JP7406387B2 - Laminate and its manufacturing method - Google Patents

Description

The present invention relates to a laminate and a method for manufacturing the same.

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

When applying a composition containing a compound having a perfluoropolyether structure to a base material, for the purpose of improving adhesion, etc., after forming another layer such as a primer layer on the base material in advance, The composition may be applied to form an antifouling or water- and oil-repellent coating.

For example, Patent Document 1 discloses a hard coat film in which a hard coat layer (X), a primer layer (Y), and a surface layer (Z) are sequentially laminated on at least one surface of a base material, and the surface layer ( A hard coat film in which Z) has a water contact angle of 110° or more 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-acryloxypropyltritrifluoride is preferably used. It is stated that silane compounds such as methoxysilane are preferred.

JP 2015-120253 Publication

Depending on the application, a laminate in which a water-repellent layer formed from a composition containing a compound having a perfluoropolyether structure is laminated on a base material such as a resin may be exposed to chemicals such as alcohol. In such cases, it is required to maintain good performance (water repellency, etc.) even after exposure to chemicals (hereinafter referred to as chemical resistance).

However, in Patent Document 1, chemical resistance was not studied. Therefore, the present invention provides a laminate in which a water-repellent layer formed from a resin base material and a composition in which a compound having a perfluoropolyether structure is mixed, the laminate having excellent chemical resistance. The purpose is to provide the body.

上記式（ｃ１１）中、
Ｚ¹、Ｚ²は、それぞれ独立に、加水分解性基及びヒドロキシ基以外の、反応性官能基であり、
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、
Ｙは、－ＮＨ－、－Ｎ（ＣＨ₃）－又は－Ｏ－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、
Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴は、ぞれぞれ独立に、－ＯＲ^c（Ｒ^cは、水素原子、炭素数１～４のアルキル基、又はアミノＣ_1-3アルキルジＣ_1-3アルコキシシリル基である）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、Ｘ²が複数存在する場合は複数のＸ²がそれぞれ異なっていてもよく、Ｘ³が複数存在する場合は複数のＸ³がそれぞれ異なっていてもよく、Ｘ⁴が複数存在する場合は複数のＸ⁴がそれぞれ異なっていてもよく、
ｐ１１は、０～２０の整数であり、ｐ１２、ｐ１３、ｐ１４は、それぞれ独立して、０～１０の整数であり、ｐ１５は、０～５の整数であり、ｐ１６は、１～１０の整数であり、ｐ１７は０又は１であり、
前記有機ケイ素化合物（Ｃ１）は、末端がＺ¹－及びＺ²－であり、－Ｏ－が－Ｏ－と連結しない限り、ｐ１１個の－｛Ｃ（Ｒ^x1）（Ｒ^x2）｝－、ｐ１２個の－｛Ｃ（Ｒｆ^x1）（Ｒｆ^x2）｝－、ｐ１３個の－｛Ｓｉ（Ｒ^x3）（Ｒ^x4）｝－、ｐ１４個の－｛Ｓｉ（Ｒｆ^x3）（Ｒｆ^x4）｝－、ｐ１５個の－Ｙ－、ｐ１６個の－｛Ｓｉ（Ｘ¹）（Ｘ²）－Ｏ｝－、ｐ１７個の－｛Ｓｉ（Ｘ³）（Ｘ⁴）｝－が任意の順で並んで結合して構成される。

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。
［２］前記有機ケイ素化合物（Ｃ２）は、
下記式（ｃ２１－１）で表される構造（ｃ２１－１）を２以上有し、前記構造（ｃ２１－１）同士が、下記＊３又は＊４で鎖状又は環状に結合した化合物であって、下記＊３又は＊４での結合は、２以上の前記有機ケイ素化合物（Ｃ１）の前記Ｘ¹又はＸ²の縮合によるものであり、
下記式（ｃ２１－１）の＊１及び＊２には、それぞれ、下記式（ｃ２１－２）のｐ１１、ｐ１２、ｐ１３、ｐ１４、ｐ１５、（ｐ１６）－１、ｐ１７で括られた単位の少なくとも１種が任意の順で結合し末端がＺ－である基が結合しており、複数の前記構造（ｃ２１－１）ごとに、＊１及び＊２に結合する基は異なっていてもよく、
複数の前記構造（ｃ２１－１）が鎖状に結合しているときの末端となる＊３は水素原子であり、＊４はヒドロキシ基である［１］に記載の積層体。

前記式（ｃ２１－２）中、
Ｚは、加水分解性基及びヒドロキシ基以外の、反応性官能基であり、
Ｒ^x1、Ｒ^x2、Ｒ^x3、Ｒ^x4、Ｒｆ^x1、Ｒｆ^x2、Ｒｆ^x3、Ｒｆ^x4、Ｙ、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴、ｐ１１～ｐ１７は、前記式（ｃ１１）中のこれら符号と同義である。
［３］前記組成物（ｃａ）は、下記式（ｂ１）で表される有機ケイ素化合物（Ｂ）が混合されている［１］又は［２］に記載の積層体。

前記式（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。
［４］前記組成物（ｃｃ）は、少なくとも前記有機ケイ素化合物（Ｃ１）が混合されている［１］～［３］のいずれかに記載の積層体。
［５］前記樹脂基材層（ｓ）は、ハードコート層である［１］～［４］のいずれかに記載の積層体。
［６］［１］～［５］のいずれかに記載の積層体の製造方法であって、
前記樹脂基材層（ｓ）に、前記組成物（ｃｃ）を塗布して層（ｃ）を形成する工程、
前記層（ｃ）に、前記組成物（ｃａ）を塗布して常温で硬化させて前記撥水層（ｒ）を形成する工程、
を含む積層体の製造方法。
［７］前記層（ｃ）を形成する工程で、前記樹脂基材層（ｓ）にプラズマ処理を施し、該プラズマ処理面に前記組成物（ｃｃ）を塗布する［６］に記載の積層体の製造方法。 The invention is as follows.
[1] A laminate in which a water-repellent layer (r) and a resin base layer (s) are laminated via a layer (c),
The layer (c) is formed by condensing an organosilicon compound (C1) represented by the following formula (c11) and/or two or more of the organosilicon compounds (C1) with at least one of the following X ¹ to X ⁴ . formed from a mixed composition (cc) of combined organosilicon compounds (C2);
A laminate, wherein the water-repellent layer (r) is a layer formed from a mixed composition (ca) of an organosilicon compound (A) represented by the following formula (a1).

In the above formula (c11),
Z ¹ and Z ² are each independently a reactive functional group other than a hydrolyzable group and a hydroxy group,
R ^x1 , R ^x2 , R ^x3 , and R ^x4 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when multiple R ^x1s exist, the multiple R ^x1s are different from each other. If there are multiple R ^x2s , the R ^x2s may be different. If there are multiple R x3s, the R ^x3s may be different. If there are multiple R ^x4s , the R ^x3s may be different. may have different R ^x4 ,
Rf ^x1 , Rf ^x2 , Rf ^x3 , and Rf ^x4 are each independently an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with a fluorine atom, and there is a plurality of Rf ^x1 If multiple Rf ^x1 exist, each of the multiple Rf x1 may be different; if multiple Rf ^x2 exists, each of the multiple Rf ^x2 may be different; if multiple Rf ^x3 exists, each of the multiple Rf ^x3 may be different If there are multiple Rf ^x4 , the multiple Rf ^x4 may be different,
Y is -NH-, -N(CH ₃ )- or -O-, and when there is a plurality of Y's, the plural Y's may be different from each other,
^{X 1 ,} X ² , _X ^{3 ,} _{and 3} alkoxysilyl group), and when a plurality of X ^1s exist, the plurality of X ^1s may be different from each other, and when a plurality of X ^2s exist, the plurality of X ^2s may be different from each other, When there are multiple X ³ 's, the multiple X ³ 's may be different, and when there are multiple X ⁴ 's, the multiple X ⁴ 's may be different,
p11 is an integer from 0 to 20, p12, p13, and p14 are each independently an integer from 0 to 10, p15 is an integer from 0 to 5, and p16 is an integer from 1 to 10. and p17 is 0 or 1,
The organosilicon compound (C1) has Z ¹ - and Z ² - terminals, and unless -O- is connected to -O-, p11 -{C(R ^x1 )(R ^x2 )}-, p12 -{C(Rf ^x1 ) (Rf ^x2 )}-, p13 -{Si(R ^x3 ) (R ^x4 )}-, p14 -{Si(Rf ^x3 ) (Rf ^x4 )}- , p15 -Y-, p16 -{Si(X ¹ ) (X ² ) -O}-, p17 -{Si(X ³ ) (X ⁴ )}- are arranged in any order. Constructed by combining.

In the above formula (a1),
Rf ^a1 is a divalent perfluoropolyether structure with oxygen atoms at both ends,
R ¹¹ , R ¹² , and R ¹³ are each independently an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^11s exist, the plurality of R ^11s may be different ^from each other; When present, the plurality of R ¹² may be different from each other, and when the plurality of R ¹³ is present, the plurality of R ¹³ may be different from each other,
E ¹ , E ² , E ³ , E ⁴ , and E ⁵ are each independently a hydrogen atom or a fluorine atom, and when a plurality of E ^1s exist, the plurality of E ^1s may be different from each other; When there are multiple ^{E 2s} , the E ^2s may be different; when there are multiple E ^3s , the E ^3s may be different; when there are multiple E ^4s , the E 2s may be different. ⁴ may be different,
G ¹ and G ² are each independently a divalent to decavalent 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, and R ¹⁴ is a methyl group. or is an ethyl group, and when there are multiple J ¹ 's, the multiple J ¹ 's may be different; when there are multiple J ² 's, the multiple J ² 's may be different, and the multiple J ³ 's may be different. If present, multiple J ³ may be different,
L ¹ and L ² are each independently a divalent linking group having 1 to 12 carbon atoms that may contain an oxygen atom, a nitrogen atom, or a ^fluorine atom; L ¹ may be different from each other, and if there are multiple L ² , the plural L ² may be different from each other,
d11 is 1 to 9,
d12 is 0 to 9,
a10 and a14 are each independently from 0 to 10,
a11 and a15 are each independently 0 or 1,
a12 and a16 are each independently 0 to 9,
a13 is 0 or 1,
a21, a22, and a23 are each independently 0 to 2,
e1, e2, and e3 are each independently 1 to 3.
[2] The organosilicon compound (C2) is
A compound having two or more structures (c21-1) represented by the following formula (c21-1), in which the structures (c21-1) are linked together in a chain or cyclic manner as shown in *3 or *4 below. Therefore, the bond in *3 or *4 below is due to the condensation of the X ¹ or X ² of two or more of the organosilicon compounds (C1),
*1 and *2 in the following formula (c21-1) each represent at least one of the units bracketed by p11, p12, p13, p14, p15, (p16)-1, and p17 in the following formula (c21-2). One type is bonded in any order and a group whose terminal is Z- is bonded, and the groups bonded to *1 and *2 may be different for each of the plurality of structures (c21-1),
The laminate according to [1], wherein *3, which is the terminal when a plurality of the structures (c21-1) are bonded in a chain, is a hydrogen atom, and *4 is a hydroxy group.

In the formula (c21-2),
Z is a reactive functional group other than a hydrolyzable group and a hydroxy group,
R ^x1 , R ^x2 , R ^x3 , R ^x4 , Rf ^x1 , Rf ^x2 , Rf ^x3 , Rf ^x4 , Y, X ¹ , X ² , X ³ , X ⁴ , p11 to p17 are These symbols are synonymous.
[3] The laminate according to [1] or [2], wherein the composition (ca) contains an organosilicon compound (B) represented by the following formula (b1).

In the 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 a fluorine atom,
R ^b11 , R ^b12 , R ^b13 and R ^b14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there is a plurality of R ^b11s , the plurality of R ^b11s are different from each other. When there are multiple R ^b12s , the R ^b12s may be different; when there are multiple R b13s, the R ^b13s may be different; and when there are multiple R ^b14s , the R ^b12s may be different. may have different R ^b14s ,
Rf ^b11 , Rf ^b12 , Rf ^b13 and Rf ^b14 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 a fluorine atom, and there is a plurality of Rf ^b11 When there are multiple Rf ^b13s , the multiple Rf b11s may be different from each other; when there are multiple Rf ^b12s , the multiple Rf ^b12s may be different; when there are multiple Rf ^b13s , the multiple Rf ^b13s may be different from each other. If there are multiple Rf ^b14s , the multiple Rf ^b14s may be different,
R ^b15 is an alkyl group having 1 to 20 carbon atoms, and when there are multiple R ^b15s , each of the R ^b15s may be different,
A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR- and the 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 there are multiple A ^1s , each of the multiple A ^1s may be different,
A ² is a hydrolyzable group, and when a plurality of A ² exists, the plural A ² may be different from each other,
b11, b12, b13, b14 and b15 are each independently an integer of 0 to 100,
c is an integer from 1 to 3,
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 -, Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c is the terminal, and as long as they do not form a perfluoropolyether structure and -O- does not connect with -O- to -F, they can be arranged in any order. Join.
[4] The laminate according to any one of [1] to [3], wherein the composition (cc) contains at least the organosilicon compound (C1).
[5] The laminate according to any one of [1] to [4], wherein the resin base layer (s) is a hard coat layer.
[6] A method for producing a laminate according to any one of [1] to [5], comprising:
a step of applying the composition (cc) to the resin base layer (s) to form a layer (c);
a step of applying the composition (ca) to the layer (c) and curing it at room temperature to form the water-repellent layer (r);
A method for producing a laminate comprising:
[7] The laminate according to [6], wherein in the step of forming the layer (c), the resin base layer (s) is subjected to plasma treatment, and the composition (cc) is applied to the plasma treated surface. manufacturing method.

According to the present invention, a laminate with excellent chemical resistance can be provided.

A laminate in which a water-repellent layer (r) formed from a mixed composition (ca) of a compound having a perfluoropolyether structure is laminated on a resin base layer (s), and has excellent chemical resistance. As a result of repeated studies by the present inventors in order to realize a laminate, it was found that the resin base layer (s) and the water repellent layer (r) are made of a specific organosilicon compound (C1) and/or organosilicon. It has been found that when laminated with a layer (c) formed from a mixed composition (cc) of compound (C2) interposed therebetween, a laminate having excellent chemical resistance can be realized. Hereinafter, the layer (c), the water-repellent layer (r), and the resin base layer (s) will be explained in this order. The mixed composition (ca) is a composition in which the organosilicon compound (A) is mixed, and is obtained by mixing the organosilicon compound (A), and contains components other than the organosilicon compound (A). When these are mixed, it can be obtained by mixing the organosilicon compound (A) and other components. The mixed composition (cc) is a composition in which an organosilicon compound (C1) and/or an organosilicon compound (C2) is mixed; When components other than the organosilicon compound (C1) and (C2) are mixed, the organosilicon compound (C1) and/or the organosilicon compound (C2) are mixed with the other components. It can be obtained by The mixed composition (ca) and the mixed composition (cc) include those in which the reaction has progressed after mixing, for example, during storage.

1. layer (c)
The layer (c) is an organosilicon compound (C1) represented by the following formula (c11) and/or an organosilicon compound in which two or more of the organosilicon compounds (C1) are condensed and bonded with the following X ¹ or X ² It is a layer formed from a mixed composition (cc) of (C2), that is, it has a structure derived from the organosilicon compound (C1) and/or the organosilicon compound (C2). Hereinafter, the organosilicon compounds (C1) and (C2) may be collectively referred to as the organosilicon compound (C).

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

In the formula (c11),
Z ¹ and Z ² are each independently a reactive functional group other than a hydrolyzable group and a hydroxy group. Examples of the reactive functional group include a vinyl group, α-methylvinyl group, styryl group, methacryloyl group, acryloyl group, amino group, epoxy group, ureido group, or mercapto group. As Z ¹ and Z ² , an amino group, a mercapto group, or a methacryloyl group is preferable, and an amino group is particularly preferable.

R ^x1 , R ^x2 , R ^x3 , and R ^x4 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when multiple R ^x1s exist, the multiple R ^x1s are different from each other. If there are multiple R ^x2s , the R ^x2s may be different. If there are multiple R x3s, the R ^x3s may be different. If there are multiple R ^x4s , the R ^x3s may be different. The plurality of R ^x4 may be different from each other. R ^x1 , R ^x2 , R ^x3 and R ^x4 are preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably a hydrogen atom.

Rf ^x1 , Rf ^x2 , Rf ^x3 , and Rf ^x4 are each independently an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with a fluorine atom, and there is a plurality of Rf ^x1 If multiple Rf ^x1 exist, each of the multiple Rf x1 may be different; if multiple Rf ^x2 exists, each of the multiple Rf ^x2 may be different; if multiple Rf ^x3 exists, each of the multiple Rf ^x3 may be different If a plurality of Rf ^x4s exist, the plurality of Rf ^x4s may be different from each other. Rf ^x1 , Rf ^x2 , Rf ^x3 and Rf ^x4 are preferably an alkyl group having 1 to 10 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with a fluorine atom.

Y is -NH-, -N(CH ₃ )- or -O-, and when a plurality of Y's exist, the plural Y's may be different from each other. Y is preferably -NH-.

^{X 1 ,} X ² , _X ^{3 ,} _{and 3} alkoxysilyl group), and when a plurality of X ^1s exist, the plurality of X ^1s may be different from each other, and when a plurality of X ^2s exist, the plurality of X ^2s may be different from each other, When a plurality of X ³ exists, the plurality of X ³ may be different from each other, and when a plurality of X ⁴ exists, the plurality of X ⁴ may be different from each other. X ¹ , X ² , X ³ , and X ⁴ are preferably -OR ^c in which R ^c is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ^c is more preferably a hydrogen atom.

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

The organosilicon compound (C1) has Z ¹ - and Z ² - terminals, and unless -O- is connected to -O-, p11 -{C(R ^x1 )(R ^x2 )}-, p12 -{C(Rf ^x1 ) (Rf ^x2 )}-, p13 -{Si(R ^x3 ) (R ^x4 )}-, p14 -{Si(Rf ^x3 ) (Rf ^x4 )}- , p15 -Y-, p16 -{Si(X ¹ ) (X ² ) -O}-, p17 -{Si(X ³ ) (X ⁴ )}- are arranged in any order. Constructed by combining. p11 -{C(R ^x1 ) (R ^x2 )}- does not need to be connected consecutively with -{C(R ^x1 ) (R ^x2 )}- through other units in the middle. They may be combined together, and the total number may be p11. The same applies to the units grouped by p12 to p17.

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

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

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

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

In formula (c12), Z ¹ , Z ² , X ¹ , X ² , X ³ , X ⁴ and Y have the same meanings as in formula (c11), and p21 to p24 each independently represent 1 to It is an integer of 6, and p25 and p26 are each independently 0 or 1.

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

1-2. Organosilicon compound (C2)
The organosilicon compound (C2) is a compound in which two or more of the organosilicon compounds (C1) are condensed and bonded with at least one of the above X ¹ to X ⁴ , and the two or more of the organosilicon compounds (C1) are , may be bonded in a chain or in a ring. The organosilicon compound (C2) is formed, for example, from the organosilicon compound (C1) in the composition (cc).

Examples of the organosilicon compound (C2) include those condensed with the above-mentioned X ^{1 or} A compound in which the structures (c21-1) are bonded to each other in a chain or cyclic manner as shown in *3 or *4 below, and the bond in *3 or *4 below is a compound in which two or more organosilicon compounds ( C1) is due to the condensation of X ¹ or X ² ,
*1 and *2 in the following formula (c21-1) each represent at least one of the units bracketed by p11, p12, p13, p14, p15, (p16)-1, and p7 in the following formula (c21-2). Examples include compounds in which one type is bonded in any order and a group having a Z-terminus is bonded. The groups bonded to *1 and *2 may be different for each of the multiple structures (c21-1), and serve as the terminal * when multiple structures (c21-1) are bonded in a chain. 3 is a hydrogen atom, and *4 is a hydroxy group.

In the formula (c21-2),
Z is a reactive functional group other than a hydrolyzable group and a hydroxy group,
R ^x1 , R ^x2 , R ^x3 , R ^x4 , Rf ^x1 , Rf ^x2 , Rf ^x3 , Rf ^x4 , Y, X ¹ , X ² , X ³ , X ⁴ , p11 to p17 are These symbols have the same meanings, and the same applies to their preferred embodiments.

When forming the organosilicon compound (C2), the number of bonds in the organosilicon compound (C1) is preferably 2 to 10, more preferably 3 to 8. Moreover, two or more organosilicon compounds (C1) constituting the organosilicon compound (C2) may be different from each other, but it is preferable that they are all the same.

When the organosilicon compound (C1) is a compound represented by the above formula (c12), the organosilicon compound (C2) may have a structure represented by the following formula (c22), for example, a chain in *3 or *4 below. Examples include compounds bonded in a shape or a ring. When the structure represented by the following formula (c22) is bonded in a chain, *3 is a hydrogen atom and *4 is a hydroxy group.

The symbols in the formula (c22) are all synonymous with the symbols in the formula (c11).

The organosilicon compound (C2) is preferably a compound in which 2 to 10 (preferably 3 to 8) structures represented by the above formula (c22) are bonded.

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

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

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

In the above formula (a1),
Rf ^a1 is a divalent perfluoropolyether structure with oxygen atoms at both ends,
R ¹¹ , R ¹² , and R ¹³ are each independently an alkyl group having 1 to 20 carbon atoms (that is, R ¹¹ , R ¹² , and R ¹³ may be the same or different); When there are multiple R ^11s , the R ^11s may be different; when there are multiple R 12s, the R ^12s may be different; and when there are multiple R ^13s , the R ^12s may be different. may have different R ^13s ,
E ¹ , E ² , E ³ , E ⁴ and E ⁵ are each independently a hydrogen atom or a fluorine atom,
When there are multiple E ^1s , the multiple E ^1s may be different; when there are multiple E ^2s , the multiple E ^2s may be different; when there are multiple E ^3s , the multiple E 1s may be different. Each E ³ may be different, and if there are multiple E ^4s , each E ⁴ may be different,
G ¹ and G ² are each independently a divalent to decavalent 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, and R ¹⁴ is a methyl group. or is an ethyl group, and when there are multiple J ¹ 's, the multiple J ¹ 's may be different; when there are multiple J ² 's, the multiple J ² 's may be different, and the multiple J ³ 's may be different. If present, multiple J ³ may be different,
L ¹ and L ² are each independently a divalent linking group having 1 to 12 carbon atoms that may contain an oxygen atom, a nitrogen atom, or a ^fluorine atom; The L ¹ may be different from each other, and when there are multiple L ² , the plural L ² may be different from each other,
d11 is 1 to 9,
d12 is 0 to 9,
a10 and a14 are each independently from 0 to 10,
a11 and a15 are each independently 0 or 1,
a12 and a16 are each independently 0 to 9,
a13 is 0 or 1,
a21, a22, and a23 are each independently 0 to 2,
e1, e2, and e3 are each independently 1 to 3.

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 ) _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 a polyoxyalkylene group are replaced with fluorine atoms, and can also be called a perfluorooxyalkylene group, and can impart water repellency to the resulting film. Moreover, it is a compound that can become a matrix of a film obtained by bonding the organosilicon compounds (A) with each other or with other monomers through a polymerization reaction (particularly a polycondensation reaction) using J ² .

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 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 and containing a fluorine atom.

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

J ¹ , J ² and J ³ are each independently preferably 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), 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. Moreover, a13 is preferably 1.

In 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 L ¹ and L ² are both carbon It is a perfluoroalkylene group of numbers 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, and J ¹ , J ² , and J ³ are each a methoxy group or an ethoxy group (especially a methoxy group), 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 to 6, a21 to a23 are each 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.

In addition, when compound a used as 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 are all -(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 and a22 are both 0, d11 is 1, d12 is 0, e1 , e2 are all 3.

In 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, L ¹ is a divalent linking group having 3 to 6 carbon atoms containing a fluorine atom and an oxygen atom, and L ² is a perfluoroalkylene group having 1 to 3 carbon atoms. , E ² and E ³ are all hydrogen atoms, E ⁵ is a fluorine atom, J ² is -(CH ₂ ) _e6 -Si(OCH ₃ ) ₃ , e6 is 2 to 4, and 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, It is also preferable to use a compound in which each of them is independently 0 or 1 (more preferably all a21 to a23 are 0), d11 is 1, d12 is 0, and e2 is 3.

Further, it is also preferable that the organosilicon compound (A) is 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 substituted with a fluorine atom,
Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^a25 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 a fluorine atom, and Rf ^a22 is a plurality of fluorine atoms. If there are multiple Rf ^a22s , each of the multiple Rf a22s may be different; if multiple Rf ^a23s exist, the multiple Rf ^a23s may be different; if multiple Rf ^a24s exist, each of the multiple Rf ^a24s may be different. They may be different, and if there are multiple Rf ^a25s , each of the Rf ^a25s may be different,
R ²⁰ , R ²¹ , R ²² , and R ²³ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when a plurality of R ^20s exist, the plurality of R ^20s are different from each other. When there are multiple R ^21s , the R ^21s may be different. When there are multiple R 22s, the R ^22s may be different. When there are multiple R ^23s , the R ^22s may be different. may have different ^R23s ,
R ²⁴ is an alkyl group having 1 to 20 carbon atoms, and when there are multiple R ^24s , each of the R ^24s may be different,
M ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when multiple M ¹ exist, each of the multiple M ¹ may be different,
M ² is a hydrogen atom or a halogen atom,
M ³ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-( R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms), and when multiple M ³ 's exist, each of the multiple M ³ 's may be different,
M ⁴ is a hydrolyzable group, and when multiple M ⁴ exist, each of the multiple M ⁴ may be different,
f11, f12, f13, f14, and f15 are each independently an integer of 0 to 600, and the total value of f11, f12, f13, f14, and f15 is 13 or more,
f16 is an integer from 1 to 20,
f17 is an integer from 0 to 2,
g1 is an integer from 1 to 3,
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 such an order that Rf ^a21 - and M ² - are terminals, and at least a portion thereof forms a perfluoropolyether structure, and Unless -O- is linked to -O- to -F, they are bonded in any order. In other words, in formula (a2-1), f11 -{C(R ²⁰ ) (R ²¹ )}- are not necessarily consecutive, and f12 -{C(Rf ^a22 ) (Rf ^a23 )}- are not necessarily consecutive. , f13 -{Si(R ²² ) (R ²³ )}- are consecutive, f14 -{Si(Rf ^a24 ) (Rf ^a25 )}- are consecutive, and f15 -M ³ - are consecutive. However, it does not mean that f16 -[CH ₂ C (M ¹ ) { (CH ₂ ) _f17 - Si (M ⁴ ) _g1 (R ²⁴ ) _3-g1 }] - are consecutively arranged in this order. , -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 } They can be arranged in any order, such as -C(Rf ^a22 )(Rf ^a23 )-M ³ -Si(R ²² )(R ²³ )-C(Rf ^a22 )(Rf ^a23 )-. 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 still more preferably an alkyl group having 1 to 10 carbon atoms. 5 perfluoroalkyl group.

Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^a25 are preferably each independently a fluorine atom or an alkyl group having 1 to 2 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, and more preferably All are preferably 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, more preferably all of them 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 carbon atoms, 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)-, 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 is 0, and particularly preferably f13 and f14 are 0. It is.

f15 is preferably ⅕ or more of the total value of f11, f12, f13, and f14, and less than or equal to the total value of f11, f12, f13, and f14.

f12 is preferably 20 to 600, more preferably 20 to 200, even more preferably 50 to 200 (even more preferably 30 to 150, especially 50 to 150, most preferably 80 to 140). f15 is preferably 4 to 600, more preferably 4 to 200, even more preferably 10 to 200 (even 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 1 to 15. More preferably, it is 1-10.

f17 is preferably 0-1.

g1 is preferably 2 to 3, more preferably 3.

f11 pieces of −{C(R ²⁰ )(R ²¹ )}−, f12 pieces of −{C(Rf ^a22 )(Rf ^a23 )}−, f13 pieces of −{Si(R ²² )(R ²³ )}− , f14 -{Si(Rf ^a24 ) (Rf ^a25 )}-, and f15 -M ³ - in the formula as long as they are arranged in an order that forms a perfluoropolyether structure at least in part. Although optional, the repeating unit enclosed in parentheses with f12 on the most fixed end side (the side bonding to the silicon atom) (i.e., -{C(Rf ^a22 ) (Rf ^a23 )}-) is preferably , is located closer to the free end than the repeating unit attached with f11 and enclosed in parentheses (i.e., -{C(R ²⁰ ) (R ²¹ )}-) on the most free end side, and more preferably on the most fixed end. The repeating units enclosed in parentheses with side f12 and f14 (i.e., -{C(Rf ^a22 )(Rf ^a23 )}- and -{Si(Rf ^a24 )(Rf ^a25 )}-) are: Repeating units enclosed in parentheses with f11 and f13 on the free end side (i.e., -{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 all M ³ are -O- , M ⁴ is all methoxy group, ethoxy group or chlorine atom (especially methoxy group or ethoxy group), M ¹ and M ² are both hydrogen atoms, f11 is 0, f12 is 30 to 150 (more preferably 80 to 140), f15 is 30 to 60, f13 and f14 are 0, f17 is 0 to 1 (especially 0), g1 is 3, and f16 is 1 to 10.

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

Further, it is also preferable that the organosilicon compound (A) is 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 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 a fluorine atom, and Rf ^a26 is a plurality of fluorine atoms. If there are multiple Rf ^a26s , each of the multiple Rf a26s may be different; if multiple Rf ^a27s exist, the multiple Rf ^a27s may be different; if multiple Rf ^a28s exist, each of the multiple Rf ^a28s may be different. They may be different, and if there are multiple Rf ^a29s , each of the Rf ^a29s may be different,
R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when multiple R ^25s exist, the multiple R ^25s are different from each other. When there are multiple ^R26s , the ^R26s may be different; when there are multiple R27s, the ^R27s may be different; and when there are multiple ^R28s , the ^R26s may be different. may have different ^R28s ,
R ²⁹ and R ³⁰ are each independently an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^29s exist, the plurality of R ^29s may be different from each other, and a plurality of R ^30s exist. In this case, multiple R ³⁰ may be different from each other,
M ⁷ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR- and the 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 there are multiple M ^{7 s} , each of the multiple M ^7s may be different,
M ⁵ and M ⁹ are each independently a hydrogen atom or an alkyl group having 1 to ⁴ carbon atoms, and when multiple M ⁵ exist, the multiple M ⁵ may be different from each other; If present, multiple ^M9s may be different,
M ⁶ and M ¹⁰ are each independently a hydrogen atom or a halogen atom,
M ⁸ and M ¹¹ are each independently a hydrolyzable group, and when a plurality of M ^8s exist, the plurality of M ^8s may be different from each other, and when a plurality of M 11s exist, a plurality of M ^8s may be different from each other. M ¹¹ may be different,
f21, f22, f23, f24, and f25 are each independently an integer from 0 to 600, and the total value of f21, f22, f23, f24, and f25 is 13 or more,
f26 and f28 are each independently an integer of 1 to 20,
f27 and f29 are each independently an integer of 0 to 2,
g2 and g3 are each independently an integer of 1 to 3,
M ¹⁰ -, M ⁶ -, f21 -{C(R ²⁵ ) (R ²⁶ )}-, f22 -{C(Rf ^a26 ) (Rf ^a27 )}-, f23 -{Si(R ²⁷ ) (R ²⁸ )}-, f24 -{Si(Rf ^a28 ) (Rf ^a29 )}-, f25 -M ⁷ -, f26 -[CH ₂ C (M ⁵ ) {(CH ₂ ) _f27 -Si(M ⁸ ) _g2 (R ²⁹ ) _3-g2 }], and f28 -[CH ₂ C(M ⁹ ) {(CH ₂ ) _f29 -Si(M ¹¹ ) _g3 (R ³⁰ ) _{3 -g3} }] are arranged in an order in which M ¹⁰ - and M ⁶ - are terminals and form a perfluoropolyether structure at least in part, and arranged in any order as long as -O- is not continuous with -O-. Combine with . The arrangement of arranging and bonding in any order is the same as explained in the above formula (a2-1), and each repeating unit is consecutively arranged in the order as 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, all M ⁷ are -O-, and M ⁸ and M ¹¹ are all methoxy groups and ethoxy groups. or a chlorine atom (especially a methoxy group or an ethoxy group), M ⁵ , M ⁶ , M ⁹ , and M ¹⁰ are all hydrogen atoms, and f21 is 0 and f22 is 30 to 150 (more preferably 80 to 140). ), f25 is preferably 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 represented by the following formula (a3).

In the above formula (a3), R ³⁰ is a perfluoroalkyl group having 2 to 6 carbon atoms, R ³¹ and R ³² are each independently a perfluoroalkylene group 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 number of carbon atoms in R ³⁰ , R ³¹ , R ³² and R ³³ is preferably 2 to 4, more preferably 2 to 3. h1 is 5-70, h2 is 1-5, and h3 is 1-10. h1 is preferably 10 to 60, more preferably 20 to 50, h2 is preferably 1 to 4, more preferably 1 to 3, and h3 is preferably 1 to 8, 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 perfluoroalkyl group having 2 to 5 carbon atoms. A fluoroalkylene group in which some of the hydrogen atoms of the alkylene group are substituted with fluorine, R ⁴³ and R ⁴⁴ are each independently an alkylene group having 2 to 5 carbon atoms, and R ⁴⁵ is a methyl group or an ethyl group. be. k1, k2, and k3 are each 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, 000 or less, more preferably 20,000 or less, still more preferably 15,000 or less.

The composition (ca) for forming the water-repellent layer (r) may contain an organosilicon compound (B) represented by the following formula (b1) mixed with the above-mentioned organosilicon compound (A). preferable. As described later, the organosilicon compound (B) has a hydrolyzable group, and the -SiOH group of the organosilicon compound (B) produced by hydrolysis usually becomes the organosilicon compound (B) produced by hydrolysis. In a preferred embodiment, the water-repellent layer (r) is a condensate derived from the organosilicon compound (A) because it is dehydrated and condensed with the -SiOH group of A) and/or the -SiOH group of the organosilicon compound (B) generated by hydrolysis. 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 a fluorine atom,
R ^b11 , R ^b12 , R ^b13 , and R ^b14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when multiple R ^b11s exist, the multiple R ^b11s are different from each other. When there are multiple R ^b12s , the R ^b12s may be different; when there are multiple R b13s, the R ^b13s may be different; and when there are multiple R ^b14s , the R ^b12s may be different. may have different R ^b14s ,
Rf ^b11 , Rf ^b12 , Rf ^b13 , and Rf ^b14 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 a fluorine atom, and there are multiple Rf ^b11s . When there are multiple Rf ^b13s , the multiple Rf b11s may be different from each other; when there are multiple Rf ^b12s , the multiple Rf ^b12s may be different; when there are multiple Rf ^b13s , the multiple Rf ^b13s may be different from each other. If there are multiple Rf ^b14s , the multiple Rf ^b14s may be different,
R ^b15 is an alkyl group having 1 to 20 carbon atoms, and when there are multiple R ^b15s , each of the R ^b15s may be different,
A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR- and the 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 there are multiple A ^1s , each of the multiple A ^1s may be different,
A ² is a hydrolyzable group, and when a plurality of A ² exists, the plural A ² may be different from each other,
b11, b12, b13, b14, b15 are each independently an integer from 0 to 100,
c is an integer from 1 to 3,
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 -, Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c is the terminal, and as long as they do not form a perfluoropolyether structure and -O- does not connect with -O- to -F, they can be arranged in any order. Join.

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

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

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

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

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

b11 is preferably from 1 to 30, more preferably from 1 to 25, even more preferably from 1 to 10, particularly preferably from 1 to 5, and most preferably from 1 to 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, preferably 5 or more, and preferably 80 or less, more preferably 50 or less, and still more 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 5. 5, b12 is preferably 0 to 5, b13, b14, and b15 are all 0, and c is preferably 3.

In addition, 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 -- is determined.

Specifically, the compound represented by the above formula (b1) is CF ₃ -Si-(OCH ₃ ) ₃ , C _j F _2j+1 -Si-(OC ₂ H ₅ ) ₃ (j is 1 to 12 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 preferred. Also, 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 Examples include (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 all cases). and preferably 8 to 15). Also, 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 1 to 10, preferably 3 to 7, and n is 1 to 5, preferably 2 to 4). ). CF ₃ (CF ₂ ) _p -(CH ₂ ) _q -Si-(CH ₂ CH=CH ₂ ) ₃ (p is 2 to 10, preferably 2 to 8, and q are all from 1 to 5, preferably from 2 to 4). Furthermore, CF ₃ (CF ₂ ) _p −(CH ₂ ) _q SiCH ₃ Cl ₂ , CF ₃ (CF ₂ ) _p −(CH ₂ ) _q SiCH ₃ (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) _p −( CH ₂ ) _q SiCH ₃ (OC ₂ H ₅ ) ₂ (p is 2 to 10, preferably 3 to 7, and q is 1 to 5, preferably 2 to 4). ).

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

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.

3. Resin base layer (s)
The material of the resin base 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 flat or curved. A combination of shapes may also be used. 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 Examples include thermoplastic resins such as alcohol, etc.; thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins, and urethane resins. Examples of inorganic materials include metals such as iron, silicon, copper, zinc, and aluminum, alloys containing these metals, ceramics, and glass. Among these, organic materials are particularly preferred. Among the resin base materials, at least one of acrylic resin, benzyl chloride resin, epoxy resin, silicone resin, and urethane resin is preferred, and acrylic resin is particularly preferred.

The resin base layer (s) in the present invention is a protective layer (hereinafter sometimes referred to as a hard coat layer) provided to protect articles from scratches in applications that require wear resistance, such as displays for electronic devices. It is preferable that the protective layer be acrylic resin-based.

The hard coat layer is a layer having surface hardness, and its hardness is usually B or more in pencil hardness, preferably HB or more, more preferably H or more, and particularly preferably 2H or more. The hard coat layer may have a single layer structure or a multilayer structure. The hard coat layer is, for example, a cured layer of ultraviolet curable resin. The hard coat layer contains a hard coat layer resin, and examples of the hard coat layer resin include acrylic resin, epoxy resin, urethane resin, amide resin, vinylbenzyl chloride resin, vinyl resin, or silicone resin. Examples include ultraviolet curable, electron beam curable, and thermosetting resins such as resins or mixed resins thereof. 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, since there is a tendency for good adhesion with the water-repellent layer (r) through the layer (c).

The hard coat layer may contain additives. The additive is not limited and may include inorganic fine particles, organic fine particles, or a mixture thereof. Examples of additives include ultraviolet absorbers, metal oxides such as silica and alumina, and inorganic fillers such as polyorganosiloxane. By including an inorganic filler, the adhesion with 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 layer (s) are arranged in this order, the layer ( c) and the resin base layer (s), and on the surface side of the layer (s), other layers may be included between the layer (r) and the layer (c). Preferably not. Moreover, 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 includes a resin layer (s2) different from the resin base layer (s), and in order from the surface of the laminate, a water-repellent layer (r), a layer (c), The resin base layer (s) and the resin layer (s2) may be formed in this order.

In particular, when the resin base layer (s) is a hard coat layer, it is preferable that a resin layer (s2) different from the resin base layer (s), which is the hard coat layer, is laminated. The resin layer (s2) laminated with the resin base layer (s), which is a hard coat layer, may be in the form of a film or a plate, and as long as it can transmit light, it can be used for display purposes such as displays. Preferable as a member. A laminate including a resin base layer (s) that is a hard coat layer and a resin layer (s2) can be used for a flexible display as a front plate of an image display device.

Examples of the resin constituting the resin layer (s2) include triacetylcellulose, acetylcellulose butyrate, ethylene-vinyl acetate copolymer, propionylcellulose, butyrylcellulose, acetylpropionylcellulose, polyester, polystyrene, polyamide, and polyetherimide. , poly(meth)acrylic, polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyetherketone, polyetheretherketone, polyethersulfone, Examples include films made of polymers such as polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, and polyamideimide. These polymers can be used alone or in combination of two or more. From the viewpoint of achieving both strength such as bending resistance and transparency, a resin film made of a polymer such as polyimide, polyamide, polyamideimide, etc. is preferable. The thickness of the resin layer (s2) may be, for example, 10 μm or more and 500 μm or less, preferably 20 μm or more and 200 μm or less, more preferably 30 μm or more and 150 μm or less, and may be 100 μm or less.

The laminate having the resin layer (s2) is preferably used as a front plate in a flexible image display device, and the front plate is sometimes referred to as a window film. The flexible image display device includes a laminate for a flexible image display device and an organic EL display panel, the laminate for a flexible image display device is arranged on the viewing side with respect to the organic EL display panel, and is configured to be foldable. ing. The laminate for a flexible image display device may further contain a polarizing plate, preferably a circularly polarizing plate, and a touch sensor, and the stacking order of these may be arbitrary. Alternatively, it is preferable that the window film, the touch sensor, and the polarizing plate are laminated in this order. It is preferable that the polarizing plate is present on the viewing side of the touch sensor because the pattern of the touch sensor becomes less visible and the visibility of the displayed image improves. Each member can be laminated using an adhesive, a pressure-sensitive adhesive, or the like. Furthermore, a light shielding pattern may be provided on at least one surface of any one of the window film, polarizing plate, and touch sensor layer.

A primer layer may be provided between the resin layer (s2) and the resin base layer (s) (especially the hard coat layer). As the primer agent, there are, for example, an ultraviolet curing type, a thermosetting type, or a two-component curing type epoxy compound primer agent. It is preferable that the compound mixed in the primer layer chemically bonds with the resin component mixed in the resin layer (s2) or the silicon material mixed as necessary. Moreover, polyamic acid may be used as a primer agent, and the adhesion between the resin layer (s2) and the resin base layer (s) (particularly the hard coat layer) can be improved. Furthermore, a silane coupling agent may be mentioned as a primer agent, and may be chemically bonded to a silicon material mixed into a resin base material 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 by a droplet method (analysis method: θ/2 method) at a liquid volume of 3 μL, for example, 105° or more, more preferably 110°. The angle is not less than 120°, and is not more than 120°, for example. In addition, water contact angle (contact angle after chemical resistance test) measured at a liquid volume of 3 μL using the droplet method (analysis method: θ/2 method) after conducting the chemical resistance test in the example described later. is, for example, 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 manufacturing a laminate according to the present invention will be explained.

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

In the step of forming the layer (c), a mixed composition (cc) of an organosilicon compound (C1) and/or an organosilicon compound (C2) is applied to the resin base layer (s). It is preferable that the composition (cc) is mixed with a solvent (E).

The total amount of the organosilicon compound (C1) and the organosilicon compound (C2) is preferably 0.01% by mass or more, more preferably 0.05% by mass when the entire composition (cc) is 100% by mass. The content is at least 0.1% by mass, more preferably at least 0.1% by mass, and preferably at most 5% by mass, more preferably at most 3% by mass, even more preferably at most 2% by mass. The amounts of the above organosilicon compounds (C1) and (C2) can be adjusted during the preparation of the composition. The amount of the organosilicon compound (A) may be calculated from the analysis results of the composition. In addition, in this specification, when the range of the amount, mass ratio, or molar ratio of each component is described, the said range can be adjusted at the time of preparation of a composition similarly to the above.

The solvent (E) preferably has an sp value [(cal/cm ³ ) ^1/2 ] of 9.00 or more, and more preferably has an sp value of 10 or more. Examples of such a solvent (E) include water, ethanol, isopropanol, etc. Those having an sp value of 15 or more are particularly preferred, and water is most preferred.

In this book, the sp value (Solubility Parameter) is a value calculated by the method described in "RF Fedors, Polym. Eng. Sci., 14 [2], 147-154 (1974)". It is. In the Fedors method, the sp value is defined as the square root of the cohesive energy density. Specifically, the sp value is defined by the following formula.
δ=(ΔE/V) ^1/2 (1)
In the above formula (1), δ means the sp value ((cal/cm ³ ) ^1/2 ), ΔE means the cohesive energy (cal/mol), and V means the molar molecular volume of the solvent (cm ³ /mol).

In the Fedors method, both the above-mentioned cohesive energy and molar molecular volume are considered to depend on the type and number of substituents contained in the solvent. Therefore, the cohesive energy is calculated from the cohesive energy and molecular volume (shown in Table 1 below) of each substituent, taking into account the number of substituents.

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

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

It is preferable to subject the resin base layer (s) to an adhesion-facilitating treatment before applying the composition (cc). Examples of the adhesion-promoting treatment include hydrophilic treatment such as corona treatment, plasma treatment, and ultraviolet treatment, with plasma treatment being more preferred. Forming functional groups such as OH groups (especially when the base material is epoxy resin) and COOH groups (especially when the base material is acrylic resin) on the surface of the base material by performing adhesion treatment such as plasma treatment. In particular, when such a functional group is formed on the surface of the base material, the adhesion between the layer (c) and the resin base layer (s) can be further improved.

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

The mixed composition of the organosilicon compound (A) preferably contains the organosilicon compound (B) and usually contains a solvent (D). As the solvent (D), it is preferable to use a fluorine-based solvent, and for example, fluorinated ether-based solvents, fluorinated amine-based solvents, fluorinated hydrocarbon-based solvents, etc. can be used, and in particular, the boiling point should be 100 ° C. or higher. is preferred. As the fluorinated ether solvent, hydrofluoroethers such as fluoroalkyl (especially perfluoroalkyl group having 2 to 6 carbon atoms)-alkyl (especially methyl group or ethyl group) ether are preferred, such as ethyl nonafluorobutyl ether or ethyl nonafluorobutyl ether. Examples include fluoroisobutyl ether. Examples of ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether include Novec (registered trademark) 7200 (manufactured by 3M Company, molecular weight approximately 264). As the fluorinated amine solvent, an amine in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group is preferable, and a tertiary amine in which all hydrogen atoms of ammonia are substituted with a fluoroalkyl group (particularly a perfluoroalkyl group) is preferable. A specific example is tris(heptafluoropropyl)amine, such as Fluorinert® FC-3283 (manufactured by 3M Company, molecular weight approximately 521). Examples of fluorinated hydrocarbon solvents include fluorinated aliphatic hydrocarbon solvents such as 1,1,1,3,3-pentafluorobutane, and fluorinated aromatic solvents such as 1,3-bis(trifluoromethylbenzene). Examples include hydrocarbon solvents. Examples of 1,1,1,3,3-pentafluorobutane include Solve 55 (manufactured by Solvex).

As the fluorine-based solvent, in addition to the above, hydrochlorofluorocarbons such as Asahiklin (registered trademark) AK225 (manufactured by AGC Corporation), hydrofluorocarbons such as Asahikulin (registered trademark) AC2000 (manufactured by AGC Corporation), etc. can be used. .

It is preferable to use at least a fluorinated amine solvent as the solvent (D). Further, as the solvent (D), it is preferable to use two or more types of fluorine-based solvents, and it is preferable to use a fluorinated amine-based solvent and a fluorinated hydrocarbon-based solvent (particularly a fluorinated aliphatic hydrocarbon-based solvent).

In addition, the composition (ca) for forming the water-repellent layer (r) may include a silanol condensation catalyst, an antioxidant, a rust preventive agent, an ultraviolet absorber, a light stabilizer, and a fungicidal agent within a range that does not impede the effects of the present invention. , antibacterial agents, biofouling inhibitors, deodorants, pigments, flame retardants, antistatic agents, and other various additives may be mixed.

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

After applying the composition for forming the water-repellent layer (r) on the layer (c), the water-repellent layer (r) can be formed by allowing it to stand at room temperature in the air for, for example, one hour or more. In the present invention, normal temperature means 5 to 60°C, and preferably a film can be formed by standing at a temperature in the range of 15 to 40°C.

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

When the organosilicon compound (B) is mixed in the composition (ca) for forming the water-repellent layer (r), the amount of the organosilicon compound (B) when the entire composition is taken as 100% by mass is , for example, 0.01% by mass or more, preferably 0.03% by mass or more, and preferably 0.3% by mass or less, 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 explained 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 invention with appropriate changes within the scope of the above and below gist, and any of these may fall within the technical scope of the present invention. Included in the range.

[Example 1]
A solution containing 0.125% by mass of KBP90 (manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following formula (c) as the organosilicon compound (C1) and 99.875% by mass of ion-exchanged water as the solvent (E) was prepared. , and stirred at room temperature to obtain a solution for forming layer (c). The resin base layer (s) having an acrylic hard coat layer (alicyclic urethane acrylate type ) was coated using OPTICOAT MS-A100 (spin coater) manufactured by MIKASA Co., Ltd. under conditions of a coating liquid volume of 200 μl, a rotation speed of 2000 rpm, and a rotation speed of 20 seconds to obtain layer (c).

Next, as the organosilicon compound (A), a compound represented by the following formula (1) (hereinafter, compound a), and as the organosilicon compound (B), FAS13E (C ₆ F ₁₃ -C ₂ H ₄ -Si(OC ₂ H ₅ ) ₃ (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and FC-3283 (C ₉ F ₂₁ N, Fluorinert, manufactured by 3M) as the solvent (D) were prepared and stirred at room temperature for a predetermined time. A solution for forming a water repellent layer (r) was obtained. When the entire water-repellent layer (r) forming solution is 100% by mass, the proportion of the organosilicon compound (A) is 0.085% by mass, and the proportion of the organosilicon compound (B) is 0.05% by mass. Met. A solution for forming the water-repellent layer (r) is applied onto the layer (c) using a spray coater manufactured by Apiros Co., Ltd., and left to stand at room temperature for 12 hours. ) and a water-repellent layer (r) in this order. The spray coating conditions were: scan speed: 600 mm/sec, pitch: 5 mm, liquid amount: 6 cc/min, atomizing air: 350 kPa, and gap: 70 mm.

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, r is 43, s is an integer from 1 to 6, The number average molecular weight is approximately 8,000.

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

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

[Comparative example 1]
Lamination was carried out in the same manner as in Example 2, except that KBM903 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-aminopropyltriethoxysilane) was used in place of the organosilicon compound (C1), and methyl ethyl ketone was used as the solvent (E). I got a body.

[Comparative example 2]
The same procedure as in Example 2 was carried out, except that KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-acryloxypropyltrimethoxysilane) was used instead of the organosilicon compound (C1), and methyl ethyl ketone was used as the solvent (E). A laminate was obtained.

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

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

(2) Measurement of water contact angle after chemical resistance test A load of 1000 g was applied to the obtained film using a scratch device equipped with an eraser manufactured by Minoan, with the eraser in contact with the film. Approximately 2.5 ml of ethanol was dropped thereon, and a chemical resistance test was conducted by moving an eraser back and forth over the film at a speed of 40 r/min (a speed of 40 reciprocations per minute). The contact angle of water was measured after the eraser moved back and forth across the film 3000 times.

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

According to Tables 2-1 and 2-2, in Examples 1 to 7 in which the layer (c) was formed from the mixed composition of the organosilicon compound (C) specified in the present invention, the water-repellent layer was cured at room temperature. (r) had a good water contact angle of 82.0° or more (particularly 90° or more) after the chemical resistance test, whereas organosilicon compound (C) of the present invention was replaced with In Comparative Examples 1 and 2, which used organosilicon compounds different from C), the water contact angle after the chemical resistance test decreased.

The laminate of the present invention is applicable to display devices such as touch panel displays, optical elements, semiconductor elements, building materials, nanoimprint technology, solar cells, window glass for automobiles and buildings, metal products such as cooking utensils, ceramic products such as tableware, and plastics. It can be suitably formed into a film on manufactured automobile parts, etc., and is industrially useful. It is also preferably used in kitchens, bathrooms, washstands, mirrors, various parts around toilets, goggles, glasses, etc.

Claims (6)

A laminate in which a water-repellent layer (r) and a resin base layer (s) are laminated via a layer (c),
The layer (c) is formed by condensing an organosilicon compound (C1) represented by the following formula (c11) and/or two or more of the organosilicon compounds (C1) with at least one of the following X ¹ to X ⁴ . formed from a mixed composition (cc) of combined organosilicon compounds (C2);
The water-repellent layer (r) is formed from a mixed composition (ca) of an organosilicon compound (A) represented by the following formula (a1) and an organosilicon compound (B) represented by the following formula (b1). 1. A laminate characterized by having layers of

In the above formula (c11),
Z ¹ and Z ² are each independently a reactive functional group other than a hydrolyzable group and a hydroxy group,
R ^x1 , R ^x2 , R ^x3 , and R ^x4 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when multiple R ^x1s exist, the multiple R ^x1s are different from each other. If there are multiple R ^x2s , the R ^x2s may be different. If there are multiple R x3s, the R ^x3s may be different. If there are multiple R ^x4s , the R ^x3s may be different. may have different R ^x4 ,
Rf ^x1 , Rf ^x2 , Rf ^x3 , and Rf ^x4 are each independently an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted with a fluorine atom, and there is a plurality of Rf ^x1 If multiple Rf ^x1 exist, each of the multiple Rf x1 may be different; if multiple Rf ^x2 exists, each of the multiple Rf ^x2 may be different; if multiple Rf ^x3 exists, each of the multiple Rf ^x3 may be different If there are multiple Rf ^x4 , the multiple Rf ^x4 may be different,
Y is -NH-, -N(CH ₃ )- or -O-, and when there is a plurality of Y's, the plural Y's may be different from each other,
^{X 1 ,} X ² , _X ^{3 ,} _{and 3} alkoxysilyl group), and when a plurality of X ^1s exist, the plurality of X ^1s may be different from each other, and when a plurality of X ^2s exist, the plurality of X ^2s may be different from each other, When there are multiple X ³ 's, the multiple X ³ 's may be different, and when there are multiple X ⁴ 's, the multiple X ⁴ 's may be different,
p11 is an integer from 0 to 20, p12, p13, and p14 are each independently an integer from 0 to 10, p15 is an integer from 0 to 5, and p16 is an integer from 1 to 10. and p17 is 0 or 1,
The organosilicon compound (C1) has Z ¹ - and Z ² - terminals, and unless -O- is connected to -O-, p11 -{C(R ^x1 )(R ^x2 )}-, p12 -{C(Rf ^x1 ) (Rf ^x2 )}-, p13 -{Si(R ^x3 ) (R ^x4 )}-, p14 -{Si(Rf ^x3 ) (Rf ^x4 )}- , p15 -Y-, p16 -{Si(X ¹ ) (X ² ) -O}-, p17 -{Si(X ³ ) (X ⁴ )}- are arranged in any order. Constructed by combining.

In the above formula (a1),
Rf ^a1 is a divalent perfluoropolyether structure with oxygen atoms at both ends,
R ¹¹ , R ¹² , and R ¹³ are each independently an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^11s exist, the plurality of R ^11s may be different ^from each other; When present, the plurality of R ¹² may be different from each other, and when the plurality of R ¹³ is present, the plurality of R ¹³ may be different from each other,
E ¹ , E ² , E ³ , E ⁴ , and E ⁵ are each independently a hydrogen atom or a fluorine atom, and when a plurality of E ^1s exist, the plurality of E ^1s may be different from each other; When there are multiple ^{E 2s} , the E ^2s may be different; when there are multiple E ^3s , the E ^3s may be different; when there are multiple E ^4s , the E 2s may be different. ⁴ may be different,
G ¹ and G ² are each independently a divalent to decavalent 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, and R ¹⁴ is a methyl group. or is an ethyl group, and when there are multiple J ¹ 's, the multiple J ¹ 's may be different; when there are multiple J ² 's, the multiple J ² 's may be different, and the multiple J ³ 's may be different. If present, multiple J ³ may be different,
L ¹ and L ² are each independently a divalent linking group having 1 to 12 carbon atoms that may contain an oxygen atom, a nitrogen atom, or a ^fluorine atom; L ¹ may be different from each other, and if there are multiple L ² , the plural L ² may be different from each other,
d11 is 1 to 9,
d12 is 0 to 9,
a10 and a14 are each independently from 0 to 10,
a11 and a15 are each independently 0 or 1,
a12 and a16 are each independently 0 to 9,
a13 is 0 or 1,
a21, a22, and a23 are each independently 0 to 2,
e1, e2, and e3 are each independently 1 to 3.

In the 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 a fluorine atom,
R ^b11 , R ^b12 , R ^b13 and R ^b14 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when there is a plurality of R ^b11s , the plurality of R ^b11s are different from each other. When there are multiple R ^b12s , the R ^b12s may be different; when there are multiple R b13s, the R ^b13s may be different; and when there are multiple R ^b14s , the R ^b12s may be different. may have different R ^b14s ,
Rf ^b11 , Rf ^b12 , Rf ^b13 and Rf ^b14 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 a fluorine atom, and there is a plurality of Rf ^b11 When there are multiple Rf ^b13s , the multiple Rf b11s may be different from each other; when there are multiple Rf ^b12s , the multiple Rf ^b12s may be different; when there are multiple Rf ^b13s , the multiple Rf ^b13s may be different from each other. If there are multiple Rf ^b14s , the multiple Rf ^b14s may be different,
R ^b15 is an alkyl group having 1 to 20 carbon atoms, and when there are multiple R ^b15s , each of the R ^b15s may be different,
A ¹ is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR- and the 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 there are multiple A 1s, ^each of the multiple A ^1s may be different,
A ² is a hydrolyzable group, and when a plurality of A ² exists, the plural A ² may be different from each other ,
b11, b12, b13, b14 and b15 are each independently an integer of 0 to 100,
c is an integer from 1 to 3,
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 -, Rf ^b10 -, -Si(A ² ) _c (R ^b15 ) _3-c is the terminal, and as long as they do not form a perfluoropolyether structure and -O- does not connect with -O- to -F, they can be arranged in any order. Join. The organosilicon compound (C2) is
A compound having two or more structures (c21-1) represented by the following formula (c21-1), in which the structures (c21-1) are linked together in a chain or cyclic manner as shown in *3 or *4 below. Therefore, the bond in *3 or *4 below is due to the condensation of the X ¹ or X ² of two or more of the organosilicon compounds (C1),
*1 and *2 in the following formula (c21-1) each represent at least one of the units bracketed by p11, p12, p13, p14, p15, (p16)-1, and p17 in the following formula (c21-2). One type is bonded in any order and a group whose terminal is Z- is bonded, and the groups bonded to *1 and *2 may be different for each of the plurality of structures (c21-1),
The laminate according to claim 1, wherein when a plurality of the structures (c21-1) are bonded in a chain, terminal *3 is a hydrogen atom and *4 is a hydroxy group.

In the formula (c21-2),
Z is a reactive functional group other than a hydrolyzable group and a hydroxy group,
R ^x1 , R ^x2 , R ^x3 , R ^x4 , Rf ^x1 , Rf ^x2 , Rf ^x3 , Rf ^x4 , Y, X ¹ , X ² , X ³ , X ⁴ , p11 to p17 are These symbols are synonymous. The laminate according to claim 1 or 2 , wherein the composition (cc) contains at least the organosilicon compound (C1). The laminate according to any one of claims 1 to 3 , wherein the resin base layer (s) is a hard coat layer. A method for manufacturing a laminate according to any one of claims 1 to 4 , comprising:
a step of applying the composition (cc) to the resin base layer (s) to form a layer (c);
A method for producing a laminate, comprising a step of applying the composition (ca) to the layer (c) and curing it at room temperature to form the water-repellent layer (r). The method for producing a laminate according to claim 5 , wherein in the step of forming the layer (c), the resin base layer (s) is subjected to plasma treatment, and the composition (cc) is applied to the plasma treated surface. .