room temperature for 10 minutes. After 1.6 mg of maleic acid and water were added dropwise to the obtained solution, the solution was stirred at 65 ° C. for 6 hours to obtain sample solution 3. The obtained sample solution 3 was diluted with 29.68 g of isopropanol to prepare a coating solution 3.
A film was formed on the glass substrate in the same manner as in Example 1 except that the obtained coating solution 3 was used, and the film was evaluated by a measurement method described later.

[實施例4]
於所述實施例3中，除了與馬來酸1.6 mg一起進而使用乙酸0.51 mg的方面、和將水的量設為0.09 g的方面以外，與所述實施例3同樣地製作塗佈溶液4。
除了使用所獲得的塗佈溶液4以外，與所述實施例1同樣地於玻璃基板上形成皮膜，並利用後述的測定方法來進行皮膜的評價。[Example 4]
In Example 3, a coating solution 4 was prepared in the same manner as in Example 3 except that an aspect of using maleic acid 1.6 mg and then using 0.51 mg of acetic acid, and an aspect of setting the amount of water to 0.09 g. .
A film was formed on the glass substrate in the same manner as in Example 1 except that the obtained coating solution 4 was used, and the film was evaluated by a measurement method described later.

[實施例5]
使所述化合物（1）0.43 g、四乙氧基矽烷0.36 g溶解於異丙醇2.04 g中，並於室溫下攪拌10分鐘。對所獲得的溶液滴加乙酸0.8352 mg及水後，於65℃下攪拌4小時，獲得試樣溶液5。利用異丙醇67.80 g對所獲得的試樣溶液5進行稀釋，製作塗佈溶液5。
除了使用所獲得的塗佈溶液5以外，與所述實施例1同樣地於玻璃基板上形成皮膜，並利用後述的測定方法來進行皮膜的評價。[Example 5]
0.43 g of the compound (1) and 0.36 g of tetraethoxysilane were dissolved in 2.04 g of isopropanol, and the mixture was stirred at room temperature for 10 minutes. After 0.8352 mg of acetic acid and water were added dropwise to the obtained solution, the solution was stirred at 65 ° C for 4 hours to obtain a sample solution 5. The obtained sample solution 5 was diluted with 67.80 g of isopropanol to prepare a coating solution 5.
A film was formed on the glass substrate in the same manner as in Example 1 except that the obtained coating solution 5 was used, and the film was evaluated by a measurement method described later.

[實施例6]
使所述表3-2中所示的（A-I-26）中n10的平均為45的化合物（以下，表述為化合物（2））0.53 g、四乙氧基矽烷0.29 g溶解於異丙醇2.07 g中，並於室溫下攪拌10分鐘。對所獲得的溶液滴加乙酸0.6169 mg及水後，於65℃下攪拌4小時，獲得試樣溶液6。利用異丙醇67.80 g對所獲得的試樣溶液6進行稀釋，製作塗佈溶液6。
除了使用所獲得的塗佈溶液6以外，與所述實施例1同樣地於玻璃基板上形成皮膜，並利用後述的測定方法來進行皮膜的評價。[Example 6]
In (AI-26) shown in Table 3-2, 0.53 g of a compound (hereinafter referred to as compound (2)) with an average of n10 of 45 was dissolved in 0.27 g of tetraethoxysilane and 2.07 in isopropanol. g and stir for 10 minutes at room temperature. After 0.6169 mg of acetic acid and water were added dropwise to the obtained solution, the solution was stirred at 65 ° C for 4 hours to obtain a sample solution 6. The obtained sample solution 6 was diluted with 67.80 g of isopropyl alcohol to prepare a coating solution 6.
A film was formed on the glass substrate in the same manner as in Example 1 except that the obtained coating solution 6 was used, and the film was evaluated by a measurement method described later.

[實施例7]
使所述化合物（2）0.28 g、四乙氧基矽烷0.54 g溶解於異丙醇1.57 g中，並於室溫下攪拌10分鐘。對所獲得的溶液滴加乙酸1.0818 mg及水後，於65℃下攪拌4小時，獲得試樣溶液7。利用異丙醇67.80 g對所獲得的試樣溶液7進行稀釋，製作塗佈溶液7。
除了使用所獲得的塗佈溶液7以外，與所述實施例1同樣地於玻璃基板上形成皮膜，並利用後述的測定方法來進行皮膜的評價。[Example 7]
0.28 g of the compound (2) and 0.54 g of tetraethoxysilane were dissolved in 1.57 g of isopropanol, and stirred at room temperature for 10 minutes. After 1.0818 mg of acetic acid and water were added dropwise to the obtained solution, the solution was stirred at 65 ° C for 4 hours to obtain a sample solution 7. The obtained sample solution 7 was diluted with 67.80 g of isopropanol to prepare a coating solution 7.
A film was formed on the glass substrate in the same manner as in Example 1 except that the obtained coating solution 7 was used, and the film was evaluated by a measurement method described later.

[實施例8]
使所述化合物（2）0.22 g、四乙氧基矽烷0.56 g溶解於異丙醇1.55 g中，並於室溫下攪拌10分鐘。對所獲得的溶液滴加乙酸1.188 mg及水後，於65℃下攪拌4小時，獲得試樣溶液8。利用異丙醇67.80 g對所獲得的試樣溶液8進行稀釋，製作塗佈溶液8。
除了使用所獲得的塗佈溶液8以外，與所述實施例1同樣地於玻璃基板上形成皮膜，並利用後述的測定方法來進行皮膜的評價。[Example 8]
0.22 g of the compound (2) and 0.56 g of tetraethoxysilane were dissolved in 1.55 g of isopropanol, and the mixture was stirred at room temperature for 10 minutes. After 1.188 mg of acetic acid and water were added dropwise to the obtained solution, the solution was stirred at 65 ° C for 4 hours to obtain a sample solution 8. The obtained sample solution 8 was diluted with 67.80 g of isopropyl alcohol to prepare a coating solution 8.
A film was formed on the glass substrate in the same manner as in Example 1 except that the obtained coating solution 8 was used, and the film was evaluated by a measurement method described later.

[比較例1]
對2-丙醇添加規定量的萊奧西路（Reoshiru）QS-30、以及水，於室溫下攪拌3小時而獲得A液體。另一方面，對甲醇0.21 g滴加矽酸甲酯（methyl silicate）53A（考魯考特（colcoat）公司製造，商品名）0.04 g、甲基三甲氧基矽烷3.96 g、以及乙酸71.40 mg，於室溫下攪拌1小時而獲得B液體。
對所獲得的A液體添加B液體，並攪拌24小時，獲得比較試樣溶液1。利用異丙醇3.11 g對所獲得的比較試樣溶液1進行稀釋，製作比較塗佈溶液1。比較塗佈溶液1中的各化合物的比例（質量%）如表1中所記載般。
除了使用所獲得的比較塗佈溶液1以外，與所述實施例1同樣地於玻璃基板上形成皮膜，並利用後述的測定方法來進行皮膜的評價。[Comparative Example 1]
A predetermined amount of Reoshiru QS-30 and water were added to 2-propanol, and the mixture was stirred at room temperature for 3 hours to obtain liquid A. On the other hand, 0.21 g of methanol was added dropwise with methyl silicate 53A (manufactured by Colcoat Co., Ltd., trade name) 0.04 g, methyltrimethoxysilane 3.96 g, and acetic acid 71.40 mg. It stirred at room temperature for 1 hour, and obtained liquid B.
Liquid B was added to the obtained liquid A and stirred for 24 hours to obtain Comparative Sample Solution 1. The obtained comparative sample solution 1 was diluted with 3.11 g of isopropyl alcohol to prepare a comparative coating solution 1. The ratio (% by mass) of each compound in the comparative coating solution 1 is as described in Table 1.
A film was formed on the glass substrate in the same manner as in Example 1 except that the obtained comparative coating solution 1 was used, and the film was evaluated by a measurement method described later.

[比較例2]
使所述化合物（1）0.06 g、四乙氧基矽烷0.11 g溶解於甲基乙基酮1.46 g中，並於室溫下攪拌10分鐘。對所獲得的溶液滴加鹽酸後，於65℃下攪拌24小時，獲得比較試樣溶液2。利用甲基乙基酮45.89 g對所獲得的比較試樣溶液2進行稀釋，製作比較塗佈溶液2。比較塗佈溶液2中的各化合物的比例（質量%）如表1中所記載般。再者，表1中示出了鹽酸中所含的氯化氫量（0.38 mg）及水量（1.04 g）。另外，表1中，為了方便起見而於酸（C）一欄中表述氯化氫。第1解離時的pKa小於1的酸的量為0.78質量%。
除了使用所獲得的比較塗佈溶液2以外，與所述實施例1同樣地於玻璃基板上形成皮膜，並利用後述的測定方法來進行皮膜的評價。[Comparative Example 2]
0.06 g of the compound (1) and 0.11 g of tetraethoxysilane were dissolved in 1.46 g of methyl ethyl ketone, and the mixture was stirred at room temperature for 10 minutes. After the obtained solution was added dropwise with hydrochloric acid, it was stirred at 65 ° C. for 24 hours to obtain Comparative Sample Solution 2. The obtained comparative sample solution 2 was diluted with 45.89 g of methyl ethyl ketone to prepare a comparative coating solution 2. The ratio (% by mass) of each compound in the comparative coating solution 2 is as described in Table 1. In addition, Table 1 shows the amount of hydrogen chloride (0.38 mg) and the amount of water (1.04 g) contained in hydrochloric acid. In addition, in Table 1, hydrogen chloride is represented in the column of acid (C) for convenience. The amount of the acid having a pKa of less than 1 at the time of the first dissociation was 0.78% by mass.
A film was formed on the glass substrate in the same manner as in Example 1 except that the obtained comparative coating solution 2 was used, and the film was evaluated by a measurement method described later.

對於所述實施例及比較例中所獲得的皮膜以如下要領進行評價。The films obtained in the examples and comparative examples were evaluated in the following manner.

（接觸角）
使用協和界面科學公司製造的接觸角測定裝置「DM700」，將水滴量設為3.0 μL並利用分析方法：θ/2法測定皮膜表面對於水的接觸角。將測定結果示於下述表5中。將對於水的接觸角為95°以上的情況評價為撥水性優異。(Contact angle)
A contact angle measuring device "DM700" manufactured by Kyowa Interface Science Co., Ltd. was used to measure the contact angle of the surface of the film to water by using an analytical method: θ / 2 method with a water droplet volume of 3.0 μL. The measurement results are shown in Table 5 below. A case where the contact angle with water was 95 ° or more was evaluated as being excellent in water repellency.

（滑落速度）
對皮膜表面滴加水，並藉由皮膜表面的水滴的滑落速度來評價撥水性。具體而言，使用協和界面科學股份有限公司製造的接觸角測定裝置「DM700」，對傾斜為20°的玻璃基板上的皮膜表面滴加50 μL的水，測定水滴自初期滴加位置滑落15 mm為止的時間，算出皮膜表面的水滴滑落速度（mm/秒）。將算出結果示於下述表5中。將水滴的滑落速度為20 mm/秒以上的情況評價為撥水性優異。再者，將滴加的水滴於2分鐘以內並未自初期滴加位置滑落15 mm以上的情況評價為未滑落。(Sliding speed)
Water was added dropwise to the surface of the film, and water repellency was evaluated by the sliding speed of water droplets on the surface of the film. Specifically, using a contact angle measuring device "DM700" manufactured by Kyowa Interface Science Co., Ltd., 50 μL of water was dropped on the surface of the film on a glass substrate inclined at 20 °, and the drop of water droplets from the initial dropping position was measured by 15 mm. For the time up to this point, the water droplet sliding speed (mm / second) on the surface of the film was calculated. The calculation results are shown in Table 5 below. The case where the drop speed of a water droplet was 20 mm / sec or more was evaluated as being excellent in water repellency. In addition, a case where the dropped water droplets did not slide more than 15 mm from the initial dropping position within 2 minutes was evaluated as not slipping.

（耐磨耗性）
對皮膜表面利用薩維那（savina）MX（註冊商標）以負荷1000 g、往返速度每分鐘1600 mm的條件且於20 mm的距離內擦拭2000次，之後，以1000次為單位進行擦拭，分別測定磨耗部位的中央部分3處的對於水的接觸角，並測定3處中2處降低至90°以下為止的次數。將測定結果示於下述表5中。將次數為2000次以上的情況評價為耐磨耗性優異。(Abrasion resistance)
The surface of the film was wiped 2,000 times at a distance of 20 mm using a Savina MX (registered trademark) at a load of 1000 g, a reciprocating speed of 1600 mm per minute, and then wiped in units of 1,000 times. The contact angle with respect to water was measured at three positions in the central portion of the abraded portion, and the number of times that two of the three positions were lowered to 90 ° or less was measured. The measurement results are shown in Table 5 below. A case where the number of times was 2,000 or more was evaluated as being excellent in abrasion resistance.

（耐硫酸性及撥油性）
對皮膜表面的3個部位分別滴加0.1 M的硫酸0.035 g，於室溫下放置12小時並使水分蒸發。水分蒸發後，用記號筆（櫻花（SAKURA）製造的朋塔奇（pen-touch）油性中字筆）於滴加有硫酸的部位畫圓，其後，利用薩維那（savina）MX（註冊商標）擦除記號筆痕跡。將3個部位的記號筆痕跡均被擦除的情況評價為耐硫酸性良好（○），將即便於1個部位中存在未被擦除的部位的情況評價為耐硫酸性差（×）。再者，油性記號筆痕跡被擦除的情況表示撥油性亦良好。將評價結果示於表5中。(Sulfuric acid resistance and oil repellency)
0.035 g of 0.1 M sulfuric acid was added dropwise to three parts of the surface of the membrane, and the solution was left at room temperature for 12 hours to evaporate water. After the water evaporates, use a marker (pen-touch oily middle-point pen made by SAKURA) to draw a circle on the part where sulfuric acid is added, and then use Savina MX (registered trademark) ) Erase marker marks. The case where all the marker marks on the three parts were erased was evaluated as being good in sulfuric acid resistance (）), and the case where there were parts that were not erased even in one part was evaluated as being poor in sulfuric acid resistance (×). Moreover, the case where the marks of the oily marker are erased indicates that the oil repellency is also good. The evaluation results are shown in Table 5.

（耐溫水特性）
作為溫水試驗，於將樣品（形成有皮膜的玻璃基板）在70℃的離子交換水中浸漬12小時後，以與所述相同的條件測定對於水的接觸角及水滴的滑落速度。將溫水試驗後測定的對於水的接觸角及水滴的滑落速度的結果示於下述表5中。將對於水的接觸角為90°以上且水滴的滑落速度為10 mm/秒以上的情況評價為耐溫水特性優異。(Temperature resistance)
As a warm water test, a sample (a glass substrate on which a film was formed) was immersed in ion-exchanged water at 70 ° C. for 12 hours, and then the contact angle with water and the sliding speed of water droplets were measured under the same conditions as described above. Table 5 below shows the results of the contact angle with water and the sliding speed of water droplets measured after the warm water test. A case where the contact angle with water was 90 ° or more and the drop speed of water droplets was 10 mm / sec or more was evaluated as being excellent in hot water resistance.

[表5]
[table 5]

使用本發明的組成物的實施例1～實施例8可製作具有良好的撥水性（尤其是水滴的滑落性）·撥油性、以及耐硫酸性的皮膜，所述本發明的組成物混合有所述有機矽化合物（A）及所述金屬化合物（B）、且混合有作為觸媒的第1解離時的pKa為1以上的酸（C）並抑制了水分量。進而，由本發明的組成物形成的皮膜的耐磨耗性亦良好。另外，得知使用本發明的組成物獲得的皮膜即便於溫水試驗後，撥水性及水滴的滑落性亦良好，具有良好的耐溫水特性。得知：有機矽化合物對於光的穩定性非常高，另一方面，具有矽氧烷鍵，因此不易具有對於水或溫水的耐久性。因此，關於由混合有有機矽化合物的組成物形成的皮膜，為了在暴露於嚴酷的環境中後亦維持良好的性能，為耐溫水特性高的膜對於在實際使用環境中亦維持性能而言可謂是重要的性能。
[產業上的可利用性]Examples 1 to 8 using the composition of the present invention can produce a film having good water repellency (especially the water drop-off property), oil repellency, and sulfuric acid resistance. The composition of the present invention is mixed with The organosilicon compound (A) and the metal compound (B) are mixed with an acid (C) having a pKa of 1 or more at the time of the first dissociation as a catalyst to suppress the amount of water. Furthermore, the abrasion resistance of the film formed from the composition of the present invention is also good. In addition, it was found that even after a warm water test, the film obtained using the composition of the present invention has good water repellency and water drop slipping properties, and has good hot water resistance characteristics. It is known that the organosilicon compound has very high stability to light. On the other hand, it has a siloxane bond, so it is difficult to have durability against water or warm water. Therefore, a film formed of a composition mixed with an organosilicon compound, in order to maintain good performance even after being exposed to a harsh environment, is a film with high resistance to hot water, so that performance is maintained in an actual use environment. Can be described as important performance.
[Industrial availability]

使用本發明的組成物獲得的皮膜的撥水·撥油性、以及耐硫酸性優異。另外，使用本發明的組成物獲得的皮膜的耐磨耗性、耐溫水特性亦優異。因此，使用本發明的組成物進行了處理的基材作為觸控面板顯示器等顯示裝置、光學元件、半導體元件、建築材料、汽車零件、奈米壓印技術等中的基材而有用。另外，由本發明的組成物形成的皮膜可適宜作為電車、汽車、船舶、飛機等運輸機器中的主體、窗玻璃（前玻璃、側玻璃、後玻璃）、後視鏡（mirror）、減震器（bumper）等物品而使用。另外，亦可用於建築物外壁、帳篷（tent）、太陽光發電模組、隔音板、混凝土等戶外用途中。亦可用於漁網、捕蟲網、水槽等中。進而，亦可用於廚房、浴室、盥洗台、鏡子、洗手間周圍的各構件的物品、吊燈（chandelier）、瓷磚（tile）等陶瓷器、人工大理石、空調等各種室內設備中。另外，亦可作為工廠內的夾具或內壁、配管等的防污處理來使用。對於護目鏡（goggle）、眼鏡、防護帽（helmet）、彈球盤（Pachinko）、纖維、傘、玩具、足球等而言亦適宜。進而，亦可作為食品用包裝材、化妝品用包裝材、罐（pot）內部等各種包裝材料的附著防止劑而使用。The film obtained using the composition of the present invention is excellent in water repellency, oil repellency, and sulfuric acid resistance. In addition, the film obtained using the composition of the present invention is also excellent in abrasion resistance and hot water resistance. Therefore, the substrate processed using the composition of the present invention is useful as a substrate in display devices such as touch panel displays, optical elements, semiconductor elements, building materials, automotive parts, nano-imprint technology, and the like. In addition, the film formed from the composition of the present invention can be suitably used as a main body, window glass (front glass, side glass, rear glass), mirror, and shock absorber in transportation equipment such as trams, automobiles, ships, and airplanes. (Bumper) and other items. In addition, it can also be used in outdoor applications such as building exterior walls, tents, solar power modules, sound insulation panels, and concrete. 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, articles of various components around the toilet, 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. It is also suitable for goggles, glasses, helmets, pachinko, fibers, umbrellas, toys, footballs, etc. Furthermore, it can be used as an adhesion preventing agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and pot interiors.

Claims (12)

一種混合組成物，其為 有機矽化合物（A）、 下述式（b1）所表示的金屬化合物（B）、 第1解離時的pKa為1以上的酸（C）、以及 水（D）的混合組成物，所述有機矽化合物（A）中，至少一個含有三烷基矽烷基的分子鏈、與至少一個水解性基鍵結於矽原子，並且 所述水（D）的量超過0質量%且小於2.20質量%， M(R^b10 )_r (A^b1 )_m-r （b1） 式（b1）中， M表示Al、Fe、In、Ge、Hf、Si、Ti、Sn、Zr、或Ta， R^b10 表示含有矽氧烷骨架的基、含有烴鏈的基、或氫原子， r為0或1； 多個A^b1 分別獨立地表示水解性基， m根據金屬原子M而為3～5的整數。A mixed composition comprising an organosilicon compound (A), a metal compound (B) represented by the following formula (b1), an acid (C) having a pKa of 1 or more at the first dissociation, and water (D) A mixed composition in which at least one molecular chain containing a trialkylsilane group and at least one hydrolyzable group in the organic silicon compound (A) are bonded to a silicon atom, and the amount of the water (D) exceeds 0 mass % And less than 2.20% by mass, M (R ^b10 ) _r (A ^b1 ) _mr (b1) In formula (b1), M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta, R ^b10 represents a group containing a siloxane skeleton, a group containing a hydrocarbon chain, or a hydrogen atom, and r is 0 or 1; a plurality of A ^b1 each independently represent a hydrolyzable group, and m is 3 to 5 depending on the metal atom M Integer. 如申請專利範圍第1項所述的混合組成物，其中所述水（D）的量超過0質量%且小於1.79質量%。The mixed composition according to item 1 of the scope of patent application, wherein the amount of the water (D) exceeds 0% by mass and less than 1.79% by mass. 如申請專利範圍第1項或第2項所述的混合組成物，其進而包含溶劑（E），且所述溶劑（E）的量為10質量%以上。The mixed composition according to claim 1 or claim 2, further comprising a solvent (E), and the amount of the solvent (E) is 10% by mass or more. 如申請專利範圍第3項所述的混合組成物，其中所述水（D）的質量相對於所述溶劑（E）的質量的比例（D/E）為50質量%以下。The mixed composition according to item 3 of the scope of patent application, wherein the ratio (D / E) of the mass of the water (D) to the mass of the solvent (E) is 50% by mass or less. 如申請專利範圍第1項至第4項中任一項所述的混合組成物，其中所述金屬化合物（B）相對於所述有機矽化合物（A）的莫耳比（B/A）為2～500。The mixed composition according to any one of claims 1 to 4, wherein the molar ratio (B / A) of the metal compound (B) to the organosilicon compound (A) is 2 to 500. 如申請專利範圍第1項至第5項中任一項所述的混合組成物，其中所述酸（C）的量為30質量%以下。The mixed composition according to any one of claims 1 to 5, in which the amount of the acid (C) is 30% by mass or less. 如申請專利範圍第1項至第6項中任一項所述的混合組成物，其中所述組成物中，第1解離時的pKa小於1的酸的量小於2.0質量%（包含0質量%）。The mixed composition according to any one of claims 1 to 6 in the scope of the patent application, wherein in the composition, the amount of the acid having a pKa of less than 1 at the time of the first dissociation is less than 2.0% by mass (including 0% by mass) ). 如申請專利範圍第1項至第7項中任一項所述的混合組成物，其中所述有機矽化合物（A）為下述式（a1）所表示的化合物， 式（a1）中， 多個A^a1 分別獨立地表示水解性基， Z^a1 表示含有三烷基矽烷基的分子鏈、含有矽氧烷骨架的基、或含有烴鏈的基， x為0或1， R^a1 表示含有三烷基矽烷基的分子鏈， Z^a1 及R^a1 的所述三烷基矽烷基中所含的氫原子可經取代為氟原子。The mixed composition according to any one of claims 1 to 7, wherein the organosilicon compound (A) is a compound represented by the following formula (a1), In formula (a1), a plurality of A ^a1 each independently represent a hydrolyzable group, Z ^a1 represents a molecular chain containing a trialkylsilyl group, a group containing a siloxane skeleton, or a group containing a hydrocarbon chain, and x is 0 or 1, R ^a1 represents a molecular chain containing a trialkylsilyl group, and a hydrogen atom contained in the trialkylsilyl group of Z ^a1 and R ^a1 may be substituted with a fluorine atom. 如申請專利範圍第8項所述的混合組成物，其中所述有機矽化合物（A）為下述式（a2）所表示的化合物， 所述式（a2）中，A^a1 、Z^a1 、x與所述A^a1 、Z^a1 、x為相同含義； Z^s1 表示-O-或二價烴基，所述二價烴基中所含的-CH₂ -可經取代為-O-， 多個R^s2 分別獨立地表示碳數1～10的烷基， n1為1以上的整數， Y^s1 表示單鍵或-Si(R^s2 )₂ -L^s1 -，所述L^s1 表示二價烴基，所述二價烴基中所含的-CH₂ -可經取代為-O-， 多個R^s1 分別獨立地表示烴基或三烷基矽烷基氧基。The mixed composition according to item 8 of the scope of patent application, wherein the organosilicon compound (A) is a compound represented by the following formula (a2), In the formula (a2), A ^a1 , Z ^a1 , and x have the same meanings as A ^a1 , Z ^a1 , and x; Z ^s1 represents -O- or a divalent hydrocarbon group, and the divalent hydrocarbon group contains- CH ₂ -may be substituted with -O-, multiple R ^s2 each independently represent an alkyl group having 1 to 10 carbon atoms, n1 is an integer of 1 or more, Y ^s1 represents a single bond or -Si (R ^s2 ) ₂ -L ^s1- , the L ^s1 represents a divalent hydrocarbon group, -CH ₂ -contained in the divalent hydrocarbon group may be substituted with -O-, and a plurality of R ^s1 each independently represent a hydrocarbon group or a trialkylsilyloxy group . 如申請專利範圍第9項所述的混合組成物，其中所述n1為1～60的整數。The mixed composition according to item 9 of the scope of patent application, wherein n1 is an integer from 1 to 60. 如申請專利範圍第1項至第10項中任一項所述的混合組成物，其中所述有機矽化合物（A）與所述金屬化合物（B）的量的合計（A+B）為0.40質量%以上。The mixed composition according to any one of claims 1 to 10 in the scope of the patent application, wherein the total (A + B) of the amounts of the organosilicon compound (A) and the metal compound (B) is 0.40 Above mass%. 如申請專利範圍第1項至第11項中任一項所述的混合組成物，其中所述金屬化合物（B）為下述式（b2）所表示的化合物， Si(OR^b11 )_y H_4-y （b2） 所述式（b2）中， R^b11 表示碳數1～6的烷基， y為3或4。The mixed composition according to any one of claims 1 to 11, wherein the metal compound (B) is a compound represented by the following formula (b2), and Si (OR ^b11 ) _y H _{4 -y} (b2) In the formula (b2), R ^b11 represents an alkyl group having 1 to 6 carbon atoms, and y is 3 or 4.