TW202136051A - Multilayer body and flexible display device - Google Patents

Abstract

A multilayer body which is sequentially provided with a base material (s), an intermediate layer (c) and a water repellent layer (r) in this order, and which is characterized by satisfying the requirements (1) and (2) described below. (1) The reflectance, which is obtained by subtracting the front surface reflection loss and the back surface reflection loss from the reflectance that is calculated, with a 2-degree field of view (C light source) of JIS Z8701, from the spectral reflectance at the wavelength of 530 nm as measured on the water repellent layer (r)-side surface at the incident angle of 12 DEG and at the reflection angle of 12 DEG, is 4.5% or less. (2) The thickness of the multilayer body is 500 [mu]m or less.

Description

Laminated body and flexible display device

The present invention relates to a laminated body and a flexible display device.

The fluorine-based water-repellent film represented by a film formed from a composition containing a compound having a perfluoropolyether structure is used in display devices such as touch panel displays, optical elements, semiconductor elements, etc. because of its very small surface free energy. It is used as anti-fouling coating, or water and oil repellent coating in various fields such as building materials, automobile or building window glass.

The water-repellent film is usually formed on a substrate and used. When the composition for forming a water-repellent film is applied to the substrate, there are cases where another layer such as an undercoat layer is formed on the substrate in advance, and then applied thereafter. The above composition is applied to form an antifouling coating or a water and oil repellent coating.

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 side of a substrate. The surface layer (Z) has a water contact angle of 110° or more. It is also stated that in order to form the above-mentioned 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 Technical Literature] [Patent Literature]

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

[The problem to be solved by the invention]

For a laminate having a water-repellent layer on a base material, in order to maintain good water repellency, abrasion resistance is required when evaluating from the side of the water-repellent layer exposed on the surface side. Therefore, the object of the present invention is to provide a laminate in which a substrate, an intermediate layer, and a water-repellent layer are laminated in this order, and even if it is a film, it has excellent wear resistance. [Technical means to solve the problem]

上述式(a1)中， Rf^a1 為兩端為氧原子之2價全氟聚醚結構， R¹¹ 、R¹² 、及R¹³ 分別獨立地為碳數1～20之烷基，於存在複數個R¹¹ 之情形時，複數個R¹¹ 可各不相同，於存在複數個R¹² 之情形時，複數個R¹² 可各不相同，於存在複數個R¹³ 之情形時，複數個R¹³ 可各不相同， E¹ 、E² 、E³ 、E⁴ 、及E⁵ 分別獨立地為氫原子或氟原子，於存在複數個E¹ 之情形時，複數個E¹ 可各不相同，於存在複數個E² 之情形時，複數個E² 可各不相同，於存在複數個E³ 之情形時，複數個E³ 可各不相同，於存在複數個E⁴ 之情形時，複數個E⁴ 可各不相同，於存在複數個E⁵ 之情形時，複數個E⁵ 可各不相同， G¹ 及G² 分別獨立地為具有矽氧烷鍵之2～10價有機矽氧烷基， 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，於存在複數個J¹ 之情形時，複數個J¹ 可各不相同，於存在複數個J² 之情形時，複數個J² 可各不相同，於存在複數個J³ 之情形時，複數個J³ 可各不相同， L¹ 及L² 分別獨立地為可包含氧原子、氮原子、或氟原子之碳數1～12之2價連結基，於存在複數個L¹ 之情形時，複數個L¹ 可各不相同，於存在複數個L² 之情形時，複數個L² 可各不相同， 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。 [化2]

上述式(b1)中， Rf^b10 為1個以上氫原子被取代為氟原子之碳數1～20之烷基或氟原子， R^b11 、R^b12 、R^b13 及R^b14 分別獨立地為氫原子或碳數為1～4之烷基，於存在複數個R^b11 之情形時，複數個R^b11 可各不相同，於存在複數個R^b12 之情形時，複數個R^b12 可各不相同，於存在複數個R^b13 之情形時，複數個R^b13 可各不相同，於存在複數個R^b14 之情形時，複數個R^b14 可各不相同， Rf^b11 、Rf^b12 、Rf^b13 及Rf^b14 分別獨立地為1個以上氫原子被取代為氟原子之碳數1～20之烷基或氟原子，於存在複數個Rf^b11 之情形時，複數個Rf^b11 可各不相同，於存在複數個Rf^b12 之情形時，複數個Rf^b12 可各不相同，於存在複數個Rf^b13 之情形時，複數個Rf^b13 可各不相同，於存在複數個Rf^b14 之情形時，複數個Rf^b14 可各不相同， R^b15 為碳數為1～20之烷基，於存在複數個R^b15 之情形時，複數個R^b15 可各不相同， A¹ 為-O-、-C(=O)-O-、-O-C(=O)-、-NR-、-NRC(=O)-、或-C(=O)NR-，上述R為氫原子、碳數1～4之烷基或碳數1～4之含氟烷基，於存在複數個A¹ 之情形時，複數個A¹ 可各不相同， A² 為水解性基，於存在複數個A² 之情形時，複數個A² 可各不相同， b11、b12、b13、b14及b15分別獨立地為0～100之整數， c為1～3之整數， 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 成為末端，不形成全氟聚醚結構，且-O-不與-O-或-F連結，則以任意順序排列而鍵結。 [6]如[1]至[5]中任一項記載之積層體，其中上述中間層(c)為下述式(c1)～(c3)之任一者所表示之有機矽化合物(C)之混合組合物(cc)之硬化層或上述有機矽化合物(C)之蒸鍍層。 [化3]

上述式(c1)中， R^x11 、R^x12 、R^x13 、R^x14 分別獨立地為氫原子或碳數為1～4之烷基，於存在複數個R^x11 之情形時，複數個R^x11 可各不相同，於存在複數個R^x12 之情形時，複數個R^x12 可各不相同，於存在複數個R^x13 之情形時，複數個R^x13 可各不相同，於存在複數個R^x14 之情形時，複數個R^x14 可各不相同， Rf^x11 、Rf^x12 、Rf^x13 、Rf^x14 分別獨立地為1個以上氫原子被取代為氟原子之碳數1～20之烷基或氟原子，於存在複數個Rf^x11 之情形時，複數個Rf^x11 可各不相同，於存在複數個Rf^x12 之情形時，複數個Rf^x12 可各不相同，於存在複數個Rf^x13 之情形時，複數個Rf^x13 可各不相同，於存在複數個Rf^x14 之情形時，複數個Rf^x14 可各不相同， R^x15 為碳數為1～20之烷基，於存在複數個R^x15 之情形時，複數個R^x15 可各不相同， X¹¹ 為水解性基，於存在複數個X¹¹ 之情形時，複數個X¹¹ 可各不相同， Y¹¹ 為-NH-、或-S-，於存在複數個Y¹¹ 之情形時，複數個Y¹¹ 可各不相同， Z¹¹ 為乙烯基、α-甲基乙烯基、苯乙烯基、甲基丙烯醯基、丙烯醯基、胺基、異氰酸基、異氰尿酸基、環氧基、脲基、或巰基， p1為1～20之整數，p2、p3、p4分別獨立地為0～10之整數，p5為1～10之整數， p6為1～3之整數， 於Z¹¹ 不為胺基之情形時，Y¹¹ 之至少1者為-NH-，於Y¹¹ 全部為-S-之情形時，Z¹¹ 為胺基， 關於Z¹¹ -、-Si(X¹¹ )_p6 (R^x15 )_3-p6 、p1個-{C(R^x11 )(R^x12 )}-、p2個-{C(Rf^x11 )(Rf^x12 )}-、p3個-{Si(R^x13 )(R^x14 )}-、p4個-{Si(Rf^x13 )(Rf^x14 )}-、p5個-Y¹¹ -，只要Z¹¹ -及-Si(X¹¹ )_p6 (R^x15 )_3-p6 成為末端，-O-不與-O-連結，則以任意順序排列而鍵結。 [化4]

上述式(c2)中， R^x20 及R^x21 分別獨立地為氫原子或碳數為1～4之烷基，於存在複數個R^x20 之情形時，複數個R^x20 可各不相同，於存在複數個R^x21 之情形時，複數個R^x21 可各不相同，Rf^x20 及Rf^x21 分別獨立地為1個以上氫原子被取代為氟原子之碳數1～20之烷基或氟原子，於存在複數個Rf^x20 之情形時，複數個Rf^x20 可各不相同，於存在複數個Rf^x21 之情形時，複數個Rf^x21 可各不相同， R^x22 及R^x23 分別獨立地為碳數為1～20之烷基，於存在複數個R^x22 及R^x23 之情形時，複數個R^x22 及R^x23 可各不相同， X²⁰ 及X²¹ 分別獨立地為水解性基，於存在複數個X²⁰ 及X²¹ 之情形時，複數個X²⁰ 及X²¹ 可各不相同， p20分別獨立地為1～30之整數，p21分別獨立地為0～30之整數，附p20或p21並且用括號括起來之重複單元之至少1者被取代為胺骨架-NR¹⁰⁰ -，上述胺骨架中之R¹⁰⁰ 為氫原子或烷基， p22及p23分別獨立地為1～3之整數， p20個-{C(R^x20 )(R^x21 )}-、p21個-{C(Rf^x20 )(Rf^x21 )}-無需p20個或p21個連續，以任意順序排列而鍵結，兩末端成為-Si(X²⁰ )_p22 (R^x22 )_3-p22 及-Si(X²¹ )_p23 (R^x23 )_3-p23 。 [化5]

上述式(c3)中， Z³¹ 、Z³² 分別獨立地為除水解性基及羥基以外之反應性官能基， R^x31 、R^x32 、R^x33 、R^x34 分別獨立地為氫原子或碳數為1～4之烷基，於存在複數個R^x31 之情形時，複數個R^x31 可各不相同，於存在複數個R^x32 之情形時，複數個R^x32 可各不相同，於存在複數個R^x33 之情形時，複數個R^x33 可各不相同，於存在複數個R^x34 之情形時，複數個R^x34 可各不相同， Rf^x31 、Rf^x32 、Rf^x33 、Rf^x34 分別獨立地為1個以上氫原子被取代為氟原子之碳數1～20之烷基或氟原子，於存在複數個Rf^x31 之情形時，複數個Rf^x31 可各不相同，於存在複數個Rf^x32 之情形時，複數個Rf^x32 可各不相同，於存在複數個Rf^x33 之情形時，複數個Rf^x33 可各不相同，於存在複數個Rf^x34 之情形時，複數個Rf^x34 可各不相同， Y³¹ 為-NH-、-N(CH₃ )-或-O-，於存在複數個Y³¹ 之情形時，複數個Y³¹ 可各不相同， X³¹ 、X³² 、X³³ 、X³⁴ 分別獨立地為-OR^c (R^c 為氫原子、碳數1～4之烷基、或胺基C_1-3 烷基二C_1-3 烷氧基矽烷基)，於存在複數個X³¹ 之情形時，複數個X³¹ 可各不相同，於存在複數個X³² 之情形時，複數個X³² 可各不相同，於存在複數個X³³ 之情形時，複數個X³³ 可各不相同，於存在複數個X³⁴ 之情形時，複數個X³⁴ 可各不相同， p31為0～20之整數，p32、p33、p34分別獨立地為0～10之整數，p35為0～5之整數，p36為1～10之整數，p37為0或1， 只要滿足Z³¹ 及Z³² 之至少一者為胺基、或Y³¹ 之至少一者為-NH-或-N(CH₃ )-之條件，且末端為Z³¹ -及Z³² -，-O-不與-O-連結，則p31個-{C(R^x31 )(R^x32 )}-、p32個-{C(Rf^x31 )(Rf^x32 )}-、p33個-{Si(R^x33 )(R^x34 )}-、p34個-{Si(Rf^x33 )(Rf^x34 )}-、p35個-Y³¹ -、p36個-{Si(X³¹ )(X³² )-O}-、p37個-{Si(X³³ )(X³⁴ )}-以任意順序排列鍵結而構成。 [7]一種可撓性顯示裝置，其包含如[1]至[6]中任一項記載之積層體、偏光板、觸控感測器、及顯示面板。 [發明之效果]The inventors of the present invention found that by adjusting the reflective properties of the surface of the laminate, even though it is a thin film, good abrasion resistance can still be achieved. Specifically, the present invention for achieving the above-mentioned problems is as follows. [1] A laminated body characterized in that it is provided with a substrate (s), an intermediate layer (c), and a water-repellent layer (r) in this order, and satisfies the following requirements (1) and (2) . (1) Calculate the spectral reflectance at a wavelength of 530 nm at an incident angle of 12° and a reflection angle of 12° measured on the surface of the water-repellent layer (r) with a 2° field of view (light source C) of JIS Z8701. The reflectance obtained by subtracting the surface reflection loss and the back surface reflection loss is less than 4.5%. (2) The thickness of the above-mentioned laminate is 500 μm or less. [2] The laminate as described in [1], which further satisfies the following requirement (3). (3) The surface fluorine element ratio on the side of the water-repellent layer (r) is 30 atomic% or more. [3] The laminate as described in [1] or [2], which further satisfies at least one of the following requirements (4) and (5). (4) The arithmetic average height Sa on the side of the water-repellent layer (r) is 0.03 to 1.00 μm. (5) The sliding angle of the water on the side of the water-repellent layer (r) is 25° or less. [4] The laminate according to any one of [1] to [3], wherein the surface Si ratio of the outermost layer on the side of the intermediate layer (c) of the substrate (s) is 1 atomic% or more. [5] The laminate according to any one of [1] to [4], wherein the water-repellent layer (r) is an organosilicon compound (A) represented by the following formula (a1) and the following formula (b1) The hardened layer of the mixed composition (ca) of the organosilicon compound (B) represented by ). [化1]

In the above 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 with 1 to 20 carbon atoms, and there are plural when the case of R ^11, the plurality of R ¹¹ may vary when in the presence of the case of a plurality of R ¹² s, the plurality of R ¹² may be different when in the presence of the case of a plurality of R ^13, the plurality of R ¹³ may each Not the same, E ¹ , E ² , E ³ , E ⁴ , and E ⁵ are each independently a hydrogen atom or a fluorine atom. When there are plural E ^{1 s} , the plural E ¹ may be different from each other. when two E scenario ^2, the plurality of E ² may be different when in the presence of a plurality of case E ^3, the plurality of E ³ may be varied, while in the case of ⁴ the presence of a plurality of E, a plurality of E ⁴ may be Each is different. When there are a plurality of E ⁵ , the plurality of E ⁵ can be different. G ¹ and G ² are independently a 2-10 valent organosiloxane alkyl group with a siloxane bond, 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, and there are multiple J ¹ In this case, the plural J ¹ may be different from each other. When there are plural J ^2s , the plural J ² may be different from each other. When there are plural J ³ , the plural J ³ may be different from each other. , L ¹ and L ² are each independently a divalent linking group with 1 to 12 carbon atoms that may contain an oxygen atom, a nitrogen atom, or a fluorine atom. When there are plural L ^1s , the plural L ^1s may be different Same, when there are a plurality of L ^2s , the plurality of L ^2s can be different, d11 is 1-9, d12 is 0-9, a10 and a14 are independently 0-10, and a11 and a15 are independently It is 0 or 1, a12 and a16 are each 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. [化2]

In the above 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 a hydrogen atom Or an alkyl group with 1 to 4 carbon atoms. When there are plural R ^b11 , the plural R ^b11 may be different from each other. When there are plural R ^b12 , the plural R ^b12 may be different from each other. When there are a plurality of R ^b13 , the plurality of R ^b13 can be different, when there are a plurality of R ^b14 , the plurality of R ^b14 can be different, Rf ^b11 , Rf ^b12 , Rf ^b13 and Rf ^b14 are independent respectively Ground is a C1-C20 alkyl group or fluorine atom where one or more hydrogen atoms are substituted with fluorine atoms. When there are more than one Rf ^b11 , the plurality of Rf ^b11 may be different. When there are more than one Rf ^b12 In this case, the plurality of Rf ^b12 can be different. When there are a plurality of Rf ^b13 , the plurality of Rf ^b13 can be different. When there are a plurality of Rf ^b14 , the plurality of Rf ^b14 can be different. , R ^b15 is an alkyl group with 1 to 20 carbons. When there are plural R ^b15 , the plural R ^b15 can be different. A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, the above R is a hydrogen atom, an alkyl group with 1 to 4 carbons or a carbon number of 1 to 4 For the fluorine-containing alkyl group, when there are multiple A ¹ , the multiple A ¹ can be different, and A ² is a hydrolyzable group. When there are multiple A ^2s , the multiple A ² can be different , B11, b12, b13, b14, and b15 are each independently an integer from 0 to 100, c is an integer from 1 to 3, regarding Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c , b11 -{C(R ^b11 )(R ^b12 )}-、b12pcs-{C(Rf ^b11 )(Rf ^b12 )}-、b13pcs-{Si(R ^b13 )(R ^b14 )}-、b14pcs-{ Si(Rf ^b13 )(Rf ^b14 )}-, b15 -A ¹ -, as long as Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c become the ends, do not form a perfluoropolyether structure, and -O- is not connected with -O- or -F, but is arranged and bonded in any order. [6] The laminate according to any one of [1] to [5], wherein the intermediate layer (c) is an organosilicon compound (C) represented by any one of the following formulas (c1) to (c3) ) The hardened layer of the mixed composition (cc) or the vapor-deposited layer of the above-mentioned organosilicon compound (C). [化3]

In the above formula (c1), R ^x11 , R ^x12 , R ^x13 , and R ^x14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When there are multiple R ^x11 , multiple R ^x11 may be Each is different. When there are multiple R ^x12 , the multiple R ^x12 can be different. When there are multiple R ^x13 , the multiple R ^x13 can be different. When there are multiple R ^x14 When, a plurality of R ^x14 may be different, Rf ^x11 , Rf ^x12 , Rf ^x13 , and Rf ^x14 are each independently an alkyl group with 1-20 carbon atoms or fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms. When there are a plurality of Rf ^x11 , the plurality of Rf ^x11 can be different, when there are a plurality of Rf ^x12 , the plurality of Rf ^x12 can be different from each other, when there are a plurality of Rf ^x13 , the plurality of Rf ^x13 can be different. When there are multiple Rf ^x14 , the multiple Rf ^x14 can be different. R ^x15 is an alkyl group with 1 to 20 carbon atoms. When there are multiple R ^x15 , multiple R ^x15 can be different from each other, X ¹¹ is a hydrolyzable group, when there are multiple X ¹¹ , the multiple X ¹¹ can be different from each other, Y ¹¹ is -NH- or -S-, when there are multiple Y ^In the case of 11, the plural Y ¹¹ can be different, and Z ¹¹ is a vinyl group, α-methyl vinyl group, styryl group, methacryl group, acryl group, amine group, isocyanate group, and isocyanate group. Cyanuric acid group, epoxy group, ureido group, or mercapto group, p1 is an integer of 1-20, p2, p3, and p4 are each independently an integer of 0-10, p5 is an integer of 1-10, and p6 is an integer of 1-3 When Z ^{11 is} not an amine group, at least one of ^{Y 11 is -NH-, and when all Y 11} is -S-, Z ¹¹ is an amine group. Regarding Z ¹¹ -, -Si (X ¹¹ ) _p6 (R ^x15 ) _3-p6 ^{, p1 pcs-} (C(R x11 )(R ^x12 ))-, p2 ^pcs- (C(Rf x11 )(Rf ^x12 ))-, p3 pcs-(Si (R ^x13 )(R ^x14 )}-, p4 -{Si(Rf ^x13 )(Rf ^x14 )}-, p5 -Y ¹¹ -, as long as Z ¹¹ -and -Si(X ¹¹ ) _p6 (R ^x15 ) _3-p6 becomes the terminal, and -O- is not connected with -O-, but is arranged in an arbitrary order and bonded. [化4]

In the formula (c2), R ^x20 and R ^x21 are each independently a hydrogen atom or an alkyl group having a carbon number of 1 to 4, when in the presence of a plurality of R ^x20 case, a plurality of R ^x20 may vary, the presence of when a plurality of R ^x21 case, a plurality of R ^x21 may vary, Rf ^x20 and Rf ^x21 each independently one or more hydrogen atoms are substituted with fluorine atoms to carbon atoms of the fluorine atom or an alkyl group of 1 to 20, in When there are a plurality of Rf ^x20 , the plurality of Rf ^x20 can be different, when there are a plurality of Rf ^x21 , the plurality of Rf ^x21 can be different from each other, and R ^x22 and R ^x23 are each independently with a carbon number of 1. The alkyl group of ~20, when there are multiple R ^x22 and R ^x23 , the multiple R ^x22 and R ^x23 can be different from each other, X ²⁰ and X ²¹ are each independently a hydrolyzable group, and there are multiple X ²⁰ and the case of X ²¹ when, a plurality of X ²⁰ and X ²¹ can vary, p20 each independently an integer of 1 to 30, the p21 each independently integers of 0 to 30, the attachment p20 or p21 and parentheses At least one of the repeating units is substituted with an amine skeleton -NR ^{100 -, R 100} in the above amine skeleton is a hydrogen atom or an alkyl group, p22 and p23 are each independently an integer of 1 to 3, and p20 -{C( R ^x20 )(R ^x21 )}-, p21-{C(Rf ^x20 )(Rf ^x21 )}-No need to p20 or p21 consecutive, arrange and bond in any order, both ends become -Si(X ²⁰ ) _p22 (R ^x22 ) _3-p22 and -Si(X ²¹ ) _p23 (R ^x23 ) _3-p23 . [化5]

In the above formula (c3), Z ³¹ and Z ³² are each independently a reactive functional group other than a hydrolyzable group and a hydroxyl group, and R ^x31 , R ^x32 , R ^x33 , and R ^x34 are each independently a hydrogen atom or a carbon number For the alkyl groups of 1 to 4, when there are multiple R ^x31 , the multiple R ^x31 can be different. When there are multiple R ^x32 , the multiple R ^x32 can be different. ^In the case of x33, the plurality of R ^x33 can be different. When there are a plurality of R ^x34 , the plurality of R ^x34 can be different. Rf ^x31 , Rf ^x32 , Rf ^x33 , and Rf ^x34 are each independently one The above hydrogen atoms are substituted with fluorine atoms and C1-C20 alkyl groups or fluorine atoms. When there are a plurality of Rf ^x31 , the plurality of Rf ^x31 may be different. When there are a plurality of Rf ^x32 , The plurality of Rf ^x32 can be different. When there are a plurality of Rf ^x33 , the plurality of Rf ^x33 can be different. When there is a plurality of Rf ^x34 , the plurality of Rf ^x34 can be different, and Y ³¹ is -NH-, -N(CH ₃ )- or -O-, when there are a plurality of Y ³¹ , the plurality of Y ³¹ can be different from each other, X ³¹ , X ³² , X ³³ , X ³⁴ 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 alkoxysilyl group), when there are a plurality of X ³¹ , The plurality of X ³¹ can be different. When there are a plurality of X ³² , the plurality of X ³² can be different. When there is a plurality of X ³³ , the plurality of X ³³ can be different. In the case of X ³⁴ , a plurality of X ³⁴ may be different, p31 is an integer from 0 to 20, p32, p33, and p34 are each independently an integer from 0 to 10, p35 is an integer from 0 to 5, and p36 is 1. An integer of ~10, p37 is 0 or 1, as long as ^{at least one of Z 31} and Z ³² is an amino group, or ^{at least one of Y 31} is -NH- or -N(CH ₃ )-, and the end Z ³¹ -and Z ³² -, -O- is not connected with -O-, then ^p31- {C(R x31 )(R ^x32 )}-, ^p32- {C(Rf x31 )(Rf ^x32 )} -, p33-{Si(R ^x33 )(R ^x34 ))-, p34-{Si(Rf ^x33 )(Rf ^x34 )}-, p35-Y ³¹ -, p36-{Si(X ³¹ ) (X ³² )-O}-, p37-{Si(X ³³ )(X ³⁴ )}- are formed by arranging the bonds in any order. [7] A flexible display device comprising the laminate described in any one of [1] to [6], a polarizing plate, a touch sensor, and a display panel. [Effects of Invention]

The laminate of the present invention, which has a base material (s), an intermediate layer (c), and a water-repellent layer (r) in this order, has the following necessary conditions: calculated by the 2 degree field of view (C light source) of JIS Z8701 Spectral reflectance at a wavelength of 530 nm at an incident angle of 12° and a reflection angle of 12° measured on the surface of the water layer, and the reflectance obtained by subtracting the surface reflection loss and the back surface reflection loss, the reflectance is less than 4.5% Therefore, it has excellent abrasion resistance, and it also has the necessary conditions for a thickness of 500 μm or less to achieve both abrasion resistance and film.

The laminated system of the present invention includes a substrate (s), an intermediate layer (c), and a water-repellent layer (r) in this order, and satisfies the following requirements (1) and (2). (1) Calculate the spectral reflectance at a wavelength of 530 nm at an incident angle of 12° and a reflection angle of 12° measured on the side surface of the water-repellent layer by using the 2° field of view of JIS Z8701 (light source C), and the resulting reflection The reflectance obtained by subtracting the surface reflection loss and the back surface reflection loss is less than 4.5%. (2) The thickness of the above-mentioned laminate is 500 μm or less.

By satisfying the above-mentioned requirement (1), good wear resistance can be achieved. In the requirement (1), the reflectance is preferably 4.3% or less, more preferably 3.5% or less, still more preferably 2.5% or less, and may be 0.5% or more.

In the requirement (2), the thickness of the laminate of the present invention is preferably 400 μm or less, more preferably 300 μm or less, still more preferably 200 μm or less, most preferably 100 μm or less, and may be 10 μm above. By setting the thickness of the above-mentioned laminate to a specific value or less, when the laminate of the present invention is used for a touch panel, the sensitivity is improved, and the visibility is improved.

Furthermore, the laminate of the present invention preferably satisfies the aforementioned requirements (1) and (2), and further satisfies at least one of the following requirements (3) to (5). It is particularly preferable that the above-mentioned necessary conditions (1) and (2) are satisfied and the following necessary condition (3) is satisfied, and it is more preferable that all the necessary conditions (1) to (5) are satisfied.

(3) The surface fluorine element ratio on the side of the water-repellent layer (r) is 30 atomic% or more. By satisfying the necessary conditions of (3) above, better water repellency can be achieved. The above-mentioned surface fluorine element ratio is more preferably 40 atomic% or more, and still more preferably 50 atomic% or more. The upper limit of the surface fluorine element ratio is not particularly limited, and is, for example, 80 atomic %. The above-mentioned surface fluorine element ratio can be measured by the method described in the following Examples.

(4) The arithmetic average height Sa on the side of the water-repellent layer (r) is 0.03 to 1.00 μm. By having the necessary conditions of (4) above, the wear resistance can be further improved. In addition, the requirement (4) above is also effective for achieving better water repellency and/or slippage. The surface height Sa on the water-repellent layer (r) side is more preferably 0.70 μm or less, still more preferably 0.50 μm or less, and more preferably 0.30 μm or less. In addition, the above-mentioned surface height Sa may be 0.04 μm or more, or may be 0.05 μm or more. Furthermore, the arithmetic average height Sa is calculated in accordance with ISO 25178.

(5) The sliding angle of the water on the side of the water-repellent layer (r) is 25° or less. Among the necessary conditions of the above (5), the sliding angle of water is more preferably 20° or less, still more preferably 15° or less, and more preferably 10° or less. The lower limit of the above-mentioned sliding angle of water is not particularly limited, and is, for example, 1°.

The water-repellent layer (r) is preferably a hardened layer of a mixed composition (ca) of an organosilicon compound (A) and an organosilicon compound (B).

I. Organosilicon compound (A) The aforementioned organosilicon compound (A) is a compound in which a monovalent group having a perfluoropolyether structure is bonded to a silicon atom, and a hydrolyzable group is bonded to the silicon atom via a linking group or not. The water-repellent layer (r) is preferably obtained by applying and curing the composition (ca), and has a structure derived from the organosilicon compound (A). As mentioned above, since the above-mentioned organosilicon compound (A) has a hydrolyzable group bonded to a silicon atom (which can be bonded via a linking group), the -SiOH group (Si and OH can be bonded via a linking group) and will be dehydrated and condensed. Therefore, the water-repellent layer (r) usually has a condensed structure derived from the organosilicon compound (A). As said hydrolyzable group, an alkoxy group, a halogen atom, a cyano group, an acetoxy group, an isocyanate group, etc. are mentioned.

The above-mentioned perfluoropolyether structure can also be referred to as perfluoroalkylene oxide. The perfluoropolyether structure has liquid repellency such as water repellency or oil repellency. The number of carbons contained in the longest linear part of the perfluoropolyether structure is, for example, preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more. The upper limit of the above-mentioned carbon number is not particularly limited, and may be about 200, for example. The monovalent group having a perfluoropolyether structure of the organosilicon compound (A) preferably further has a perfluoroalkyl group at the free end.

The water-repellent layer (r) may also be present in the form of a layer having a perfluoropolyether structure and a polysiloxane skeleton, and preferably further has a perfluoroalkyl group. The water-repellent layer (r) preferably has a structure on the silicon atom of a part of the polysiloxane skeleton: the free end is a perfluoroalkyl group, and a monovalent group having a perfluoropolyether structure is bonded. The presence of the perfluoroalkyl group on the free end side improves the water repellency.

The carbon number of the perfluoroalkyl group (especially the carbon number of the longest linear part) is, for example, preferably 3 or more, more preferably 5 or more, and more preferably 7 or more. Furthermore, the upper limit of the above-mentioned carbon number is not particularly limited. For example, even if it is about 20, excellent water-repellent properties can be exhibited.

The above-mentioned perfluoroalkyl group may be bonded to a hydrocarbon group and/or a group in which at least a part of the hydrogen atoms of the hydrocarbon group is substituted with a fluorine atom to form a fluorine-containing group such as a fluoroalkyl group, for example: CF ₃ (CF ₂ ) _m- (CH ₂ ) _n -, CF ₃ (CF ₂ ) _m -C ₆ H _4- (m is 1-10, preferably 3-7, n is 1-5, preferably 2-4), Preferably, it is CF ₃ (CF ₂ ) _m -(CH ₂ ) _n- (m is 1-10, preferably 3-7, n is 1-5, preferably 2-4). The above-mentioned perfluoroalkyl group is more preferably directly bonded to the perfluoropolyether structure.

Regarding the above-mentioned organosilicon compound (A), the monovalent group having a perfluoropolyether structure and the silicon atom may be bonded via an appropriate linking group, or there may be no such linking group. The above-mentioned monovalent group having a perfluoropolyether is directly Bonded with silicon atoms. As the linking group, for example, a hydrocarbon group such as an alkylene group and an aromatic hydrocarbon group, a (poly)alkylene glycol group, or a group in which a part of these hydrogen atoms is substituted with a fluorine atom or a substituent. And the bases that are properly connected. The carbon number of the linking group is, for example, 1 or more and 20 or less, preferably 2 or more and 15 or less.

The above-mentioned hydrolyzable group has a function of bonding organosilicon compounds (A) to each other or organosilicon compounds (A) to active hydrogen (hydroxyl groups, etc.) on the surface of the substrate through hydrolysis and dehydration condensation reaction. As such a hydrolyzable group, for example, an alkoxy group (especially a C1-C4 alkoxy group), a hydroxyl group, an acetoxy group, a halogen atom (especially a chlorine atom), etc. may be mentioned. Preferable hydrolyzable groups are alkoxy groups and halogen atoms, and particularly preferable are methoxy groups, ethoxy groups, and chlorine atoms.

The above-mentioned hydrolyzable group may be bonded to the silicon atom via a linking group, or may be directly bonded to the silicon atom without a linking group. The number of hydrolyzable groups bonded to the silicon atom may be one or more, and may be 2 or 3, preferably 2 or 3, and particularly preferably 3. When two or more hydrolyzable groups are bonded to the silicon atom, different hydrolyzable groups are bonded to the silicon atom, and the same hydrolyzable group is preferably bonded to the silicon atom. The total number of fluorine-containing groups and hydrolyzable groups bonded to silicon atoms is usually 4, but may be 2 or 3 (especially 3). In the case of 3 or less, the remaining bonding bonds may also be bonded with monovalent groups other than hydrolyzable groups, such as alkyl groups (especially alkyl groups with 1 to 4 carbons), H , NCO, etc.

The monovalent group having a perfluoropolyether structure of the organosilicon compound (A) may be linear or have side chains, and is preferably linear.

The above-mentioned organosilicon compound (A) can be represented by the following formula (a), for example.

[化6]

In the above formula (a), D ¹ is a monovalent group having a perfluoropolyether structure, and the end of the side ^{where D 1 is bonded to D 2} _{is -CF 2} -O-*, -CFD ⁹ -* (* is The bonding bond on the D ^{2 side), D 2} is a single bond or a divalent hydrocarbon group that ^{is not substituted by a fluorine atom, and D 3} is a trivalent hydrocarbon group that is not substituted by a fluorine atom. A part of the methylene group of the hydrocarbon group can pass through an oxygen atom Substitution, D ⁴ is a hydrogen atom or a fluorine atom, D ⁵ is a single bond or a divalent hydrocarbon group, D ⁶ is a monovalent group other than a hydrolyzable group, D ⁷ is a divalent group or a single bond, and D ⁸ is a hydrolyzable group , D ⁹ is a hydrogen atom, a fluorine atom, or a hydrocarbon group, n1 is 1-30, and n2 is 1-3. The hydrolyzable group of D ⁸ may, for example, be the above-mentioned hydrolyzable group.

The organosilicon compound (A) is preferably represented by the following formula (a1).

[化7]

In the above 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 with 1 to 20 carbon atoms. When there are plural R ¹¹ , the plural R ¹¹ may be different from each other. When there are plural R ¹² , the plural R ¹² may vary when in the presence of the case of a plurality of R ^13, the plurality of 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, in When there are a plurality of E ¹ , the plurality of E ¹ can be different, when there is a plurality of E ² , the plurality of E ² can be different from each other, when there is a plurality of E ³ , the plurality of E ³ can be different. When there are a plurality of E ⁴ , the plurality of E ⁴ can be different. When there is a plurality of E ⁵ , the plurality of E ⁵ can be different, and G ¹ and G ² are respectively. Each independently is a 2-10 valent organosiloxane group having a siloxane bond, 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 methyl or ethyl. When there are multiple J ^1s , the multiple J ^1s can be different. When there are multiple J ^2s , the multiple J ^2s can be different. Not the same. When there are a plurality of J ^3s , the plurality of J ^3s may be different, and L ¹ and L ² are each independently 2 of carbon number 1-12 that may contain an oxygen atom, a nitrogen atom, or a fluorine atom. Valence linking base, when there are multiple L ^{1 s} , the multiple L ^1s can be different, and when there are multiple L ^2s , the multiple L ^2s 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 It is 0-2 independently, and e1, e2, and e3 are 1-3 independently, respectively.

Regarding the aforementioned organosilicon compound (A), as represented by the aforementioned formula (a1), it has a ^{perfluoropolyether structure represented by Rf a1} , and at least one hydrolyzable group represented by ^{J 2} _{or -(CH 2} ) _e6 -Si(OR ¹⁴ ) ₃ (wherein R ¹⁴ is a methyl group or an ethyl group). The perfluoropolyether structure is a structure in which all hydrogen atoms of the polyoxyalkylene group are substituted with fluorine atoms, also called perfluorooxyalkylene group, which can impart water repellency to the obtained film. In addition, by means of J ² , the above-mentioned organosilicon compounds (A) are bonded to each other or other monomers through polymerization reactions (especially polycondensation reactions), thereby being compounds that can become the substrate of the obtained film.

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 divalent linking group having 1 to 5 carbon atoms containing a fluorine atom.

Preferably, G ¹ and G ² are each independently a 2- to 5-valent organosiloxane group having a siloxane bond.

Preferably, J ¹ , J ² , and J ³ are 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 to 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 aforementioned organosilicon compound (A), the following compounds are preferably used: Rf ^a1 of the aforementioned formula (a1) is -O-(CF ₂ CF ₂ CF ₂ O) _e5 -, e5 is 35-50, L ¹ and L ² are all perfluoroalkylene groups with carbon numbers of 1 to 3, E ¹ , E ² , and E ³ are all hydrogen atoms, E ⁴ and E ⁵ are hydrogen atoms or fluorine atoms, J ¹ , J ² , and J ³ All are methoxy or ethoxy (especially methoxy), 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 ~6, a21 to a23 are each 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 compounds.

As the above-mentioned organosilicon compound (A), it is also preferable to use the following compound: Rf ^a1 of the above formula (a1) is -O-(CF ₂ CF ₂ CF ₂ O) _e5 -, e5 is 25-40, and L ¹ is A bivalent linking group with 3-6 carbons containing a fluorine atom and an oxygen atom, L ² is a perfluoroalkylene group with 1 to 3 carbons, E ² and E ³ are both hydrogen atoms, E ⁵ is a fluorine atom, 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 a compound of 3.

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

[化8]

In the above formula (a2-1), Rf ^a21 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, and Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^a25 are each independently A C1-C20 alkyl group or fluorine atom where one or more hydrogen atoms are substituted with fluorine atoms. When there are more than one Rf ^a22 , the plurality of Rf ^a22 may be different from each other. When there are more than one Rf ^a23 In the case, a plurality of Rf ^a23 can be different from each other, when there are a plurality of Rf ^a24 , the plurality of Rf ^a24 can be different from each other, when there are a plurality of Rf ^a25 , the plurality of Rf ^a25 can be different from each other, R ²⁰ , R ²¹ , R ²² , and R ²³ are each independently a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. When there are plural R ²⁰ , the plural R ²⁰ may be different from each other. In the case of R ²¹ , the plurality of R ²¹ can be different. When there are a plurality of R ²² , the plurality of R ²² can be different. When there are a plurality of R ²³ , the plurality of R ²³ can be different. Each is different, R ²⁴ is an alkyl group with 1 to 20 carbons. When there are multiple R ^24s , the plurality of R ^24s may be different from each other. M ¹ is a hydrogen atom or an alkyl group with 1 to 4 carbons. When there are a plurality of M ¹ , the plurality of M ¹ may be different, M ² is a hydrogen atom or a halogen atom, and M ³ is -O-, -C(=O)-O-, -OC(=O )-, -NR-, -NRC(=O)-, or -C(=O)NR- (R is a hydrogen atom, an alkyl group with 1 to 4 carbons or a fluorinated alkyl group with 1 to 4 carbons) , When there are a plurality of M ³ , the plurality of M ³ can be different, M ⁴ is a hydrolyzable group, when there are a plurality of M ⁴ , the plurality of M ⁴ can be different, f11, f12, f13, f14, and f15 are each independently an integer of 0 to 600, the total value of f11, f12, f13, f14, and f15 is 13 or more, f16 is an integer of 1 to 20, f17 is an integer of 0 to 2, g1 It is an integer of 1 to 3, about 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 -become the ends, at least part of them are arranged in the order of forming a perfluoropolyether structure, and- O- is not connected with -O- or -F, then Arrange and bind in any order. That is, formula (a2-1) is not necessarily 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 this order means each 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., arranged in any order.

Rf ^{a21 is} preferably an alkyl group having 1 to 10 carbons substituted by 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 base.

Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^{a25 are} preferably each independently a fluorine atom, or an alkyl group with 1 to 2 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, more preferably all of them 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 20-600, more preferably 20-200, and still more preferably 50-200 (more preferably 30-150, particularly preferably 50-150, most preferably 80-140). f15 is preferably 4 to 600, more preferably 4 to 200, and still more preferably 10 to 200 (more 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 at least a part is arranged in the order of forming the perfluoropolyether structure, it is arbitrary in the formula, preferably The repeating unit enclosed in parentheses with f12 attached to the most fixed end side (the side bonded to the silicon atom) (i.e. -{C(Rf ^a22 )(Rf ^a23 ))-) is attached to the free end side attached to f11 and The repeating unit enclosed in brackets (ie -{C(R ²⁰ )(R ²¹ )}-) is on the free end side, more preferably the repeating unit enclosed in brackets with f12 and f14 attached to the most fixed end side (ie -{C(Rf ^a22 )(Rf ^a23 )}-, and -{Si(Rf ^a24 )(Rf ^a25 )}-) is located on the free end side with f11 and f13 and is enclosed in parentheses (i.e. -{C(R ²⁰ )(R ²¹ )}-, and -{Si(R ²² )(R ²³ )}-) are on the free end side.

In the above formula (a2-1), it is preferred that Rf ^a21 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^{a25 are} all fluorine atoms, and ^{all M 3} are -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.

Furthermore, it is also preferable that the organosilicon compound (A) is a compound represented by the following formula (a2-2).

[化9]

In the formula ^{(a2-2), Rf a26, Rf} a27, Rf a28, and Rf ^a29 each independently one or more hydrogen atoms are substituted with fluorine atoms to carbon atoms of the fluorine atom or an alkyl group of 1 to 20, in the presence of when a plurality of Rf case ^a26, the plurality Rf ^a26 may vary, the presence of the case of a plurality of Rf ^A27 of the time, a plurality of Rf ^A27 may vary when in the presence of the case of a plurality of Rf ^A28, the plurality Rf ^A28 They may be different. When there are a plurality of Rf ^a29 , the plurality of Rf ^a29 may be different. R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ are each independently a hydrogen atom or an alkane with 1 to 4 carbon atoms. Basically, when there are a plurality of R ²⁵ , the plurality of R ²⁵ can be different, when there is a plurality of R ²⁶ , the plurality of R ²⁶ can be different, when there is a plurality of R ²⁷ , The plurality of R ²⁷ may be different from each other. When there are a plurality of R ²⁸ , the plurality of R ²⁸ may be different from each other. R ²⁹ and R ³⁰ are each independently an alkyl group with 1 to 20 carbon atoms. when R ²⁹ of a case, a plurality of R ²⁹ may be different, in the case of the presence of a plurality of R ^30, R ³⁰ may be a plurality of different, M ⁷ is -O -, - C (= O ) -O -, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, the above R is a hydrogen atom, an alkyl group with 1 to 4 carbons or a carbon number of 1 the fluorine-containing alkyl group of 4 ~, in the case of the presence of a plurality of M ^7, M ⁷ may be a plurality of different, M ^5, M ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, the presence in the when a plurality of case ^{M. 5,} the plurality of ^{M. 5} may vary when in the presence of a plurality of M case ^9, the plurality of M ⁹ may vary, ^{M. 6,} and M ¹⁰ are each independently a hydrogen atom or a halogen Atoms, M ⁸ and M ¹¹ are independently hydrolyzable groups. When there are plural M ⁸ , the plural M ⁸ may be different from each other, and when there are plural M ¹¹ , the plural M ¹¹ may be different. Each is different, f21, f22, f23, f24, and f25 are each independently an integer from 0 to 600, the total value of f21, f22, f23, f24, and f25 is 13 or more, and f26, and f28 are each independently 1 An integer of ～20, f27 and f29 are each independently an integer of 0-2, g2, g3 are each independently an integer of 1-3, about M ¹⁰ -, M ⁶ -, f21-{C(R ²⁵ ) (R ^26)} -, f22 a ^{- {C (Rf a26) (} Rf a27)} -, f23 a ^{- {Si (R 27) (} R 28)} -, f24 a ^{- {Si (Rf a28) (} Rf ^a29 ))-, f25 -M ⁷ -, f2 6-[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 -and M ⁶ -become the ends, at least part of them are arranged in the order of forming a perfluoropolyether structure, and -O- does not correspond to -O-continuous, then arrange and bond in any order. Regarding the arrangement and bonding in an arbitrary order, it is the same as that described in the above formula (a2-1), and is not limited to the meaning that each repeating unit is continuous and arranged in the order described in the above formula (a2-2).

In the above 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 a methoxy group, Ethoxy group or chlorine atom (especially methoxy group or ethoxy group), 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 (particularly 0), g2 and g3 are 3, and f26 and f28 are 1-10.

As said organosilicon compound (A), the compound of following formula (a3) can be mentioned more specifically.

[化10]

In the above formula (a3), R ³⁰ is a perfluoroalkyl group with a carbon number of 2-6, R ³¹ and R ³² are independent of each other and both are a ^{perfluoroalkylene group with a carbon number of 2-6, and R 33} is a carbon number It is a trivalent saturated hydrocarbon group of 2 to 6, and R ³⁴ is an alkyl group of 1 to 3 carbons. Regarding the carbon numbers of R ³⁰ , R ³¹ , R ³² , and R ³³ , each independently is preferably 2 to 4, and more preferably 2 to 3. h1 is from 5 to 70, h2 is from 1 to 5, and h3 is from 1 to 10. h1 is preferably 10-60, more preferably 20-50, h2 is preferably 1-4, more preferably 1-3, h3 is preferably 1-8, more preferably 1-6.

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

[化11]

In the above 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 part of the hydrogen atom is substituted with a fluoroalkylene group of 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 to 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, and preferably 40,000 or less, more preferably 20,000 or less, and further Preferably it is 15,000 or less.

As the above-mentioned organosilicon compound (A), for example, a compound represented by the following formula (1) or a compound having a similar structure to the compound, such as OPTOOL (registered trademark) UF503 manufactured by DAIKIN INDUSTRIES Co., Ltd. Wait. [化12]

Examples of the compound represented by the above formula (1) include those synthesized by the method described in Synthesis Examples 1 and 2 of JP 2014-15609 A, where r is 43 and s is an integer of 1 to 6. , The number average molecular weight is about 8000.

Examples of the above-mentioned similar structures include: the structure in which the carbon number of the hydrocarbyl group of the above formula (1) or the carbon number of the hydrocarbyl group substituted by a fluorine atom is different, the structure in which the perfluoropolyether structure and the silicon atom are not bonded via a linking group, The structure in which other hydrocarbon groups (including hydrocarbon groups in which at least part of the hydrogen atoms are replaced by fluorine atoms) are interposed at any position of the linking group between the perfluoropolyether structure and the silicon atom, and the silicon atom and the hydrolyzable group are bonded via the linking group Structures, structures with different values of r and s, etc., but are not limited to these structures.

II. The organic silicon compound (B) organic silicon compound of the following formula (b1) represented by the (B) described below, having a hydrolyzable group represented by A ² of, typically, an organic silicon compound (B produced by the hydrolysis of The -SiOH group of) will undergo dehydration condensation with the -SiOH group of the organosilicon compound (A) produced by hydrolysis and/or the -SiOH group of the organosilicon compound (B) produced by hydrolysis, so it is in a better state Here, the water-repellent layer (r), which is the hardened layer of the above-mentioned mixed composition (ca), has a condensation structure derived from the organosilicon compound (B) together with the condensation structure derived from the organosilicon compound (A). As said hydrolyzable group, an alkoxy group, a halogen atom, a cyano group, an acetoxy group, an isocyanate group, etc. are mentioned.

[化13]

In the above 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 a hydrogen atom Or an alkyl group with 1 to 4 carbon atoms. When there are plural R ^b11 , the plural R ^b11 may be different from each other. When there are plural R ^b12 , the plural R ^b12 may be different from each other. When there are a plurality of R ^b13 , the plurality of R ^b13 can be different, when there are a plurality of R ^b14 , the plurality of R ^b14 can be different, and Rf ^b11 , Rf ^b12 , Rf ^b13 , and Rf ^b14 are independent Ground is a C1-C20 alkyl group or fluorine atom where one or more hydrogen atoms are substituted with fluorine atoms. When there are more than one Rf ^b11 , the plurality of Rf ^b11 may be different. When there are more than one Rf ^b12 In this case, the plurality of Rf ^b12 can be different. When there are a plurality of Rf ^b13 , the plurality of Rf ^b13 can be different. When there are a plurality of Rf ^b14 , the plurality of Rf ^b14 can be different. , R ^b15 is an alkyl group with 1 to 20 carbons. When there are plural R ^b15 , the plural R ^b15 can be different. A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, the above R is a hydrogen atom, an alkyl group with 1 to 4 carbons or a carbon number of 1 to 4 For the fluorine-containing alkyl group, when there are multiple A ¹ , the multiple A ¹ can be different, and A ² is a hydrolyzable group. When there are multiple A ^2s , the multiple A ² can be different , B11, b12, b13, b14, and b15 are each independently an integer from 0 to 100, c is an integer from 1 to 3, regarding Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c , b11 -{C(R ^b11 )(R ^b12 )}-、b12pcs-{C(Rf ^b11 )(Rf ^b12 )}-、b13pcs-{Si(R ^b13 )(R ^b14 )}-、b14pcs-{ Si(Rf ^b13 )(Rf ^b14 )}-, b15 -A ¹ -, as long as Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c become the ends, do not form a perfluoropolyether structure, and -O- is not connected with -O- or -F, but is arranged and bonded 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, and 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, and preferably 80 or less, more preferably 50 or less, and still more preferably 20 or less.

Particularly ^{preferably, Rf b10} is a fluorine atom or a perfluoroalkyl group with 1 to 5 carbon atoms, R ^b11 and R ^b12 are both hydrogen atoms, A ² is methoxy or ethoxy, and b11 is 1 to 5, and b12 is 0-5, b13, b14, and b15 are all 0, and c is 3.

Furthermore, if the FAS13E used as compound (B) in the examples described below is represented by the above formula (b1), it can be specified 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 -becomes the terminal and becomes C ₆ F ₁₃ -.

Specific examples of the compound represented by the above formula (b1) include: CF ₃ -Si-(OCH ₃ ) ₃ , C _j F _2j+1 -Si-(OC ₂ H ₅ ) ₃ (j is 1-12 Integer), 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 . Also, exemplified: 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). Also, exemplified: 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). It can also be exemplified: 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 2 to 4). Further examples include: 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14]

In the above 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.

Furthermore, the above-mentioned mixed composition (ca) is a composition obtained by mixing the above-mentioned organosilicon compound (A) and the above-mentioned organosilicon compound (B) by combining the above-mentioned organosilicon compound (A) and the above-mentioned organosilicon compound ( B) It is obtained by mixing. In the case of mixing components other than the above-mentioned organosilicon compound (A) and the above-mentioned organosilicon compound (B), it is obtained by combining the above-mentioned organosilicon compound (A) and the above-mentioned organosilicon compound (B). Compound (B) and other components are mixed and obtained. The above-mentioned mixed composition (ca) also includes one that has been reacted after mixing, for example, in storage.

III. Solvent (D) The above-mentioned mixed composition (ca) is usually mixed with a solvent (D). 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. As fluorinated ether solvents, hydrofluoroethers such as fluoroalkyl (especially perfluoroalkyl with carbon number of 2-6)-alkyl (especially methyl or ethyl) ether are preferred, for example: Ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether. As ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether, for example, Novec (registered trademark) 7200 (manufactured by 3M Corporation, molecular weight approximately 264) may be mentioned. The fluorinated amine-based solvent is preferably an amine in which at least one of the hydrogen atoms of ammonia is substituted by a fluoroalkyl group, and preferably is a tertiary level in which all hydrogen atoms of ammonia are substituted by a fluoroalkyl group (especially a perfluoroalkyl group) Amine, specifically, tris(heptafluoropropyl) amine, Fluorinert (registered trademark) FC-3283 (manufactured by 3M company, molecular weight about 521) belongs to tris(heptafluoropropyl). Examples of fluorinated hydrocarbon solvents include: fluorinated aliphatic hydrocarbon solvents such as 1,1,1,3,3-pentafluorobutane, and fluorinated aromatics such as 1,3-bis(trifluoromethylbenzene) Group hydrocarbon solvent. The 1,1,1,3,3-pentafluorobutane may, for example, be Sorb 55 (manufactured by Solvex).

As the fluorine-based solvent, in addition to the above, hydrofluorochlorocarbon compounds such as Asahiklin (registered trademark) AK225 (manufactured by AGC Corporation), hydrofluorocarbon compounds such as Asahiklin (registered trademark) AC2000 (manufactured by Asahi Glass Corporation), and the like can be used.

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 kinds of 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).

Regarding the amount of the above-mentioned organosilicon compound (A) in the above-mentioned mixed composition (ca), relative to the total of the composition is 100% by mass, for example, 0.01% by mass or more, preferably 0.03% by mass or more, and more It is preferably 0.05% by mass or more, more preferably 1.0% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less.

Regarding the amount of the aforementioned organosilicon compound (B) in the aforementioned mixed composition (ca), relative to the entire composition of 100% by mass, for example, 0.01% by mass or more, preferably 0.03% by mass or more, and It is preferably 0.3% by mass or less, and more preferably 0.2% by mass or less.

Regarding the mass ratio of the organosilicon compound (B) to the organosilicon compound (A), it is preferably 0.01 or more, more preferably 0.1 or more, still more preferably 0.3 or more, and preferably 2.0 or less, more preferably 1.5 or less, more preferably 1.0 or less.

The amounts of the aforementioned organosilicon compounds (A) and (B) can be adjusted when preparing the composition. The amounts of the aforementioned organosilicon compounds (A) and (B) can be calculated based on the analysis results of the composition.

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

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

The above-mentioned intermediate layer (c) is a hardened layer of a mixed composition (cc) of an organosilicon compound (C) having a silicon atom and an amine group or an amine skeleton (-NR ¹⁰⁰ -, R ^{100 is a hydrogen atom or an alkyl group)} Or the vapor-deposited layer of the aforementioned organosilicon compound (C), and the intermediate layer (c) has an amine group or an amine skeleton. In a preferred aspect, it is preferable that the silicon atom of the organosilicon compound (C) has a hydrolyzable group or a hydroxyl group, and the Si-OH group possessed by the organosilicon compound (C) may be bonded to the silicon atom The -SiOH groups of the organosilicon compound (C) produced by the hydrolysis of the hydrolyzable group will be dehydrated and condensed with each other, so the intermediate layer (c) has a condensation structure derived from the organosilicon compound (C). The intermediate layer (c) can function as a primer layer of the water-repellent layer (r). Examples of the hydrolyzable group bonded to the silicon atom of the organosilicon compound (C) include an alkoxy group, a halogen atom, a cyano group, an acetoxy group, and an isocyanate group. The silicon atom of the organosilicon compound (C) is preferably bonded to an alkoxy group or a hydroxyl group having 1 to 4 carbon atoms.

The organosilicon compound (C) is preferably a compound represented by any of the following formulas (c1) to (c3).

IV-1. Organosilicon compound (C) represented by the following formula (c1) (hereinafter referred to as organosilicon compound (C1)) [Chemical 15]

In the above formula (c1), R ^x11 , R ^x12 , R ^x13 , and R ^x14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When there are multiple R ^x11 , multiple R ^x11 may be Each is different. When there are multiple R ^x12 , the multiple R ^x12 can be different. When there are multiple R ^x13 , the multiple R ^x13 can be different. When there are multiple R ^x14 When, a plurality of R ^x14 may be different, Rf ^x11 , Rf ^x12 , Rf ^x13 , and Rf ^x14 are each independently an alkyl group with 1-20 carbon atoms or fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms. When there are a plurality of Rf ^x11 , the plurality of Rf ^x11 can be different, when there are a plurality of Rf ^x12 , the plurality of Rf ^x12 can be different from each other, when there are a plurality of Rf ^x13 , the plurality of Rf ^x13 can be different. When there are multiple Rf ^x14 , the multiple Rf ^x14 can be different. R ^x15 is an alkyl group with 1 to 20 carbon atoms. When there are multiple R ^x15 , multiple R ^x15 can be different from each other, X ¹¹ is a hydrolyzable group, when there are multiple X ¹¹ , the multiple X ¹¹ can be different from each other, Y ¹¹ is -NH- or -S-, when there are multiple Y ^In the case of 11, the plural Y ¹¹ can be different, and Z ¹¹ is a vinyl group, α-methyl vinyl group, styryl group, methacryl group, acryl group, amine group, isocyanate group, and isocyanate group. Cyanuric acid group, epoxy group, ureido group, or mercapto group, p1 is an integer of 1-20, p2, p3, and p4 are each independently an integer of 0-10, p5 is an integer of 1-10, and p6 is an integer of 1-3 When Z ^{11 is} not an amine group, at least one of ^{Y 11 is -NH-, and when all Y 11} is -S-, Z ¹¹ is an amine group. Regarding Z ¹¹ -, -Si (X ¹¹ ) _p6 (R ^x15 ) _3-p6 ^{, p1 pcs-} (C(R x11 )(R ^x12 ))-, p2 ^pcs- (C(Rf x11 )(Rf ^x12 ))-, p3 pcs-(Si (R ^x13 )(R ^x14 )}-, p4 -{Si(Rf ^x13 )(Rf ^x14 )}-, p5 -Y ¹¹ -, as long as Z ¹¹ -and -Si(X ¹¹ ) _p6 (R ^x15 ) _3-p6 becomes the terminal, and -O- is not connected with -O-, and it is arranged in an arbitrary order and bonded.

R ^x11 , R ^x12 , R ^x13 , and R ^{x14 are} preferably hydrogen atoms.

Rf ^x11 , Rf ^x12 , Rf ^x13 , and Rf ^{x14 are} preferably each independently 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.

R ^{x15 is} preferably an alkyl group having 1 to 5 carbon atoms.

X ^{11 is} preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, and still more preferably a methoxy group or an ethoxy group.

Y ^{11 is} preferably -NH-.

Z ^{11 is} preferably a methacryl group, an acryl group, a mercapto group or an amino group, more preferably a mercapto group or an amino group, and still more preferably an amino group.

p1 is preferably 1-15, more preferably 2-10. p2, p3, and p4 are independent of each other, preferably 0-5, and more preferably all 0-2. p5 is preferably 1-5, more preferably 1-3. p6 is preferably 2 to 3, more preferably 3.

As the organosilicon compound (C), it is preferable to use the above formula (c1) where R ^x11 and R ^x12 are both hydrogen atoms, Y ¹¹ is -NH-, and X ¹¹ is an alkoxy group (especially a methoxy group or an ethoxy group). Group), Z ¹¹ is an amine group or a mercapto group, p1 is 1-10, p2, p3 and p4 are all 0, p5 is 1-5 (especially 1-3), and p6 is a compound of 3.

The organosilicon compound (C1) is preferably represented by the following formula (c1-2).

[化16]

In the above formula (c1-2), X ¹² is a hydrolyzable group. When there are a plurality of X ¹² , the plurality of X ¹² may be different from each other, Y ¹² is -NH-, Z ¹² is an amine group or a mercapto group , R ^x16 is an alkyl group with a carbon number of 1-20. When there are a plurality of R ^x16s , the plurality of R ^x16s may be different, p is an integer of 1 to 3, q is an integer of 2 to 5, r It is an integer of 0-5.

X ^{12 is} preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, and still more preferably an alkoxy group having 1 to 4 carbon atoms.

Z ^{12 is} preferably an amino group.

R ^{x16 is} preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.

p is preferably an integer of 2 to 3, more preferably 3.

q is preferably an integer of 2-3, and r is preferably an integer of 2-4.

IV-2. Organosilicon compound (C) represented by the following formula (c2) (hereinafter referred to as organosilicon compound (C2))

上述式(c2)中， R^x20 及R^x21 分別獨立地為氫原子或碳數為1～4之烷基，於存在複數個R^x20 之情形時，複數個R^x20 可各不相同，於存在複數個R^x21 之情形時，複數個R^x21 可各不相同， Rf^x20 及Rf^x21 分別獨立地為1個以上氫原子被取代為氟原子之碳數1～20之烷基或氟原子，於存在複數個Rf^x20 之情形時，複數個Rf^x20 可各不相同，於存在複數個Rf^x21 之情形時，複數個Rf^x21 可各不相同， R^x22 及R^x23 分別獨立地為碳數為1～20之烷基，於存在複數個R^x22 及R^x23 之情形時，複數個R^x22 及R^x23 可各不相同， X²⁰ 及X²¹ 分別獨立地為水解性基，於存在複數個X²⁰ 及X²¹ 之情形時，複數個X²⁰ 及X²¹ 可各不相同， p20為1～30之整數，p21為0～30之整數，附p20或p21並且用括號括起來之重複單元之至少1者被取代為胺骨架-NR¹⁰⁰ -，上述胺骨架中之R¹⁰⁰ 為氫原子或烷基， p22及p23分別獨立地為1～3之整數， p20個-{C(R^x20 )(R^x21 )}-、p21個-{C(Rf^x20 )(Rf^x21 )}-無需p20或p21個連續，係以任意順序排列而鍵結，且兩末端成為-Si(X²⁰ )_p22 (R^x22 )_3-p22 及-Si(X²¹ )_p23 (R^x23 )_3-p23 。[化17]

In the formula (c2), R ^x20 and R ^x21 are each independently a hydrogen atom or an alkyl group having a carbon number of 1 to 4, when in the presence of a plurality of R ^x20 case, a plurality of R ^x20 may vary, the presence of when a plurality of R ^x21 case, a plurality of R ^x21 may vary, Rf ^x20 and Rf ^x21 each independently one or more hydrogen atoms are substituted with fluorine atoms to carbon atoms of the fluorine atom or an alkyl group of 1 to 20, in When there are a plurality of Rf ^x20 , the plurality of Rf ^x20 can be different, when there are a plurality of Rf ^x21 , the plurality of Rf ^x21 can be different from each other, and R ^x22 and R ^x23 are each independently with a carbon number of 1. The alkyl group of ~20, when there are multiple R ^x22 and R ^x23 , the multiple R ^x22 and R ^x23 can be different from each other, X ²⁰ and X ²¹ are each independently a hydrolyzable group, and there are multiple X ²⁰ and the case of X ²¹ when, a plurality of X ²⁰ and X ²¹ can vary, p20 is an integer of 1 to 30, the p21 is an integer of 0 to 30, the attachment p20 or p21 and parentheses of repeating units of at least 1 Is substituted with an amine skeleton -NR ^{100 -, R 100} in the above amine skeleton is a hydrogen atom or an alkyl group, p22 and p23 are each independently an integer of 1 to 3, p20 -{C(R ^x20 )(R ^x21 )}-, p21-{C(Rf ^x20 )(Rf ^x21 )}-No need for p20 or p21 to be continuous, they are arranged in any order and bonded, and the two ends become -Si(X ²⁰ ) _p22 (R ^x22 ) _3-p22 and -Si(X ²¹ ) _p23 (R ^x23 ) _3-p23 .

R ^x20 and R ^{x21 are} preferably hydrogen atoms.

Preferably, Rf ^x20 and Rf ^x21 are each independently 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.

R ^x22 and R ^{x23 are} preferably alkyl groups having 1 to 5 carbon atoms.

X ²⁰ and X ^{21 are} preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, and still more preferably a methoxy group or an ethoxy group.

Regarding the amine skeleton -NR ¹⁰⁰ -, as described above, at least one of the repeating units enclosed in parentheses with p20 or p21 may be substituted with the above-mentioned amine skeleton. It is part of the repeating unit with p20 attached and enclosed in parentheses. There may be a plurality of amine skeletons. In this case, the number of amine skeletons is preferably 1-10, more preferably 1-5, and still more preferably 2-5. In this case, it is preferable to have an alkylene group between adjacent amine skeletons, and the carbon number of the alkylene group is preferably 1-10, more preferably 1-5. The carbon number of the alkylene group between adjacent amine skeletons is included in the total number of p20 or p21.

In the amine skeleton -NR ¹⁰⁰ -, when R ¹⁰⁰ is an alkyl group, the carbon number is preferably 5 or less, more preferably 3 or less. The amine skeleton -NR ¹⁰⁰ -is preferably -NH- (R ¹⁰⁰ is a hydrogen atom).

Regarding p20, excluding the number of repeating units substituted with an amine skeleton, it is preferably 1-15, more preferably 1-10.

Regarding p21, excluding the number of repeating units substituted with an amine skeleton, it is preferably 0-5, and more preferably all 0-2.

p22 and p23 are preferably 2 to 3, more preferably 3.

As the organosilicon compound (C2), it is preferably used in the above formula (c2), R ^x20 and R ^x21 are both hydrogen atoms, and X ²⁰ and X ²¹ are alkoxy groups (especially methoxy or ethoxy) , At least one of the repeating units enclosed in parentheses with p20 attached is substituted with an amine skeleton -NR ¹⁰⁰ -, R ¹⁰⁰ is a hydrogen atom, and p20 is 1-10 (except for the number of repeating units substituted with an amine skeleton) , P21 is 0, p22 and p23 are 3 compounds.

Furthermore, if the above-mentioned formula (c2) represents the N-2-(aminoethyl)-3-in Japanese Patent Laid-Open No. 2012-197330 used as the compound (C) in the examples described below, The reactant of aminopropyltrimethoxysilane and chloropropyltrimethoxysilane (trade name: X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.), R ^x20 and R ^x21 are both hydrogen atoms, p20 It is 8, p21 is 0, amine skeleton is 2 (in either R ¹⁰⁰ are hydrogen atoms), both ends are the same, p22 and p23 are 3, and X ²⁰ and X ²¹ are methoxy groups.

The organosilicon compound (C2) is preferably a compound represented by the following formula (c2-2).

[化18]

In the above formula (c2-2), X ²² and X ²³ are independently hydrolyzable groups. When there are a plurality of X ²² and X ²³ , the plurality of X ²² and X ²³ may be different from each other, R ^{x 24} and R ^{x25 is} each independently an alkyl group having 1 to 20 carbon atoms. When there are a plurality of R ^x24 and R ^x25 , the plurality of R ^x24 and R ^x25 may be different from each other. Regarding -C _w H _2w -, which At least one of a part of the methylene group is substituted with an amine skeleton -NR ¹⁰⁰ -, R ¹⁰⁰ is a hydrogen atom or an alkyl group, and w is an integer of 1-30 (wherein, the number of methylene groups substituted with an amine skeleton is excluded ), p24 and p25 are each independently an integer of 1 to 3.

X ²² and X ^{23 are} preferably an alkoxy group, a halogen atom, a cyano group, or an isocyanate group, more preferably an alkoxy group, and still more preferably an alkoxy group having 1 to 4 carbon atoms (especially a methoxy group). Or ethoxy).

There may be a plurality of amine skeletons -NR ¹⁰⁰ -. In this case, the number of amine skeletons is preferably 1-10, more preferably 1-5, and still more preferably 2-5. In this case, it is preferable to have an alkylene group between adjacent amine skeletons. The carbon number of the above-mentioned alkylene group is preferably 1-10, more preferably 1-5. The carbon number of the alkylene group between adjacent amine skeletons is included in the total number of w.

In the amine skeleton -NR ¹⁰⁰ -, when R ¹⁰⁰ is an alkyl group, the carbon number is preferably 5 or less, more preferably 3 or less. The amine skeleton -NR ¹⁰⁰ -is preferably -NH- (R ¹⁰⁰ is a hydrogen atom).

R ^x24 and R ^{x25 are} preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

p24 and p25 are preferably an integer of 2 to 3, more preferably 3.

w is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 10 or less.

IV-3. Organosilicon compound (C) represented by the following formula (c3) (hereinafter referred to as organosilicon compound (C3))

上述式(c3)中， Z³¹ 、Z³² 分別獨立地為除水解性基及羥基以外之反應性官能基。作為反應性官能基，可例舉：乙烯基、α-甲基乙烯基、苯乙烯基、甲基丙烯醯基、丙烯醯基、胺基、環氧基、脲基、或巰基。作為Z³¹ 、Z³² ，較佳為胺基、巰基、或甲基丙烯醯基，尤佳為胺基。[化19]

In the above formula (c3), Z ³¹ and Z ³² are each independently a reactive functional group other than a hydrolyzable group and a hydroxyl group. The reactive functional group may, for example, be a vinyl group, an α-methylvinyl group, a styryl group, a methacryl group, an acryl group, an amino group, an epoxy group, a ureido group, or a mercapto group. As Z ³¹ and Z ³² , an amino group, a mercapto group, or a methacryl group is preferable, and an amino group is particularly preferable.

R ^x31 , R ^x32 , R ^x33 , and R ^x34 are each independently a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. When there are multiple R ^x31 , the multiple R ^x31 may be different from each other. In the case of R ^x32 , the plurality of R ^x32 can be different. When there are a plurality of R ^x33 , the plurality of R ^x33 can be different. When there are a plurality of R ^x34 , the plurality of R ^x34 can be different. Each is different. R ^x31 , R ^x32 , R ^x33 , and R ^{x34 are} preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom.

Rf ^x31 , Rf ^x32 , Rf ^x33 , and Rf ^x34 are each independently an alkyl group with 1 to 20 carbon atoms or fluorine atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and when there are plural Rf ^x31 , plural Rf ^x31 can be different. When there are a plurality of Rf ^x32 , the plurality of Rf ^x32 can be different. When there are a plurality of Rf ^x33 , the plurality of Rf ^x33 can be different. ^In the case of x34, a plurality of Rf ^x34 can be different. Rf ^x31 , Rf ^x32 , Rf ^x33 , and Rf ^{x34 are} preferably alkyl groups having 1 to 10 carbon atoms or fluorine atoms in which one or more hydrogen atoms are substituted with fluorine atoms.

Y ³¹ is -NH-, -N(CH ₃ )- or -O-. When there are plural Y ³¹ , the plural Y ³¹ may be different from each other. Y ^{31 is} preferably -NH-.

X ³¹ , X ³² , X ³³ , and X ³⁴ are each independently -OR ^c (R ^c is a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or an amino group C _1-3 alkyl di C _1-3 alkoxy Silyl group). When there are multiple X ³¹ , the multiple X ³¹ can be different. When there are multiple X ³² , the multiple X ³² can be different. When there are multiple X ³³ In the case, the plurality of X ³³ may be different from each other, and when there are a plurality of X ³⁴ , the plurality of X ³⁴ may be different from each other. ^{X 31, X 32, X 33} , X 34 is preferably R ^c is a hydrogen atom, or an alkyl group having 1 to 2 carbon atoms of the -OR ^c, R ^c is more preferably a hydrogen atom.

p31 is an integer of 0-20, p32, p33, and p34 are each independently an integer of 0-10, p35 is an integer of 0-5, p36 is an integer of 1-10, and p37 is 0 or 1. p31 is preferably 1-15, more preferably 3-13, and still more preferably 5-10. p32, p33, and p34 are independent of each other, preferably 0-5, and more preferably all 0-2. p35 is preferably 1-5, more preferably 1-3. p36 is preferably 1-5, more preferably 1-3. p37 is preferably 1.

Regarding the organosilicon compound (C3), as long as it satisfies the condition that at least one of ^{Z 31} and Z ^{32 is an amine group, or that at least one of Y 31} is -NH- or -N(CH ₃ )-, and the end is Z ^{31 -And} Z ³² -, -O- is not connected with -O-, then p31-{C(R x31 )(R ^x32 )}-, ^p32- {C(Rf x31 )(Rf ^x32 )}-, p33 -{Si(R ^x33 )(R ^x34 ))-, p34-{Si(Rf ^x33 )(Rf ^x34 )}-, p35-Y ³¹ -, p36-{Si(X ³¹ )(X ³² )-O}-, p37-{Si(X ³³ )(X ³⁴ )}- to arrange the bonding in any order to form. ^p31- {C(R x31 )(R ^x32 )}-no ^need- {C(R x31 )(R ^x32 )}- continuous bonding, can be bonded via other units in the middle, as long as the total is p31 . The same applies to the units enclosed by p32 to p37.

As the organosilicon compound (C3), the following compounds are preferred: Z ³¹ and Z ³² are amino groups, R ^x31 and R ^x32 are hydrogen atoms, p31 is ^{3-13 (preferably 5-10), R x33} and R ^x34 are all hydrogen atoms, Rf ^x31 to Rf ^x34 are all C1-C10 alkyl groups or fluorine atoms in which one or more hydrogen atoms are substituted with fluorine atoms, p32-p34 are all 0-5, and Y ³¹ is -NH -, p35 is 0 to 5 (preferably 0 to 3), X ³¹ to X ³⁴ are all -OH, p36 is 1 to 5 (preferably 1 to 3), and p37 is 1.

The organosilicon compound (C3) is preferably represented by the following formula (c3-2).

[化20]

In the above formula (c3-2), Z ³¹ , Z ³² , X ³¹ , X ³² , X ³³ , X ³⁴ , Y ³¹ and the equivalent in formula (c3), p41 to p44 are independently 1 to 6 The integers, p45 and 46 are independently 0 or 1, respectively.

In the formula (c3-2), Z ³¹ and Z ^{32 are} preferably an amine group, a mercapto group, or a methacryl group, and particularly preferably an amine group. X ³¹ , X ³² , X ³³ , and X ^{34 are} preferably ^{-OR c in which R c} is a hydrogen atom or an alkyl group with 1 to 2 carbon atoms, more preferably R ^c is a hydrogen atom. Y ^{31 is} preferably -NH-. p41 to p44 are preferably 2 or more, preferably 5 or less, and more preferably 4 or less. Both p45 and p46 are preferably 0.

The mixed composition (cc) is a composition in which the organosilicon compound (C) is mixed, and the organosilicon compound (C) may be one type or two or more types. The mixed composition (cc) can be obtained by mixing the organosilicon compound (C). In the case of mixing components other than the organosilicon compound (C), it can be obtained by mixing the organosilicon compound (C) with other The ingredients are mixed to obtain. The above-mentioned mixed composition (cc) also includes one that has been reacted during storage, for example, after mixing.

As an example in which the above-mentioned mixed composition (cc) has reacted during storage, the above-mentioned mixed composition (cc) includes the condensate of the above-mentioned organosilicon compound (C); more specifically, the above-mentioned The mixed composition (cc) contains the organosilicon compound (C3') in which at least any one of ^{the aforementioned X 31} to X ^{34 of the aforementioned organosilicon compound (C3) is condensed and bonded.}

The above-mentioned organosilicon compound (C3') has two or more structures (c31-1) represented by the following formula (c31-1) and the above-mentioned structures (c31-1) are mutually linked by the following *3 or *4 A compound formed by bonding in a cyclic or cyclic manner is formed by the following *3 or *4 bonding by the condensation of ^{two or more of the above-mentioned organosilicon compounds (C3) of the above X 31} or X ^{32, in} The following formula (c31-1) *1 and *2 are respectively bonded with the units of the following formula (c31-2) enclosed by p31, p32, p33, p34, p35, (p36)-1, p37 At least one of the above-mentioned structures (c31-1) is bound to at least one of the groups in any order and the terminal is Z-, and in each of the above-mentioned structures (c31-1), the groups bonded to *1 and *2 may be different, and plural of the above-mentioned structures ( c31-1) When chain-linked, the terminal *3 is a hydrogen atom, and *4 is a hydroxyl group.

[化21]

[化22]

In the above formula (c31-2), Z is a reactive functional group other than a hydrolyzable group and a hydroxyl group, R ^x31 , R ^x32 , R ^x33 , R ^x34 , Rf ^x31 , Rf ^x32 , Rf ^x33 , Rf ³⁴ , Y ³¹ , X ³¹ , X ³² , X ³³ , X ³⁴ , and p31 to p37 are synonymous with the symbols in the above formula (c3).

When the organosilicon compound (C3) is the compound represented by the above formula (c3-2), as the organosilicon compound (C3'), for example, the structure represented by the following formula (c31-3) can be exemplified by Said *3 or *4 chain-like or cyclically bonded compound. In the case where the structure represented by the following formula (c31-3) is bonded in a chain, *3 that becomes the terminal is a hydrogen atom, and *4 that becomes the terminal is a hydroxyl group.

[化23]

The symbols in the above formula (c31-3) are all synonymous with the symbols in the above formula (c3-2).

The organosilicon compound (C3') is preferably a compound in which 2-10 (preferably 3-8) structures represented by the above formula (c31-3) are bonded.

V. Solvent (E) The above-mentioned mixed composition (cc) is preferably mixed with a solvent (E). The solvent (E) is not particularly limited. For example, water, alcohol-based solvents, ketone-based solvents, ether-based solvents, hydrocarbon-based solvents, ester-based solvents, etc. can be used, and water, alcohol-based solvents, ketone-based solvents, and hydrocarbon-based solvents are particularly preferred. Solvent.

As an alcohol solvent, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, etc. are mentioned. As a ketone solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. are mentioned. The ether-based solvent may, for example, be diethyl ether, dipropyl ether, tetrahydrofuran, 1,4-dioxane, and the like. Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents such as pentane and hexane, alicyclic hydrocarbon solvents such as cyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. As an ester solvent, ethyl acetate, propyl acetate, butyl acetate, etc. are mentioned.

Regarding the total amount of the organosilicon compound (C) when the entire composition (cc) is 100% by mass, it is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.02% by mass % Or more, more preferably 0.1% by mass or more, and 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 aforementioned organosilicon compound (C) can be adjusted when preparing the composition. The amount of the aforementioned organosilicon compound (C) can be calculated based on the analysis result of the composition. In addition, in this specification, when the range of the amount, mass ratio, or molar ratio of each component is described, it is the same as the above, and the range can be adjusted when preparing the composition.

The substrate (s) is preferably a layer having a function of preventing the reflection of incident light on the surface on the side of the intermediate layer (c). Specifically, it is preferably in the visible light region of 380 to 780 nm. The surface on the side of the intermediate layer (c) exhibits a reflective characteristic with a reflectance of 5.0% or less, more preferably 4.80% or less, and still more preferably 4.5% or less. The reflectance can also be evaluated by the spectral reflectance at a wavelength of 530 nm.

The substrate (s) is preferably at least the outermost layer on the side of the intermediate layer (c), and the surface Si ratio is 1 atomic% or more, and the substrate (s) is preferably an organic material or an inorganic material. If the above-mentioned surface Si ratio is more than specified, the surface of the substrate (s) and the components constituting the intermediate layer (c) or the water-repellent layer (r) are easily combined, and the water-repellent layer (r) of the laminate of the present invention will be further improved Wear resistance of the side surface. The above-mentioned surface Si ratio is more preferably 5 atomic% or more, still more preferably 10 atomic% or more, more preferably 20 atomic% or more, and may be 40 atomic% or less.

The aforementioned substrate (s) may be composed of one type of material, or may be composed of two or more types of materials. Examples of the material constituting the substrate (s) include: acrylic resin, polycarbonate resin, polyester resin (polyethylene terephthalate, etc.), styrene resin, acrylic-styrene copolymer resin , Cellulose resin, polyolefin resin, vinyl resin (polyethylene, polyvinyl chloride, polystyrene, vinyl benzyl chloride resin, polyvinyl alcohol, etc.) and other thermoplastic resins; or phenol resin, urea resin, melamine resin , Epoxy resin, unsaturated polyester, polysiloxane resin, urethane resin and other thermosetting resins; or polyamide resin, polyimide resin, polyimide resin, etc. Resin materials such as engineering plastics, or metal oxides such as titanium, zirconium, aluminum, niobium, tantalum, lanthanum, or silicon.

When the above-mentioned base material (s) is made of one material, it is a resin layer, and may be a layer with a surface Si ratio of 1 atomic% or more, or may be a metal oxide layer such as silicon dioxide.

When the above-mentioned substrate (s) is composed of two or more materials, it is preferable to provide a protective layer on the resin layer to protect items from scratches for applications requiring abrasion resistance such as displays of electronic devices (Hereinafter, it may be referred to as a hard coat layer). As the material constituting the above-mentioned resin layer, the above-mentioned thermosetting resin, thermoplastic resin, or engineering plastic can be used, and polyester resin is particularly preferred. The above-mentioned hard coat layer is a layer having surface hardness, and its hardness is, for example, 2H or more in pencil hardness. The hard coat layer may have a single-layer structure or a multilayer structure. The hard coat system contains a hard coat resin. Examples of the hard coat resin include acrylic resins, epoxy resins, urethane resins, vinylbenzyl chloride resins, and vinyl resins. UV-curable, electron-beam-curable, or thermo-curable resins such as resins or silicone-based resins or mixed resins of these, preferably as described above, in the resin forming the hard coat layer, the surface The Si ratio is 1 atomic% or more. In order to express high hardness, it is particularly preferable that the hard coat layer contains an acrylic resin and has a surface Si ratio of 1 atomic% or more. From the viewpoint that the adhesiveness with the water-repellent layer (r) interposed between the intermediate layer (c) is seen to be good, it is also preferable to include an epoxy resin.

The hard coat layer may further include an ultraviolet absorber, or may include metal oxides such as silica and alumina, or inorganic fillers such as polyorganosiloxane. By including such an inorganic filler, the adhesiveness with the water-repellent layer (r) interposed between the intermediate layer (c) can be improved.

When the base material (s) is composed of two or more materials, it can be one with an anti-reflective layer on the resin layer, and it is also better to have an anti-reflective layer on a hard coat layer on the resin layer. Preferably, in this case, the resin layer, the hard coat layer, the anti-reflection layer, the intermediate layer (c), and the water-repellent layer (r) are laminated in the order. As the material constituting the above-mentioned resin layer, the above-mentioned thermosetting resin, thermoplastic resin, or engineering plastic can be used. The above-mentioned anti-reflection layer is a layer that has a function of preventing the reflection of incident light, and is a layer that exhibits a reflection characteristic with a reflectance of less than 5% in the visible light region of 380 to 780 nm. The structure of the anti-reflection layer is not particularly limited, and may be a single-layer structure or a multilayer structure. In the case of a multilayer structure, a structure in which low-refractive index layers and high-refractive index layers are alternately laminated is preferable, and the number of laminated layers is preferably 2-20 in total. Examples of the material constituting the high refractive index layer include oxides of titanium, zirconium, aluminum, niobium, tantalum or lanthanum, and examples of the material constituting the low refractive index layer include oxides of silicon (ie silicon dioxide) Wait. As the multilayer structure of the antireflection layer, preferably of SiO ₂ and ZrO _2, or SiO ₂ and Nb ₂ O ₅ are alternately laminated, and the substrate (s) of the outermost layer of the opposite side of the SiO ₂ structure. The anti-reflection layer can be formed by, for example, an evaporation method.

In the above-mentioned substrate (s), the above-mentioned reflection characteristics and/or the above-mentioned material only need to be satisfied on the outermost layer of at least the intermediate layer (c) side of the above-mentioned substrate (s). ) The thickness of the outermost layer on the side of the intermediate layer (c) is 10% or more (the thickness of the substrate (s)), more preferably 40% or more, and more preferably the substrate (s) is satisfied in the whole.

The thickness of the substrate (s) is, for example, 1 to 498 μm, preferably 1 to 300 μm, more preferably 1 to 100 μm, more preferably 10 to 95 μm, and particularly preferably 30 to 90 μm.

Regarding the water contact angle (initial contact angle) when evaluating the laminate of the present invention according to the method described in the following examples, it is, for example, 105° or more, more preferably 110° or more, and, for example, 125° or less.

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

The first method of manufacturing the laminate of the present invention includes the following steps: (i) coating the above-mentioned mixed composition (cc) on a substrate (s); (ii) coating the top of the above-mentioned mixed composition (cc) Cloth the above-mentioned mixed composition (ca); (iii) harden the above-mentioned mixed composition (cc) and the above-mentioned mixed composition (ca); form the above-mentioned intermediate layer (c) from the coating layer of the above-mentioned mixed composition (cc), The water-repellent layer (r) is formed from the coating layer of the mixed composition (ca).

As a method of applying the above-mentioned mixed composition (cc), a known method can be used, and a spin coating method or a dip coating method is preferable.

Then, the above-mentioned mixed composition (ca) for forming the water-repellent layer (r) can be applied to the coated surface of the above-mentioned mixed composition (cc) and dried to obtain The coating layer forms the intermediate layer (c), and the water-repellent layer (r) is formed from the coating layer of the mixed composition (ca). The intermediate layer (c) may be formed during the application of the mixed composition (cc), or may be formed after the application of the mixed composition (cc), or the intermediate layer (c) and the above-mentioned dialing may be carried out at the same time. The formation of water layer (r). As a method of coating the composition for forming the water-repellent layer (r), for example, dip coating method, roll coating method, bar coating method, spin coating method, spray coating method, die coating method may be mentioned. Cloth method, gravure coating method, etc.

After coating the composition for forming a water-repellent layer (r), it is allowed to stand in the air at room temperature, for example, for 1 hour or more (usually 24 hours or less) to produce the laminate of the present invention. In the present invention, the so-called normal temperature is 5 to 60°C, preferably 15 to 40°C. The humidity condition can be set to 50～90%RH when standing still at room temperature. In addition, after the composition for forming the water-repellent layer (r) is applied, it can be heated to a temperature exceeding 60°C (usually 100°C or lower; may also be 80°C or lower) for 5 minutes to 60 minutes (preferably 20°C) Minutes to 40 minutes) or so.

In addition, the second method for manufacturing the laminate of the present invention is to vapor-deposit the organic silicon compound (C) on the substrate (s) to form the intermediate layer (c), and apply the above-mentioned intermediate layer (c) to the intermediate layer (c). The mixed composition (ca) is hardened, and the above-mentioned water-repellent layer (r) is formed from the coating layer of the above-mentioned mixed composition (ca). When the aforementioned organosilicon compound (C) is vapor-deposited to form the aforementioned intermediate layer (c), a single component of the aforementioned organosilicon compound (C) can be vapor-deposited on the substrate (s), or the aforementioned organosilicon compound ( C) The mixed composition with a solvent The solid matter obtained by removing the solvent (that is, the above-mentioned organosilicon compound (C)) is vapor-deposited on the substrate (s). After coating the composition for forming a water-repellent layer (r), it may be treated in the same manner as in the above-mentioned first method.

It is preferable to perform a hydrophilization treatment on the substrate (s) before applying the composition (cc) or vapor-depositing the organosilicon compound (C). Examples of the hydrophilization treatment include corona treatment, plasma treatment, ultraviolet treatment, ion cleaning treatment, and other hydrophilization treatments, and plasma treatment and ion cleaning treatment are more preferable. By performing hydrophilization treatment such as plasma treatment, functional groups such as OH groups or COOH groups can be formed on the surface of the substrate. When such functional groups are formed on the surface of the substrate, the intermediate layer (c ) Adhesion to the above-mentioned substrate (s).

＜Flexible display device＞ The present invention also provides a flexible display device provided with the optical laminate of the present invention. The laminate of the present invention can preferably be used as a front panel in a flexible display device, and the front panel is sometimes referred to as a window film. The flexible display device preferably includes a laminate for flexible display devices and an organic EL (Electroluminescence) display panel, and the flexible display device is arranged on the visible side of the organic EL display panel. Laminated body and configured to be flexible. The laminated body for the flexible display device may further contain a polarizing plate (preferably a circular polarizing plate), a touch sensor, etc., and the order of these layers is arbitrary, preferably from the visible side, in accordance with the window film (ie , The laminated body of the present invention), the polarizer, the touch sensor, or the window film, the touch sensor, and the polarizer are laminated in the order. If there is a polarizer on the side that is more visible than the touch sensor, the pattern of the touch sensor is not easily visible, and the visibility of the displayed image becomes better, which is better. Each member can be laminated using adhesives, adhesives, etc. In addition, the flexible display device may have a light-shielding pattern formed on at least one surface of any one of the above-mentioned window film, polarizing plate, and touch sensor.

＜Circular Polarizing Plate＞ As described above, the flexible display device of the present invention preferably includes a polarizing plate, especially a circular polarizing plate. The circular polarizing plate is a functional layer that has a function of transmitting only right-handed or left-handed circularly polarized light components by laminating a λ/4 phase difference plate on the linear polarizing plate. For example, it can be used to block the external light that is converted into right-handed circularly polarized light and then reflected on the organic EL panel to become left-handed circularly polarized light outer boundary light, so that only the light-emitting component of the organic EL is transmitted, thereby suppressing the influence of the reflected light. The image is easy to see. In order to achieve the circularly polarized light function, the absorption axis of the linear polarizer and the late axis of the λ/4 retardation plate need to be 45 degrees in theory, but 45±10 degrees in practice. The linear polarizing plate and the λ/4 retardation plate do not necessarily need to be laminated adjacently, as long as the relationship between the absorption axis and the slow phase axis satisfies the above range. It is preferable to achieve complete circularly polarized light at the full wavelength, but this is not necessary in practice. Therefore, the circular polarizing plate of the present invention also includes an elliptical polarizing plate. It is also preferable to laminate a λ/4 retardation film on the visual recognition side of the linear polarizer to make the emitted light circularly polarized light, thereby improving the visual recognition in the state of wearing polarized sunglasses.

The linear polarizer is a functional layer that has the function of passing light that vibrates in the direction of the transmission axis, but blocking the polarization of the vibration component perpendicular to it. The above-mentioned linear polarizing plate may be a structure having a linear polarizing element alone or a structure having a linear polarizing element and a protective film attached to at least one surface thereof. The thickness of the linear polarizer may be 200 μm or less, preferably 0.5-100 μm. If the thickness of the linear polarizing plate is in the above range, the flexibility of the linear polarizing plate tends not to decrease easily.

The linear polarizing element described above may also be a film-type polarizing element manufactured by dyeing and stretching a polyvinyl alcohol (hereinafter, abbreviated as PVA) film. The dichroic dye such as iodine is adsorbed on the PVA-based film aligned by stretching or stretched while being adsorbed on the PVA, thereby aligning the dichroic dye to exhibit polarization performance. In the manufacture of the above-mentioned film-type polarizing element, there may be additional steps such as swelling, cross-linking with boric acid, washing with aqueous solution, and drying. The stretching or dyeing step can be performed in a PVA-based film alone, or in a state where the PVA-based film and other films such as polyethylene terephthalate are laminated. The thickness of the PVA-based film used is preferably 10-100 μm, and the above-mentioned stretching ratio is preferably 2-10 times. Furthermore, as another example of the above-mentioned polarizing element, a liquid crystal coating type polarizing element formed by applying a liquid crystal polarizing composition can be exemplified. The liquid crystal polarizing composition may include a liquid crystal compound and a dichroic dye compound. The above-mentioned liquid crystalline compound only needs to have the property of being in a liquid crystal state, and in particular, if it has an alignment state of the order of the order of smectic alignment, it can exhibit high polarization performance, so it is preferable. Moreover, it is preferable that the liquid crystal compound has a polymerizable functional group. The dichroic dye compound is a dye aligned with the liquid crystal compound to exhibit dichroism, and may have a polymerizable functional group, or the dichroic dye itself may have liquid crystallinity. Any of the compounds contained in the liquid crystal polarizing composition has a polymerizable functional group. The above-mentioned liquid crystal polarizing composition may further include a starter, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like. The above-mentioned liquid crystal polarizing layer can be manufactured by coating a liquid crystal polarizing composition on an alignment film to form a liquid crystal polarizing layer. The liquid crystal polarizing layer can be formed by being thinner than the film-type polarizing element, and its thickness is preferably 0.5-10 μm, more preferably 1-5 μm.

The above-mentioned alignment film can be produced, for example, by coating an alignment film forming composition on a substrate, and imparting alignment by rubbing, polarized light irradiation, or the like. The aforementioned alignment film forming composition includes an alignment agent, and may further include a solvent, a crosslinking agent, an initiator, a dispersant, a leveling agent, a silane coupling agent, and the like. Examples of the alignment agent include polyvinyl alcohols, polyacrylates, polyamides, and polyimines. In the case of using an alignment agent that imparts alignment properties by polarized light irradiation, it is preferable to use an alignment agent containing a cinnamate group. The weight average molecular weight of the polymer used as the above-mentioned alignment agent is, for example, about 10,000 to 1,000,000. The thickness of the alignment film is preferably 5 to 10,000 nm, and more preferably 10 to 500 nm in terms of sufficiently expressing the alignment restriction force. The liquid crystal polarizing layer may be peeled from the base material and transferred to be laminated, or the base material may be directly laminated. It is also preferable that the above-mentioned base material serves as a transparent base material of a protective film, a phase difference plate, and a window film.

As the above-mentioned protective film, any transparent polymer film may be used, and the same materials or additives as those used for the transparent substrate of the above-mentioned window film can be used. Moreover, it may be a coating type protective film obtained by applying and curing a cationic curing composition such as an epoxy resin or a radical curing composition such as an acrylate. The protective film may also contain plasticizers, ultraviolet absorbers, infrared absorbers, coloring agents such as pigments or dyes, fluorescent whitening agents, dispersants, heat stabilizers, light stabilizers, antistatic agents, Antioxidants, lubricants, solvents, etc. The thickness of the protective film is preferably 200 μm or less, more preferably 1-100 μm. If the thickness of the protective film is within the above range, there is a tendency that the flexibility of the film is not easily reduced.

The above-mentioned λ/4 retardation plate is a film that provides a λ/4 retardation in a direction perpendicular to the traveling direction of incident light (in-plane direction of the film). The above-mentioned λ/4 retardation plate may be a stretched retardation plate manufactured by stretching a polymer film such as a cellulose-based film, an olefin-based film, or a polycarbonate-based film. The above-mentioned λ/4 retardation plate may optionally contain retardation modifiers, plasticizers, ultraviolet absorbers, infrared absorbers, coloring agents such as pigments or dyes, fluorescent brighteners, dispersants, heat stabilizers, Light stabilizers, antistatic agents, antioxidants, lubricants, solvents, etc. The thickness of the above-mentioned extended phase difference plate is preferably 200 μm or less, more preferably 1-100 μm. If the thickness of the extended phase difference plate is in the above range, the flexibility of the extended phase difference plate tends to be less likely to decrease. Furthermore, as another example of the above-mentioned λ/4 retardation plate, a liquid crystal coating type retardation plate formed by applying a liquid crystal composition can be exemplified. The above-mentioned liquid crystal composition contains a liquid crystal compound in a liquid crystal state such as nematic, cholesterol, smectic, and the like. The above-mentioned liquid crystal compound has a polymerizable functional group. The above-mentioned liquid crystal composition may further include a starter, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like. The liquid crystal coating type retardation plate is the same as the liquid crystal polarizing layer, and can be manufactured by coating a liquid crystal composition on a substrate and curing to form a liquid crystal retardation layer. The liquid crystal coating type retardation plate can be formed thinner than the extension type retardation plate. The thickness of the above-mentioned liquid crystal polarizing layer is preferably 0.5 to 10 μm, more preferably 1 to 5 μm. The liquid crystal coating type retardation plate may be peeled from the base material and transferred to be laminated, or the base material may be directly laminated. The above-mentioned base material is also preferably used as a transparent base material for a protective film, a phase difference plate, and a window film.

Generally speaking, most materials show a tendency that the shorter the wavelength, the greater the birefringence, and the longer the wavelength, the smaller the birefringence. In this case, the phase difference of λ/4 cannot be achieved in the full visible light region. Therefore, the in-plane phase difference is designed to be preferably 100-180 nm, more preferably 130-150 nm, so that The high sensitivity near 560 nm becomes λ/4. The reverse dispersion λ/4 retardation plate using a material having a birefringence wavelength dispersion characteristic opposite to the usual one is preferable in terms of good visibility. As such a material, for example, the extension type retardation plate can be described in Japanese Patent Laid-Open No. 2007-232873, and the liquid crystal coating type retardation plate can be used as described in the Japanese Patent Laid-Open No. 2010-30979. In addition, as another method, a technique of obtaining a wide-band λ/4 retardation plate by combining with a λ/2 retardation plate is also known (for example, Japanese Patent Laid-Open No. 10-90521, etc.). The λ/2 retardation plate can also be manufactured by the same materials and methods as the λ/4 retardation plate. The combination of the extension type retardation plate and the liquid crystal coating type retardation plate is arbitrary, and the thickness can be reduced by using the liquid crystal coating type retardation plate. A method of laminating a positive C plate on the above-mentioned circular polarizing plate to improve the visibility in an oblique direction is known (for example, Japanese Patent Laid-Open No. 2014-224837, etc.). The positive C plate can be a liquid crystal coating type retardation plate or an extended type retardation plate. The retardation in the thickness direction of the retardation plate is preferably -200 to -20 nm, more preferably -140 to -40 nm.

＜Touch sensor＞ As described above, the flexible display device of the present invention preferably has a touch sensor. The touch sensor can be used as an input mechanism. As the touch sensor, various types such as a resistive film method, a surface acoustic wave method, an infrared method, an electromagnetic induction method, and an electrostatic capacitance method can be exemplified, and an electrostatic capacitance method is preferable. The capacitive touch sensor is divided into an active area and an inactive area located at the outer contour of the active area. The active area is the area corresponding to the area (display part) of the display panel in the display panel, and the active area will perceive the user's touch, and the inactive area corresponds to the area (non-display part) of the display device that does not display the picture的区。 The area. The touch sensor may include: a substrate with flexible characteristics; a sensing pattern formed on the active area of the substrate; and an inactive area formed on the substrate for communication with the outside via the sensing pattern and the bonding pad. Each sensing line connected to the drive circuit. As a substrate with flexible properties, the same material as the transparent substrate of the above-mentioned window film can be used.

The aforementioned sensing pattern may include a first pattern formed in the first direction and a second pattern formed in the second direction. The first pattern and the second pattern are arranged in different directions. The first pattern and the second pattern are formed on the same layer, and each pattern must be electrically connected in order to sense the touched part. The first pattern is a form in which a plurality of unit patterns are connected to each other through a joint, and the second pattern is a structure in which a plurality of unit patterns are separated from each other into an island shape. Therefore, in order to electrically connect the second pattern, an additional bridge electrode is required. Regarding the electrode for connecting to the second pattern, a well-known transparent electrode can be used. Examples of the material of the transparent electrode include: indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium zinc tin oxide (IZTO), indium gallium zinc oxide (IGZO), cadmium oxide Tin (CTO), PEDOT (poly(3,4-ethylenedioxythiophene), poly(3,4-ethylenedioxythiophene)), carbon nanotube (CNT), graphene, metal wire, etc., preferably available Take ITO as an example. These can be used individually or in mixture of 2 or more types. The metal used in the metal wire is not particularly limited, for example, silver, gold, aluminum, copper, iron, nickel, titanium, telenium, chromium, etc., can be used alone or in a mixture of two or more . The bridge electrode can be formed on the upper part of the above-mentioned insulating layer via the insulating layer on the upper part of the sensing pattern, and the bridge electrode can be formed on the substrate, and the insulating layer and the sensing pattern can be formed thereon. The above-mentioned bridge electrode can also be formed using the same material as the sensing pattern, or can be formed using molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium, or an alloy of two or more of these. Since the first pattern and the second pattern must be electrically insulated, an insulating layer is formed between the sensing pattern and the bridge electrode. The insulating layer may be formed only between the joints of the first pattern and the bridging electrodes, or may be formed in the form of a layer covering the entire sensing pattern. In the case of covering the whole layer of the sensing pattern, the bridge electrode may be connected to the second pattern through the contact hole formed in the insulating layer.

The above-mentioned touch sensor may further include an optical adjustment layer between the substrate and the electrode to appropriately compensate for the difference in transmittance between the pattern area where the sensing pattern is formed and the non-pattern area where the sensing pattern is not formed (specifically, In other words, the difference in light transmittance induced by the difference in refractive index in these regions). The optical adjustment layer may include an inorganic insulating material or an organic insulating material. The optical adjustment layer can be formed by coating a photo-curing composition containing a photo-curing organic adhesive and a solvent on a substrate. The above-mentioned photocurable composition may further contain inorganic particles. The above-mentioned inorganic particles can increase the refractive index of the optical adjustment layer. The above-mentioned photocurable organic adhesive may include copolymers of monomers such as acrylic ester monomers, styrene monomers, and carboxylic acid monomers within a range that does not impair the effects of the present invention. The photocurable organic adhesive may be, for example, a copolymer containing different repeating units such as epoxy-containing repeating units, acrylate repeating units, and carboxylic acid repeating units. Examples of the above-mentioned inorganic particles include zirconia particles, titania particles, and alumina particles. The above-mentioned photocurable composition may further contain various additives such as a photopolymerization initiator, a polymerizable monomer, and a curing auxiliary agent.

＜Adhesive layer＞ The layers (window film, circular polarizer, touch sensor) and the film members (linear polarizer, λ/4 phase difference plate, etc.) constituting each layer can be formed by Adhesives are used for joining. As the adhesive, water-based adhesives, organic solvent-based, solvent-free adhesives, solid adhesives, solvent-volatile adhesives, moisture-curing adhesives, heat-curing adhesives, anaerobic-curing adhesives, and active adhesives can be used. Commonly used adhesives, such as energy ray hardening adhesive, hardener mixed adhesive, hot-melt adhesive, pressure sensitive adhesive (adhesive), remoisturizing adhesive, etc., preferably water-based Solvent volatile adhesive, active energy ray hardening adhesive, adhesive. The thickness of the adhesive layer can be appropriately adjusted depending on the required adhesive force, etc., preferably 0.01-500 μm, more preferably 0.1-300 μm. There are a plurality of adhesive layers in the above-mentioned laminate for flexible image display devices, and the thickness or type of each may be the same or different.

As the above-mentioned aqueous solvent volatile adhesive, water-dispersed polymers such as polyvinyl alcohol-based polymers, starches, etc., ethylene-vinyl acetate-based latex, styrene-butadiene-based latex, and other water-dispersed polymers can be used as the main components. Agent polymer. In addition to the above-mentioned main agent polymer and water, crosslinking agents, silane-based compounds, ionic compounds, crosslinking catalysts, antioxidants, dyes, pigments, inorganic fillers, organic solvents, etc. can also be formulated. In the case of bonding by the above-mentioned water-based solvent-volatile adhesive, adhesiveness can be imparted by injecting the above-mentioned water-based solvent-volatile adhesive between the layers to be bonded to bond the bonded layers, and then drying . In the case of using the above-mentioned water-based solvent-volatile adhesive, the thickness of the adhesive layer is preferably 0.01-10 μm, more preferably 0.1-1 μm. When the above-mentioned water-based solvent-volatile adhesive is used for multiple layers, the thickness or type of each layer may be the same or different.

The active energy ray curable adhesive can be formed by curing an active energy ray curable composition that includes a reactive material that forms an adhesive layer by irradiating active energy rays. The active energy ray hardening composition may contain at least one polymer that is the same as the radical polymerizable compound and the cationic polymerizable compound contained in the hard coat composition. The radical polymerizable compound can be the same compound as the radical polymerizable compound in the hard coat composition. As the above-mentioned cationically polymerizable compound, the same compound as the cationically polymerizable compound in the hard coat composition can be used. As the cationic polymerizable compound used in the active energy ray hardening composition, an epoxy compound is particularly preferred. In order to reduce the viscosity of the adhesive composition, it is preferable to include a monofunctional compound as a reactive diluent.

The active energy ray composition may contain monofunctional compounds to reduce viscosity. Examples of the monofunctional compound include: an acrylate monomer having one (meth)acrylic acid group in one molecule, or a compound having one epoxy group or oxetanyl group in one molecule , Such as glycidyl (meth)acrylate and the like. The active energy ray composition may further include a polymerization initiator. As this polymerization initiator, a radical polymerization initiator, a cationic polymerization initiator, a radical and a cationic polymerization initiator, etc. can be mentioned, These can be selected suitably and used. The polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate free radicals or cations, thereby allowing radical polymerization and cationic polymerization to proceed. In the description of the hard coating composition, an initiator capable of starting at least any one of radical polymerization or cationic polymerization by active energy ray irradiation can be used. The active energy ray hardening composition may further include an ion scavenger, an antioxidant, a chain transfer agent, an adhesion imparting agent, a thermoplastic resin, a filler, a fluid viscosity adjuster, a plasticizer, a defoamer solvent, an additive, and a solvent. In the case where two adhesive layers are bonded by the above-mentioned active energy ray-curing adhesive, the bonding can be performed by applying the above-mentioned active energy ray-curing composition to either or both of the layers to be bonded. After that, bonding is performed, and any one of the bonded layers or two of the bonded layers is irradiated with active energy rays to harden them. In the case of using the active energy ray-curable adhesive, the thickness of the adhesive layer is preferably 0.01-20 μm, more preferably 0.1-10 μm. When the above-mentioned active energy ray-curable adhesive is used for the formation of a plurality of adhesive layers, the thickness or type of each layer may be the same or different.

As the above-mentioned adhesive, depending on the main agent polymer, any one classified into an acrylic adhesive, a urethane adhesive, a rubber adhesive, and a silicone adhesive may be used. In addition to the main agent polymer, the adhesive can also be formulated with crosslinking agents, silane-based compounds, ionic compounds, crosslinking catalysts, antioxidants, adhesion imparting agents, plasticizers, dyes, pigments, inorganic fillers, etc. Dissolve and disperse the components constituting the above-mentioned adhesive in a solvent to obtain an adhesive composition, apply the adhesive composition on a substrate, and then dry it to form an adhesive layer. Floor. The adhesive layer can be formed directly, or it can be formed on the substrate by transfer printing. In order to protect the adhesive surface before bonding, it is also preferable to use a release film. In the case of using the above-mentioned active energy ray-curable adhesive, the thickness of the adhesive layer is preferably 0.1 to 500 μm, more preferably 1 to 300 μm. When the above-mentioned adhesive is used for multiple layers, the thickness or type of each layer may be the same or different.

＜Shading pattern＞ The above-mentioned light-shielding pattern can be applied as at least a part of the frame or housing of the above-mentioned flexible image display device. With the light-shielding pattern, the wiring arranged at the edge of the flexible image display device is hidden and cannot be easily recognized, thereby improving the visibility of the image. The above-mentioned light-shielding pattern may be in the form of a single layer or multiple layers. The color of the shading pattern is not particularly limited, and can be various colors such as black, white, and metallic. The light-shielding pattern can be formed by pigments used to express colors, and polymers such as acrylic resins, ester resins, epoxy resins, polyurethanes, and silicones. These can also be used alone or in the form of a mixture of two or more kinds. The above-mentioned light-shielding pattern can be formed by various methods such as printing, lithography, and inkjet. The thickness of the light-shielding pattern is preferably 1-100 μm, more preferably 2-50 μm. Moreover, it is also preferable to give a shape such as an inclination in the thickness direction of the light-shielding pattern. [Example]

Hereinafter, the present invention will be explained in more detail with examples. The present invention is not limited by the following embodiments. Of course, it can be implemented with appropriate changes within the scope that can conform to the above-mentioned and following gist, and these are all included in the technical scope of the present invention.

The layers or laminates obtained in the following Examples and Comparative Examples were evaluated by the following methods.

Determination of the surface Si ratio of the substrate (s) and the surface fluorine ratio of the water-repellent layer (r) Use JFS-9010 manufactured by JEOL Co., Ltd., excited X-ray: MgKα, X-ray output is set to 110 W, photoelectron escape angle is 45°, to pass energy 50 eV for the fluorine (F1s) of the water-repellent layer (r) , The substrate (s) of various elements of silicon are measured.

Determination of the arithmetic mean height Sa Using a laser microscope (OLS4000, manufactured by Olympus), observe the surface of the water-repellent layer (r) of the laminate at a magnification of 20 times. The arithmetic average height Sa is evaluated in accordance with ISO25178. The arithmetic average height Sa is the average value of N=2.

Contact angle and sliding angle Drop 3.0 μL of water droplets on the water-repellent layer (r) of the obtained laminate, and use a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., DM700) to measure the liquid volume by the θ/2 method: 3.0 μL of water The contact angle. In addition, 6.0 μL of water droplets were dropped on the water-repellent layer (r) of the obtained laminate, and the above-mentioned contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., DM700) was used by the sliding method (amount of water drop: 6.0 μL, Tilting method: continuous tilting, sliding detection: after sliding, sliding judgment distance: 0.25 mm) Determine the dynamic water-repellent characteristics (sliding angle) of the water-repellent layer (r) surface of the laminated body.

Surface reflectance Using a colorimeter (CM-3700A, light source: D65) manufactured by Konica Minolta, measured from the surface of the water-repellent layer (r) of the laminate by using the 2 degree field of view (light source C) of JIS Z8701 Spectral reflectance at a wavelength of 530 nm at an incident angle of 12° and a reflection angle of 12°. From this value, the surface reflection loss of 4.2% and the back surface reflection loss of 4.2% were subtracted to calculate the reflectance. In addition, the surface reflectance on the side surface of the intermediate layer (c) of the substrate (s) was also measured in the same manner.

Abrasion resistance test Use a steel wool tester (manufactured by Daiei Seiki Co., Ltd.) equipped with steel wool #0000 (manufactured by BONSTAR), with the steel wool in contact with the surface of the laminate (water repellent layer (r)), and apply a load of 1000 g. In the abrasion test, the test is repeated until peeling and damage are visually confirmed, and the abrasion resistance is evaluated by the number of tests when the peeling and damage are confirmed. In addition, confirmation of the presence or absence of peeling and damage was performed at an illuminance of 1000 lux.

Thickness measurement The thickness of the substrate (s) was measured using DIGIMICRO (model: MFC-101A) manufactured by Nikon Corporation. Furthermore, in any of the Examples and Comparative Examples, the thickness of the water-repellent layer (r) is a few nm, and the thickness of the intermediate layer (c) is about 5-30 nm.

Example 1 The N-2-(aminoethyl)-3-aminopropyltrimethoxysilane described in Japanese Patent Laid-Open No. 2012-197330, which is represented by the following formula as the organosilicon compound (C), and chlorine The reactant of propyltrimethoxysilane (trade name; X-12-5263HP, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.25% by mass was mixed with 99.75% by mass of hexane as the solvent (E), and the resulting solution was mixed in Stirring was performed at room temperature to obtain a solution for forming the intermediate layer (c).

[化24]

Then, an AR (Anti-reflection) film with a thickness of 84 μm is prepared as the substrate(s). _{The above-mentioned AR film is a film in which SiO 2} and metal oxides (except for SiO ₂ ) are alternately laminated on a resin layer by a vacuum vapor deposition method, and the outermost surface is made of SiO ₂ . The surface Si ratio of the substrate (s) measured by the above method is 31.5 atomic %. The surface of the above AR film was activated by atmospheric piezoelectric slurry treatment. On the activated surface, the OPTICOAT MS-A100 (spin coater) manufactured by MIKASA Co., Ltd. was used with a coating liquid volume of 200 μl and a rotation speed of 2000. The solution for forming the intermediate layer (c) was applied under conditions of rpm and rotation seconds of 20 seconds to obtain the intermediate layer (c).

Then, OPTOOL (registered trademark) UF503 manufactured by DAIKIN INDUSTRIES Co., Ltd. as the organosilicon compound (A) (containing 20% by mass of the organosilicon compound (A), and 80% by mass of Novec 7200 as a solvent) was used as the organosilicon Compound (B) FAS13E (C ₆ F ₁₃ -C ₂ H ₄ -Si (OC ₂ H ₅ ) ₃ , manufactured by Tokyo Chemical Industry Co., Ltd.), and FC-3283 (C ₉ F _{21) as solvent (D)} N, Fluorinert (manufactured by 3M Company) and mixed and stirred at room temperature for a specific time to obtain a solution for forming a water-repellent layer (r). Here, OPTOOL (registered trademark) UF503 is an organosilicon compound in which a monovalent group and a hydrolyzable group having a perfluoropolyether structure are respectively bonded to silicon atoms. The ratio (solid content) of the organosilicon compound (A) in 100% by mass of the water-repellent layer (r) forming solution was 0.085% by mass, and the ratio of the organosilicon compound (B) was 0.05% by mass. The solution for forming the water-repellent layer (r) was coated on the intermediate layer (c) using a spray coater manufactured by Apiros Co., Ltd. The spraying conditions are: scanning speed: 600 mm/sec, spacing: 5 mm, liquid volume: 6 cc/min, atomizing air: 350 kPa, gap: 70 mm. Thereafter, it was fired at 80°C for 30 minutes to obtain a laminate including the base material (s), the intermediate layer (c), and the water-repellent layer (r) in this order.

Example 2 The base material (s) was changed to an AR film with a surface Si ratio of 31.3 atomic %, except that the same method as in Example 1 was used to obtain the base material (s), the intermediate layer (c), and the water repellent in this order. The layered body of layer (r).

Example 3 Except for using butyl acetate as the solvent (E), in the same manner as in Example 2, a laminate including the substrate (s), the intermediate layer (c), and the water-repellent layer (r) in this order was obtained.

Example 4 The base material (s) was changed to a hard coat film with a thickness of 45 μm, except that the same method as in Example 1 was used to obtain a base material (s), an intermediate layer (c), and a water-repellent layer ( r) The laminated body. The above-mentioned hard coat film is formed by laminating an acrylic hard coat layer with a surface Si ratio of 1.8 at% on a resin layer containing polyethylene terephthalate. The acrylic hard coat layer is applied to the surface of the hard coat film. Those who have undergone the same activation treatment as in Example 1 by atmospheric pressure electric slurry treatment.

Example 5 The organosilicon compound (C) was changed to KBM-903 (manufactured by Shin-Etsu Chemical Co., Ltd.), and butyl acetate was used as the solvent (E), except that the sequential inclusion group was obtained in the same manner as in Example 1. Laminated body of material (s), intermediate layer (c), and water-repellent layer (r).

Comparative example 1 The base material (s) was changed to an acrylic hard coat layer with a thickness of 60 μm and a surface Si ratio of 0 atomic %, except that the same method as in Example 1 was used to obtain the base material (s), the middle The layered body of layer (c) and water-repellent layer (r).

Comparative example 2 Except for changing the solvent (E) to methyl ethyl ketone, in the same manner as in Comparative Example 1, a laminate layer including a substrate (s), an intermediate layer (c), and a water-repellent layer (r) in this order was obtained in the same manner as in Comparative Example 1. body.

The laminates obtained in the examples and comparative examples were evaluated by the above methods, and the obtained results are shown in Table 1.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2 Water repellent layer (r) Organosilicon compound (A) UF503 UF503 UF503 UF503 UF503 UF503 UF503 0.425% 0.425% 0.425% 0.425% 0.425% 0.425% 0.425% Organosilicon compound (B) FAS13E FAS13E FAS13E FAS13E FAS13E FAS13E FAS13E 0.05% 0.05% 0.05% 0.05% 0.05% 0.05% 0.05% Solvent (D) FC3283 FC3283 FC3283 FC3283 FC3283 FC3283 FC3283 99.525% 99.525% 99.525% 99.525% 99.525% 99.525% 99.525% Intermediate layer (c) Organosilicon compound (C) X-12-5263HP X-12-5263HP X-12-5263HP X-12-5263HP KBM903 X-12-5263HP X-12-5263HP 0.25% 0.25% 0.25% 0.25% 0.25% 0.25% 0.25% Solvent (E) Hexane Hexane Butyl acetate Hexane Butyl acetate Hexane MEK 99.75% 99.75% 99.75% 99.75% 99.75% 99.75% 99.75% Substrate(s) Thickness μm 84 84 84 45 84 60 60 Surface Si ratio atm% 31.5 31.3 31.3 1.8 31.5 0 0 Surface reflectance% (530 nm) 0.70 0.63 0.63 4.25 0.70 4.83 4.83 Multilayer evaluation Initial contact angle ° 116.1 115.8 116.1 115.8 117.2 113.3 117 Slip angle ° 8 10 23.5 6 28 39 27.5 Surface reflectance %(530 nm) 1.36 0.77 1.09 4.22 0.69 4.88 4.8 Arithmetic mean height Sa μm 0.040 0.076 0.101 0.062 0.141 0.029 1.067 Abrasion resistance test Number of damages 20000 15000 4000 5000 1000 200 100＞ Surface F ratio atm% 53.1 52.4 49.4 55.9 49.4 50.7 53.2 [Industrial availability]

The laminated body of the present invention can be used in display devices such as touch panel displays, optical components, semiconductor components, building materials, nanoimprint technology, solar cells, metal products such as window glass of automobiles or buildings, conditioning appliances, and ceramics such as tableware. The film is preferably formed on products, plastic automobile parts, etc., and is useful in industry. In addition, it can also be used well in kitchens, bathrooms, wash basins, mirrors, and other parts around the toilet.

Claims (7)

A laminate, characterized in that it is provided with a substrate (s), an intermediate layer (c), and a water-repellent layer (r) in this order, and meets the following necessary conditions (1) and (2); (1) Calculate the spectral reflectance at a wavelength of 530 nm at an incident angle of 12° and a reflection angle of 12° measured on the surface of the water-repellent layer (r) with a 2 degree field of view (light source C) of JIS Z8701. The reflectance obtained by subtracting the surface reflection loss and the back surface reflection loss is less than 4.5%; (2) The thickness of the above-mentioned laminate is 500 μm or less. For example, the layered body of claim 1, which further satisfies the necessary conditions of (3) below: (3) The surface fluorine element ratio on the side of the water-repellent layer (r) is 30 atomic% or more. Such as the laminated body of claim 1 or 2, which further meets at least 1 of the following necessary conditions (4) and (5): (4) The arithmetic average height Sa on the side of the water-repellent layer (r) is 0.03～1.00 μm; (5) The sliding angle of the water on the side of the water-repellent layer (r) is 25° or less. The laminate according to any one of claims 1 to 3, wherein the surface Si ratio of the outermost layer on the side of the intermediate layer (c) of the substrate (s) is 1 atomic% or more. The laminate of any one of claims 1 to 4, wherein the water-repellent layer (r) is an organosilicon compound (A) represented by the following formula (a1) and an organosilicon represented by the following formula (b1) The hardened layer of the mixed composition (ca) of the compound (B); [化1]

In the above 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 with 1 to 20 carbon atoms, and there are plural when the case of R ^11, the plurality of R ¹¹ may vary when in the presence of the case of a plurality of R ¹² s, the plurality of R ¹² may be different when in the presence of the case of a plurality of R ^13, the plurality of R ¹³ may each Not the same, E ¹ , E ² , E ³ , E ⁴ , and E ⁵ are each independently a hydrogen atom or a fluorine atom. When there are plural E ^{1 s} , the plural E ¹ may be different from each other. when two E scenario ^2, the plurality of E ² may be different when in the presence of a plurality of case E ^3, the plurality of E ³ may be varied, while in the case of ⁴ the presence of a plurality of E, a plurality of E ⁴ may be Each is different. When there are a plurality of E ⁵ , the plurality of E ⁵ can be different. G ¹ and G ² are independently a 2-10 valent organosiloxane alkyl group with a siloxane bond, 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, and there are multiple J ¹ In this case, the plural J ¹ may be different from each other. When there are plural J ^2s , the plural J ² may be different from each other. When there are plural J ³ , the plural J ³ may be different from each other. , L ¹ and L ² are each independently a divalent linking group with 1 to 12 carbon atoms that may contain an oxygen atom, a nitrogen atom, or a fluorine atom. When there are plural L ^1s , the plural L ^1s may be different Same, when there are a plurality of L ^2s , the plurality of L ^2s can be different, d11 is 1-9, d12 is 0-9, a10 and a14 are independently 0-10, and a11 and a15 are independently Is 0 or 1, a12 and a16 are each independently 0-9, a13 is 0 or 1, a21, a22, and a23 are each independently 0-2, e1, e2, and e3 are each independently 1 to 3; [化2]

In the above 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 a hydrogen atom Or an alkyl group with 1 to 4 carbon atoms. When there are plural R ^b11 , the plural R ^b11 may be different from each other. When there are plural R ^b12 , the plural R ^b12 may be different from each other. When there are a plurality of R ^b13 , the plurality of R ^b13 can be different, when there are a plurality of R ^b14 , the plurality of R ^b14 can be different, Rf ^b11 , Rf ^b12 , Rf ^b13 and Rf ^b14 are independent respectively Ground is a C1-C20 alkyl group or fluorine atom where one or more hydrogen atoms are substituted with fluorine atoms. When there are more than one Rf ^b11 , the plurality of Rf ^b11 may be different. When there are more than one Rf ^b12 In this case, the plurality of Rf ^b12 can be different. When there are a plurality of Rf ^b13 , the plurality of Rf ^b13 can be different. When there are a plurality of Rf ^b14 , the plurality of Rf ^b14 can be different. , R ^b15 is an alkyl group with 1 to 20 carbons. When there are plural R ^b15 , the plural R ^b15 can be different. A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, the above R is a hydrogen atom, an alkyl group with 1 to 4 carbons or a carbon number of 1 to 4 For the fluorine-containing alkyl group, when there are multiple A ¹ , the multiple A ¹ can be different, and A ² is a hydrolyzable group. When there are multiple A ^2s , the multiple A ² can be different , B11, b12, b13, b14, and b15 are each independently an integer from 0 to 100, c is an integer from 1 to 3, regarding Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c , b11 -{C(R ^b11 )(R ^b12 )}-、b12pcs-{C(Rf ^b11 )(Rf ^b12 )}-、b13pcs-{Si(R ^b13 )(R ^b14 )}-、b14pcs-{ Si(Rf ^b13 )(Rf ^b14 )}-, b15 -A ¹ -, as long as Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c become the ends, do not form a perfluoropolyether structure, and -O- is not connected with -O- or -F, and the bonds are arranged in any order. The laminate according to any one of claims 1 to 5, wherein the intermediate layer (c) is a mixed composition of an organosilicon compound (C) represented by any one of the following formulas (c1) to (c3) ( cc) the hardened layer or the vapor-deposited layer of the above-mentioned organosilicon compound (C); [化3]

In the above formula (c1), R ^x11 , R ^x12 , R ^x13 , and R ^x14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When there are multiple R ^x11 , multiple R ^x11 may be Each is different. When there are multiple R ^x12 , the multiple R ^x12 can be different. When there are multiple R ^x13 , the multiple R ^x13 can be different. When there are multiple R ^x14 When, a plurality of R ^x14 may be different, Rf ^x11 , Rf ^x12 , Rf ^x13 , and Rf ^x14 are each independently an alkyl group with 1-20 carbon atoms or fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms. When there are a plurality of Rf ^x11 , the plurality of Rf ^x11 can be different, when there are a plurality of Rf ^x12 , the plurality of Rf ^x12 can be different from each other, when there are a plurality of Rf ^x13 , the plurality of Rf ^x13 can be different. When there are multiple Rf ^x14 , the multiple Rf ^x14 can be different. R ^x15 is an alkyl group with 1 to 20 carbon atoms. When there are multiple R ^x15 , multiple R ^x15 can be different from each other, X ¹¹ is a hydrolyzable group, when there are multiple X ¹¹ , the multiple X ¹¹ can be different from each other, Y ¹¹ is -NH- or -S-, when there are multiple Y ^In the case of 11, the plural Y ¹¹ can be different, and Z ¹¹ is a vinyl group, α-methyl vinyl group, styryl group, methacryl group, acryl group, amine group, isocyanate group, and isocyanate group. Cyanuric acid group, epoxy group, ureido group, or mercapto group, p1 is an integer of 1-20, p2, p3, and p4 are each independently an integer of 0-10, p5 is an integer of 1-10, and p6 is an integer of 1-3 When Z ^{11 is} not an amine group, at least one of ^{Y 11 is -NH-, and when all Y 11} is -S-, Z ¹¹ is an amine group. Regarding Z ¹¹ -, -Si (X ¹¹ ) _p6 (R ^x15 ) _3-p6 ^{, p1 pcs-} (C(R x11 )(R ^x12 ))-, p2 ^pcs- (C(Rf x11 )(Rf ^x12 ))-, p3 pcs-(Si (R ^x13 )(R ^x14 )}-, p4 -{Si(Rf ^x13 )(Rf ^x14 )}-, p5 -Y ¹¹ -, as long as Z ¹¹ -and -Si(X ¹¹ ) _p6 (R ^x15 ) _3-p6 becomes the end, -O- is not connected with -O-, then the bonds are arranged in any order; [化4]

In the formula (c2), R ^x20 and R ^x21 are each independently a hydrogen atom or an alkyl group having a carbon number of 1 to 4, when in the presence of a plurality of R ^x20 case, a plurality of R ^x20 may vary, the presence of when a plurality of R ^x21 case, a plurality of R ^x21 may vary, Rf ^x20 and Rf ^x21 each independently one or more hydrogen atoms are substituted with fluorine atoms to carbon atoms of the fluorine atom or an alkyl group of 1 to 20, in When there are a plurality of Rf ^x20 , the plurality of Rf ^x20 can be different, when there are a plurality of Rf ^x21 , the plurality of Rf ^x21 can be different from each other, and R ^x22 and R ^x23 are each independently with a carbon number of 1. The alkyl group of ~20, when there are multiple R ^x22 and R ^x23 , the multiple R ^x22 and R ^x23 can be different from each other, X ²⁰ and X ²¹ are each independently a hydrolyzable group, and there are multiple X ²⁰ and the case of X ²¹ when, a plurality of X ²⁰ and X ²¹ can vary, p20 each independently an integer of 1 to 30, the p21 each independently integers of 0 to 30, the attachment p20 or p21 and parentheses At least one of the repeating units is substituted with an amine skeleton -NR ^{100 -, R 100} in the above amine skeleton is a hydrogen atom or an alkyl group, p22 and p23 are each independently an integer of 1 to 3, and p20 -{C( R ^x20 )(R ^x21 )}-, p21-{C(Rf ^x20 )(Rf ^x21 )}- No need to p20 or p21 consecutive, arrange the bonding in any order, the two ends become -Si(X ²⁰ ) _p22 (R ^x22 ) _3-p22 and -Si(X ²¹ ) _p23 (R ^x23 ) _3-p23 ; [化5]

In the above formula (c3), Z ³¹ and Z ³² are each independently a reactive functional group other than a hydrolyzable group and a hydroxyl group, and R ^x31 , R ^x32 , R ^x33 , and R ^x34 are each independently a hydrogen atom or a carbon number For the alkyl groups of 1 to 4, when there are multiple R ^x31 , the multiple R ^x31 can be different. When there are multiple R ^x32 , the multiple R ^x32 can be different. ^In the case of x33, the plurality of R ^x33 can be different. When there are a plurality of R ^x34 , the plurality of R ^x34 can be different. Rf ^x31 , Rf ^x32 , Rf ^x33 , and Rf ^x34 are each independently one The above hydrogen atoms are substituted with fluorine atoms and C1-C20 alkyl groups or fluorine atoms. When there are a plurality of Rf ^x31 , the plurality of Rf ^x31 may be different. When there are a plurality of Rf ^x32 , The plurality of Rf ^x32 can be different. When there are a plurality of Rf ^x33 , the plurality of Rf ^x33 can be different. When there is a plurality of Rf ^x34 , the plurality of Rf ^x34 can be different, and Y ³¹ is -NH-, -N(CH ₃ )- or -O-, when there are a plurality of Y ³¹ , the plurality of Y ³¹ can be different from each other, X ³¹ , X ³² , X ³³ , X ³⁴ 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 alkoxysilyl group), when there are a plurality of X ³¹ , The plurality of X ³¹ can be different. When there are a plurality of X ³² , the plurality of X ³² can be different. When there is a plurality of X ³³ , the plurality of X ³³ can be different. In the case of X ³⁴ , a plurality of X ³⁴ may be different, p31 is an integer from 0 to 20, p32, p33, and p34 are each independently an integer from 0 to 10, p35 is an integer from 0 to 5, and p36 is 1. An integer of ~10, p37 is 0 or 1, as long as ^{at least one of Z 31} and Z ³² is an amino group, or ^{at least one of Y 31} is -NH- or -N(CH ₃ )-, and the end Z ³¹ -and Z ³² -, -O- is not connected with -O-, then ^p31- {C(R x31 )(R ^x32 )}-, ^p32- {C(Rf x31 )(Rf ^x32 )} -, p33-{Si(R ^x33 )(R ^x34 ))-, p34-{Si(Rf ^x33 )(Rf ^x34 )}-, p35-Y ³¹ -, p36-{Si(X ³¹ ) (X ³² )-O}-, p37-{Si(X ³³ )(X ³⁴ )}- are formed by arranging the bonds in any order. A flexible display device, which comprises a laminated body as claimed in any one of claims 1 to 6, a polarizing plate, a touch sensor, and a display panel.