JP6934002B2 - Laminate - Google Patents

Description

The present invention relates to a laminate.

Since the surface free energy of a film formed from a composition containing a compound having a perfluoropolyether structure is very small, display devices such as touch panel displays, optical elements, semiconductor elements, building materials, windows of automobiles and buildings It is used as an antifouling coating, a water-repellent oil-repellent coating, and the like in various fields such as glass.

When a composition containing a compound having a perfluoropolyether structure is applied to a base material, another layer such as a primer layer is formed on the base material in advance, and then the composition is applied to provide an antifouling coating or water repellency. May form an oil repellent coating.

For example, Patent Document 1 describes a hard coat film in which a hard coat layer (X), a primer layer (Y), and a surface layer (Z) are laminated in this order on at least one surface of a base material, and the surface layer (X). A hard coat film having a water contact angle of 110 ° or more in Z) is disclosed. In order to form the surface layer (Z), it is preferable to use a fluorine-based compound having a polyperfluoropolyether chain, and in order to form the primer layer (Y), 3-acryloxypropyltri It is described that a silane compound such as methoxysilane is preferable.

JP-A-2015-120253

When a film formed from a composition containing a compound having a perfluoropolyether structure is laminated with a substrate via another layer, it may be exposed to a chemical such as alcohol depending on the application. In such cases, it is required that good performance (water repellency, etc.) can be maintained even after being exposed to chemicals (hereinafter referred to as chemical resistance).

Therefore, the present invention is a laminate in which a layer formed from a composition containing a compound having a perfluoropolyether structure is laminated with a base material via another layer, and is a laminate having excellent chemical resistance. The purpose is to provide.

The present invention that has achieved the above problems is as follows.

上記式（ａ１）中、
Ｒｆ^a1は、両端が酸素原子である２価のパーフルオロポリエーテル構造であり、
Ｒ¹¹、Ｒ¹²、及びＲ¹³は、それぞれ独立して炭素数１〜２０のアルキル基であり、Ｒ¹¹が複数存在する場合は複数のＲ¹¹がそれぞれ異なっていてもよく、Ｒ¹²が複数存在する場合は複数のＲ¹²がそれぞれ異なっていてもよく、Ｒ¹³が複数存在する場合は複数のＲ¹³がそれぞれ異なっていてもよく、
Ｅ¹、Ｅ²、Ｅ³、Ｅ⁴、及びＥ⁵は、それぞれ独立して水素原子又はフッ素原子であり、Ｅ¹が複数存在する場合は複数のＥ¹がそれぞれ異なっていてもよく、Ｅ²が複数存在する場合は複数のＥ²がそれぞれ異なっていてもよく、Ｅ³が複数存在する場合は複数のＥ³がそれぞれ異なっていてもよく、Ｅ⁴が複数存在する場合は複数のＥ⁴がそれぞれ異なっていてもよく、
Ｇ¹及びＧ²は、それぞれ独立して、シロキサン結合を有する２〜１０価のオルガノシロキサン基であり、
Ｊ¹、Ｊ²、及びＪ³は、それぞれ独立して、加水分解性基又は−（ＣＨ₂）_e6−Ｓｉ（ＯＲ¹⁴）₃であり、ｅ６は１〜５であり、Ｒ¹⁴はメチル基又はエチル基であり、Ｊ¹が複数存在する場合は複数のＪ¹がそれぞれ異なっていてもよく、Ｊ²が複数存在する場合は複数のＪ²がそれぞれ異なっていてもよく、Ｊ³が複数存在する場合は複数のＪ³がそれぞれ異なっていてもよく、
Ｌ¹及びＬ²は、それぞれ独立して、酸素原子、窒素原子、又はフッ素原子を含んでいてもよい炭素数１〜１２の２価の連結基であり、Ｌ¹が複数存在する場合は複数のＬ¹がそれぞれ異なっていてもよく、Ｌ²が複数存在する場合は複数のＬ²がそれぞれ異なっていてもよく、
ｄ１１は、１〜９であり、
ｄ１２は、０〜９であり、
ａ１０及びａ１４は、それぞれ独立して０〜１０であり、
ａ１１及びａ１５は、それぞれ独立して０又は１であり、
ａ１２及びａ１６は、それぞれ独立して０〜９であり、
ａ１３は、０又は１であり、
ａ２１、ａ２２、及びａ２３は、それぞれ独立して０〜２であり、
ｅ１、ｅ２、及びｅ３は、それぞれ独立して１〜３である。 [1] An organosilicon compound (C) in which the water-repellent layer (r) and the resin substrate layer (s) have a silicon atom to which a hydrolyzable group is bonded and have an amino group or an amine skeleton. A laminated body laminated via a layer (c) formed from a composition containing the above.
The water-repellent layer (r) is a laminate formed from a composition containing an organosilicon compound (A) represented by the following formula (a1).

In the above formula (a1),
Rf ^a1 has a divalent perfluoropolyether structure in which both ends are oxygen atoms.
R ^11, R ^12, and R ¹³ are each independently an alkyl group having 1 to 20 carbon atoms, if R ¹¹ there are a plurality may be different plural R ¹¹ are each, R ¹² is more if present may be different plurality of R ¹² each may be the case where R ¹³ there are a plurality of different plural R ¹³ are each,
^{E 1, E 2, E 3} , E 4, and E ⁵ is, independently represents a hydrogen atom or a fluorine atom, if E ¹ there are a plurality may be different plurality of E ^1, respectively, E ² may be the case where there are plural different multiple E ² respectively, when the E ³ there are a plurality may be different plurality of E ³ respectively, the plurality of E if E ⁴ there are a plurality of ⁴ may be different,
G ¹ and G ² are 2 to 10-valent organosiloxane groups each independently having a siloxane bond.
J ¹ , J ² , and J ³ are independently hydrolyzable groups _{or-(CH 2} ) _e6- Si (OR ¹⁴ ) ₃ , e 6 is 1-5, and R ¹⁴ is a methyl group. or an ethyl group, if J ¹ there are a plurality may be different plurality of J ^1, respectively, when J ² there are a plurality may be different plurality of J ^2, respectively, J ³ is more ^{Multiple J 3s} may be different if they exist
L ¹ and L ² are divalent linking groups having 1 to 12 carbon atoms which may independently contain an oxygen atom, a nitrogen atom, or a fluorine atom, and ^{when a plurality of L 1s} are present, a plurality of L 1 and L 2 are divalent linking groups. It may be different for L ^1, respectively, if L ² there are a plurality may be different plurality of L ^2, respectively,
d11 is 1-9,
d12 is 0-9,
a10 and a14 are 0 to 10 independently, respectively.
a11 and a15 are independently 0 or 1, respectively.
a12 and a16 are 0 to 9 independently of each other.
a13 is 0 or 1,
a21, a22, and a23 are 0 to 2 independently, respectively.
e1, e2, and e3 are 1 to 3 independently of each other.

上記式（ｃ１）中、
Ｒ^x1、Ｒ^x2、Ｒ^x3、Ｒ^x4は、それぞれ独立して、水素原子又は炭素数が１〜４のアルキル基であり、Ｒ^x1が複数存在する場合は複数のＲ^x1がそれぞれ異なっていてもよく、Ｒ^x2が複数存在する場合は複数のＲ^x2がそれぞれ異なっていてもよく、Ｒ^x3が複数存在する場合は複数のＲ^x3がそれぞれ異なっていてもよく、Ｒ^x4が複数存在する場合は複数のＲ^x4がそれぞれ異なっていてもよく、
Ｒｆ^x1、Ｒｆ^x2、Ｒｆ^x3、Ｒｆ^x4は、それぞれ独立して、１個以上の水素原子がフッ素原子に置換された炭素数１〜２０のアルキル基又はフッ素原子であり、Ｒｆ^x1が複数存在する場合は複数のＲｆ^x1がそれぞれ異なっていてもよく、Ｒｆ^x2が複数存在する場合は複数のＲｆ^x2がそれぞれ異なっていてもよく、Ｒｆ^x3が複数存在する場合は複数のＲｆ^x3がそれぞれ異なっていてもよく、Ｒｆ^x4が複数存在する場合は複数のＲｆ^x4がそれぞれ異なっていてもよく、
Ｒ^x5は、炭素数が１〜２０のアルキル基であり、Ｒ^x5が複数存在する場合は複数のＲ^x5がそれぞれ異なっていてもよく、
Ｘは、加水分解性基であり、Ｘが複数存在する場合は複数のＸがそれぞれ異なっていてもよく、
Ｙは、−ＮＨ−、又は−Ｓ−であり、Ｙが複数存在する場合は複数のＹがそれぞれ異なっていてもよく、
Ｚは、ビニル基、α−メチルビニル基、スチリル基、メタクリロイル基、アクリロイル基、アミノ基、イソシアネート基、イソシアヌレート基、エポキシ基、ウレイド基、又はメルカプト基であり、
ｐ１は、１〜２０の整数であり、ｐ２、ｐ３、ｐ４は、それぞれ独立して、０〜１０の整数であり、ｐ５は、１〜１０の整数であり、
ｐ６は、１〜３の整数であり、
Ｚ−、−Ｓｉ（Ｘ）_ｐ6（Ｒ^x5）_3-ｐ6、ｐ１個の−｛Ｃ（Ｒ^x1）（Ｒ^x2）｝−、ｐ２個の−｛Ｃ（Ｒｆ^x1）（Ｒｆ^x2）｝−、ｐ３個の−｛Ｓｉ（Ｒ^x3）（Ｒ^x4）｝−、ｐ４個の−｛Ｓｉ（Ｒｆ^x3）（Ｒｆ^x4）｝−、ｐ５個の−Ｙ−は、Ｚ−及び−Ｓｉ（Ｘ）_ｐ6（Ｒ^x5）_3-ｐ6が末端となり、−Ｏ−が−Ｏ−と連結しない限り、任意の順で並んで結合し、アミノ基及び−ＮＨ−のいずれかを少なくとも１つ含有する。

上記式（ｃ１０）中、
Ｒ^x10及びＲ^x11は、それぞれ独立して、水素原子又は炭素数が１〜４のアルキル基であり、Ｒ^x10が複数存在する場合は複数のＲ^x10がそれぞれ異なっていてもよく、Ｒ^x11が複数存在する場合は複数のＲ^x11がそれぞれ異なっていてもよく、
Ｒｆ^x10及びＲｆ^x11は、それぞれ独立して、１個以上の水素原子がフッ素原子に置換された炭素数１〜２０のアルキル基又はフッ素原子であり、Ｒｆ^x10が複数存在する場合は複数のＲｆ^x10がそれぞれ異なっていてもよく、Ｒｆ^x11が複数存在する場合は複数のＲｆ^x11がそれぞれ異なっていてもよく、
Ｒ^x50及びＲ^x50’はそれぞれ独立して、炭素数が１〜２０のアルキル基であり、Ｒ^x50及びＲ^x50’が複数存在する場合は複数のＲ^x50及びＲ^x50’がそれぞれ異なっていてもよく、
Ｘ²⁰及びＸ²¹はそれぞれ独立して、加水分解性基であり、Ｘ²⁰及びＸ²¹が複数存在する場合は複数のＸ²⁰及びＸ²¹がそれぞれ異なっていてもよく、
ｐ１０は、それぞれ独立して１〜３０の整数であり、ｐ２０は、それぞれ独立して０〜３０の整数であり、ｐ１０又はｐ２０を付して括弧でくくられた繰り返し単位の少なくとも１つは、アミン骨格−ＮＲ¹⁰⁰−に置き換わっており、前記アミン骨格におけるＲ¹⁰⁰は水素原子又はアルキル基であり、
ｐ６０及びｐ６０’はそれぞれ独立して、１〜３の整数であり、
ｐ１０個の−｛Ｃ（Ｒ^x10）（Ｒ^x11）｝−、ｐ２０個の−｛Ｃ（Ｒｆ^x10）（Ｒｆ^x11）｝−は、ｐ１０個又はｐ２０個が連続である必要はなく、任意の順で並んで結合し、両末端が−Ｓｉ（Ｘ²⁰）_ｐ60（Ｒ^x50）_3-ｐ60及び−Ｓｉ（Ｘ²¹）_ｐ60'（Ｒ^x50’）_3-ｐ60'となる。 [2] The laminate according to the above [1], wherein the organosilicon compound (C) is an organosilicon compound represented by the following formula (c1) or an organosilicon compound represented by the following formula (c10). body.

In the above formula (c1),
R ^x1 , R ^x2 , R ^x3 , and R ^x4 are independent alkyl groups with hydrogen atoms or 1 to 4 carbon atoms, and ^{when multiple R x1s} are present, the plurality of R ^x1s are different from each other. may, if R ^x2 there are a plurality may be different plural R ^x2 are each, it may be the case where R ^x3 there are a plurality of different plural R ^x3 are each if R ^x4 there are multiple ^May have different R x4s,
Rf ^x1 , Rf ^x2 , Rf ^x3 , and Rf ^x4 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and there are a plurality of ^{Rf x1.} If you want may be different multiple of Rf ^x1, respectively, different from the case where Rf ^x2 there is more than one may be different from each of the plurality of Rf ^x2, a plurality of Rf ^x3 If Rf ^x3 there is more than one, respectively even if well, if Rf ^x4 there are a plurality may be different plurality of Rf ^x4, respectively,
R ^x5 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R ^x5 there are a plurality of different plural R ^x5 are each,
X is a hydrolyzable group, and when a plurality of Xs are present, the plurality of Xs may be different from each other.
Y is -NH- or -S-, and when there are a plurality of Ys, the plurality of Ys may be different from each other.
Z is a vinyl group, an α-methylvinyl group, a styryl group, a methacryloyl group, an acryloyl group, an amino group, an isocyanate group, an isocyanurate group, an epoxy group, a ureido group, or a mercapto group.
p1 is an integer of 1 to 20, p2, p3, and p4 are independently integers of 0 to 10, and p5 is an integer of 1 to 10.
p6 is an integer from 1 to 3 and
_{Z-, -Si} (X) p6 (R ^x5 ) _3-p6 , p1-{C (R ^x1 ) (R ^x2 )}-, p2-{C (Rf ^x1 ) (Rf ^x2 )}- , P3-{Si (R ^x3 ) (R ^x4 )}-, p4-{Si (Rf ^x3 ) (Rf ^x4 )}-, p5 -Y- are Z- and -Si (X) ) _P6 (R ^x5 ) _3-p6 is the terminal, and unless -O- is linked to -O-, it is bonded side by side in any order and contains at least one amino group or -NH-.

In the above formula (c10),
R ^x10 and R ^x11 are each independently a hydrogen atom or an alkyl group having a carbon number of 1 to 4, if R ^x10 there are a plurality may be different plural R ^x10 are each, R ^x11 is If there are multiple R ^x11s , they may be different.
Rf ^x10 and Rf ^x11 are each independently an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms, and ^{when a plurality of Rf x10} are present, a plurality of Rfs are present. ^x10 well be different from each other, when the Rf ^x11 there is more than one may be different multiple of Rf ^x11, respectively,
R ^x50 and R ^{x50 'is} independently an alkyl group having a carbon number of 1 to 20, R ^x50 and R ^x50' even if there are a plurality of different respective plurality of R ^x50 and R ^{x50 '} Often,
X ²⁰ and X ²¹ are each independently a hydrolysable group, if X ²⁰ and X ²¹ there are a plurality may be different plurality of X ²⁰ and X ²¹ are each,
p10 is an integer of 1 to 30 independently, p20 is an integer of 0 to 30 independently, and at least one of the repeating units in parentheses with p10 or p20 is It has been replaced by an amine skeleton −NR ^{100 −, where R 100} in the amine skeleton is a hydrogen atom or an alkyl group.
p60 and p60'are independent integers of 1-3, respectively.
The p10 − {C (R ^x10 ) (R ^x11 )} − and the p20 − {C (Rf ^x10 ) (Rf ^x11 )} − need not be continuous with p10 or p20, and are arbitrary. They are joined side by side in order, and both ends are -Si (X ²⁰ ) _p60 (R ^x50 ) _3-p60 and -Si (X ²¹ ) _p60' (R ^x50' ) _3-p60' .

上記式（ｂ１）中、
Ｒｆ^b10は、１個以上の水素原子がフッ素原子に置換された炭素数１〜２０のアルキル基又はフッ素原子であり、
Ｒ^b11、Ｒ^b12、Ｒ^b13及びＲ^b14は、それぞれ独立して、水素原子又は炭素数が１〜４のアルキル基であり、Ｒ^b11が複数存在する場合は複数のＲ^b11がそれぞれ異なっていてもよく、Ｒ^b12が複数存在する場合は複数のＲ^b12がそれぞれ異なっていてもよく、Ｒ^b13が複数存在する場合は複数のＲ^b13がそれぞれ異なっていてもよく、Ｒ^b14が複数存在する場合は複数のＲ^b14がそれぞれ異なっていてもよく、
Ｒｆ^b11、Ｒｆ^b12、Ｒｆ^b13及びＲｆ^b14は、それぞれ独立して、１個以上の水素原子がフッ素原子に置換された炭素数１〜２０のアルキル基又はフッ素原子であり、Ｒｆ^b11が複数存在する場合は複数のＲｆ^b11がそれぞれ異なっていてもよく、Ｒｆ^b12が複数存在する場合は複数のＲｆ^b12がそれぞれ異なっていてもよく、Ｒｆ^b13が複数存在する場合は複数のＲｆ^b13がそれぞれ異なっていてもよく、Ｒｆ^b14が複数存在する場合は複数のＲｆ^b14がそれぞれ異なっていてもよく、
Ｒ^b15は、炭素数が１〜２０のアルキル基であり、Ｒ^b15が複数存在する場合は複数のＲ^b15がそれぞれ異なっていてもよく、
Ａ¹は、−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−、−ＮＲ−、−ＮＲＣ（＝Ｏ）−、又は−Ｃ（＝Ｏ）ＮＲ−であり、前記Ｒは水素原子、炭素数１〜４のアルキル基又は炭素数１〜４の含フッ素アルキル基であり、Ａ¹が複数存在する場合は複数のＡ¹がそれぞれ異なっていてもよく、
Ａ²は、加水分解性基であり、Ａ²が複数存在する場合は複数のＡ²がそれぞれ異なっていてもよく、
ｂ１１、ｂ１２、ｂ１３、ｂ１４及びｂ１５は、それぞれ独立して０〜１００の整数であり、
ｃは、１〜３の整数であり、
Ｒｆ^b10−、−Ｓｉ（Ａ²）_c（Ｒ^b15）_3-c、ｂ１１個の−｛Ｃ（Ｒ^b11）（Ｒ^b12）｝−、ｂ１２個の−｛Ｃ（Ｒｆ^b11）（Ｒｆ^b12）｝−、ｂ１３個の−｛Ｓｉ（Ｒ^b13）（Ｒ^b14）｝−、ｂ１４個の−｛Ｓｉ（Ｒｆ^b13）（Ｒｆ^b14）｝−、ｂ１５個の−Ａ¹−は、Ｒｆ^b10−、−Ｓｉ（Ａ²）_c（Ｒ^b15）_3-cが末端となり、パーフルオロポリエーテル構造を形成せず、かつ−Ｏ−が−Ｏ−乃至−Ｆと連結しない限り、任意の順で並んで結合する。 [3] The water-repellent layer (r) is formed from a composition containing an organosilicon compound (A) represented by the above formula (a1) and an organosilicon compound (B) represented by the following formula (b1). The laminate according to the above [1] or [2], which is a layer.

In the above formula (b1),
Rf ^b10 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms.
R ^b11, R ^b12, R ^b13 and R ^b14 are each independently a hydrogen atom or a carbon number from 1 to 4 alkyl groups, if R ^b11 there are a plurality differ plurality of R ^b11 each may, if R ^b12 there are a plurality may be different plural R ^b12 each may be the case where R ^b13 there are a plurality of different plural R ^b13 are each if R ^b14 there are multiple ^May have different R b14s,
Rf ^b11, Rf ^b12, Rf ^b13 and Rf ^b14 are each independently one or more alkyl group or a fluorine atom and having from 1 to 20 carbon atoms hydrogen atoms are substituted by fluorine atoms, Rf ^b11 multiple presence If you may be different plurality of Rf ^b11, respectively, differ if the Rf ^b12 there are a plurality may be different plurality of Rf ^b12, respectively, a plurality of Rf ^b13 If Rf ^b13 is present in plural even if well, if Rf ^b14 there are a plurality may be different plurality of Rf ^b14, respectively,
R ^b15 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R ^b15 there are a plurality of different plural R ^b15 are each,
A ¹ is −O−, −C (= O) −O−, −OC (= O) −, −NR−, −NRC (= O) −, or −C (= O) NR−. There, wherein R is a hydrogen atom, a fluorine-containing alkyl group of 1 to 4 alkyl groups or carbon atoms having 1 to 4 carbon atoms, if a ¹ there are a plurality may be different plurality of a ^1, respectively,
A ² is a hydrolyzable group, if A ² there are a plurality may be different plurality of A ^2, respectively,
b11, b12, b13, b14 and b15 are independently integers from 0 to 100, respectively.
c is an integer from 1 to 3 and
Rf ^b10 −, ^{−Si (A 2} ) _c (R ^b15 ) _3-c , b11 − {C (R ^b11 ) (R ^b12 )} −, b12 − {C (Rf ^b11 ) (Rf ^b12 ) } −, b13 − {Si (R ^b13 ) (R ^b14 )} −, b14 − {Si (Rf ^b13 ) (Rf ^b14 )} −, b15 ^{− A 1} − are Rf ^b10 −, Arranged in any order as long as −Si (A ² ) _c (R ^b15 ) _3-c is the terminal, does not form a perfluoropolyether structure, and -O− is not linked to −O− to −F. Join.

上記式（ｃ２）中、
Ｘ¹は、メトキシ基又はエトキシ基であり、Ｘ¹が複数存在する場合は複数のＸ¹がそれぞれ異なっていてもよく、
Ｙ¹は、−ＮＨ−であり、
Ｚ¹は、アミノ基、又はメルカプト基であり、
Ｒ^ｘ51は、炭素数が１〜２０のアルキル基であり、Ｒ^x51が複数存在する場合は複数のＲ^x51がそれぞれ異なっていてもよく、
ｐ６１は、１〜３の整数であり、ｑは２〜５の整数であり、ｒは０〜５の整数である。 [4] The laminate according to the above [2], wherein the organosilicon compound (C) represented by the formula (c1) is represented by the following formula (c2).

In the above formula (c2),
X ¹ is a methoxy group or an ethoxy group, if X ¹ there are a plurality may be different plurality of X ¹ are each,
Y ¹ is -NH-
Z ¹ is an amino group or a mercapto group,
R ^x51 is an alkyl group having 1 to 20 carbon atoms, may be the case where R ^x51 there are a plurality of different plural R ^x51 are each,
p61 is an integer of 1 to 3, q is an integer of 2 to 5, and r is an integer of 0 to 5.

上記式（ｃ２０）中、
Ｘ³⁰及びＸ³¹は、それぞれ独立して、加水分解性基であり、Ｘ³⁰及びＸ³¹が複数存在する場合は複数のＸ³⁰及びＸ³¹がそれぞれ異なっていてもよく、
Ｒ^x55及びＲ^x56は、それぞれ独立して、炭素数が１〜２０のアルキル基であり、Ｒ^x55及びＲ^x56が複数存在する場合は複数のＲ^x55及びＲ^x56がそれぞれ異なっていてもよく、
−Ｃ_wＨ_2w−は、その一部のメチレン基の少なくとも１つがアミン骨格−ＮＲ¹⁰⁰−に置き換わっており、Ｒ¹⁰⁰は水素原子又はアルキル基であり、
ｗは１〜３０の整数であり（ただし、アミン骨格に置き換わったメチレン基の数を除く）、
ｐ６５及びｐ６６は、それぞれ独立して、１〜３の整数である。 [5] The laminate according to the above [2], wherein the organosilicon compound (C) represented by the formula (c10) is represented by the following formula (c20).

In the above formula (c20),
X ³⁰ and X ³¹ are each independently a hydrolyzable group, when X ³⁰ and X ³¹ there are a plurality may be different plurality of X ³⁰ and X ³¹ are each,
R ^x55 and R ^x56 are each independently an alkyl group having 1 to 20 carbon atoms, may be the case where R ^x55 and R ^x56 there are a plurality of different plural R ^x55 and R ^x56 are each,
In −C _w H _2w −, at least one of its methylene groups is replaced by an ^{amine backbone −NR 100 −, and R 100} is a hydrogen atom or an alkyl group.
w is an integer from 1 to 30 (excluding the number of methylene groups replaced by the amine backbone).
p65 and p66 are each independently an integer of 1 to 3.

[6] The laminate according to any one of the above [1] to [5], wherein the resin base material layer (s) is an acrylic resin-based hard coat layer.

[7] The method for producing a laminate according to any one of [1] to [6] above.
A step of applying the composition containing the organosilicon compound (C) to the resin base material layer (s) to form the layer (c).
Production of a laminate comprising a step of applying a composition containing the organosilicon compound (A) to the layer (c) and curing it at room temperature to form a water-repellent layer (r). Method.

[8] Production of the laminate according to the above [7], wherein the composition containing the organosilicon compound (A) further contains the organosilicon compound (B) in the step of forming the water-repellent layer (r). Method.

[9] The laminate according to the above [7] or [8], wherein the resin base material layer (s) is subjected to plasma treatment, and the composition containing the organosilicon compound (C) is applied to the plasma-treated surface. Production method.

In the laminate of the present invention, the water-repellent layer formed from the composition containing the predetermined organosilicon compound (A) having a perfluoropolyether structure is formed from the composition containing the predetermined organosilicon compound (C). Since it is laminated with the base material via a layer, good chemical resistance can be realized.

In the laminate of the present invention, the water-repellent layer (r) and the resin base material layer (s) are laminated via a layer (c) formed from a composition containing a predetermined organosilicon compound (C). .. The water-repellent layer (r), the layer (c), and the resin base material layer (s) will be described in order below.

1. 1. Water repellent layer (r)
The water-repellent layer (r) is a layer formed from a composition containing the organosilicon compound (A) represented by the following formula (a1), that is, has a structure derived from the organosilicon compound (A). .. As will be described later, the organosilicon compound (A) has a hydrolyzable group, and the −SiOH groups of the organosilicon compound (A) generated by hydrolysis are dehydrated and condensed, so that the water-repellent layer (r) is formed. , Usually has a condensed structure derived from an organosilicon compound (A).

In the above formula (a1),
Rf ^a1 has a divalent perfluoropolyether structure in which both ends are oxygen atoms.
R ¹¹ , R ¹² , and R ¹³ are independent alkyl groups having 1 to 20 carbon atoms (that is, R ¹¹ and R ¹² and R ¹³ may be the same or different from each other). , and the case where R ¹¹ there are a plurality may be different plurality of R ¹¹ each may be the case where R ¹² there are a plurality of different plural R ¹² are each, if R ¹³ there are a plurality of plurality may be multiple R ¹³ are different from each ^{E 1, E 2, E 3} , E 4, and E ⁵ is, each independently represent a hydrogen atom or a fluorine atom, if E ¹ there are a plurality of may be different E ¹ of each may be different plurality of E ² respectively when the E ² there are a plurality, it may be the case where E ³ there are a plurality of different multiple E ³ respectively If the E ⁴ there are a plurality may be different plurality of E ^4, respectively,
G ¹ and G ² are 2 to 10-valent organosiloxane groups each independently having a siloxane bond.
J ¹ , J ² , and J ³ are independently hydrolyzable groups _{or-(CH 2} ) _e6- Si (OR ¹⁴ ) ₃ , e 6 is 1-5, and R ¹⁴ is a methyl group. or an ethyl group, if J ¹ there are a plurality may be different plurality of J ^1, respectively, when J ² there are a plurality may be different plurality of J ^2, respectively, J ³ is more ^{Multiple J 3s} may be different if they exist
L ¹ and L ² are divalent linking groups having 1 to 12 carbon atoms which may independently contain an oxygen atom, a nitrogen atom, or a fluorine atom, and ^{when a plurality of L 1s} are present, a plurality of L 1 and L 2 are divalent linking groups. It may be different for L ^1, respectively, if L ² there are a plurality may be different plurality of L ^2, respectively,
d11 is 1-9,
d12 is 0-9,
a10 and a14 are 0 to 10 independently, respectively.
a11 and a15 are independently 0 or 1, respectively.
a12 and a16 are 0 to 9 independently of each other.
a13 is 0 or 1,
a21, a22, and a23 are 0 to 2 independently, respectively.
e1, e2, and e3 are 1 to 3 independently of each other.

As represented by the above formula (a1), the organosilicon compound (A) has a perfluoropolyether structure represented by ^{Rf a1} and a hydrolyzable group represented by ^{J 2} _{or-(CH 2} ). _{It has at least one e6-} Si (OR ¹⁴ ) ₃ (where 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 replaced with fluorine atoms, and can be said to be a perfluorooxyalkylene group, which can impart water repellency to the obtained film. Further, it is a compound that can be a matrix of a film obtained by bonding organosilicon compounds (A) with each other or with other monomers through a polymerization reaction (particularly polycondensation reaction) by ^{J 2.}

Rf ^a1 is preferably −O− (CF ₂ CF ₂ O) _e4− or −O− (CF ₂ CF ₂ CF ₂ O) _e5-− . e4 and e5 are both 15 to 80.

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

L ¹ and L ² are each independently preferably a divalent linking group having 1 to 5 carbon atoms containing a fluorine atom.

G ¹ and G ² are preferably 2 to 5 valent organosiloxane groups having a siloxane bond independently of each other.

J ¹ , J ² and J ³ are preferably methoxy group, ethoxy group or − (CH ₂ ) _e6- Si (OR ¹⁴ ) ₃ independently of each other.

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 all preferably 0 or 1 (more preferably all 0), and 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 all preferably 3. Further, a13 is preferably 1.

As the compound (A), Rf ^a1 of the above formula (a1) is −O − (CF ₂ CF ₂ CF ₂ O) _e5 −, e5 is 35 to 50, and both L ¹ and L ² are carbon. Numbers 1 to 3 are perfluoroalkylene groups, E ¹ , E ² , and E ³ are all hydrogen atoms, and E ⁴ and E ⁵ are hydrogen or fluorine atoms, and J ¹ , J ² , And J ³ are all methoxy groups or ethoxy groups (particularly methoxy groups), a10 is 1 to 3, a11 is 0, a12 is 0 to 5, a13 is 1, and a14 is 2. ~ 5, a15 is 0, a16 is 0-6, a21 to a23 are independently 0 or 1 (more preferably, a21 to a23 are all 0), and d11 is 1. It is preferable to use a compound in which d12 is 0 or 1 and e1 to e3 are all 3.

When the compound a used as the compound (A) in the examples described later is represented by the above formula (a1), Rf ^a1 is −O− (CF ₂ CF ₂ CF ₂ O) ₄₃₋ , and L ¹ and L ² is − (CF ₂ ) −, E ¹ , E ² and E ³ are all hydrogen atoms, E ⁵ is a fluorine atom, and J ¹ and J ² are both methoxy groups. , A10 is 2, a11 is 0, a12 is 0-5, a13 is 1, a14 is 3, a15 is 0, a16 is 0, a21, a22 are all 0, d11 is 1, d12 is 0, e1. , E2 are all 3.

As the compound (A), Rf ^a1 of the above formula (a1) is −O− (CF ₂ CF ₂ CF ₂ O) _e5 −, e5 is 25 to 40, and L ¹ is a fluorine atom and an oxygen atom. It is a divalent linking group containing 3 to 6 carbon atoms, L ² is a perfluoroalkylene group having 1 to 3 carbon atoms, E ² and E ³ are both hydrogen atoms, and E ⁵ is a fluorine atom. Yes, J ² is − (CH ₂ ) _e6 −Si (OCH ₃ ) ₃ , e6 is 2-4, a10 is 1-3, a11 is 0, a12 is 0, a13. Is 0, a14 is 2-5, a15 is 0, a16 is 0, and a21 to a23 are independently 0 or 1 (more preferably, a21 to a23 are all 0). ), D11 is 1, d12 is 0, and e2 is 3. It is also preferable to use a compound.

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

In the above formula (a2-1),
Rf ^a21 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced with fluorine atoms.
Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^a25 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and there are a plurality of ^{Rf a22s.} if present may be different plurality of Rf ^a22 respectively, if Rf ^a23 there are a plurality may be different plurality of Rf ^a23, respectively, a plurality of Rf ^a24 If Rf ^a24 are present in plural It may be different, if Rf ^a25 there are a plurality may be different plurality of Rf ^a25 respectively,
R ^20, R ^21, R ^22, and R ²³ are each independently hydrogen atom or an alkyl group having 1 to 4 carbon atoms, if R ²⁰ there are a plurality differ plurality of R ²⁰ each may, if R ²¹ there are a plurality may be different plurality of R ²¹ each may be the case where R ²² there are a plurality of different plural R ²² are each, if R ²³ there are a plurality of It may be a different multiple of R ^23, respectively,
R ²⁴ is an alkyl group having 1 to 20 carbon atoms, it may be the case where R ²⁴ there are a plurality of different plural R ²⁴ are each,
M ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, if M ¹ there are a plurality may be different plurality of M ^1, respectively,
M ² is a hydrogen atom or a halogen atom,
M ³ is -O-, -C (= O) -O-, -OC (= O)-, -NR-, -NRC (=
O)-or -C (= O) NR- (R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms), and when a plurality of ^{M 3s are present} Multiple M ^3s may be different
M ⁴ is a hydrolysable group, if M ⁴ there are a plurality may be different plurality of M ^4, respectively,
f11, f12, f13, f14, and f15 are independently integers from 0 to 600, and the total value of f11, f12, f13, f14, and f15 is 13 or more.
f16 is an integer of 1 to 20 and
f17 is an integer from 0 to 2 and
g1 is an integer from 1 to 3 and
Rf ^a21 −, M ² −, f11 − {C (R ²⁰ ) (R ²¹ )} −, f12 − {C (Rf ^a22 ) (Rf ^a23 )} −, f13 − {Si (R) ²² ) (R ²³ )}-, f14-{Si (Rf ^a24 ) (Rf ^a25 )}-, f15 -M ^3- , and f16- [CH ₂ C (M ¹ ) {(CH) ₂ ) _f17 −Si (M ⁴ ) _g1 (R ²⁴ ) _3-g1 }] − is arranged in the order of forming a perfluoropolyether structure at least in part, with ^{Rf a21} − and M ^{2 − at the ends.} Unless -O- is connected to -O- to -F, they are connected side by side in any order. That is, in the equation (a2-1), f11 − {C (R ²⁰ ) (R ²¹ )} − are necessarily continuous, and f12 − {C (Rf ^a22 ) (Rf ^a23 )} − are continuous. , F13 − {Si (R ²² ) (R ²³ )} − are continuous, f14 − {Si (Rf ^a24 ) (Rf ^a25 )} − are continuous, and f15 −M ³ − are continuous. However, it does not mean that f16- [CH ₂ C (M ¹ ) {(CH ₂ ) _f17-Si (M ⁴ ) _g1 (R ²⁴ ) _3-g1 }]-are arranged in this order in succession. , -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 )-and so on, each can be arranged in any order. be.

Rf ^a21 is preferably an alkyl group having 1 to 10 carbon atoms substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and further preferably 1 to 10 carbon atoms. It is a perfluoroalkyl group of 5.

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

R ²⁰ , R ²¹ , R ²² and R ²³ are preferably independent hydrogen atoms or alkyl groups having 1 to 2 carbon atoms, and more preferably all hydrogen atoms.

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

M ¹ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms independently of each other, and more preferably all hydrogen atoms.

M ² is preferably a hydrogen atom.

M ³ is preferably −C (= O) −O−, −O−, −OC (= O) −, and more preferably all −O−.

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

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

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

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

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

f17 is preferably 0 to 1.

g1 is preferably 2 to 3, more preferably 3.

f11-{C (R ²⁰ ) (R ²¹ )}-, f12-{C (Rf ^a22 ) (Rf ^a23 )}-, f13-{Si (R ²² ) (R ²³ )}- , F14 − {Si (Rf ^a24 ) (Rf ^a25 )} −, and f15 −M ³ − are arranged in the formula in the order of forming a perfluoropolyether structure at least in part. ^{The repeating unit (ie-} {C (Rf a22) (Rf ^a23 )}-) enclosed in parentheses with f12 on the most fixed end side (the side that bonds to the silicon atom) is optional, but preferably. ^{, Located on the free end side of the repeating unit (ie-{C (R 20} ) (R ²¹ )}-) enclosed in parentheses with f11 on the most free end side, more preferably the most fixed end. The repeating units in parentheses with f12 and f14 on the sides ( ^ie- {C (Rf a22) (Rf ^a23 )}-and-{Si (Rf ^a24 ) (Rf ^a25 )}-) are Repeat units in parentheses with f11 and f13 on the most free end side (ie-{C (R ²⁰ ) (R ²¹ )}-and-{Si (R ²² ) (R ²³ )}- ) Is located on the free end side.

In the above formula (a2-1), 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 M ³ is all −O−. M ⁴ is all a methoxy group, an ethoxy group or a chlorine atom (particularly a methoxy group or an ethoxy group), M ¹ and M ² are both hydrogen atoms, f11 is 0, and f12 is 30 to 150 (from). It is preferable that 80 to 140), f15 is 30 to 60, f13 and f14 are 0, f17 is 0 to 1 (particularly 0), g1 is 3, and f16 is 1-10.

In the compound a used as the compound (A) in the examples described later, when expressed by the above formula (a2-1), Rf ^a1 is C ₃ F ₇ −, and both Rf ^a22 and Rf ^a23 are fluorine atoms. Yes, f11 = f13 = f14 = 0, f12 is 131, f15 is 44, f16 is 1 to 6, f17 is 0, M ¹ and M ² are hydrogen atoms, M ³ is -O-, and M ⁴ Is a methoxy group and g1 is 3.

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

In the above formula (a2-2),
Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and there are a plurality of ^{Rf a26.} if present may be different plurality of Rf ^a26 respectively, if Rf ^a27 there are a plurality may be different plurality of Rf ^a27, respectively, a plurality of Rf ^a28 If Rf ^a28 are present in plural It may be different, if Rf ^a29 there are a plurality may be different plurality of Rf ^a29 respectively,
R ^25, R ^26, R ^27, and R ²⁸ are each independently hydrogen atom or an alkyl group having 1 to 4 carbon atoms, if R ²⁵ there are a plurality differ plurality of R ²⁵ each may, if R ²⁶ there are a plurality may be different plurality of R ²⁶ each may be the case where R ²⁷ there are a plurality of different plural R ²⁷ are each, if R ²⁸ there are a plurality of It may be a different multiple of R ^28, respectively,
R ^29, and R ³⁰ are each independently an alkyl group having 1 to 20 carbon atoms, if R ²⁹ there are a plurality may be different plural R ²⁹ are each, R ³⁰ there are a plurality of In some cases, multiple R ^30s may be different,
M ⁷ is −O−, −C (= O) −O−, −OC (= O) −, −NR−, −NRC (= O) −, or −C (= O) NR−. There, wherein R is a hydrogen atom, a fluorine-containing alkyl group of 1 to 4 alkyl groups or carbon atoms having 1 to 4 carbon atoms, if M ⁷ there are a plurality may be different plurality of M ^7, respectively,
M ^5, M ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, if M ⁵ there are a plurality may be different plurality of M ^5, respectively, M ⁹ are multiple if present may be different plurality of M ^9, respectively,
M ⁶ and M ¹⁰ are independently hydrogen or halogen atoms, respectively.
M ^8, and M ¹¹ are each independently a hydrolysable group, if M ⁸ there are a plurality may be different plurality of M ^8, respectively, of a plurality if M ¹¹ there are a plurality of M ¹¹ may be different,
f21, f22, f23, f24, and f25 are independently integers from 0 to 600, and the total value of f21, f22, f23, f24, and f25 is 13 or more.
f26 and f28 are independently integers of 1 to 20, respectively.
f27 and f29 are independently integers of 0 to 2, respectively.
g2 and g3 are independently integers of 1 to 3, respectively.
M ¹⁰ −, M ⁶ −, f21 − {C (R ²⁵ ) (R ²⁶ )} −, f22 − {C (R f ^a26 ) (R f ^a27 )} −, f 23 − {Si (R) ^{27) (R 28)} -} , f24 amino ^{- {Si (Rf a28) (} Rf a29)} -, f25 amino -M ⁷ -, f26 amino ^{_{- [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} }] are ^{arranged in the order in which M 10} − and M ⁶ − are the ends and form a perfluoropolyether structure at least in part, and are arranged in any order unless −O− is continuous with −O−. Combine with. The joining in any order is the same as described in the above formula (a2-1), and the repeating units are continuously arranged in the order described in the above formula (a2-2). Not limited to meaning.

In the above formula (a2-2), Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are all fluorine atoms, M ⁷ are all −O−, and M ⁸ and M ¹¹ are all methoxy and ethoxy groups. Alternatively, it is a chlorine atom (particularly a methoxy group or an ethoxy group), M ⁵ , M ⁶ , M ⁹ , and M ¹⁰ are all hydrogen atoms, f21 is 0, and f22 is 30 to 150 (more preferably 80 to 140). ), F25 is 30 to 60, f23 and f24 are 0, f27 and f29 are 0 to 1 (particularly preferably 0), g2 and g3 are 3, and f26 and f28 are 1 to 10.

More specifically, the compound (A) includes a compound of the following formula (a3).

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

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

In the above formula (a4), R ⁴⁰ is a perfluoroalkyl group having 2 to 5 carbon atoms ^{, R 41 is a perfluoroalkylene group having 2 to 5 carbon atoms, and R 42} is a perfluoroalkylene group having 2 to 5 carbon atoms. A part of the hydrogen atom of the alkylene group is a fluoroalkylene group substituted with fluorine, R ⁴³ and R ⁴⁴ are independently alkylene groups having 2 to 5 carbon atoms, and R ⁴⁵ is a methyl group or an ethyl group. be. k1, k2, and k3 are independently integers 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 40, It is preferably 000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.

The water-repellent layer (r) is preferably a layer formed from a composition containing the above-mentioned organosilicon compound (A) and the organosilicon compound (B) represented by the following formula (b1). As will be described later, the organosilicon compound (B) has a hydrolyzable group, and usually, the −SiOH group of the organosilicon compound (B) generated by hydrolysis is an organosilicon compound (B) generated by hydrolysis. In a preferred embodiment, the water-repellent layer (r) is condensed from the organosilicon compound (A) because it dehydrates and condenses with the −SiOH group of A) and / or the −SiOH group of the organosilicon compound (B) generated by hydrolysis. Along with the structure, it has a condensed structure derived from the organosilicon compound (B).

In the above formula (b1),
Rf ^b10 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms.
^{R b11, R b12, R b13} , R b14 are each independently a hydrogen atom or a carbon number from 1 to 4 alkyl groups, if R ^b11 there are a plurality differ plurality of R ^b11 each may, if R ^b12 there are a plurality may be different plural R ^b12 each may be the case where R ^b13 there are a plurality of different plural R ^b13 are each if R ^b14 there are multiple ^May have different R b14s,
^{Rf b11, Rf b12, Rf b13} , Rf b14 each independently 1 or more alkyl group or a fluorine atom and having from 1 to 20 carbon atoms hydrogen atoms are substituted by fluorine atoms, Rf ^b11 multiple presence If you may be different plurality of Rf ^b11, respectively, differ if the Rf ^b12 there are a plurality may be different plurality of Rf ^b12, respectively, a plurality of Rf ^b13 If Rf ^b13 is present in plural even if well, if Rf ^b14 there are a plurality may be different plurality of Rf ^b14, respectively,
R ^b15 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R ^b15 there are a plurality of different plural R ^b15 are each,
A ¹ is −O−, −C (= O) −O−, −OC (= O) −, −NR−, −NRC (= O) −, or −C (= O) NR−. There, wherein R is a hydrogen atom, a fluorine-containing alkyl group of 1 to 4 alkyl groups or carbon atoms having 1 to 4 carbon atoms, if a ¹ there are a plurality may be different plurality of a ^1, respectively,
A ² is a hydrolyzable group, if A ² there are a plurality may be different plurality of A ^2, respectively,
b11, b12, b13, b14, and b15 are independently integers from 0 to 100, respectively.
c is an integer from 1 to 3 and
Rf ^b10 −, ^{−Si (A 2} ) _c (R ^b15 ) _3-c , b11 − {C (R ^b11 ) (R ^b12 )} −, b12 − {C (Rf ^b11 ) (Rf ^b12 ) } −, b13 − {Si (R ^b13 ) (R ^b14 )} −, b14 − {Si (Rf ^b13 ) (Rf ^b14 )} −, b15 ^{− A 1} − are Rf ^b10 −, Arranged in any order as long as −Si (A ² ) _c (R ^b15 ) _3-c is the terminal, does not form a perfluoropolyether structure, and -O− is not linked to −O− to −F. Join.

Rf ^b10 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 10 carbon atoms (more preferably 1 to 5 carbon atoms) independently of each other.

^{R b11, R b12, R b13} , and R ^b14 is preferably a hydrogen atom.

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 to 30, more preferably 1 to 25, further preferably 1 to 10, particularly preferably 1 to 5, and most preferably 1 to 2.

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

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

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

b15 is preferably 0 to 4, more preferably 0 to 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, preferably 5 or more, preferably 80 or less, more preferably 50 or less, and further preferably 20 or less.

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

In the examples described later, when FAS13E used as compound (B) is represented by the above formula (b1), R ^b11 and R ^b12 are all hydrogen atoms, b11 is 2, b13, b14, and b15 are all 0. , C is 3, A ² is an ethoxy group, Rf ^b10 − {C (Rf ^b11 ) (Rf ^b12 )} _b12 − is the terminal, and 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 to 12). Of these, 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 and C ₈ F ₁₇ −Si− (OC ₂ H ₅ ) ₃ are preferable. In addition, CF ₃ CH ₂ O (CH ₂ ) _k SiCl ₃ , CF ₃ CH ₂ O (CH ₂ ) _k Si (OCH ₃ ) ₃ , CF ₃ CH ₂ O (CH ₂ ) _k Si (OC ₂ H ₅ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) _k SiCl ₃ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) _k Si (OCH ₃ ) ₃ , CF ₃ ( CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) _k Si (OC ₂ H ₅ ) ₃ , CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) _k SiCl ₃ , CF ₃ (CH ₂₎ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) _k Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) _k Si (OC ₂ H ₅ ) ₃ , CF ₃ COO (CH ₂ ) _k SiCl ₃ , CF ₃ COO (CH ₂ ) _k Si (OCH ₃ ) ₃ , CF ₃ COO (CH ₂ ) _k Si (OC ₂ H _{5 ) 3} (k is 5 to 20 in each case). It is preferably 8 to 15). In addition, CF ₃ (CF ₂ ) _m − (CH ₂ ) _n SiCl ₃ , CF ₃ (CF ₂ ) _m − (CH ₂ ) _n Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) _m − (CH ₂ ) _n Si (OC ₂ H ₅ ) ₃ can also be mentioned (m is 1 to 10 and preferably 3 to 7, and n is 1 to 5 and preferably 2 to 4). ). CF ₃ (CF ₂ ) _p − (CH ₂ ) _{q −} Si − (CH ₂ CH = CH ₂ ) ₃ can also be mentioned (p is 2 to 10, preferably 2 to 8, q. Is 1 to 5, preferably 2 to 4). Furthermore, CF ₃ (CF ₂ ) _p − (CH ₂ ) _q SiCH ₃ Cl ₂ , CF ₃ (CF ₂ ) _p − (CH ₂ ) _q SiCH ₃ (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) _p − ( CH ₂ ) _q SiCH ₃ (OC ₂ H ₅ ) ₂ can be mentioned (p is 2 to 10 and preferably 3 to 7, and q is 1 to 5 and preferably 2 to 4). Is).

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

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

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

2. Layer (c)
The layer (c) is an organosilicon compound having a silicon atom to which a hydrolyzable group is bonded, and is formed from a composition containing an organosilicon compound (C) having an amino group or an amine skeleton. The organosilicon compound (C) preferably has one or more amine skeletons. In the present specification, the organosilicon compound (C) having an amino group or an amine skeleton may be simply referred to as an organosilicon compound (C). The layer (c) can function as a primer layer for the water-repellent layer (r). As described above, the organosilicon compound (C) has a hydrolyzable group bonded to silicon, and the −SiOH groups of the organosilicon compound (C) generated by hydrolysis are dehydrated and condensed, so that the layer (c) ) Usually has a condensed structure derived from the organosilicon compound (C).

Examples of the organic silicon compound (C) having an amino group or an amine skeleton include an organic silicon compound represented by the following formula (c1) and one or more amine skeletons represented by the following formula (c10). Examples thereof include organic silicon compounds having one or more hydrolyzable groups. Hereinafter, these organosilicon compounds will be described. The amine skeleton is ^{represented by −NR 10} −, and R ¹⁰ is a hydrogen or alkyl group. R ¹⁰ is preferably hydrogen or an alkyl group having 1 to 5 carbon atoms. When the organosilicon compound (C) contains a plurality of amine skeletons, the plurality of amine skeletons may be the same or different.

The layer (c) can be formed from a composition containing the organosilicon compound (C) represented by the following formula (c1).

In the above formula (c1),
R ^x1 , R ^x2 , R ^x3 , and R ^x4 are independent alkyl groups with hydrogen atoms or 1 to 4 carbon atoms, and ^{when multiple R x1s} are present, the plurality of R ^x1s are different from each other. at best, if the R ^x2 there are a plurality may be different plural R ^x2 are each, may be the case where R ^x3 there are a plurality of different plural R ^x3 are each R ^x4 there are a plurality of In some cases, multiple R ^x4s may be different,
Rf ^x1 , Rf ^x2 , Rf ^x3 , and Rf ^x4 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and Rf ^x1 is plural. If there may be different multiple of Rf ^x1, respectively, when the Rf ^x2 there is more than one may be different from each of the plurality of Rf ^x2, a plurality of Rf ^x3 If Rf ^x3 there is more than one, respectively It may be different, if Rf ^x4 there are a plurality may be different plurality of Rf ^x4, respectively,
R ^x5 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R ^x5 there are a plurality of different plural R ^x5 are each,
X is a hydrolyzable group, and when a plurality of Xs are present, the plurality of Xs may be different from each other.
Y is -NH- or -S-, and when there are a plurality of Ys, the plurality of Ys may be different from each other.
Z is a vinyl group, an α-methylvinyl group, a styryl group, a methacryloyl group, an acryloyl group, an amino group, an isocyanate group, an isocyanurate group, an epoxy group, a ureido group, or a mercapto group.
p1 is an integer of 1 to 20, p2, p3, and p4 are independently integers of 0 to 10, and p5 is an integer of 1 to 10.
p6 is an integer from 1 to 3 and
_{Z-, -Si} (X) p6 (R ^x5 ) _3-p6 , p1-{C (R ^x1 ) (R ^x2 )}-, p2-{C (Rf ^x1 ) (Rf ^x2 )}- , P3 − {Si (R ^x3 ) (R ^x4 )} −, p4 − {Si (Rf ^x3 ) (Rf ^x4 )} −, and p5 −Y− are Z− and −Si ( X) _p6 (R ^x5 ) _3-p6 is the terminal, and unless -O- is linked to -O-, it is bonded side by side in any order and contains at least one amino group or -NH-. ..

R ^x1 , R ^x2 , R ^x3 , and R ^x4 are preferably hydrogen atoms.

It is preferable that Rf ^x1 , Rf ^x2 , Rf ^x3 , and Rf ^x4 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 ^x5 is preferably an alkyl group having 1 to 5 carbon atoms.

X is preferably an alkoxy group, a halogeno group, a cyano group, or an isocyanate group, more preferably an alkoxy group, and even more preferably a methoxy group or an ethoxy group.

Y is preferably −NH−.

Z is preferably a methacryloyl group, an acryloyl group, a mercapto group or an amino group, more preferably a mercapto group or an amino group, and even more preferably an amino group.

p1 is preferably 1 to 15, more preferably 2 to 10.

Independently, p2, p3 and p4 are preferably 0 to 5, more preferably all 0 to 2.

The p5 is preferably 1 to 5, more preferably 1 to 3.

The p6 is preferably 2 to 3, more preferably 3.

As the organosilicon compound (C), in the above formula (c1), both R ^x1 and R ^x2 are hydrogen atoms, Y is -NH-, and X is an alkoxy group (particularly a methoxy group or an ethoxy group). Yes, Z is an amino group or a mercapto group, p1 is 1-10, p2, p3 and p4 are all 0, p5 is 1-5 (particularly 1-3), and p6 is 3. It is preferable to use a certain compound.

When N-2- (aminoethyl) -3-aminopropyltrimethoxysilane used as the compound (C) in the examples described later is represented by the above formula (c1), Z is an amino group, and R ^x1 and R ^x2 are. All of them are hydrogen atoms, p1 is 5, p2, p3 and p4 are all 0, Y is -NH-, p5 is 1, p6 is 3, and X is a methoxy group.

The organosilicon compound (C) is preferably represented by the following formula (c2).

In the above formula (c2),
X ¹ is a hydrolyzable group, when X ¹ there are a plurality may be different plurality of X ¹ are each,
Y ¹ is -NH-
Z ¹ is an amino group or a mercapto group,
R ^x51 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R ^x51 there are a plurality of different plural R ^x51 are each,
p61 is an integer of 1 to 3, q is an integer of 2 to 5, and r is an integer of 0 to 5.

X ¹ is preferably an alkoxy group, a halogeno group, a cyano group, or an isocyanate group, and more preferably an alkoxy group.

Z ¹ is preferably an amino group.

R ^x51 is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

p61 is preferably an integer of 2 to 3, and more preferably 3.

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

The layer (c) is formed from a composition containing an organosilicon compound (C) having one or more amine skeletons and two or more hydrolyzable groups represented by the following formula (c10). be able to.

In the above formula (c10),
R ^x10 and R ^x11 are each independently a hydrogen atom or an alkyl group having a carbon number of 1 to 4, if R ^x10 there are a plurality may be different plural R ^x10 are each, R ^x11 is If there are multiple R ^x11s , they may be different.
Rf ^x10 and Rf ^x11 are each independently an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms, and ^{when a plurality of Rf x10} are present, a plurality of Rfs are present. ^x10 well be different from each other, when the Rf ^x11 there is more than one may be different multiple of Rf ^x11, respectively,
R ^x50 and R ^{x50 'is} independently an alkyl group having a carbon number of 1 to 20, R ^x50 and R ^x50' even if there are a plurality of different respective plurality of R ^x50 and R ^{x50 '} Often,
X ²⁰ and X ²¹ are each independently a hydrolysable group, if X ²⁰ and X ²¹ there are a plurality may be different plurality of X ²⁰ and X ²¹ are each,
p10 is an integer of 1 to 30 independently, p20 is an integer of 0 to 30 independently, and at least one of the repeating units in parentheses with p10 or p20 is It has been replaced by an amine skeleton −NR ^{100 −, where R 100} in the amine skeleton is a hydrogen atom or an alkyl group.
p60 and p60'are independent integers of 1-3, respectively.
The p10 − {C (R ^x10 ) (R ^x11 )} − and the p20 − {C (Rf ^x10 ) (Rf ^x11 )} − need not be continuous with p10 or p20, and are arbitrary. They are joined side by side in order, and both ends are -Si (X ²⁰ ) _p60 (R ^x50 ) _3-p60 and -Si (X ²¹ ) _p60' (R ^x50' ) _3-p60' .

R ^x10 and R ^x11 are preferably hydrogen atoms.

It is preferable that Rf ^x10 and Rf ^x11 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.

It is preferably an alkyl group having R ^x50 and R ^{x50'and having 1 to 5 carbon atoms.}

X ²⁰ and X ²¹ are preferably an alkoxy group, a halogeno group, a cyano group, or an isocyanate group, more preferably an alkoxy group, and even more preferably a methoxy group or an ethoxy group.

At least one amine skeleton −NR ¹⁰⁰ − may be present in the molecule as described above, and any of the repeating units in parentheses with p10 or p20 may be replaced with the amine skeleton. , P10 and are preferably part of a repeating unit enclosed in parentheses. A plurality of the amine skeletons may be present, and in that case, the number of amine skeletons is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5. Further, in this case, it is preferable to have an alkylene group between adjacent amine skeletons. The alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. The number of carbon atoms of the alkylene group between adjacent amine skeletons is included in the total number of p10 or p20.

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

p10 is preferably 1 to 15, more preferably 1 to 10, except for the number of repeating units replaced by the amine skeleton.

p20 is preferably 0-5, more preferably all 0-2, except for the number of repeating units replaced by the amine skeleton.

The p60 and p60'are preferably 2 to 3, more preferably 3.

As the organic silicon compound (C), in the above formula (c10), R ^x10 and R ^x11 are both hydrogen atoms, X ²⁰ and X ²¹ are alkoxy groups (particularly methoxy group or ethoxy group), and p10 is used. The repeating units in parentheses are replaced with at least one amine skeleton −NR ¹⁰⁰ −, where R ¹⁰⁰ is a hydrogen atom and p10 is 1-10 (but replaced with an amine skeleton). (Excluding the number of repeating units), it is preferable to use a compound in which p20 is 0 and p60 and p60'are 3.

A reaction product of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane described in JP2012-197330A, which is used as compound (C) in Examples described later. Product name: X-12-5263HP, manufactured by Shin-Etsu Chemical Industry Co., Ltd. is represented by the above formula (c10). R ^x10 and R ^x11 are both hydrogen atoms, p10 is 8, p20 is 0, and amine skeleton is 2. One (R ¹⁰⁰ is a hydrogen atom), both ends are the same, p60 and p60'are 3, and X ²⁰ and X ²¹ are methoxy groups.

The organosilicon compound (C) is preferably a compound represented by the following formula (c20).

In the above formula (c20),
X ³⁰ and X ³¹ are each independently a hydrolyzable group, when X ³⁰ and X ³¹ there are a plurality may be different plurality of X ³⁰ and X ³¹ are each,
R ^x55 and R ^x56 are each independently an alkyl group having 1 to 20 carbon atoms, may be the case where R ^x55 and R ^x56 there are a plurality of different plural R ^x55 and R ^x56 are each,
In −C _w H _2w −, at least one of its methylene groups is replaced by an ^{amine backbone −NR 100 −, and R 100} is a hydrogen atom or an alkyl group.
w is an integer from 1 to 30 (excluding the number of methylene groups replaced by the amine backbone).
p65 and p66 are each independently an integer of 1 to 3.

X ³⁰ and X ³¹ are preferably an alkoxy group, a halogeno group, a cyano group, or an isocyanate group, and more preferably an alkoxy group.

There may be a plurality of amine skeletons −NR ¹⁰⁰ −, and in that case, the number of amine skeletons is preferably 1 to 10, more preferably 1 to 5, and preferably 2 to 5. More preferred. Further, in this case, it is preferable to have an alkylene group between adjacent amine skeletons. The alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. The number of carbon atoms 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 number of carbon atoms is preferably 5 or less, and more preferably 3 or less. The amine skeleton −NR ¹⁰⁰ − is preferably −NH − (R ¹⁰⁰ is a hydrogen atom).

R ^x55 and R ^x56 are preferably alkyl groups having 1 to 10 carbon atoms, and more preferably alkyl groups having 1 to 5 carbon atoms.

p65 and p66 are preferably integers of 2 to 3, and more preferably 3.

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

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

3. 3. Resin base layer (s)
The material of the resin base material layer (s) of the present invention is not particularly limited, and may be either an organic material or an inorganic material, and the shape of the base material may be either a flat surface or a curved surface. It may be a combined shape. Organic materials include acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose resin, polyolefin resin, vinyl resin (polyethylene, polyvinyl chloride, polystyrene, vinylbenzyl chloride resin, polyvinyl). Thermoplastic resins such as alcohols); thermocurable resins such as phenolic resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins, urethane resins and the like. Examples of the inorganic material include metals such as iron, silicon, copper, zinc and aluminum, alloys containing these metals, ceramics and glass. Of these, organic materials are particularly preferable. Among the resin substrates, at least one of an acrylic resin, a benzyl chloride resin, an epoxy resin, a silicone resin, and a urethane resin is preferable, and an acrylic resin is particularly preferable.

The resin base material layer (s) in the present invention is a protective layer provided to protect an article from scratches in an application requiring abrasion resistance such as a display of an electronic device (hereinafter, may be referred to as a hard coat layer). It is more preferable that the protective layer is made of an acrylic resin.

The above-mentioned hard coat layer is a layer having a surface hardness, and the hardness is, for example, a pencil hardness of 2H or more. The hard coat layer may have a single layer structure or a multi-layer structure. The hard coat layer contains a hard coat layer resin, and examples of the hard coat layer resin include acrylic resin, epoxy resin, urethane resin, vinylbenzyl chloride resin, vinyl resin, silicone resin, and these. Examples thereof include ultraviolet curable type, electron beam curable type, and heat curable type resins such as mixed resins. In particular, the hard coat layer preferably contains an acrylic resin in order to exhibit high hardness. It is preferable to contain an epoxy resin because the adhesion to the water-repellent layer (r) via the layer (c) tends to be good.

The hard coat layer may further contain an ultraviolet absorber, a metal oxide such as silica or alumina, or an inorganic filler such as polyorganosiloxane. By including such an inorganic filler, the adhesion to the water-repellent layer (r) via the layer (c) can be improved. The thickness of the hard coat layer is, for example, 1 to 100 μm.

In the laminate of the present invention, as long as the water-repellent layer (r), the layer (c) and the resin base material layer (s) are arranged in this order, the layer ( Another layer may be contained between the c) and the resin base material layer (s) on the surface side of the layer (s), but there is another layer between the layer (r) and the layer (c). It is preferable that there is no such thing. When the resin base material layer (s) is a hard coat layer, it is preferable that there is no other layer between the resin base material layer (s) and the layer (c). The laminate of the present invention preferably further contains a resin layer (s2) different from the resin base material layer (s), and the water-repellent layer (r), the layer (c), and the layers (c) are arranged in this order from the surface of the laminate. The order may be the resin base material layer (s) and the resin layer (s2). The resin component of the resin layer (s2) is not particularly limited, but when the resin base material layer (s) is a hard coat layer, it is particularly polyacrylate-based resin, polyamide-based resin, polyimide-based resin, polyamideimide-based resin, and polyurethane-based. Resins, polyester resins, polycarbonate resins, polyether sulfone resins, acetyl cellulose resins, cycloolefin resins, polyvinyl alcohol resins, etc. are preferable because they easily improve the adhesion to the hard coat layer, and among them, polyimide resins. Resins and polyamideimide-based resins are preferable. The thickness of the resin layer (s2) is, for example, 10 to 500 μm.

A primer layer may be provided between the resin layer (s2) and the resin base material layer (s) (particularly the hard coat layer). Examples of the primer agent include a primer agent such as an ultraviolet curable type, a thermosetting type, or a two-component curable type epoxy compound. It is preferable that the compound contained in the primer layer is chemically bonded to the resin component contained in the resin layer (s2) or the silicon material contained if necessary. Further, a polyamic acid may be used as the primer agent, and the adhesion between the resin layer (s2) and the resin base material layer (s) (particularly the hard coat layer) can be improved. Further, a silane coupling agent can be mentioned as a primer agent, which may be chemically bonded to a silicon material contained in the resin substrate as necessary by a condensation reaction. The thickness of the primer layer is, for example, 0.1 to 20 μm.

The laminate of the present invention has a water contact angle (initial contact angle) measured at a liquid volume of 3 μL by the sessile drop method (analysis method: θ / 2 method), for example, 105 ° or more, more preferably 110. It is greater than or equal to ° and, for example, less than or equal to 120 °. In addition, after performing the chemical resistance test conducted in the examples described later, the water contact angle (contact angle after the chemical resistance test) measured at a liquid volume of 3 μL by the sessile drop method (analysis method: θ / 2 method). However, for example, it is 82.0 ° or more, preferably 85 ° or more, more preferably 90 ° or more, and the upper limit is, for example, 110 ° or less, and may be 100 ° or less.

Next, a method for producing the laminate of the present invention will be described.

The method for producing the laminate of the present invention includes a step of forming (i) a layer (c) having a structure derived from (i) an organosilicon compound (C) on a resin base material layer (s), and (ii) a water-repellent layer. Includes a step of forming (r).

In the step of forming the layer (c), the composition containing the organosilicon compound (C) is applied to the resin base material layer (s). The composition preferably contains an organosilicon compound (C) and a solvent (E). The solvent (E) is not particularly limited, and for example, an alcohol solvent, a ketone solvent, an ether solvent, a hydrocarbon solvent and the like can be used, and an alcohol solvent and a ketone solvent are particularly preferable.

Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and the like.
Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
Examples of the ether solvent include diethyl ether, dipropyl ether, tetrahydrofuran, 1,4-dioxane and the like.
Examples of the hydrocarbon solvent include an aliphatic hydrocarbon solvent such as pentane and hexane, an alicyclic hydrocarbon solvent such as cyclohexane, and an aromatic hydrocarbon solvent such as benzene, toluene and xylene.

The organosilicon compound (C) is preferably 0.05% by mass or more, more preferably 0.08% by mass or more, and further preferably 0.1 in 100% by mass of the composition containing the organosilicon compound (C). It is 5% by mass or more, preferably 2% by mass or less, more preferably 1.5% by mass or less, and further preferably 1.2% by mass or less.

Examples of the method for applying the composition for forming the layer (c) include a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, a die coating method, a gravure coating method, and the like. The coating method is preferred.

Before applying the composition containing the organosilicon compound (C), it is preferable that the resin base material layer (s) is subjected to an easy-adhesion treatment. Examples of the easy-adhesion treatment include hydrophilization treatments such as corona treatment, plasma treatment, and ultraviolet treatment. By performing an easy adhesion treatment such as plasma treatment, functional groups such as OH groups (especially when the base material is an epoxy resin) and COOH groups (especially when the base material is an acrylic resin) are formed on the surface of the base material. When such a functional group is formed on the surface of the base material, the adhesion between the layer (c) and the resin base material layer (s) can be further improved.

After applying the composition containing the organosilicon compound (C) to form the layer (c), the composition containing the organosilicon compound (A) is applied and cured at room temperature to obtain a water-repellent layer ( r) can be formed.

The composition containing the organosilicon compound (A) preferably further contains the organosilicon compound (B), and usually contains a solvent (D). As the solvent (D), it is preferable to use a fluorine-based solvent, for example, a fluorinated ether solvent, a fluorinated amine solvent, a fluorinated hydrocarbon solvent and the like can be used, and the boiling point is particularly 100 ° C. or higher. Is preferable. As the fluorinated ether solvent, hydrofluoro ethers such as fluoroalkyl (particularly perfluoroalkyl group having 2 to 6 carbon atoms) -alkyl (particularly methyl group or ethyl group) ether are preferable, and for example, ethyl nona fluorobutyl ether or ethyl nona. Fluoroisobutyl ether can be mentioned. Examples of the ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether include Novec® 7200 (manufactured by 3M, molecular weight of about 264). The fluorinated amine-based solvent is preferably an amine in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group, and a third in which all hydrogen atoms of ammonia are substituted with a fluoroalkyl group (particularly a perfluoroalkyl group). Primary amines are preferred, and specific examples thereof include tris (heptafluoropropyl) amines, such as Florinate (registered trademark) FC-3283 (manufactured by 3M, molecular weight: about 521). Examples of the fluorinated hydrocarbon solvent include a fluorinated aliphatic hydrocarbon solvent such as 1,1,1,3,3-pentafluorobutane, and a fluorinated aromatic solvent such as 1,3-bis (trifluoromethylbenzene). Hydrocarbon-based solvents can be mentioned. Examples of 1,1,1,3,3-pentafluorobutane include Solve 55 (manufactured by Solvex).

In addition to the above, hydrochlorofluorocarbons such as Asahiclean (registered trademark) AK225 (manufactured by Asahi Glass Co., Ltd.) and hydrofluorocarbons such as Asahiclean (registered trademark) AC2000 (manufactured by Asahi Glass Co., Ltd.) may be used as the fluorocarbon solvent. Can be done.

As the solvent (D), it is preferable to use at least a fluorinated amine solvent. The solvent (D) preferably contains two or more kinds of fluorine-based solvents, and contains a fluorinated amine-based solvent and a fluorinated hydrocarbon-based solvent (particularly, a fluorinated aliphatic hydrocarbon-based solvent). Is preferable.

The composition for forming the water-repellent layer (r) is a silanol condensation catalyst, an antioxidant, a rust preventive, an ultraviolet absorber, a light stabilizer, a fungicide, and an antibacterial agent as long as the effect of the present invention is not impaired. , Bioadhesion inhibitor, deodorant, pigment, flame retardant, antistatic agent and various other additives may be contained.

The water-repellent layer (r) can be formed by applying the composition for forming the water-repellent layer (r) on the layer (c) and drying it. Examples of the method for applying the composition for forming the water-repellent layer (r) include a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, a die coating method, and a gravure coating method.

The conditions after the composition for forming the water-repellent layer (r) is applied onto the layer (c) are not particularly limited, and may be allowed to stand at room temperature in the air for, for example, 1 hour or more. In the present invention, the room temperature is 5 to 60 ° C., and a film can be formed by allowing the mixture to stand in a temperature range of preferably 15 to 40 ° C. Then, it may be further heated (baked) at a temperature of 50 to 300 ° C., preferably 100 to 200 ° C. for about 10 to 60 minutes.

The content of the organosilicon compound (A) in the composition for forming the water-repellent layer (r) is, for example, 0.01% by mass or more, preferably 0.05% by mass or more, based on 100% by mass of the composition. Yes, and is preferably 0.5% by mass or less, more preferably 0.3% by mass or less.

When the composition for forming the water-repellent layer (r) contains the organosilicon compound (B), the content of the organosilicon compound (B) in the composition is, for example, 0.01% by mass or more, preferably 0.01% by mass or more. It is preferably 0.03% by mass or more, preferably 0.3% by mass or less, and more preferably 0.2% by mass or less.

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

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited by the following examples, and it is of course possible to carry out the present invention with appropriate modifications within a range that can be adapted to the above-mentioned purpose, and all of them are technical of the present invention. Included in the range.

[Example 1]
KBM-603 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., N-2- (aminoethyl) -3-aminopropyltrimethoxysilane) is contained in an amount of 0.25% by mass as an organosilicon compound (C), and methyl ethyl ketone is used as a solvent (E). The solution containing 99.75% by mass was stirred at room temperature to obtain a solution for forming the layer (c). The obtained solution was applied to a substrate having an acrylic hard coat layer whose surface to be coated was activated using an atmospheric pressure plasma device (manufactured by Fuji Machine Manufacturing Co., Ltd.) on an OPTICOAT MS-A100 manufactured by MIKASA Corporation. Using (spin coater), coating was performed under the conditions of a coating liquid volume of 200 μl, a rotation speed of 2000 rpm, and a rotation speed of 20 seconds to obtain a layer (c).

Next, as the organosilicon compound (A), a compound represented by the following formula (1) (hereinafter, compound a), and as a solvent (D), FC-3283 (C ₉ F ₂₁ N, manufactured by Fluorinert, 3M). The mixture was mixed and stirred at room temperature for a predetermined time to obtain a solution for forming a water-repellent layer (r). The proportion of the organosilicon compound (A) in the water-repellent layer (r) forming solution was 0.085% by mass. The water-repellent layer (r) forming solution was applied onto the layer (c) using a spray coater manufactured by Apiros Co., Ltd. The conditions for spray coating are scan speed: 600 mm / sec, pitch: 5 mm, liquid volume: 6 cc / min, atomizing air: 350 kPa, and gap: 70 mm. Then, it was fired at 120 ° C. for 20 minutes to obtain a laminate containing the resin base material layer (s), the layer (c), and the water-repellent layer (r) in this order.

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

[Example 2]
_{FAS13E (C 6} F _13- C ₂ H _4- Si (OC ₂ H ₅ ) ₃ , manufactured by Tokyo Chemical Industry Co., Ltd.) was further added to the water-repellent layer (r) forming solution as the organosilicon compound (B). A laminate was obtained in the same manner as in Example 1 except that the solution contained 0.05% by mass.

[Comparative Example 1]
Lamination in the same manner as in Example 1 except that KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-acryloyloxypropyltrimethoxysilane) was used as the layer (c) forming solution instead of KBM-603. I got a body.

[Comparative Example 2]
Lamination in the same manner as in Example 2 except that KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-acryloyloxypropyltrimethoxysilane) was used as the layer (c) forming solution instead of KBM-603. I got a body.

[Example 3]
As the organosilicon compound (C), a reaction product (commercial product) of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and chloropropyltrimethoxysilane described in JP2012-197330A, which is represented by the following formula. Name; X-12-5263HP, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was used, and a laminate was obtained in the same manner as in Example 2 except that it contained 0.50% by mass.

[Comparative Example 3 and Comparative Example 4]
Instead of the organosilicon compound (C), KBM3086 (manufactured by Shin-Etsu Chemical Co., Ltd., 1,8-bis (trimethylsilyl) octane) having no amino group in the molecule is used, and this is 0.25% by mass or 0.25% by mass, respectively. A laminate was obtained in the same manner as in Example 2 except that it contained 0.50% by mass.

The following measurements were carried out on the films obtained in the above Examples and Comparative Examples.

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

(2) Measurement of Water Contact Angle after Chemical Resistance Test A scratch device equipped with a minoan eraser was used on the obtained film, and a load of 1000 g was applied to the obtained film with the eraser in contact with the film. Approximately 2.5 ml of ethanol was added dropwise thereto, and the eraser was reciprocated on the film at a speed of 40 r / min (40 reciprocating speeds per minute) to perform a chemical resistance test. The contact angle of water after the eraser reciprocated the film 3000 times was measured.

The results are shown in Table 1.

In Examples 1 to 3 in which the layer (c) was formed using the organosilicon compound (C) specified in the present invention, the water contact angle after the chemical resistance test was 82.0 ° or more (particularly 90 ° or more), which was good. However, in Comparative Examples 1 to 4 in which an organosilicon compound different from the organosilicon compound (C) was used instead of the organosilicon compound (C) of the present invention, the water contact angle after the chemical resistance test was It has decreased.

The laminate of the present invention includes display devices such as touch panel displays, optical elements, semiconductor elements, building materials, nanoimprint technology, solar cells, windowpanes of automobiles and buildings, metal products such as cooking utensils, ceramic products such as tableware, and plastics. It can be suitably formed on automobile parts and the like, and is industrially useful. It is also preferably used in kitchens, bathrooms, wash basins, mirrors, articles for various members around toilets, goggles, eyeglasses, and the like.

Claims (5)

A composition in which the water-repellent layer (r) and the resin base material layer (s) are an organosilicon compound having a silicon atom to which a hydrolyzable group is bonded and include an organosilicon compound (C) having an amino group or an amine skeleton. It is a laminated body laminated via a layer (c) formed from an object, and is a laminated body.
The organosilicon compound (C) is an organosilicon compound represented by the following formula (c2 ) or an organosilicon compound represented by the following formula (c20).
The water-repellent layer (r) is Ri layer der formed from a composition containing an organic silicon compound (A) represented by the following formula (a3),
The resin base layer (s) is a laminate wherein an acrylic resin-based hard coat layer der Rukoto.

In the above formula (c2),
X ¹ is a methoxy group or an ethoxy group, if X ¹ there are a plurality may be different plurality of X ¹ are each,
R ^x51 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R ^x51 there are a plurality of different plural R ^x51 are each,
p61 is an integer of 1 to 3, q is an integer of 2 to 5, and r is an integer of 0 to 5.

In the above formula (c20),
X ³⁰ and X ³¹ are each independently a hydrolyzable group, when X ³⁰ and X ³¹ there are a plurality may be different plurality of X ³⁰ and X ³¹ are each,
R ^x55 and R ^x56 are each independently an alkyl group having 1 to 20 carbon atoms, may be the case where R ^x55 and R ^x56 there are a plurality of different plural R ^x55 and R ^x56 are each,
In −C _w H _2w −, at least one of its methylene groups is replaced with an ^{amine skeleton −NR 100 −, R 100} is a hydrogen atom or an alkyl group, and the number of amine skeletons is 2 to 5. can be,
w is an integer from 1 to 30 (excluding the number of methylene groups replaced by the amine backbone).
p65 and p66 are each independently an integer of 1 to 3.

In the above formula (a3), R ³⁰ is a perfluoroalkyl group having 2 to 6 carbon atoms, and R ³¹ and R ³² are independently perfluoroalkylene groups having 2 to 6 carbon atoms. R ³³ is a trivalent saturated hydrocarbon group having 2 to 6 carbon atoms, R ³⁴ is an alkyl group having 1 to 3 carbon atoms, h1 is 5 to 70, and h2 is 1 to 5. , H3 is 1-10. The water-repellent layer (r) is a layer formed from a composition containing an organosilicon compound (A) represented by the above formula (a3 ) and an organosilicon compound (B) represented by the following formula (b1). The laminate according to claim 1.

In the above formula (b1),
Rf ^b10 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with fluorine atoms.
R ^b11, R ^b12, R ^b13 and R ^b14 are each independently a hydrogen atom or a carbon number from 1 to 4 alkyl groups, if R ^b11 there are a plurality differ plurality of R ^b11 each may, if R ^b12 there are a plurality may be different plural R ^b12 each may be the case where R ^b13 there are a plurality of different plural R ^b13 are each if R ^b14 there are multiple ^May have different R b14s,
Rf ^b11, Rf ^b12, Rf ^b13 and Rf ^b14 are each independently one or more alkyl group or a fluorine atom and having from 1 to 20 carbon atoms hydrogen atoms are substituted by fluorine atoms, Rf ^b11 multiple presence If you may be different plurality of Rf ^b11, respectively, differ if the Rf ^b12 there are a plurality may be different plurality of Rf ^b12, respectively, a plurality of Rf ^b13 If Rf ^b13 is present in plural even if well, if Rf ^b14 there are a plurality may be different plurality of Rf ^b14, respectively,
R ^b15 is an alkyl group having 1 to 20 carbon atoms, it may be the case where R ^b15 there are a plurality of different plural R ^b15 are each,
A ¹ is −O−, −C (= O) −O−, −OC (= O) −, −NR−, −NRC (= O) −, or −C (= O) NR−. There, wherein R is a hydrogen atom, a fluorine-containing alkyl group of 1 to 4 alkyl groups or carbon atoms having 1 to 4 carbon atoms, if a ¹ there are a plurality may be different plurality of a ^1, respectively,
A ² is a hydrolyzable group, if A ² there are a plurality may be different plurality of A ^2, respectively,
b11, b12, b13, b14 and b15 are independently integers from 0 to 100, respectively.
c is an integer from 1 to 3 and
Rf ^b10 −, ^{−Si (A 2} ) _c (R ^b15 ) _3-c , b11 − {C (R ^b11 ) (R ^b12 )} −, b12 − {C (Rf ^b11 ) (Rf ^b12 ) } −, b13 − {Si (R ^b13 ) (R ^b14 )} −, b14 − {Si (Rf ^b13 ) (Rf ^b14 )} −, b15 ^{− A 1} − are Rf ^b10 −, Arranged in any order as long as −Si (A ² ) _c (R ^b15 ) _3-c is the terminal, does not form a perfluoropolyether structure, and -O− is not linked to −O− to −F. Join. The method for producing a laminate according to claim 1 or 2.
A step of applying the composition containing the organosilicon compound (C) to the resin base material layer (s) to form the layer (c).
Production of a laminate comprising a step of applying a composition containing the organosilicon compound (A) to the layer (c) and curing it at room temperature to form a water-repellent layer (r). Method. The method for producing a laminate according to claim 3 , wherein the composition containing the organosilicon compound (A) further contains the organosilicon compound (B) in the step of forming the water-repellent layer (r). The method for producing a laminate according to claim 3 or 4 , wherein the resin base material layer (s) is subjected to plasma treatment, and the composition containing the organosilicon compound (C) is applied to the plasma-treated surface.