TW202041373A - Layered body and production method therefor - Google Patents

Abstract

This layered body comprises a water repellent layer (r) and a resin base material layer (s), which have been layered onto one another via a layer (c). The layer (c) is formed from a mixed composition (cc) of an organic silicon compound (C1) represented by formula (c11) and/or an organic silicon compound (C2) wherein two or more of the organic silicon compound (C1) have been condensed and bonded with at least any from X1 to X4. The water repellent layer (r) is a layer formed from a mixed composition (ca) of an organic silicon compound (A) having a divalent perfluoropolyether structure. In the formula (c11), Z1 and Z2 each represent independently a reactive functional group excluding hydrolytic groups and the hydroxy group.

Description

Laminated body and its manufacturing method

The present invention relates to a laminate and a manufacturing method thereof.

The surface free energy of a film formed by mixing a compound with a perfluoropolyether structure is very small, so it is used in display devices such as touch panel displays, optical components, semiconductor components, building materials, windows of automobiles or buildings. It is used as an antifouling coating or a water and oil repellent coating in various fields such as glass.

When a composition mixed with a compound having a perfluoropolyether structure is applied to a substrate, sometimes for the purpose of improving adhesion, etc., after forming other layers such as a primer layer on the substrate in advance, coating The composition is applied to form an antifouling coating layer or a water and oil repellent coating layer.

For example, Patent Document 1 discloses a hard coat film in which a hard coat layer (X), an undercoat layer (Y), and a surface layer (Z) are sequentially laminated on at least one surface of a substrate. coat film), wherein the surface layer (Z) has a water contact angle of 110° or more. It is also stated that in order to form the surface layer (Z), it is preferable to use a fluorine-based compound having a polyperfluoropolyether chain, and in order to form the undercoat layer (Y), 3-propenoxypropyl is preferable Silane compounds such as trimethoxysilane. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-120253

[The problem to be solved by the invention]

A laminate formed by laminating a water-repellent layer formed of a composition mixed with a compound having a perfluoropolyether structure on a substrate such as a resin may be exposed to chemicals such as alcohol depending on the application. , It is required to maintain good performance (water repellency, etc.) even after exposure to chemicals (hereinafter referred to as chemical resistance).

However, the patent document 1 does not conduct research on chemical resistance. Therefore, an object of the present invention is to provide a laminate in which a water-repellent layer formed of a composition mixed with a compound having a perfluoropolyether structure is laminated on a resin base material and is excellent in chemical resistance. [Means to solve the problem]

所述式（c11）中， Z¹ 、Z² 分別獨立地為水解性基及羥基以外的反應性官能基， R^x1 、R^x2 、R^x3 、R^x4 分別獨立地為氫原子或碳數1～4的烷基，於存在多個R^x1 的情況下，多個R^x1 可分別不同，於存在多個R^x2 的情況下，多個R^x2 可分別不同，於存在多個R^x3 的情況下，多個R^x3 可分別不同，於存在多個R^x4 的情況下，多個R^x4 可分別不同， Rf^x1 、Rf^x2 、Rf^x3 、Rf^x4 分別獨立地為一個以上的氫原子被取代為氟原子的碳數1～20的烷基或氟原子，於存在多個Rf^x1 的情況下，多個Rf^x1 可分別不同，於存在多個Rf^x2 的情況下，多個Rf^x2 可分別不同，於存在多個Rf^x3 的情況下，多個Rf^x3 可分別不同，於存在多個Rf^x4 的情況下，多個Rf^x4 可分別不同， Y為-NH-、-N(CH₃ )-或-O-，於存在多個Y的情況下，多個Y可分別不同， X¹ 、X² 、X³ 、X⁴ 分別獨立地為-OR^c （R^c 為氫原子、碳數1～4的烷基或胺基C_1-3 烷基二C_1-3 烷氧基矽基），於存在多個X¹ 的情況下，多個X¹ 可分別不同，於存在多個X² 的情況下，多個X² 可分別不同，於存在多個X³ 的情況下，多個X³ 可分別不同，於存在多個X⁴ 的情況下，多個X⁴ 可分別不同， p11為0～20的整數，p12、p13、p14分別獨立地為0～10的整數，p15為0～5的整數，p16為1～10的整數，p17為0或1， 所述有機矽化合物（C1）的末端為Z¹ -及Z² -，只要-O-不與-O-連結，則由p11個-{C(R^x1 )(R^x2 )}-、p12個-{C(Rf^x1 )(Rf^x2 )}-、p13個-{Si(R^x3 )(R^x4 )}-、p14個-{Si(Rf^x3 )(Rf^x4 )}-、p15個-Y-、p16個-{Si(X¹ )(X² )-O}-、p17個-{Si(X³ )(X⁴ )}-以任意的順序排列鍵結而構成； [化2]

所述式（a1）中， Rf^a1 是兩端為氧原子的二價全氟聚醚結構， R¹¹ 、R¹² 及R¹³ 分別獨立地為碳數1～20的烷基，於存在多個R¹¹ 的情況下，多個R¹¹ 可分別不同，於存在多個R¹² 的情況下，多個R¹² 可分別不同，於存在多個R¹³ 的情況下，多個R¹³ 可分別不同， E¹ 、E² 、E³ 、E⁴ 及E⁵ 分別獨立地為氫原子或氟原子，於存在多個E¹ 的情況下，多個E¹ 可分別不同，於存在多個E² 的情況下，多個E² 可分別不同，於存在多個E³ 的情況下，多個E³ 可分別不同，於存在多個E⁴ 的情況下，多個E⁴ 可分別不同， G¹ 及G² 分別獨立地為具有矽氧烷鍵的2價～10價的有機矽氧烷基， J¹ 、J² 及J³ 分別獨立地為水解性基或-(CH₂ )_e6 -Si(OR¹⁴ )₃ ，e6為1～5，R¹⁴ 為甲基或乙基，於存在多個J¹ 的情況下，多個J¹ 可分別不同，於存在多個J² 的情況下，多個J² 可分別不同，於存在多個J³ 的情況下，多個J³ 可分別不同， L¹ 及L² 分別獨立地為可包含氧原子、氮原子、或氟原子的碳數1～12的2價連結基，於存在多個L¹ 的情況下，多個L¹ 可分別不同，於存在多個L² 的情況下，多個L² 可分別不同， d11為1～9， d12為0～9， a10及a14分別獨立地為0～10， a11及a15分別獨立地為0或1， a12及a16分別獨立地為0～9， a13為0或1， a21、a22及a23分別獨立地為0～2， e1、e2及e3分別獨立地為1～3。 [2]如[1]所述的積層體，其中所述有機矽化合物（C2）為 具有兩個以上下述式（c21-1）所表示的結構（c21-1），且所述結構（c21-1）彼此藉由下述*3或*4而鍵結為鏈狀或環狀的化合物，並且藉由下述*3或*4的鍵結是基於兩個以上所述有機矽化合物（C1）的所述X¹ 或X² 的縮合， 下述式（c21-1）的*1及*2中分別鍵結有下述式（c21-2）的以p11、p12、p13、p14、p15、(p16)-1、p17括起來的單元的至少一種以任意的順序鍵結且末端為Z-的基，多個所述結構（c21-1）各者中，鍵結於*1及*2的基可不同， 多個所述結構（c21-1）鍵結為鏈狀時成為末端的*3為氫原子，*4為羥基； [化3]

[化4]

所述式（c21-2）中， Z為水解性基及羥基以外的反應性官能基， R^x1 、R^x2 、R^x3 、R^x4 、Rf^x1 、Rf^x2 、Rf^x3 、Rf^x4 、Y、X¹ 、X² 、X³ 、X⁴ 、p11～p17與所述式（c11）中的該些符號意義相同。 [3]如[1]或[2]所述的積層體，其中所述組成物（ca）混合有下述式（b1）所表示的有機矽化合物（B）； [化5]

所述式（b1）中， Rf^b10 為一個以上的氫原子被取代為氟原子的碳數1～20的烷基或氟原子， R^b11 、R^b12 、R^b13 及R^b14 分別獨立地為氫原子或碳數1～4的烷基，於存在多個R^b11 的情況下，多個R^b11 可分別不同，於存在多個R^b12 的情況下，多個R^b12 可分別不同，於存在多個R^b13 的情況下，多個R^b13 可分別不同，於存在多個R^b14 的情況下，多個R^b14 可分別不同， Rf^b11 、Rf^b12 、Rf^b13 及Rf^b14 分別獨立地為一個以上的氫原子被取代為氟原子的碳數1～20的烷基或氟原子，於存在多個Rf^b11 的情況下，多個Rf^b11 可分別不同，於存在多個Rf^b12 的情況下，多個Rf^b12 可分別不同，於存在多個Rf^b13 的情況下，多個Rf^b13 可分別不同，於存在多個Rf^b14 的情況下，多個Rf^b14 可分別不同， R^b15 為碳數1～20的烷基，於存在多個R^b15 的情況下，多個R^b15 可分別不同， A¹ 為-O-、-C(=O)-O-、-O-C(=O)-、-NR-、-NRC(=O)-或-C(=O)NR-，所述R為氫原子、碳數1～4的烷基或碳數1～4的含氟烷基，於存在多個A¹ 的情況下，多個A¹ 可分別不同， A² 為水解性基，於存在多個A² 的情況下，多個A² 可分別不同， b11、b12、b13、b14及b15分別獨立地為0～100的整數， c為1～3的整數， 關於Rf^b10 -、-Si(A² )_c (R^b15 )_3-c 、b11個-{C(R^b11 )(R^b12 )}-、b12個-{C(Rf^b11 )(Rf^b12 )}-、b13個-{Si(R^b13 )(R^b14 )}-、b14個-{Si(Rf^b13 )(Rf^b14 )}-、b15個-A¹ -，只要Rf^b10 -、-Si(A² )_c (R^b15 )_3-c 為末端，未形成全氟聚醚結構，且-O-與-O-或-F不連結，則可以任意的順序排列鍵結。 [4]如[1]至[3]中任一項所述的積層體，其中所述組成物（cc）至少混合有所述有機矽化合物（C1）。 [5]如[1]至[4]中任一項所述的積層體，其中所述樹脂基材層（s）為硬塗層。 [6]一種積層體的製造方法，其為如請求項1至請求項5中任一項所述的積層體的製造方法，包括： 於所述樹脂基材層（s）上塗佈所述組成物（cc）以形成層（c）的步驟；以及 於所述層（c）上塗佈所述組成物（ca），於常溫下使其硬化而形成所述斥水層（r）的步驟。 [7]如[6]所述的積層體的製造方法，其中於形成所述層（c）的步驟中，對所述樹脂基材層（s）實施電漿處理，於所述電漿處理面塗佈所述組成物（cc）。 [發明的效果]The present invention is as follows. [1] A laminate in which a water-repellent layer (r) and a resin base material layer (s) are laminated via a layer (c), the layer (c) being formed of a mixed composition (cc), the The mixed composition (cc) is an organosilicon compound (C1) represented by the following formula (c11), and/or two or more of the organosilicon compounds (C1) having at least ^{one of the} following X ¹ to X ⁴ A mixed composition of an organosilicon compound (C2) formed by condensation and bonding of any one, wherein the water-repellent layer (r) is a mixed composition of an organosilicon compound (A) represented by the following formula (a1) The layer formed by the thing (ca); [化1]

In the formula (c11), Z ¹ and Z ² are each independently a hydrolyzable group and a reactive functional group other than a hydroxyl group, and R ^x1 , R ^x2 , R ^x3 , and R ^x4 are each independently a hydrogen atom or a carbon number of 1. For the alkyl group of ~4, when there are multiple R ^x1s , the multiple R ^x1s may be different respectively. When there are multiple R ^x2s , the multiple R ^x2s may be different respectively. When there are multiple R ^x3s Below, a plurality of R ^x3 may be different, and when there are a plurality of R ^x4 , a plurality of R ^x4 may be different respectively, Rf ^x1 , Rf ^x2 , Rf ^x3 , Rf ^x4 are each independently one or more hydrogen atoms are substituted It is an alkyl group with 1 to 20 carbon atoms or a fluorine atom that is a fluorine atom. When there are a plurality of Rf ^x1 , the plurality of Rf ^x1 may be different, and when there are a plurality of Rf ^x2 , the plurality of Rf ^x2 may be different Different, when there are multiple Rf ^x3 , multiple Rf ^x3 can be different respectively, when there are multiple Rf ^x4 , multiple Rf ^x4 can be different respectively, Y is -NH-, -N(CH ₃ ) -Or -O-, when there are multiple Ys, the multiple Ys may be different, and X ¹ , X ² , X ³ , and X ⁴ are each independently -OR ^c (R ^c is a hydrogen atom, carbon number 1 ～4 alkyl group or amino group (C _1-3 alkyl group (C _1-3 alkoxysilyl group)), when there are multiple X ¹ , the multiple X ¹ may be different, and when there are multiple X ² under the circumstances, the plurality of X ² may be different from each other, in the case where there are a plurality of X ^3, a plurality of X ³ may be different from each other, in the case where there is a plurality of X ^4, X ⁴ may be different from each other plurality, as P11 An integer of 0-20, p12, p13, and p14 are each independently an integer of 0-10, p15 is an integer of 0-5, p16 is an integer of 1-10, p17 is 0 or 1, the organosilicon compound (C1 The ends of) are Z ¹ -and Z ² -. As long as -O- is not connected to -O-, there are p11 -{C(R ^x1 )(R ^x2 )}-, p12 -{C(Rf ^x1 ) (Rf ^x2 ))-, p13-(Si(R ^x3 )(R ^x4 ))-, p14-(Si(Rf ^x3 )(Rf ^x4 ))-, p15-Y-, p16-(Si (X ¹ )(X ² )-O}-, p17-{Si(X ³ )(X ⁴ )}- are formed by arranging the bonding in any order; [化2]

In the formula (a1), Rf ^a1 is a divalent perfluoropolyether structure with oxygen atoms at both ends, and R ¹¹ , R ¹² and R ¹³ are each independently an alkyl group having 1 to 20 carbons, and there are multiple in the case of R ^11, a plurality of R ¹¹ may be different from each other, in a case where a plurality of R ^12, R ¹² may be each a plurality of different, in a case where a plurality of R ^13, R ¹³ s may be different from each other, E ¹ , E ² , E ³ , E ^4, and E ⁵ are each independently a hydrogen atom or a fluorine atom. When there are multiple E ¹ , the multiple E ¹ may be different, and when there are multiple E ² Below, multiple E ² can be different respectively, when there are multiple E ³ , multiple E ³ can be different respectively, when there are multiple E ⁴ , multiple E ⁴ can be different, G ¹ and G ² are each independently a divalent to 10-valent organosiloxane group having a siloxane bond, and J ¹ , J ² and J ³ are each independently a hydrolyzable group or -(CH ₂ ) _e6 -Si(OR ¹⁴ ) ₃ , e6 is 1 to 5, R ¹⁴ is a methyl group or an ethyl group, when there are multiple J ¹ , the multiple J ¹ may be different, and when there are multiple J ² , multiple J ² They may be different. When there are multiple J ^3s , the multiple J ^3s may be different. L ¹ and L ² are each independently ² with 1 to 12 carbon atoms, which may contain an oxygen atom, a nitrogen atom, or a fluorine atom. For the valence linking group, when there are multiple L ^1s , the multiple L ^1s may be different, and if there are multiple L ^2s , the multiple L ^2s may be different, d11 is 1-9, and d12 is 0- 9, a10 and a14 are independently 0-10, a11 and a15 are 0 or 1, a12 and a16 are 0-9, a13 are 0 or 1, a21, a22, and a23 are independently 0 to 2, e1, e2, and e3 are independently 1 to 3, respectively. [2] The laminate according to [1], wherein the organosilicon compound (C2) has two or more structures (c21-1) represented by the following formula (c21-1), and the structure ( c21-1) Compounds that are bonded to each other in a chain or cyclic form by the following *3 or *4, and the bonding by the following *3 or *4 is based on two or more of the aforementioned organosilicon compounds ( The condensation of X ¹ or X ² in C1), in the following formula (c21-1) *1 and *2, the following formula (c21-2) is bonded with p11, p12, p13, p14, At least one of the units enclosed by p15, (p16)-1, and p17 is bonded in an arbitrary order and the terminal is a group of Z-, and among each of the plurality of structures (c21-1), it is bonded to *1 and The groups of *2 may be different. When multiple structures (c21-1) are bonded in a chain shape, the terminal *3 is a hydrogen atom, and *4 is a hydroxyl group; [化3]

[化4]

In the formula (c21-2), Z is a hydrolyzable group and a reactive functional group other than a hydroxyl group, R ^x1 , R ^x2 , R ^x3 , R ^x4 , Rf ^x1 , Rf ^x2 , Rf ^x3 , Rf ^x4 , Y, X ¹ , X ² , X ³ , X ⁴ , p11 to p17 have the same meaning as the symbols in the formula (c11). [3] The laminate according to [1] or [2], wherein the composition (ca) is mixed with an organosilicon compound (B) represented by the following formula (b1); [化5]

In the formula (b1), Rf ^b10 is a C 1-20 alkyl group or fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms, and R ^b11 , R ^b12 , R ^b13 and R ^b14 are each independently hydrogen Alkyl group having 1 to 4 atoms or carbon number, when there are multiple R ^b11 , the multiple R ^b11 may be different respectively, and when there are multiple R ^b12 , the multiple R ^b12 may be different respectively. a case where R ^b13 and R ^b13 may be respectively a plurality of different, in a case where there are plural R ^b14 and R ^b14 may be respectively a plurality of ^{different, Rf b11, Rf b12, Rf} b13 and Rf ^b14 each independently represent a more The hydrogen atom of is replaced with a fluorine atom, a C 1-20 alkyl group or a fluorine atom. When there are multiple Rf ^b11 , the multiple Rf ^b11 may be different. When there are multiple Rf ^b12 , more Each Rf ^b12 can be different. When there are multiple Rf ^b13 , the multiple Rf ^b13 can be different. When there are multiple Rf ^b14 , the multiple Rf ^b14 can be different. R ^b15 is a carbon number of 1~ The alkyl group of 20, when there are multiple R ^b15 , multiple R ^b15 can be different respectively, A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR -, -NRC(=O)- or -C(=O)NR-, said R is a hydrogen atom, a C1-C4 alkyl group or a C1-C4 fluoroalkyl group, when there are more than one in the case of a ^1, a plurality of a ¹ may be different from each other, a ² is a hydrolyzable group, in the case where there are a plurality of a ^2, a ² may be different from each other plurality, b11, b12, b13, b14 and b15 are each independently Ground is an integer from 0 to 100, c is an integer from 1 to 3, about Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c , b11 -{C(R ^b11 )(R ^b12 )} -, b12-{C(Rf ^b11 )(Rf ^b12 )}-, b13-{Si(R ^b13 )(R ^b14 )}-, b14-{Si(Rf ^b13 )(Rf ^b14 )}-, b15 -A ¹ -, as long as Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c are the ends, no perfluoropolyether structure is formed, and -O- and -O- or -F are not connected , You can arrange the bonds in any order. [4] The laminate according to any one of [1] to [3], wherein the composition (cc) is mixed with at least the organosilicon compound (C1). [5] The laminate according to any one of [1] to [4], wherein the resin substrate layer (s) is a hard coat layer. [6] A method for manufacturing a laminate, which is the method for manufacturing a laminate according to any one of claims 1 to 5, comprising: coating the resin substrate layer (s) with the The step of forming the layer (c) with the composition (cc); and coating the composition (ca) on the layer (c) and curing it at room temperature to form the water-repellent layer (r) step. [7] The method for manufacturing a laminate according to [6], wherein in the step of forming the layer (c), the resin base material layer (s) is subjected to plasma treatment, and the plasma treatment The composition (cc) is coated on the surface. [Effects of the invention]

According to the present invention, it is possible to provide a laminate having excellent chemical resistance.

In order to realize a laminated body with a water-repellent layer (r) formed by laminating a compound (ca) of a compound having a perfluoropolyether structure on the resin substrate layer (s) and excellent chemical resistance, this The inventors continued to conduct research and found that if the resin base layer (s) and the water-repellent layer (r) are mixed with a specific organosilicon compound (C1) and/or organosilicon compound (C2) The layer (c) formed by the composition (cc) is laminated to achieve a laminate with excellent chemical resistance. Hereinafter, the layer (c), the water-repellent layer (r), and the resin base layer (s) will be described in order. Furthermore, the mixed composition (ca) is a composition mixed with an organosilicon compound (A), obtained by mixing an organosilicon compound (A), and is mixed with components other than the organosilicon compound (A) In the case, it is obtained by mixing the organosilicon compound (A) with other ingredients. The mixed composition (cc) is a composition mixed with an organosilicon compound (C1) and/or an organosilicon compound (C2), which is obtained by mixing an organosilicon compound (C1) and/or an organosilicon compound (C2) Obtained by mixing the organosilicon compound (C1) and/or organosilicon compound (C2) with other ingredients in the case of mixing components other than the organosilicon compound (C1) and organosilicon compound (C2) . The mixed composition (ca) and the mixed composition (cc) also include those that react after mixing, for example, during storage.

1. Layer (c) Layer (c) is an organosilicon compound (C1) represented by the following formula (c11) and/or two or more of the organosilicon compounds (C1) by the following X ¹ or X ² A layer formed by a mixed composition (cc) of an organosilicon compound (C2) formed by condensation and bonding, that is, a layer having a structure derived from an organosilicon compound (C1) and/or an organosilicon compound (C2). Hereinafter, the organosilicon compound (C1) and organosilicon compound (C2) are sometimes collectively referred to as organosilicon compound (C).

1-1. Organosilicon compound (C1) The organosilicon compound (C1) is represented by the following formula (c11).

[化6]

In the formula (c11), Z ¹ and Z ² are each independently a hydrolyzable group and a reactive functional group other than a hydroxyl group. As the reactive functional group, a vinyl group, an α-methyl vinyl group, a styryl group, a methacryl group, an acryl group, an amino group, an epoxy group, a ureido group, or a mercapto group can be mentioned. As Z ¹ and Z ² , an amino group, a mercapto group or a methacryl group is preferable, and an amino group is particularly preferable.

R ^x1 , R ^x2 , R ^x3 , and R ^x4 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbons. When there are multiple R ^x1s , the multiple R ^x1s may be different. When there are multiple Rs ^In the case of ^x2 , a plurality of R ^x2 may be different respectively, when there are a plurality of R ^x3s , a plurality of R ^x3s may be different respectively, and when there are a plurality of R ^x4s , a plurality of R ^x4s may be different. R ^x1 , R ^x2 , R ^x3 , and R ^{x4 are} preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom.

Rf ^x1 , Rf ^x2 , Rf ^x3 , and Rf ^x4 are each independently an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms, and when there are multiple Rf ^x1 , multiple Rf ^x1 may be different from each other, in a case where there are a plurality of Rf ^x2, a plurality of different Rf ^x2 respectively, in a case where there are a plurality of Rf ^x3, a plurality of different Rf ^x3 respectively, in the presence of a plurality of Rf ^x4 Below, multiple Rf ^x4 can be different. Rf ^x1 , Rf ^x2 , Rf ^x3 , and Rf ^{x4 are} preferably an alkyl group having 1 to 10 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms.

Y is -NH-, -N(CH ₃ )-, or -O-, and when there are a plurality of Ys, the plurality of Ys may be different. Y is preferably -NH-.

X ¹ , X ² , X ³ , and X ⁴ are each independently -OR ^c (R ^c is a hydrogen atom, a C _1-4 alkyl group or an amino group C _1-3 alkyl di C _1-3 alkoxy Silicon-based), when there are multiple X ¹ , the multiple X ¹ can be different, if there are multiple X ² , the multiple X ² can be different, and if there are multiple X ³ , The plurality of X ³ may be different respectively, and when there are a plurality of X ⁴ , the plurality of X ⁴ may be different respectively. ^{X 1, X 2, X 3} , X 4 is preferably R ^c is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, -OR ^c, R ^c is more preferably a hydrogen atom.

p11 is an integer of 0-20, p12, p13, and p14 are each independently an integer of 0-10, p15 is an integer of 0-5, p16 is an integer of 1-10, and p17 is 0 or 1. p11 is preferably 1-15, more preferably 3-13, and still more preferably 5-10. p12, p13, and p14 are each independently preferably 0-5, and more preferably all are 0-2. p15 is preferably 1-5, more preferably 1-3. p16 is preferably 1-5, more preferably 1-3. p17 is preferably 1.

The ends of the organosilicon compound (C1) are Z ¹ -and Z ² -, as long as -O- is not connected with -O-, there are p11 -{C(R ^x1 )(R ^x2 )}-, p12 -{C(Rf ^x1 )(Rf ^x2 )}-、p13pcs-{Si(R ^x3 )(R ^x4 ))-、p14pcs-(Si(Rf ^x3 )(Rf ^x4 ))-、p15pcs-Y -, p16-{Si(X ¹ )(X ² )-O}-, p17-{Si(X ³ )(X ⁴ )}- are arranged and bonded in an arbitrary order. p11 th ^{- {C (R x1) (} R x2)} - , the unnecessary to ^{- {C (R x1) (} R x2)} - continuously bonded, may be in the middle via other units bonded total p11 a OK. The same applies to the units enclosed in p12 to p17.

As the organosilicon compound (C1), Z ¹ and Z ² are preferably amino groups, R ^x1 and R ^x2 are hydrogen atoms, p11 is 3-13 (preferably 5-10), and R ^x3 and R ^x4 are both Hydrogen atoms, Rf ^x1 to Rf ^x4 are all C1-C10 alkyl groups or fluorine atoms in which one or more hydrogen atoms are substituted with fluorine atoms, p12-p14 are all 0-5, Y is -NH-, p15 is 0 to 5 (preferably 0 to 3), X ¹ to X ⁴ are all -OH, p16 is 1 to 5 (preferably 1 to 3), and p17 is a compound.

KBP90 used in the following examples is that Z ¹ and Z ² in the formula (c11) are both amino groups, R ^x1 and R ^x2 are both hydrogen atoms, p11 is 6, p12 to p15 are all 0, X ¹ , X ² , X ³ and X ⁴ are all -OH, and p16 and p17 are all 1 compounds.

KBP64 used in the following examples is that Z ¹ and Z ² in the formula (c11) are both amino groups, R ^x1 and R ^x2 are both hydrogen atoms, p11 is 10, p12 to p14 are all 0, and p15 is 2. , Y is NH, X ¹ , X ² , X ³ and X ⁴ are all -OH, and p16 and p17 are all 1 compounds.

The organosilicon compound (C1) is preferably represented by the following formula (c12).

[化7]

In the formula (c12), Z ¹ , Z ² , X ¹ , X ² , X ³ , X ⁴ , and Y have the same meanings as those in the formula (c11), and p21 to p24 are independently 1 to 6 Integer, p25 and p26 are 0 or 1 independently.

In the formula (c12), Z ¹ and Z ^{2 are} preferably an amine group, a mercapto group or a methacryl group, and particularly preferably an amine group. X ¹ , X ² , X ³ , and X ^{4 are} preferably -OR ^{c in} which R ^c is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably R ^c is a hydrogen atom. Y is preferably -NH-. p21 to p24 are preferably 2 or more, more preferably 5 or less, and more preferably 4 or less. Preferably, both p25 and p26 are 0 or both p25 and p26 are 1, and more preferably, both p25 and p26 are 0.

1-2. Organosilicon compound (C2) The organosilicon compound (C2) is formed by condensing and bonding two or more of the organosilicon compounds (C1) by at least any one of X ¹ to X ⁴ Two or more of the organosilicon compounds (C1) can be bonded in a chain shape or a ring shape. The organosilicon compound (C2) is formed of, for example, the organosilicon compound (C1) in the composition (cc).

Examples of the organosilicon compound (C2) include those obtained by condensation of the above-mentioned X ¹ or X ² , specifically one having two or more structures represented by the following formula (c21-1) (c21- 1), and the structures (c21-1) are bonded to each other as chain or cyclic compounds by the following *3 or *4, and the bonding by the following *3 or *4 is based on two For the condensation of X ¹ or X ² of more than one organosilicon compound (C1), the following formula (c21-1) *1 and *2 are respectively bonded to the following formula (c21-2) A compound in which at least one of the units enclosed by p11, p12, p13, p14, p15, (p16)-1, and p17 is bonded in an arbitrary order and the terminal is a Z-group. In each of the multiple structures (c21-1), the groups bonded to *1 and *2 may be different. In addition, when the multiple structures (c21-1) are bonded in a chain shape, the terminal *3 is a hydrogen atom, *4 is a hydroxyl group.

[化8]

[化9]

In the formula (c21-2), Z is a hydrolyzable group and a reactive functional group other than a hydroxyl group, R ^x1 , R ^x2 , R ^x3 , R ^x4 , Rf ^x1 , Rf ^x2 , Rf ^x3 , Rf ^x4 , Y, X ¹ , X ² , X ³ , X ⁴ , and p11 to p17 have the same meaning as the symbols in the formula (c11), and the preferred aspects are also the same.

The number of bonding of the organosilicon compound (C1) when forming the organosilicon compound (C2) is preferably 2-10, more preferably 3-8. In addition, two or more organosilicon compounds (C1) constituting the organosilicon compound (C2) may be different from each other, but preferably all are the same.

In the case where the organosilicon compound (C1) is a compound represented by the above formula (c12), as the organosilicon compound (C2), for example, the structure represented by the following formula (c22) can be exemplified by the following *3 or *4 A compound that is bonded in a chain or cyclic form. When the structure represented by the following formula (c22) is bonded in a chain shape, *3 is a hydrogen atom and *4 is a hydroxyl group.

[化10]

The symbols in the formula (c22) all have the same meaning as the symbols in the formula (c11).

The organosilicon compound (C2) is preferably a compound in which 2-10 (preferably 3-8) of the structure represented by the formula (c22) are bonded.

The composition (cc) is mixed with at least one of the organosilicon compound (C1) and the organosilicon compound (C2), preferably at least the organosilicon compound (C1) is mixed.

The thickness of the layer (c) is, for example, about 1 nm to 1000 nm.

2. Water repellent layer (r) The water-repellent layer (r) is a layer formed of the mixed composition (ca) of the organosilicon compound (A) represented by the following formula (a1), that is, it has a structure derived from the organosilicon compound (A). As described later, the organosilicon compound (A) has hydrolyzable groups, and the -SiOH groups of the organosilicon compound (A) produced by hydrolysis undergo dehydration and condensation with each other, so the water-repellent layer (r) usually has organosilicon-derived Condensed structure of compound (A).

[化11]

In the formula (a1), Rf ^a1 is a divalent perfluoropolyether structure with oxygen atoms at both ends, and R ¹¹ , R ¹² and R ¹³ are each independently (that is, R ¹¹ and R ¹² and R ¹³ may be the same, (May be different from each other) is an alkyl group having 1 to 20 carbon atoms. When there are multiple R ¹¹ , the multiple R ¹¹ may be different, and if there are multiple R ¹² , the multiple R ¹² may be different. , When there are multiple R ¹³ , the multiple R ¹³ may be different, E ¹ , E ² , E ³ , E ⁴ and E ⁵ are each independently a hydrogen atom or a fluorine atom, when there are multiple E ¹ In this case, multiple E ¹ can be different respectively. If there are multiple E ² , multiple E ² can be different respectively. If there are multiple E ³ , multiple E ³ can be different. In the case of a single E ⁴ , a plurality of E ⁴ may be different, G ¹ and G ² are each independently a divalent to 10-valent organosiloxane group having a siloxane bond, J ¹ , J ² and J ³ Each independently is a hydrolyzable group or -(CH ₂ ) _e6 -Si(OR ¹⁴ ) ₃ , e6 is 1 to 5, R ¹⁴ is a methyl group or an ethyl group, and when there are multiple J ¹ , multiple J ¹ can be different respectively. When there are multiple J ^2s , the multiple J ^2s can be different. When there are multiple J ^3s , the multiple J ^3s can be different. L ¹ and L ² are independently A divalent linking group with 1 to 12 carbon atoms that may contain oxygen atoms, nitrogen atoms, or fluorine atoms. When there are multiple L ¹ s, the multiple L ^1s may be different, and when there are multiple L ^2s , Multiple L ² can be different, d11 is 1-9, d12 is 0-9, a10 and a14 are independently 0-10, a11 and a15 are independently 0 or 1, a12 and a16 are independently 0-9, a13 is 0 or 1, a21, a22, and a23 are each independently 0-2, and e1, e2, and e3 are independently 1 to 3, respectively.

The organosilicon compound (A) has a perfluoropolyether structure represented by Rf ^a1 , as shown in the formula (a1), and has at least one hydrolyzable group represented by J ² or -(CH ₂ ) _e6 -Si( OR ¹⁴ ) ₃ (wherein R ¹⁴ is methyl or ethyl). The perfluoropolyether structure is a structure in which all hydrogen atoms of polyoxyalkylene are replaced with fluorine atoms. It can also be called perfluorooxyalkylene, which can impart water repellency to the obtained film . In addition, it is the following compound: By means of J ² , the organosilicon compound (A) is bonded to each other or with other monomers by polymerization reaction (especially polycondensation reaction), and can become the film obtained Matrix (matrix).

Rf ^{a1 is} preferably -O-(CF ₂ CF ₂ O) _e4 -or -O-(CF ₂ CF ₂ CF ₂ O) _e5 -. Both e4 and e5 are 15-80.

Preferably, R ¹¹ , R ¹² and R ¹³ are each independently an alkyl group having 1 to 10 carbon atoms.

It is preferable that L ¹ and L ² are each independently a C1-C5 divalent linking group containing a fluorine atom.

Preferably, G ¹ and G ² are each independently a divalent to pentavalent organosiloxane group having a siloxane bond.

J ¹ , J ² and J ^{3 are} preferably each independently a methoxy group, an ethoxy group or -(CH ₂ ) _e6 -Si(OR ¹⁴ ) ₃ .

a10 is preferably 0 to 5 (more preferably 0 to 3), a11 is preferably 0, a12 is preferably 0 to 7 (more preferably 0 to 5), and a14 is preferably 1 to 6 (more preferably 1 ~3), a15 is preferably 0, a16 is preferably 0-6, a21 to a23 are preferably all 0 or 1 (more preferably all are 0), d11 is preferably 1 to 5 (more preferably 1 ~3), d12 is preferably 0 to 3 (more preferably 0 or 1), and e1 to e3 are preferably 3. In addition, a13 is preferably 1.

As the compound (A), the following compound is preferably used: Rf ^a1 of the formula (a1) is -O-(CF ₂ CF ₂ CF ₂ O) _e5 -, e5 is 35-50, and both L ¹ and L ² Perfluoroalkylene having 1 to 3 carbon atoms, E ¹ , E ² and E ³ are all hydrogen atoms, E ⁴ and E ⁵ are hydrogen or fluorine atoms, and J ¹ , J ² and J ³ are all methoxy Group or ethoxy group (especially methoxy group), a10 is 1 to 3, a11 is 0, a12 is 0 to 5, a13 is 1, a14 is 2 to 5, a15 is 0, a16 is 0 to 6, a21 ~a23 is independently 0 or 1 (more preferably, a21 to a23 are all 0), d11 is 1, d12 is 0 or 1, and e1 to e3 are all 3.

Furthermore, if the compound a used as the compound (A) in the following examples is represented by the formula (a1), Rf ^a1 is -O-(CF ₂ CF ₂ CF ₂ O) ₄₃ -, L ¹ and L ² is -(CF ₂ )-, E ¹ , E ² and E ³ are all hydrogen atoms, E ⁵ is fluorine atom, J ¹ and J ² are both methoxy groups, a10 is 2, a11 is 0, a12 It is 0-5, a13 is 1, a14 is 3, a15 is 0, a16 is 0, a21 and a22 are both 0, d11 is 1, d12 is 0, and e1 and e2 are both 3.

As the compound (A), it is also preferable to use the following compound: Rf ^a1 of the formula (a1) is -O-(CF ₂ CF ₂ CF ₂ O) _e5 -, e5 is 25-40, and L ¹ contains fluorine A divalent linking group with 3 to 6 carbon atoms and oxygen atoms, L ² is a perfluoroalkylene group with 1 to 3 carbon atoms, E ² and E ³ are both hydrogen atoms, E ⁵ is a fluorine atom, and J ² is -(CH ₂ ) _e6 -Si(OCH ₃ ) ₃ , e6 is 2 to 4, a10 is 1 to 3, a11 is 0, a12 is 0, a13 is 0, a14 is 2 to 5, a15 is 0, a16 is 0, a21 to a23 are each independently 0 or 1 (more preferably, a21 to a23 are all 0), d11 is 1, d12 is 0, and e2 is 3.

In addition, the organosilicon compound (A) is also preferably a compound represented by the following formula (a2-1).

[化12]

In the above formula (a2-1), Rf ^a21 is a C 1-20 alkyl group or fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms, and Rf ^a22 , Rf ^a23 , Rf ^a24 and Rf ^a25 are each independently It is an alkyl group with 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms. When there are multiple Rf ^a22 , the multiple Rf ^a22 may be different, and when there are multiple Rf ^a23 next, a plurality of different Rf ^a23 respectively, in the presence of a plurality of Rf ^a24, a plurality of different Rf ^a24 respectively, in the case where there are a plurality of Rf ^a25, respectively different plurality Rf ^a25, R ^20, R ²¹ , R ^22, and R ²³ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When there are multiple R ²⁰ , the multiple R ²⁰ may be different, and when there are multiple R ²¹ , A plurality of R ²¹ can be different respectively, when there are a plurality of R ²² , a plurality of R ²² can be different respectively, when there are a plurality of R ²³ , a plurality of R ²³ can be different respectively, R ²⁴ is the carbon number An alkyl group of 1-20. When there are multiple R ^24s , the multiple R ^24s may be different. M ¹ is a hydrogen atom or an alkyl group with 1 to 4 carbons. When there are multiple M ^1s , Multiple M ¹ can be different, M ² is a hydrogen atom or a halogen atom, M ³ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(= O)- or -C(=O)NR- (R is a hydrogen atom, an alkyl group having 1 to 4 carbons or a fluorinated alkyl group having 1 to 4 carbons), when there are more than one M ³ , more Each M ³ may be different, and M ⁴ is a hydrolyzable group. When there are multiple M ^4s , the multiple M ^4s may be different, and f11, f12, f13, f14, and f15 are each independently an integer from 0 to 600 , The total value of f11, f12, f13, f14, and f15 is 13 or more, f16 is an integer of 1-20, f17 is an integer of 0-2, g1 is an integer of 1-3, and Rf ^a21 -, M ² -, f11-(C(R ²⁰ )(R ²¹ ))-, f12-(C(Rf ^a22 )(Rf ^a23 ))-, f13-(Si(R ²² )(R ²³ ))-, f14 -{Si(Rf ^a24 )(Rf ^a25 )}-, f15 -M ³ -and f16 -[CH ₂ C(M ¹ ){(CH ₂ ) _f17 -Si(M ⁴ ) _g1 (R ²⁴ ) _{3 -g1} }]-, as long as Rf ^a21 -and M ² -are the ends, they are arranged in the order that at least a part of the perfluoropolyether structure is formed and -O- and -O- or -F are not connected, the bonds can be arranged in any order Knot. That is, the formula (a2-1) does not necessarily have the following meaning: f11-{C(R ²⁰ )(R ²¹ )}-continuous, f12-{C(Rf ^a22 )(Rf ^a23 )}-continuous, f13- {Si(R ²² )(R ²³ )}-continuous, ^f14- {Si(Rf ^a24 )(Rf ^a25 )}-continuous, f15-M ^{3 -continuous, f16-} [CH ₂ C(M ¹ ) {(CH ₂ ) _f17 -Si(M ⁴ ) _g1 (R ²⁴ ) _3-g1 }]-continuous and arranged in sequence; can be like -C(R ²⁰ )(R ²¹ )-Si(Rf ^a24 )(Rf ^a25 )-CH ₂ C(M ¹ )((CH ₂ ) _f17 -Si(M ⁴ ) _g1 (R ²⁴ ) _3-g1 )-C(Rf ^a22 )(Rf ^a23 )-M ³ -Si(R ²² )( R ²³ )-C(Rf ^a22 )(Rf ^a23 )- etc. are generally arranged in any order.

Rf ^{a21 is} preferably an alkyl group having 1 to 10 carbons substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbons, and still more preferably a perfluoroalkyl group having 1 to 5 carbons.

Rf ^a22 , Rf ^a23 , Rf ^a24 and Rf ^{a25 are} preferably each independently a fluorine atom, or an alkyl group having 1 to 2 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and more preferably all are fluorine atoms.

R ²⁰ , R ²¹ , R ²² and R ^{23 are} preferably each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably all are hydrogen atoms.

R ^{24 is} preferably an alkyl group having 1 to 5 carbon atoms.

M ^{1 is} preferably each independently a hydrogen atom or an alkyl group having 1 to 2 carbons, and more preferably all of them are hydrogen atoms.

M ^{2 is} preferably a hydrogen atom.

M ^{3 is} preferably -C(=O)-O-, -O-, -OC(=O)-, and more preferably all are -O-.

M ^{4 is} preferably an alkoxy group or a halogen atom, more preferably a methoxy group, an ethoxy group, or a chlorine atom.

Preferably, f11, f13, and f14 are each less than 1/2 of f12, more preferably less than 1/4, more preferably f13 or f14 is 0, and particularly preferably f13 and f14 are 0.

f15 is preferably 1/5 or more of the total value of f11, f12, f13, and f14 and less than the total value of f11, f12, f13, and f14.

f12 is preferably 20 to 600, more preferably 20 to 200, further preferably 50 to 200 (further preferably 30 to 150, particularly preferably 50 to 150, most preferably 80 to 140). f15 is preferably 4 to 600, more preferably 4 to 200, still more preferably 10 to 200 (further preferably 30 to 60). The total value of f11, f12, f13, f14, and f15 is preferably 20-600, more preferably 20-200, and still more preferably 50-200.

f16 is preferably 1-18. More preferably, it is 1-15. More preferably, it is 1-10.

Preferably, f17 is 0-1.

g1 is preferably 2 to 3, more preferably 3.

About f11-{C(R ²⁰ )(R ²¹ )}-, f12-{C(Rf ^a22 )(Rf ^a23 )}-, f13-{Si(R ²² )(R ²³ )}-, f14 The order of -{Si(Rf ^a24 )(Rf ^a25 )}- and f15 -M ³ -, as long as they are arranged in the order in which at least a part of the perfluoropolyether structure is formed, are arbitrary in the formula, but the most preferred The fixed end side (the side bonded to the silicon atom) with f12 and bracketed repeating units (ie, -{C(Rf ^a22 )(Rf ^a23 )}-) is compared to the free end side The repeating unit with f11 attached and enclosed in parentheses (ie, -{C(R ²⁰ )(R ²¹ )}-) is located on the free end side, and it is more preferable to have f12 and f14 attached to the most fixed end side And the repetitive units enclosed in parentheses (ie, -{C(Rf ^a22 )(Rf ^a23 )}- and -{Si(Rf ^a24 )(Rf ^a25 )}-) are compared to the free end side with The repeating units of f11 and f13 enclosed in parentheses (that is, -{C(R ²⁰ )(R ²¹ )}- and -{Si(R ²² )(R ²³ )}-) are located on the free end side.

In the formula (a2-1), Rf ^a21 is preferably a perfluoroalkyl group having 1 to 5 carbons, Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^{a25 are} all fluorine atoms, and M ^{3 is} all -O- , M ^{4 are} all methoxy, ethoxy or chlorine atoms (especially methoxy or ethoxy), M ¹ and M ² are both hydrogen atoms, f11 is 0, f12 is 30 to 150 (more preferably 80-140), f15 is 30-60, f13 and f14 are 0, f17 is 0-1 (especially 0), g1 is 3, and f16 is 1-10.

In addition, regarding compound a used as compound (A) in the following examples, if represented by the above formula (a2-1), Rf ^a21 is C ₃ H ₇ -, and Rf ^a22 and Rf ^a23 are both fluorine atoms , F11=f13=f14=0, f12 is 131, f15 is 44, f16 is 1 to 6, f17 is 0, M ¹ and M ² are hydrogen atoms, M ³ is -O-, M ⁴ is a methoxy group, g1 is 3.

In addition, the organosilicon compound (A) is also preferably a compound represented by the following formula (a2-2).

[化13]

In the formula ^{(a2-2), Rf a26, Rf} a27, Rf a28 and Rf ^a29 are each independently a hydrogen atom or more carbon atoms is substituted with a fluorine atom or an alkyl group having 1 to 20 fluorine atoms, in the presence of Rf ^a26 case where a plurality of the plurality may be different from each Rf ^a26, in case where there is a plurality of Rf ^a27, the plurality may be different from each Rf ^a27, in a case where there are a plurality of Rf ^a28, respectively, a plurality of Rf ^a28 Different, when there are multiple Rf ^a29s , the multiple Rf ^a29s may be different. R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are each independently a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. R ²⁵ is a case where a plurality of R ²⁵ may be different from each other, in the presence of a plurality of R ^26, a plurality of R ²⁶ may be different from each other, in a case where a plurality of R ^27, R ²⁷ may be each a plurality of different , When there are multiple R ²⁸ , the multiple R ²⁸ may be different, R ²⁹ and R ³⁰ are each independently an alkyl group having 1 to 20 carbons, and when there are multiple R ²⁹ , multiple R ²⁹ may be different from each other, in a case where a plurality of R ^30, R ³⁰ may be each a plurality of different, M ⁷ is -O -, - C (= O ) -O -, - OC (= O) -, - NR -, -NRC(=O)- or -C(=O)NR-, said R is a hydrogen atom, a C1-C4 alkyl group or a C1-C4 fluoroalkyl group, when there are more than one in the case of M ^7, M ⁷ may be respectively a plurality of different, M ^5, M ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and in the presence of a plurality of M ^5, M ⁵ may be a plurality of When there are multiple M ^9s , the multiple M ^9s may be different. M ⁶ and M ¹⁰ are each independently a hydrogen atom or a halogen atom, and M ⁸ and M ¹¹ are each independently a hydrolyzable group. When there are multiple M ⁸ , the multiple M ⁸ may be different, and when there are multiple M ¹¹ , the multiple M ¹¹ may be different, and f21, f22, f23, f24 and f25 are independently 0 to An integer of 600, the total value of f21, f22, f23, f24, and f25 is 13 or more, f26 and f28 are each independently an integer from 1 to 20, f27 and f29 are each independently an integer from 0 to 2, g2, g3, respectively independently an integer of 1 to 3, on ^{M 10 -, M 6 -,} f21 a ^{- {C (R 25) (} R 26)} -, f22 a ^{- {C (Rf a26) (} Rf a27)} -, f23-{Si(R ²⁷ )(R ²⁸ )}-, f24-{Si(Rf ^a28 )(Rf ^a29 )}-, f25-M ⁷ -, f26-[CH ₂ C(M ⁵ ) {(CH ₂ ) _f27 -Si(M ⁸ ) _g2 (R ²⁹ ) _3-g2 }] and f28-[CH ₂ C(M ⁹ ){(CH ₂ ) _f29 -Si(M ¹¹ ) _g3 (R ³⁰ ) _3-g3 }], as long as M ¹⁰ -, M ^6- As the terminal, it is arranged in the order in which at least a part of the perfluoropolyether structure is formed and -O- and -O- are not continuous, and the bonding can be arranged in any order. Regarding arranging the bonds in an arbitrary order, it is the same as that described in the above formula (a2-1), and is not limited to that the repeating units are continuous and arranged in the order described in the above formula (a2-2) Meaning.

In the formula (A2-2), is preferably Rf ^a26, Rf ^a27, Rf ^a28 and Rf ^a29 are all fluorine atoms, M ⁷ are all -O-, M ⁸ and M ¹¹ are all methoxy, ethoxy Groups or chlorine atoms (especially methoxy or ethoxy), M ⁵ , M ⁶ , M ⁹ and M ¹⁰ are all hydrogen atoms, f21 is 0, f22 is 30 to 150 (more preferably 80 to 140), F25 is 30-60, f23 and f24 are 0, f27 and f29 are 0-1 (more preferably, 0), g2 and g3 are 3, and f26 and f28 are 1-10.

As a compound (A), the compound of following formula (a3) is mentioned more specifically.

[化14]

In the formula (a3), R ³⁰ is a perfluoroalkyl group having 2 to 6 carbons, R ³¹ and R ³² are each independently a perfluoroalkylene group having 2 to 6 carbons, and R ³³ is a carbon number 2 ~6 trivalent saturated hydrocarbon group, R ³⁴ is an alkyl group having 1 to 3 carbons. The carbon numbers of R ³⁰ , R ³¹ , R ³² , and R ³³ are preferably 2-4 independently, and more preferably 2-3. h1 is 5 to 70, h2 is 1 to 5, and h3 is 1 to 10. h1 is preferably 10-60, more preferably 20-50, h2 is preferably 1-4, more preferably 1-3, and h3 is preferably 1-8, more preferably 1-6.

As a compound (A), the compound represented by following formula (a4) can also be mentioned.

[化15]

In the formula (a4), R ⁴⁰ is a perfluoroalkyl group having 2 to 5 carbons, R ⁴¹ is a perfluoroalkylene group having 2 to 5 carbons, and R ⁴² is an alkylene group having 2 to 5 carbons. A fluoroalkylene group in which a part of hydrogen atoms is substituted with fluorine, R ⁴³ and R ⁴⁴ are each independently an alkylene group having 2 to 5 carbon atoms, and R ⁴⁵ is a methyl group or an ethyl group. k1, k2, and k3 are each independently an integer of 1-5.

The number average molecular weight of the organosilicon compound (A) is preferably 2,000 or more, more preferably 4,000 or more, still more preferably 6,000 or more, particularly preferably 7,000 or more, further preferably 40,000 or less, more preferably 20,000 or less, and still more preferably Below 15,000.

The composition (ca) for forming the water-repellent layer (r) is preferably a mixture of the organosilicon compound (A) and the organosilicon compound (B) represented by the following formula (b1). As described later, the organosilicon compound (B) has hydrolyzable groups. Usually the -SiOH group of the organosilicon compound (B) produced by hydrolysis and the -SiOH group of the organosilicon compound (A) produced by hydrolysis and/ Or the -SiOH group of the organosilicon compound (B) produced by hydrolysis undergoes dehydration and condensation, so in a preferred form, the water-repellent layer (r) has a condensation structure derived from the organosilicon compound (A) and has a condensation structure derived from Condensed structure of organosilicon compound (B).

[化16]

In the formula (b1), Rf ^b10 is a C 1-20 alkyl group or fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms, and R ^b11 , R ^b12 , R ^b13 , and R ^b14 are each independently hydrogen Alkyl group having 1 to 4 atoms or carbon number, when there are multiple R ^b11 , the multiple R ^b11 may be different respectively, and when there are multiple R ^b12 , the multiple R ^b12 may be different respectively. a case where R ^b13 and R ^b13 may be respectively a plurality of different, in a case where there are plural R ^b14 and R ^b14 may be respectively a plurality of ^{different, Rf b11, Rf b12, Rf} b13, Rf b14 each independently represent a more The hydrogen atom of is replaced with a fluorine atom, a C 1-20 alkyl group or a fluorine atom. When there are multiple Rf ^b11 , the multiple Rf ^b11 may be different. When there are multiple Rf ^b12 , more Each Rf ^b12 can be different. When there are multiple Rf ^b13 , the multiple Rf ^b13 can be different. When there are multiple Rf ^b14 , the multiple Rf ^b14 can be different. R ^b15 is a carbon number of 1~ The alkyl group of 20, when there are multiple R ^b15 , multiple R ^b15 can be different respectively, A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR -, -NRC(=O)- or -C(=O)NR-, said R is a hydrogen atom, a C1-C4 alkyl group or a C1-C4 fluoroalkyl group, when there are more than one in the case of a ^1, a ¹ may be a plurality of respective different, a ² is a hydrolyzable group, in the presence of a plurality of a ^2, a ² may be different from each other plurality, b11, b12, b13, b14 , b15 are each independently Ground is an integer from 0 to 100, c is an integer from 1 to 3, about Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c , b11 -{C(R ^b11 )(R ^b12 )} -, b12-{C(Rf ^b11 )(Rf ^b12 )}-, b13-{Si(R ^b13 )(R ^b14 )}-, b14-{Si(Rf ^b13 )(Rf ^b14 )}-, b15 -A ¹ -, as long as Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c are the ends, no perfluoropolyether structure is formed, and -O- and -O- or -F are not connected , You can arrange the bonds in any order.

Rf ^{b10 is} preferably a fluorine atom or a perfluoroalkyl group having 1 to 10 (more preferably 1 to 5) carbon atoms.

R ^b11 , R ^b12 , R ^b13 and R ^{b14 are} preferably hydrogen atoms.

R ^{b15 is} preferably an alkyl group having 1 to 5 carbon atoms.

A ^{1 is} preferably -O-, -C(=O)-O- or -OC(=O)-.

A ^{2 is} preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group, or a chlorine atom.

b11 is preferably 1-30, more preferably 1-25, still more preferably 1-10, particularly preferably 1-5, most preferably 1-2.

b12 is preferably 0-15, more preferably 0-10.

b13 is preferably 0-5, more preferably 0-2.

b14 is preferably 0-4, more preferably 0-2.

b15 is preferably 0-4, more preferably 0-2.

c is preferably 2 to 3, more preferably 3.

The total value of b11, b12, b13, b14, and b15 is preferably 3 or more, more preferably 5 or more, more preferably 80 or less, more preferably 50 or less, and still more preferably 20 or less.

In particular, it is preferable that Rf ^b10 is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, R ^b11 and R ^b12 are both hydrogen atoms, A ² is a methoxy group or an ethoxy group, and b11 is 1 to 5. b12 is 0-5, b13, b14, and b15 are all 0, and c is 3.

In addition, in the examples described later, if FAS13E used as compound (B) is represented by the formula (b1), it is defined as: R ^b11 and R ^b12 are both hydrogen atoms, b11 is 2, b13, b14 and b15 are all 0, c is 3, A ² is an ethoxy group, and Rf ^b10 -{C(Rf ^b11 )(Rf ^b12 )} _b12 -is a terminal and becomes C ₆ F ₁₃ -.

As the compound represented by the formula (b1), specifically, CF ₃ -Si-(OCH ₃ ) ₃ , C _j F _2j+1 -Si-(OC ₂ H ₅ ) ₃ (j is 1-12 Integer of ), of which C ₄ F ₉ -Si-(OC ₂ H ₅ ) ₃ , C ₆ F ₁₃ -Si-(OC ₂ H ₅ ) ₃ , C ₇ F ₁₅ -Si-(OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ -Si-(OC ₂ H ₅ ) ₃ . In addition, CF ₃ CH ₂ O(CH ₂ ) _k SiCl ₃ , CF ₃ CH ₂ O(CH ₂ ) _k Si(OCH ₃ ) ₃ , CF ₃ CH ₂ O(CH ₂ ) _k Si(OC ₂ H ₅ ) ₃ , CF ₃ (CH ₂ ) ₂ Si(CH ₃ ) ₂ (CH ₂ ) _k SiCl ₃ , CF ₃ (CH ₂ ) ₂ Si(CH ₃ ) ₂ (CH ₂ ) _k Si(OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si(CH ₃ ) ₂ (CH ₂ ) _k Si(OC ₂ H ₅ ) ₃ , CF ₃ (CH ₂ ) ₆ Si(CH ₃ ) ₂ (CH ₂ ) _k SiCl ₃ , CF ₃ (CH ₂ ) ₆ Si(CH ₃ ) ₂ (CH ₂ ) _k Si(OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₆ Si(CH ₃ ) ₂ (CH ₂ ) _k Si(OC ₂ H ₅ ) ₃ , CF ₃ COO(CH ₂ ) _k SiCl ₃ , CF ₃ COO(CH ₂ ) _k Si(OCH ₃ ) ₃ , CF ₃ COO(CH ₂ ) _k Si(OC ₂ H ₅ ) ₃ (k are all 5～20, Preferably 8-15). In addition, CF ₃ (CF ₂ ) _m -(CH ₂ ) _n SiCl ₃ , CF ₃ (CF ₂ ) _m -(CH ₂ ) _n Si(OCH ₃ ) ₃ , CF ₃ (CF ₂ ) _m- (CH ₂ ) _n Si(OC ₂ H ₅ ) ₃ (m is all 1-10, preferably 3-7, n is all 1-5, preferably 2-4). CF ₃ (CF ₂ ) _p -(CH ₂ ) _q -Si-(CH ₂ CH=CH ₂ ) ₃ (p is 2-10, preferably 2-8, q is 1-5, Preferably it is 2 to 4). Furthermore, CF ₃ (CF ₂ ) _p -(CH ₂ ) _q SiCH ₃ Cl ₂ , CF ₃ (CF ₂ ) _p -(CH ₂ ) _q SiCH ₃ (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) _p -(CH ₂ ) _q SiCH ₃ (OC ₂ H ₅ ) ₂ (p are all 2-10, preferably 3-7, q are all 1-5, preferably 2-4).

Among the compounds represented by the above formula (b1), a compound represented by the following formula (b2) is preferred.

[化17]

In the formula (b2), R ⁶⁰ is a perfluoroalkyl group having 3 to 8 carbons, R ⁶¹ is an alkylene group having 1 to 5 carbons, and R ⁶² is an alkyl group having 1 to 3 carbons.

The thickness of the water repellent layer (r) is, for example, about 1 nm to 1000 nm.

3. Resin substrate layer (s) The material of the resin substrate layer (s) of the present invention is not particularly limited. It may be any one of organic materials and inorganic materials. In addition, the shape of the substrate may be either flat or curved, or it may be The combination has these shapes. Examples of organic materials include acrylic resins, polycarbonate resins, polyester resins, styrene resins, acrylic-styrene copolymer resins, cellulose resins, polyolefin resins, vinyl resins (polyethylene, polyvinyl chloride, Thermoplastic resins such as polystyrene, vinylbenzyl chloride (Vinylbenzyl chloride) resin, polyvinyl alcohol, etc.); phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester, silicone resin, urethane resin Thermosetting resins such as acid ester resins, etc. Examples of inorganic materials include metals such as iron, silicon, copper, zinc, and aluminum, alloys containing these metals, ceramics, and glass. Among them, organic materials are particularly preferred. Among the resin substrates, at least one of acrylic resin, benzyl chloride resin, epoxy resin, silicone resin, and urethane resin is preferred, and acrylic resin is particularly preferred.

The resin substrate layer (s) of the present invention is preferably a protective layer (hereinafter, sometimes referred to as a hard coat layer) provided to protect articles from damage in applications requiring abrasion resistance such as displays of electronic equipment It is more preferable that the protective layer is acrylic resin.

The hard coat layer is a layer having surface hardness, and its hardness is usually B or higher in pencil hardness, preferably HB or higher, more preferably H or higher, and particularly preferably 2H or higher. The hard coat layer may have a single-layer structure or a multilayer structure. The hard coat layer is, for example, a cured layer of ultraviolet curable resin. The hard coat layer contains a hard coat resin. Examples of the hard coat resin include acrylic resins, epoxy resins, urethane resins, amide resins, vinylbenzyl chloride resins, and vinyl. UV-curable, electron beam-curable, or thermosetting resins such as resins, silicone-based resins, or mixed resins of these. In particular, it is also preferable that the hard coat layer contains an acrylic resin in order to express high hardness. Since the adhesion with the water-repellent layer (r) via the layer (c) tends to become better, it is preferable to include an epoxy resin.

The hard coat layer may also contain additives. The additives are not particularly limited, and examples include inorganic fine particles, organic fine particles, or mixtures of these. Examples of additives include ultraviolet absorbers, metal oxides such as silica and alumina, and inorganic fillers such as polyorganosiloxanes. By including the inorganic filler, the adhesion with the water-repellent layer (r) passing through the layer (c) can be improved. The thickness of the hard coat layer is, for example, 1 μm to 100 μm.

Regarding the laminate of the present invention, as long as the water-repellent layer (r), layer (c), and resin base material layer (s) are arranged in this order, they may also be placed between the water-repellent layer (r) and layer (c). Between the layer (c) and the resin substrate layer (s), the surface layer of the layer (s) includes other layers, but it is preferable that no other layer exists between the layer (r) and the layer (c) . In addition, when the resin base material layer (s) is a hard coat layer, it is preferable that no other layer exists between the resin base material layer (s) and the layer (c). The laminate of the present invention preferably further includes a resin layer (s2) different from the resin base layer (s), and it is assumed that the water repellent layer (r), the layer (c), and the resin base are in order from the surface of the laminate. The order of material layer (s) and resin layer (s2) is sufficient.

Especially when the resin base material layer (s) is a hard coat layer, it is preferable to laminate|stack a resin layer (s2) different from the resin base material layer (s) which is a hard coat layer. The resin layer (s2) laminated with the resin substrate layer (s) as a hard coat layer may be in the form of a film or a plate, and as long as it can transmit light, it is suitable as a display member such as a display. A laminate including a resin substrate layer (s) and a resin layer (s2) as a hard coat layer can be used as a front panel of an image display device for a flexible display.

As the resin constituting the resin layer (s2), for example, triacetyl cellulose, acetyl cellulose butyrate, ethylene-vinyl acetate copolymer, propylene cellulose, butyl cellulose, acetyl propylene Cellulose, polyester, polystyrene, polyamide, polyetherimide, poly(meth)acrylic acid, polyimide, polyether ash, poly ash, polyethylene, polypropylene, polymethylpentene , Polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether ether, polymethyl methacrylate, polyethylene terephthalate, poly Films formed by polymers such as butylene terephthalate, polyethylene naphthalate, polycarbonate, and polyamide imide. These polymers can be used alone or in combination of two or more. From the viewpoint of both strength and transparency such as bending resistance, a resin film formed of a polymer such as polyimide, polyimide, and polyimide is preferred. The thickness of the resin layer (s2) may be, for example, 10 μm or more and 500 μm or less, preferably 20 μm or more and 200 μm or less, more preferably 30 μm or more and 150 μm or less, and may be 100 μm or less.

The laminate having the resin layer (s2) is preferably used as a front panel in a flexible image display device, and the front panel is sometimes referred to as a window film. The flexible image display device includes a laminate for a flexible image display device and an organic electro-luminescence (EL) display panel, and is arranged on the visual confirmation side with respect to the organic EL display panel. The laminated body for an image display device is configured to be bendable. As a laminated body for a flexible image display device, it may further include a polarizing plate, preferably a circular polarizing plate, and a touch sensor. The order of these layers is arbitrary, but it is preferably in order from the visual confirmation side The laminate has a window film, a polarizing plate, a touch sensor or a window film, a touch sensor, and a polarizing plate. Compared with the touch sensor, if the polarizing plate exists on the visual confirmation side, it is difficult to visually confirm the pattern of the touch sensor, and the visual confirmation of the displayed image becomes better, which is preferable. Each member can be laminated using adhesives, adhesives, etc. In addition, it may be provided with a light-shielding pattern formed on at least one surface of any layer of the window film, polarizer, and touch sensor.

A primer layer may also be provided between the resin layer (s2) and the resin substrate layer (s) (especially the hard coat layer). As the primer, for example, there are primers such as ultraviolet curing type, thermosetting type, or two-component curing type epoxy compound. Preferably, the compound mixed in the primer layer is chemically bonded with the resin component mixed in the resin layer (s2) or the silicon material mixed as necessary. Moreover, as a primer, polyamic acid can be used, and the adhesiveness of a resin layer (s2) and a resin base material layer (s) (especially hard-coat layer) can be improved. Furthermore, as a primer, a silane coupling agent can be mentioned, and it can also chemically bond with the silicon material mixed as needed in a resin base material by a condensation reaction. The thickness of the primer layer is, for example, 0.1 μm to 20 μm.

Regarding the laminate of the present invention, the water contact angle (initial contact angle) measured by the droplet method (analysis method: θ/2 method) with a liquid volume: 3 μL is, for example, 105° or more, more preferably 110° or more, and For example, it is 120° or less. In addition, after the chemical resistance test performed in the examples described later, the water contact angle (contact angle after the chemical resistance test) measured by the drop method (analysis method: θ/2 method) with a liquid volume: 3 μL For example, it is 82.0° or more, preferably 85° or more, more preferably 90° or more, and the upper limit is, for example, 110° or less, and may be 100° or less.

Next, the manufacturing method of the laminated body of this invention is demonstrated.

The method of manufacturing the laminate of the present invention includes (i) a step of forming a layer (c) on a resin base material layer (s), and (ii) a step of forming a water-repellent layer (r).

In the step of forming the layer (c), the resin substrate layer (s) is coated with an organic silicon compound (C1) and/or a mixed composition (cc) of an organic silicon compound (C2). The composition (cc) is preferably mixed with a solvent (E).

When the whole composition (cc) is 100% by mass, the total amount of the organosilicon compound (C1) and the organosilicon compound (C2) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, It is more preferably 0.1% by mass or more, more preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 2% by mass or less. The amount of the organosilicon compound (C1) and organosilicon compound (C2) can be adjusted when preparing the composition. The amount of the organosilicon compound (A) can also be calculated from the analysis result of the composition. In addition, when the range of the amount, mass ratio, or molar ratio of each component is described in this specification, the range can be adjusted at the time of preparation of a composition similarly to the above.

The solvent (E) preferably has an sp value [(cal/cm ³ ) ^1/2 ] of 9.00 or more, and more preferably an sp value of 10 or more, for example. As such a solvent (E), water, ethanol, isopropanol, etc. are mentioned, and the sp value is 15 or more, and water is the most preferable.

In this book, the sp value (Solubility Parameter, solubility parameter) is based on "RF Fedors, Polymer Engineering Science, 14[2], 147-154 (1974)"("RFFedors, Polym.Eng.Sci., 14[2], 147-154 (1974)"). In the Fedors method, the sp value is defined by the square root of the condensed energy density. Specifically, the sp value is defined by the following formula. δ=(ΔE/V) ^1/2 (1) In the formula (1), δ refers to the sp value ((cal/cm ³ ) ^1/2 ), ΔE refers to the condensation energy (cal/mol), V Refers to the molar molecular volume of the solvent (cm ³ /mol).

In the Fedors method, it is believed that the cohesion energy and the volume of the mole molecule are both dependent on the type and number of substituents contained in the solvent. Therefore, the calculation of the condensing energy is based on the condensing energy and molecular volume of each substituent (shown in Table 1 below), and also considering the number of substituents.

[Table 1] Substituent Condensed energy ΔE Mole molecular volume V cal/mol cm ³ /mol -CH ₃ 1125 33.5 -CH _2- 1180 16.1 -CH> 820 -1 >C> 350 -19.2 -CO- 4149 10.8 -COO- 4300 18 -O- 800 3.8 -OH 7120 10

For example, the isopropanol used as the solvent (E) in the examples described later is a solvent having two -CH ₃ , one -CH>, and one -OH. The aggregation energy ΔE of isopropanol is calculated as ΔE (cal/mol)=1125×2+820+7120. In addition, the molar molecular volume V of isopropanol is calculated as V (cm ³ /mol)=33.5×2+(-1)+10. Therefore, by using these values in the formula (1), the sp value of isopropanol can be calculated as 11.58 (cal/cm ³ ) ^1/2 .

Examples of methods for applying the composition (cc) include dip coating, roll coating, bar coating, spin coating, spray coating, die coating, and gravure coating. The spin coating method is particularly preferred.

Before coating the composition (cc), it is preferable to perform easy adhesion treatment on the resin substrate layer (s). As the easy bonding treatment, hydrophilization treatments such as corona treatment, plasma treatment, and ultraviolet treatment are exemplified, and plasma treatment is more preferable. By performing easy bonding treatments such as plasma treatment, OH groups (especially when the substrate is epoxy resin) or COOH groups (especially when the substrate is acrylic resin) can be formed on the surface of the substrate When the functional group is formed on the surface of the substrate, the adhesion between the layer (c) and the resin substrate layer (s) can be further improved.

After the layer (c) is formed, the mixed composition of the organosilicon compound (A) is coated and cured at room temperature, thereby forming the water-repellent layer (r).

The mixed composition of the organosilicon compound (A) is preferably mixed with the organosilicon compound (B), and usually a solvent (D) is mixed. As the solvent (D), a fluorine-based solvent is preferably used. For example, a fluorinated ether-based solvent, a fluorinated amine-based solvent, a fluorinated hydrocarbon-based solvent, etc. can be used, and the boiling point is more preferably 100°C or higher. The fluorinated ether-based solvent is preferably hydrofluoroether such as fluoroalkyl (especially perfluoroalkyl having 2 to 6 carbons)-alkyl (especially methyl or ethyl) ether, for example, ethyl Nonafluorobutyl ether or ethyl nonafluoroisobutyl ether. Examples of ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether include Novec (registered trademark) 7200 (manufactured by 3M Corporation, molecular weight approximately 264). The fluorinated amine-based solvent is preferably an amine in which at least one hydrogen atom of ammonia is substituted by a fluoroalkyl group, and preferably a tertiary amine in which all hydrogen atoms of ammonia are substituted by a fluoroalkyl group (especially a perfluoroalkyl group) Specifically, tris(heptafluoropropyl)amine can be cited, which corresponds to Fluorinert (registered trademark) FC-3283 (manufactured by 3M, molecular weight approximately 521). Examples of fluorinated hydrocarbon solvents include fluorinated aliphatic hydrocarbon solvents such as 1,1,1,3,3-heptafluorobutane, and fluorinated aromatic hydrocarbons such as 1,3-bis(trifluoromethylbenzene). Department solvent. As 1,1,1,3,3-heptafluorobutane, for example, Soluble 55 (manufactured by Solvent) and the like can be cited.

As the fluorine-based solvent, in addition to the above, hydrochlorofluorocarbons such as asahiklin (registered trademark) AK225 (manufactured by AGC), asahiklin (registered trademark) AC2000 (AGC) can be used Company manufacture) and other HFCs.

As the solvent (D), it is preferable to use at least a fluorinated amine-based solvent. In addition, as the solvent (D), it is preferable to use two or more fluorine-based solvents, and it is preferable to use a fluorinated amine-based solvent and a fluorinated hydrocarbon-based solvent (especially a fluorinated aliphatic hydrocarbon-based solvent).

In addition, the composition (ca) for forming the water-repellent layer (r) may be mixed with a silanol condensation catalyst, antioxidant, rust inhibitor, ultraviolet absorber, and light stabilizer within a range that does not hinder the effects of the present invention. , Antifungal agents, antibacterial agents, biological adhesion inhibitors, deodorants, pigments, flame retardants, antistatic agents and other additives.

The composition (ca) for forming the water-repellent layer (r) is coated on the layer (c) and dried to form the water-repellent layer (r). Examples of methods for coating the composition for forming the water-repellent layer (r) include: dip coating, roll coating, bar coating, spin coating, spray coating, die coating, and gravure Printing and coating method, etc.

After coating the composition for forming the water-repellent layer (r) on the layer (c), it is allowed to stand in the atmosphere at room temperature, for example, for 1 hour or more, thereby forming the water-repellent layer (r). In the present invention, normal temperature refers to 5°C to 60°C, and it is preferable to form a film by standing still in the temperature range of 15°C to 40°C.

The amount of the organosilicon compound (A) in the composition (ca) for forming the water-repellent layer (r) is, for example, 0.01% by mass or more, preferably 0.05% by mass or more, relative to 100% by mass of the entire composition In addition, it is preferably 0.5% by mass or less, and more preferably 0.3% by mass or less.

When the organosilicon compound (B) is mixed in the composition (ca) for forming the water repellent layer (r), the amount of the organosilicon compound (B) when the entire composition is 100% by mass is, for example 0.01% by mass or more, preferably 0.03% by mass or more, more preferably 0.3% by mass or less, and more preferably 0.2% by mass or less.

The mass ratio of the organosilicon compound (B) with respect to the organosilicon compound (A) is preferably 0.2 or more, more preferably 0.4 or more, more preferably 3 or less, and more preferably 1.5 or less. [Example]

Hereinafter, examples are given to explain the present invention more specifically. The present invention is not limited by the following embodiments, and of course it can also be implemented with appropriate changes within a range that can be adapted to the gist described later, and these are all included in the technical scope of the present invention.

[Example 1] 0.125% by mass of KBP90 (manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following formula (c) as the organosilicon compound (C1) and 99.875% by mass as the solvent (E) of ion-exchanged water were mixed with stirring at room temperature The resulting solution is a solution for forming layer (c). Use the OPTICOAT MS-A100 (spin coater) manufactured by MIKASA Co., Ltd. to apply the obtained solution to the surface to be coated with an atmospheric pressure slurry device (manufactured by Fuji Machinery Manufacturing Co., Ltd.) On the resin substrate layer (s) (alicyclic urethane acrylate) of the activated acrylic hard coat layer, the amount of coating liquid is 200 μl, the rotation speed is 2000 rpm, and the rotation second Coating was performed under conditions of several 20 seconds to obtain layer (c).

[化18]

Next, a compound represented by the following formula (1) as the organosilicon compound (A) (hereinafter, compound a), and FAS13E (C ₆ F ₁₃ -C ₂ H ₄ -Si) as the organosilicon compound (B) are prepared (OC ₂ H ₅ ) ₃ , Tokyo Chemical Industry Co., Ltd.), as a solvent (D) FC-3283 (C ₉ F ₂₁ N, Fluorinert (Fluorinert), 3M company manufacturing) mixed solution, The mixture was stirred for a predetermined time at room temperature to obtain a solution for forming a water-repellent layer (r). When the entire water-repellent layer (r) forming solution is 100% by mass, the ratio of the organosilicon compound (A) is 0.085% by mass, and the ratio of the organosilicon compound (B) is 0.05% by mass. A spray coater manufactured by Apeiros Co., Ltd. was used to apply the solution for forming the water-repellent layer (r) onto the layer (c) and let it stand at room temperature for 12 hours to obtain a resin substrate in turn. Layer (s), layer (c), water repellent layer (r) layered body. The conditions of spray coating are scanning speed: 600 mm/sec, pitch: 5 mm, liquid volume: 6 cc/min, atomizing air: 350 kPa, gap: 70 mm.

[化19]

The compound a represented by the formula (1) is synthesized by the method described in Synthesis Example 1 and Synthesis Example 2 of JP 2014-15609 A, r is 43, and s is an integer of 1 to 6. The number average molecular weight is about 8,000.

[Example 2 to Example 7] Except that the amount of KBP90 as the organosilicon compound (C1) and/or the type of solvent (E) are as described in Table 2-1, a laminate was obtained in the same manner as in Example 1.

[Example 8 to Example 9] Except that KBP64 (manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following formula (c') is used as the organosilicon compound (C1), and the amount and/or the type of solvent (E) are set as shown in Table 2-1 Except as described in the above, a laminate was obtained in the same manner as in Example 1.

[化20]

[Comparative Example 1] Except that KBM903 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-aminopropyltriethoxysilane) was used instead of the organosilicon compound (C1), and methyl ethyl ketone was used as the solvent (E), the same as in Example 2. In the same way, a laminate is obtained.

[Comparative Example 2] Except that KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-propenoxypropyltrimethoxysilane) is used instead of the organosilicon compound (C1), and methyl ethyl ketone is used as the solvent (E), the same as the examples 2 In the same manner, a laminate is obtained.

The following measurements were performed on the films obtained in the above-mentioned Examples and Comparative Examples.

(1) Measurement of water contact angle (initial contact angle) 3 μL of water droplets were dropped on the obtained film, and the contact angle of water was measured by the droplet method (analysis method: θ/2 method) using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., DM700).

(2) Measurement of water contact angle after chemical resistance test To the obtained film, a scratching device with a rubber made by Minoan was used, and a load of 1000 g was applied with the rubber in contact with the film. Approximately 2.5 ml of ethanol was added dropwise to the rubber, and the rubber was moved back and forth on the film at a speed of 40 r/min (40 times a minute) to conduct a chemical resistance test. The contact angle of water after the rubber reciprocated 3000 times on the film was measured.

The results are shown in Table 2-1 and Table 2-2.

[table 2-1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Layer (r) Organosilicon compound (A) Compound (a) Compound (a) Compound (a) Compound (a) Compound (a) Compound (a) Compound (a) Compound (a) Compound (a) 0.085% 0.085% 0.085% 0.085% 0.085% 0.085% 0.085% 0.085% 0.085% Organosilicon compound (B) FAS13E FAS13E FAS13E FAS13E FAS13E FAS13E FAS13E FAS13E FAS13E 0.05% 0.05% 0.05% 0.05% 0.05% 0.05% 0.05% 0.05% 0.05% Solvent (D) FC3283 FC3283 FC3283 FC3283 FC3283 FC3283 FC3283 FC3283 FC3283 Layer (c) Organosilicon compound (C) KBP90 KBP90 KBP90 KBP90 KBP90 KBP90 KBP90 KBP64 KBP64 0.125% 0.25% 0.50% 0.75% 1.00% 0.25% 0.25% 0.25% 0.25% Solvent (E) species Ion exchange water Ion exchange water Ion exchange water Ion exchange water Ion exchange water IPA Ethanol Ion exchange water IPA sp value* 26.68 26.68 26.68 26.68 26.68 11.58 12.58 26.68 11.58 Initial contact angle (°) 114 114 114 114 114 114 114 114 114 Contact angle after chemical resistance test (°) 108.2 113 109.1 91.8 91.6 94.4 92.2 106.3 95.1 *The unit of sp value is (cal/cm ³ ) ^1/2

[Table 2-2] Comparative example 1 Comparative example 2 Layer (r) Organosilicon compound (A) Compound (a) Compound (a) 0.085% 0.085% Organosilicon compound (B) FAS13E FAS13E 0.05% 0.05% Solvent (D) FC3283 FC3283 Layer (c) Organosilicon compound (C) KBM903 KBM5103 0.25% 0.25% Solvent (E) species Methyl ethyl ketone Methyl ethyl ketone sp value* 8.98 8.98 Initial contact angle (°) 113 114 Contact angle after chemical resistance test (°) 28.5 20.2 *The unit of sp value is (cal/cm ³ ) ^1/2

According to Table 2-1 and Table 2-2, in Examples 1 to 7 where the layer (c) is formed by the mixed composition of the specific organosilicon compound (C) of the present invention, the water-repellent layer cured at room temperature ( r) The water contact angle after the chemical resistance test was 82.0° or more (especially 90° or more), which was good. In contrast, instead of the organosilicon compound (C) of the present invention, an organosilicon compound ( C) In Comparative Examples 1 to 2 of different organosilicon compounds, the water contact angle after the chemical resistance test decreased. [Industrial availability]

The laminate of the present invention can be used in display devices such as touch panel displays, optical elements, semiconductor elements, building materials, nanoimprint technology, solar cells, metal products such as window glass of automobiles or buildings, cooking utensils, and ceramic products such as tableware. , Plastic automobile parts, etc. are preferably formed into films, which is useful in industry. In addition, it can also be preferably used for articles, goggles, glasses, etc. around each member of the kitchen, bathroom, washstand, mirror, and toilet.

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Claims (7)

A laminate in which a water-repellent layer (r) and a resin substrate layer (s) are laminated via a layer (c), the layer (c) is formed of a mixed composition (cc), the mixed composition (Cc) is an organosilicon compound (C1) represented by the following formula (c11), and/or two or more of the organosilicon compounds (C1) having at least any one of the following X ¹ to X ⁴ A mixed composition of an organosilicon compound (C2) formed by condensation and bonding, wherein the water-repellent layer (r) is a mixed composition (ca) of an organosilicon compound (A) represented by the following formula (a1) ) And the resulting layer;

In the formula (c11), Z ¹ and Z ² are each independently a hydrolyzable group and a reactive functional group other than a hydroxyl group, and R ^x1 , R ^x2 , R ^x3 , and R ^x4 are each independently a hydrogen atom or a carbon number of 1. For the alkyl group of ~4, when there are multiple R ^x1s , the multiple R ^x1s may be different respectively. When there are multiple R ^x2s , the multiple R ^x2s may be different respectively. When there are multiple R ^x3s Below, a plurality of R ^x3 may be different, and when there are a plurality of R ^x4 , a plurality of R ^x4 may be different respectively, Rf ^x1 , Rf ^x2 , Rf ^x3 , Rf ^x4 are each independently one or more hydrogen atoms are substituted It is an alkyl group with 1 to 20 carbon atoms or a fluorine atom that is a fluorine atom. When there are a plurality of Rf ^x1 , the plurality of Rf ^x1 may be different, and when there are a plurality of Rf ^x2 , the plurality of Rf ^x2 may be different Different, when there are multiple Rf ^x3 , multiple Rf ^x3 can be different respectively, when there are multiple Rf ^x4 , multiple Rf ^x4 can be different respectively, Y is -NH-, -N(CH ₃ ) -Or -O-, when there are multiple Ys, the multiple Ys may be different, and X ¹ , X ² , X ³ , and X ⁴ are each independently -OR ^c (R ^c is a hydrogen atom, carbon number 1 ～4 alkyl group or amino group (C _1-3 alkyl group (C _1-3 alkoxysilyl group)), when there are multiple X ¹ , the multiple X ¹ may be different, and when there are multiple X ² under the circumstances, the plurality of X ² may be different from each other, in the case where there are a plurality of X ^3, a plurality of X ³ may be different from each other, in the case where there is a plurality of X ^4, X ⁴ may be different from each other plurality, as P11 An integer of 0-20, p12, p13, and p14 are each independently an integer of 0-10, p15 is an integer of 0-5, p16 is an integer of 1-10, p17 is 0 or 1, the organosilicon compound (C1 The ends of) are Z ¹ -and Z ² -. As long as -O- is not connected to -O-, there are p11 -{C(R ^x1 )(R ^x2 )}-, p12 -{C(Rf ^x1 ) (Rf ^x2 ))-, p13-(Si(R ^x3 )(R ^x4 ))-, p14-(Si(Rf ^x3 )(Rf ^x4 ))-, p15-Y-, p16-(Si (X ¹ )(X ² )-O}-, p17-{Si(X ³ )(X ⁴ )}- are arranged and bonded in any order;

In the formula (a1), Rf ^a1 is a divalent perfluoropolyether structure with oxygen atoms at both ends, and R ¹¹ , R ¹² and R ¹³ are each independently an alkyl group having 1 to 20 carbons, and there are multiple in the case of R ^11, a plurality of R ¹¹ may be different from each other, in a case where a plurality of R ^12, R ¹² may be each a plurality of different, in a case where a plurality of R ^13, R ¹³ s may be different from each other, E ¹ , E ² , E ³ , E ^4, and E ⁵ are each independently a hydrogen atom or a fluorine atom. When there are multiple E ¹ , the multiple E ¹ may be different, and when there are multiple E ² Below, multiple E ² can be different respectively, when there are multiple E ³ , multiple E ³ can be different respectively, when there are multiple E ⁴ , multiple E ⁴ can be different, G ¹ and G ² are each independently a divalent to 10-valent organosiloxane group having a siloxane bond, and J ¹ , J ² and J ³ are each independently a hydrolyzable group or -(CH ₂ ) _e6 -Si(OR ¹⁴ ) ₃ , e6 is 1 to 5, R ¹⁴ is a methyl group or an ethyl group, when there are multiple J ¹ , the multiple J ¹ may be different, and when there are multiple J ² , multiple J ² They may be different. When there are multiple J ^3s , the multiple J ^3s may be different. L ¹ and L ² are each independently ² with 1 to 12 carbon atoms, which may contain an oxygen atom, a nitrogen atom, or a fluorine atom. For the valence linking group, when there are multiple L ^1s , the multiple L ^1s may be different, and if there are multiple L ^2s , the multiple L ^2s may be different, d11 is 1-9, and d12 is 0- 9, a10 and a14 are independently 0-10, a11 and a15 are 0 or 1, a12 and a16 are 0-9, a13 are 0 or 1, a21, a22, and a23 are independently 0 to 2, e1, e2, and e3 are independently 1 to 3, respectively. The layered product according to claim 1, wherein the organosilicon compound (C2) has two or more structures (c21-1) represented by the following formula (c21-1), and the structure (c21- 1) Compounds that are bonded to each other in a chain or cyclic form by the following *3 or *4, and the bonding by the following *3 or *4 is based on two or more of the aforementioned organosilicon compounds (C1) The condensation of X ¹ or X ² in the following formula (c21-1) *1 and *2 are respectively bonded to the following formula (c21-2) with p11, p12, p13, p14, p15, At least one of the units enclosed in (p16)-1 and p17 is bonded in an arbitrary order and the terminal is a group of Z-, and among each of the plurality of structures (c21-1), they are bonded to *1 and *2 The groups of can be different. When multiple of the structures (c21-1) are bonded in a chain shape, the terminal *3 is a hydrogen atom, and *4 is a hydroxyl group;

In the formula (c21-2), Z is a hydrolyzable group and a reactive functional group other than a hydroxyl group, R ^x1 , R ^x2 , R ^x3 , R ^x4 , Rf ^x1 , Rf ^x2 , Rf ^x3 , Rf ^x4 , Y, X ¹ , X ² , X ³ , X ⁴ , p11 to p17 have the same meaning as the symbols in the formula (c11). The laminate according to claim 1 or claim 2, wherein the composition (ca) is mixed with an organosilicon compound (B) represented by the following formula (b1);

In the formula (b1), Rf ^b10 is a C 1-20 alkyl group or fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms, and R ^b11 , R ^b12 , R ^b13 and R ^b14 are each independently hydrogen Alkyl group having 1 to 4 atoms or carbon number, when there are multiple R ^b11 , the multiple R ^b11 may be different respectively, and when there are multiple R ^b12 , the multiple R ^b12 may be different respectively. a case where R ^b13 and R ^b13 may be respectively a plurality of different, in a case where there are plural R ^b14 and R ^b14 may be respectively a plurality of ^{different, Rf b11, Rf b12, Rf} b13 and Rf ^b14 each independently represent a more The hydrogen atom of is replaced with a fluorine atom, a C 1-20 alkyl group or a fluorine atom. When there are multiple Rf ^b11 , the multiple Rf ^b11 may be different. When there are multiple Rf ^b12 , more Each Rf ^b12 can be different. When there are multiple Rf ^b13 , the multiple Rf ^b13 can be different. When there are multiple Rf ^b14 , the multiple Rf ^b14 can be different. R ^b15 is a carbon number of 1~ The alkyl group of 20, when there are multiple R ^b15 , multiple R ^b15 can be different respectively, A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR -, -NRC(=O)- or -C(=O)NR-, said R is a hydrogen atom, a C1-C4 alkyl group or a C1-C4 fluoroalkyl group, when there are more than one in the case of a ^1, a plurality of a ¹ may be different from each other, a ² is a hydrolyzable group, in the case where there are a plurality of a ^2, a ² may be different from each other plurality, b11, b12, b13, b14 and b15 are each independently Ground is an integer from 0 to 100, c is an integer from 1 to 3, about Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c , b11 -{C(R ^b11 )(R ^b12 )} -, b12-{C(Rf ^b11 )(Rf ^b12 )}-, b13-{Si(R ^b13 )(R ^b14 )}-, b14-{Si(Rf ^b13 )(Rf ^b14 )}-, b15 -A ¹ -, as long as Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c are the ends, no perfluoropolyether structure is formed, and -O- and -O- or -F are not connected , You can arrange the bonds in any order. The laminate according to any one of claims 1 to 3, wherein the composition (cc) is mixed with at least the organosilicon compound (C1). The laminate according to any one of claims 1 to 4, wherein the resin substrate layer (s) is a hard coat layer. A method for manufacturing a laminate, which is the method for manufacturing a laminate according to any one of claims 1 to 5, comprising: The step of coating the composition (cc) on the resin substrate layer (s) to form a layer (c); and The step of coating the composition (ca) on the layer (c) and hardening at room temperature to form the water-repellent layer (r). The method for manufacturing a laminate according to claim 6, wherein in the step of forming the layer (c), the resin substrate layer (s) is subjected to plasma treatment, and the plasma treatment surface is coated The composition (cc).