JP2019085566A - Composition - Google Patents

Abstract

To provide a composition containing a compound having a perfluoropolyether structure, the composition capable of realizing a coating having chemical resistance.SOLUTION: The present invention provides a composition containing an organic silicon compound (A) represented by formula (a1), an organic silicon compound (B) represented by formula (b1) and an organic silicon compound (C) represented by formula (c1). In the formula (a1), Rfis a divalent perfluoropolyether structure with both ends being oxygen atoms.SELECTED DRAWING: None

Description

  The present invention relates to a composition.

  A film formed from a composition containing a compound having a perfluoropolyether structure has a very small surface free energy, and thus, a display device such as a touch panel display, an optical element, a semiconductor element, a building material, a window of a car or a building It is used as an antifouling coating or a water and oil repellent coating in various fields such as glass.

  For example, Patent Document 1 discloses a first organosilicon compound in which a fluorine-containing group having a perfluoroalkyl group or a perfluoropolyether group on the free end side and a hydrolyzable group are bonded to a silicon atom (A A water- and oil-repellent coating composition comprising a hydrolyzable silane oligomer or a second organosilicon compound (B) in which a fluorocarbon-containing group and a hydrolyzable group are bonded to a silicon atom; There is.

International Publication No. 2016/076245

  A film formed from a composition containing a compound having a perfluoropolyether structure may be exposed to a chemical such as alcohol depending on the application, and in such a case, it is good even after being exposed to the chemical Good performance (water repellency etc.) can be maintained (hereinafter referred to as chemical resistance).

  Then, this invention is a composition containing the compound which has a perfluoropolyether structure, Comprising: It aims at providing the composition which can implement | achieve the film which has chemical resistance.

  The present invention which achieved the above-mentioned subject 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。

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。

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、−Ｏ−、−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、０〜１０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する。 [1] A composition containing the organosilicon compound (A) represented by the formula (a1), the organosilicon compound (B) represented by the formula (b1) and the organosilicon compound (C) represented by the formula (c1) object.

In the above formula (a1),
Rf ^a1 is 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 from each other,
G ¹ and G ² are each independently a di- to 10-valent organosiloxane group having a siloxane bond,
J ¹ , J ² and J ³ are each independently a hydrolyzable group or — (CH ₂ ) _{e 6} —Si (OR ¹⁴ ) ₃ , e 6 is 1 to 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 If present, multiple J ³ may be different from each other,
L ¹ and L ² each independently represent an oxygen atom, a nitrogen atom, or a divalent C 1-12 linking group which may contain a fluorine atom, and a plurality of L ^{1 s} may be present when a plurality of L ^{1 s} are present. 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 to 9,
d12 is 0 to 9,
a10 and a14 are each independently 0 to 10,
a11 and a15 are each independently 0 or 1, and
a12 and a16 are each independently 0 to 9,
a13 is 0 or 1;
and a21, a22 and a23 are each independently 0 to 2;
Each of e1, e2 and e3 is independently 1 to 3.

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 by a fluorine atom,
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 And R ^{b14 's} may be different from each other,
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 In the case of multiple Rf ^b11 may be different from each other, when multiple R f ^b12 are present, multiple R f ^b12 may be different from each other, and when multiple R f ^b13 is present, multiple R f ^b13 are different from each other 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—, —O—C (= 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 each independently an integer of 0 to 100,
c is an integer of 1 to 3,
^{Rf b10 -, - Si (A} 2) c (R b15) 3-c, b11 amino ^{- {C (R b11) (} R b12)} -, b12 amino ^{- {C (Rf b11) (} Rf b12) }-, B13 pieces of-{Si (R ^b13 ) (R ^b14 )}-, b14 pieces of-{Si (Rf ^b13 ) (Rf ^b14 )}-, b15 pieces of -A ¹ -are Rf ^b10- , As long as -Si (A ² ) _c (R ^b15 ) _3-c is terminated to form a perfluoropolyether structure and -O- is not linked to -O- to -F, they may be arranged in any order. Join.

In the above formula (c1),
^{R x1, R x2, R x3} , R x4 are each independently a hydrogen atom or a carbon number from 1 to 4 alkyl groups, if R ^x1 there exist a plurality differ plurality of R ^x1, respectively 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 And each R ^{x 4} may be different from each other,
Rf ^x1 , R f ^x2 , R f ^x3 and R f ^x4 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted by fluorine atoms or a fluorine atom, and a plurality of R f ^x1 are present 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, 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 X are present, the plurality of X may be different from each other,
Y is -O-, -NH-, or -S-, and when there are a plurality of Y, a plurality of Y may be different from each other,
Z is a vinyl group, an α-methyl vinyl 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 each independently an integer of 0 to 10, and p5 is an integer of 0 to 10,
p6 is an integer of 1 to 3,
_{Z -, - Si (X)} p6 (R x5) 3-p6, p1 amino ^{- {C (R x1) (} R x2)} -, p2 amino ^{- {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 ^{x 5} ) _3-p6 is terminated, and so long as -O- is not linked to -O-, they are linked in any order.

  [2] The composition according to the above [1], wherein the organosilicon compound (C) is 0.1% by mass or more and 1% by mass or less in the total mass of the composition.

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−、−ＣＨ₂−、又は−Ｏ−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。 [3] The composition according to [1] or [2], wherein the organosilicon compound (C) 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—, —CH ₂ — or —O—
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.

  [4] A surface-treated resin substrate having a film comprising the composition according to any one of the above [1] to [3] on the surface of the resin substrate.

  [5] The surface-treated resin substrate according to [4], wherein the resin substrate is an acrylic resin substrate.

  [6] A method for producing a surface-treated resin substrate, comprising applying the composition according to any one of the above [1] to [3] on the surface of a resin substrate and curing the composition at normal temperature.

  According to the composition of the present invention, the obtained film is obtained because it contains the given two other organosilicon compounds (B) and (C) together with the given organosilicon compound (A) having the perfluoropolyether structure. Chemical resistance is improved.

  The organosilicon compounds (A), (B) and (C) will be sequentially described below.

1. Organosilicon Compound (A)
The organosilicon compound (A) is represented by the following formula (a1).

In the above formula (a1),
Rf ^a1 is a divalent perfluoropolyether structure in which both ends are oxygen atoms,
R ¹¹ , R ¹² and R ¹³ are each independently (that is, R ¹¹ , R ¹² and R ¹³ may be identical or different from each other) an alkyl group having 1 to 20 carbon atoms , 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 And each R ¹³ may be different from each other,
^{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 from each other,
G ¹ and G ² are each independently a di- to 10-valent organosiloxane group having a siloxane bond,
J ¹ , J ² and J ³ are each independently a hydrolyzable group or — (CH ₂ ) _{e 6} —Si (OR ¹⁴ ) ₃ , e 6 is 1 to 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 If present, multiple J ³ may be different from each other,
L ¹ and L ² each independently represent an oxygen atom, a nitrogen atom, or a divalent C 1-12 linking group which may contain a fluorine atom, and a plurality of L ^{1 s} may be present when a plurality of L ^{1 s} are present. 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 to 9,
d12 is 0 to 9,
a10 and a14 are each independently 0 to 10,
a11 and a15 are each independently 0 or 1, and
a12 and a16 are each independently 0 to 9,
a13 is 0 or 1;
and a21, a22 and a23 are each independently 0 to 2;
Each of e1, e2 and e3 is independently 1 to 3.

The organosilicon compound (A) has a perfluoropolyether structure represented by ^Rfa1 as represented by the above formula (a1), and a hydrolyzable group represented by J ² or-(CH ₂ ) _e6 -Si (oR ¹⁴⁾ ₃ (where, R ¹⁴ is a methyl group or an ethyl group) has at least one. The perfluoropolyether structure is a structure in which all hydrogen atoms of the polyoxyalkylene group are replaced with fluorine atoms, and it can be said that a perfluorooxyalkylene group can impart water repellency to the obtained film. Further, it is a compound which can be a matrix of a film obtained by bonding J ² together with organic silicon compounds (A) or with other monomers through a polymerization reaction (particularly a polycondensation reaction).

Rf ^a1 _{is, -O- (CF 2 CF 2 O} ) e4 -, or _{-O- (CF 2 CF 2 CF 2} O) e5 - is preferred. Each of e4 and e5 is 15 to 80.

Each of R ¹¹ , R ¹² and R ¹³ is preferably independently an alkyl group having 1 to 10 carbon atoms.

Each of L ¹ and L ² is preferably independently a divalent C ¹ -C 5 linking group containing a fluorine atom.

Each of G ¹ and G ² is preferably independently 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 ) _{e 6} -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), a14 is preferably 1 to 6 (more preferably 1) -3), a15 is preferably 0, a16 is preferably 0 to 6, and all of a21 to a23 are preferably 0 or 1 (more preferably 0), and d11 is preferably 1 to 5 (more preferably 1) -3) and d12 are preferably 0 to 3 (more preferably 0 or 1), and all of e1 to e3 are preferably 3. In addition, a13 is preferably 1.

The compound (A), Rf ^a1 in the formula (a1) is _{-O- (CF 2 CF 2 CF 2} O) e5 - a and, e5 is 35 to 50, carbon both L ¹ and L ² And each of E ¹ , E ² and E ³ is a hydrogen atom, E ⁴ and E ⁵ are a hydrogen atom or a fluorine atom, and J ¹ , J ² , and J ³ are both methoxy or ethoxy group (particularly methoxy group), a10 is 1 to 3, a11 is 0, a12 is 0-5, is a13 is 1, a14 is 2 A15 is 0, a16 is 0 to 6, and a21 to a23 are each independently 0 or 1 (more preferably all of a21 to a23 are 0), and d11 is 1 Using a compound in which d12 is 0 or 1 and e1 to e3 are all 3 It is preferable.

The compound in Example to be described later Compound a to be used as (A), is represented by the formula (a1), Rf ^a1 is _{-O- (CF 2 CF 2 CF 2} O) 43 - a and, L ¹ and L ² is all-(CF ₂ )-, E ¹ , E ² and E ³ are all hydrogen atoms, E ⁵ is a fluorine atom, J ¹ and J ² are all 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 all 0, d11 is 1, d12 is 0, e1 And e2 are both 3.

The compound (A), Rf ^a1 in the formula (a1) is _{-O- (CF 2 CF 2 CF 2} O) e5 - a and, e5 is 25 to 40, L ¹ is a fluorine atom and an oxygen atom L ² is a C 1-3 perfluoroalkylene group, E ² and E ³ are both hydrogen atoms, and E ⁵ is a fluorine atom. And J ² is — (CH ₂ ) _{e 6} —Si (OCH ₃ ) ₃ , e 6 is 2 to 4, a 10 is 1 to 3, a 11 is 0, a 12 is 0, a 13 Is 0, a14 is 2 to 5, a15 is 0, a16 is 0, and a21 to a23 are each independently 0 or 1 (more preferably all of a21 to a23 are 0) It is also preferable to use a compound in which d11 is 1, d12 is 0 and e2 is 3.

  Moreover, it is preferable that an organosilicon compound (A) is also a compound represented by a following formula (a2-1).

In the above formula (a2-1),
^Rfa21 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted by a fluorine atom,
Rf ^a22 , R f ^a23 , R f ^a24 and R f ^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 by a fluorine atom, or a plurality of Rf ^a22 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 And each R ²³ may be different from each other,
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—, —O—C (= O) —, —NR—, —NRC (= O) —, or —C (= O) NR— ( R is a hydrogen atom, an alkyl group or a fluorinated alkyl group having 1 to 4 carbon atoms) having 1 to 4 carbon atoms, if M ³ there are a plurality may be different plurality of M ^3, respectively,
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 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 of 1 to 20,
f17 is an integer of 0 to 2,
g1 is an integer of 1 to 3,
^{Rf a21 -, M 2 -,} f11 amino ^{- {C (R 20) (} R 21)} -, f12 amino ^{- {C (Rf a22) (} Rf a23)} -, f13 amino - {Si (R ^{22) (R 23)} -} , f14 amino ^{- {Si (Rf a24) (} Rf a25)} -, f15 amino -M ³ -, and f16 amino ^{_{- [CH 2 C (M 1}} ) {(CH ^{_{2) f17 -Si (M 4)}} g1 (R 24) 3-g1}] - is, Rf ^a21 -, M ² - is terminated, the arrangement in order to form a perfluoropolyether structure at least in part, and As long as -O- is not linked to -O- to -F, they are linked in any order. That is, the formula (a2-1) is not necessarily f11 amino ^{- {C (R 20) (} R 21)} - are continuous, f12 amino ^{- {C (Rf a22) (} Rf a23)} - is continuously , f13 amino ^{- {Si (R 22) (} R 23)} - are continuous, f14 amino ^{- {Si (Rf a24) (} Rf a25)} - are continuous, f15 amino -M ³ - is continuously _{And f16-} [CH ₂ C (M ¹ ) {(CH ₂ ) _{f 17} -Si (M ⁴ ) _{g 1} (R ²⁴ ) _{3-g 1} }]-are not continuously 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} ^{-C (Rf a22) (Rf a23} ) -M 3 -Si (R 22) (R 23) -C (Rf a22) (Rf a23) - such as, you can be respectively are arranged in any order is there.

^Rfa21 is preferably a C1-C10 alkyl group substituted with one or more fluorine atoms, more preferably a C1-C10 perfluoroalkyl group, and still more preferably a C1-C1 alkyl group. 5 is a perfluoroalkyl group.

Rf ^a22 , R f ^a23 , R f ^a24 and R f ^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 by a fluorine atom, Preferably all are fluorine atoms.

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

M ² is preferably a hydrogen atom.

M ³ is preferably —C (= O) —O—, —O—, —O—C (= O) —, more preferably all —O—.

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

  Preferably, f11, f13 and f14 are each 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 is 0 It is.

  f15 is preferably 1⁄5 or more of the total value of f11, f12, f13 and f14, and is not more than the total value of f11, f12, f13 and f14.

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

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

  f17 is preferably 0-1.

  2-3 are preferable and, as for g1, 3 are more preferable.

f11 amino ^{- {C (R 20) (} R 21)} -, f12 amino ^{- {C (Rf a22) (} Rf a23)} -, f13 amino ^{- {Si (R 22) (} R 23)} - , f14 amino ^{- {Si (Rf a24) (} Rf a25)} -, and f15 amino -M ³ - order of as long as arranged in the order of forming the perfluoropolyether structure at least in part, in the formula Although it is optional, preferably the parenthesized repeating unit (ie,-{C ( ^Rfa22 ) ( ^Rfa23 )}-) attached with f12 on the most fixed end side (the side to be bonded to a silicon atom) is , most free end repeating units in parentheses are given the f11 ^{(i.e., - {C (R 20)} (R 21)} -) located at the free end than, more preferably most fixed end Parenthesized repeat units with f12 and f14 on the side (ie,-{C (Rf ^a22 ) ( ^Rfa23 )}- ^and- {Si ( ^Rfa24 ) ( ^Rfa25 )}-) are the repeating units bracketed with f11 and f13 at the free end side (ie,-{- It is located on the free end side of C (R ²⁰ ) (R ²¹ )}-and-{Si (R ²² ) (R ²³ )}-).

In the above formula (a2-1), Rf ^a21 is a perfluoroalkyl group having 1 to 5 carbon ^{atoms, Rf a22, Rf a23, Rf} a24, Rf a25 are all fluorine atoms, M ³ are all -O- M ⁴ is all methoxy, ethoxy or chlorine (especially methoxy or ethoxy), M ¹ and M ² are both hydrogen atoms, f 11 is 0, f 12 is 30 to 150 Preferably, 80 to 140), f15 of 30 to 60, f13 and f14 of 0, f17 of 0 to 1 (especially 0), g1 of 3 and f16 of 1 to 10 are preferred.

In compound a used as compound (A) examples described later, is represented by the formula (a2-1), Rf ^a21 is C ₃ F ₇ - a and, both Rf ^a22 and Rf ^a23 is a fluorine atom Yes,
f11 = f13 = f14 = a 0, f12 is 131, f15 is 44, f16 is 1 to 6, f17 is 0, M ¹ and M ² is a hydrogen atom, M ³ is -O-, M ⁴ is methoxy And g1 is 3.

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

In the above formula (a2-2),
^{Each of Rfa26} , ^Rfa27 , ^Rfa28 and ^Rfa29 is independently an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are substituted by a fluorine atom, or a plurality of ^Rfa26 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 And each R ²⁸ may be different from each other,
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 If multiple R ³⁰ may be different,
M ⁷ is —O—, —C (= O) —O—, —O—C (= 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 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, multiple Ms ⁹ may be different from each other,
M ⁶ and M ¹⁰ each independently represent a hydrogen atom or a halogen atom,
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 from each other,
f21, f22, f23, f24 and f25 are each independently an integer of 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 amino ^{- {C (R 25) (} R 26)} -, f22 amino ^{- {C (Rf a26) (} Rf a27)} -, f23 amino - {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 amino ^{_{- [CH 2 C (M 9}} ) {(CH 2) f29 -Si (M 11) g3 (R 30) 3 _-g3 }] are lined in the order in which M ¹⁰ -and M ^6- end and form a perfluoropolyether structure at least in part, and so long as -O- is not continuous with -O- Combine with Bonding in arbitrary order is the same as described in the above formula (a2-1), and each repeating unit is continuously arranged in the order as described in the above formula (a2-2) It is not limited to the 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-, all methoxy groups M ⁸ and M ¹¹ are, ethoxy group Or a chlorine atom (in particular, a methoxy group or an ethoxy group), and M ⁵ , M ⁶ , M ⁹ and M ¹⁰ are all hydrogen atoms, f21 is 0, f22 is 30 to 150 (more preferably 80 to 140) F25 is 30 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 preferably 1 to 10.

  More specific examples of the compound (A) include compounds of 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. R ^30, R ^31, the carbon number of R ^32, R ³³ each independently is preferably 2-4, 2-3 is more preferable. h1 is 5 to 70, h2 is 1 to 5, and h3 is 1 to 10. 10-60 are preferable, 20-50 are more preferable, 1-4 are preferable, 1-3 are more preferable, 1-8 are preferable, and h1 is more preferable.

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

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

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

2. Organosilicon compound (B)
The organosilicon compound (B) is represented by the following formula (b1).

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 by a fluorine atom,
^{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 And R ^{b14 's} may be different from each other,
^{Rf b11, Rf b12, Rf b13} , 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 In the case of multiple Rf ^b11 may be different from each other, when multiple R f ^b12 are present, multiple R f ^b12 may be different from each other, and when multiple R f ^b13 is present, multiple R f ^b13 are different from each other 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—, —O—C (= 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 each independently an integer of 0 to 100,
c is an integer of 1 to 3,
^{Rf b10 -, - Si (A} 2) c (R b15) 3-c, b11 amino ^{- {C (R b11) (} R b12)} -, b12 amino ^{- {C (Rf b11) (} Rf b12) }-, B13 pieces of-{Si (R ^b13 ) (R ^b14 )}-, b14 pieces of-{Si (Rf ^b13 ) (Rf ^b14 )}-, b15 pieces of -A ¹ -are Rf ^b10- , As long as -Si (A ² ) _c (R ^b15 ) _3-c is terminated to form a perfluoropolyether structure and -O- is not linked to -O- to -F, they may be arranged in any order. Join.

Each of Rf ^b10 is preferably independently 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 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 —O—C (= O) —.

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

  1 to 30 is preferable, 1 to 25 is more preferable, 1 to 10 is more preferable, 1 to 5 is particularly preferable, and b1 is most preferably 1 to 2.

  0-15 are preferable and, as for b12, 0-10 are more preferable.

  0-5 are preferable and, as for b13, 0-2 are more preferable.

  0-4 are preferable and, as for b14, 0-2 are more preferable.

  0-15 are preferable and, as for b15, 0-2 are more preferable.

  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, still more preferably 20 or less.

In particular, Rf ^b10 is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, each of R ^b11 and R ^b12 is a hydrogen atom, A ² is a methoxy group or an ethoxy group, and ^{b 11} is 1 to 1 It is preferable that 5 and b12 are 0 to 5, and b13, b14 and b15 are all 0 and c is 3.

In the examples described later, when FAS13E used as the compound (B) is represented by the above formula (b1), each of R ^b11 and R ^b12 is a hydrogen atom, b11 is 2, b13, ^b14 and b15 are all 0. , c is 3, a ² is ethoxy ^{group, Rf b10 - {C (Rf} b11) (Rf b12)} b12 - is terminated, C ₆ F ₁₃ - is defined to be.

Examples of the compound represented by the formula (b1), _{specifically, CF 3 -Si- (OCH 3)} 3, C j F 2j + 1 -Si- (OC 2 H 5) 3 (j from 1 to 12 In particular, 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 (CF 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 and the like (k Yes Re is also 5 to 20, 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 can also be mentioned (m is 1 to 10, preferably 3 to 7 and n is 1 to 5, preferably 2 to 4). ). There may also be mentioned CF ₃ (CF ₂ ) _p- (CH ₂ ) _q -Si- (CH ₂ CH = CH ₂ ) ₃ (p is any of 2 to 10, preferably 2 to 8, q Are all 1 to 5, preferably 2 to 4). Further, 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 may be mentioned (p is 2 to 10, preferably 3 to 7 and q is 1 to 5, preferably 2 to 4). Is).

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

In the 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, R ⁶² is an alkyl group having 1 to 3 carbon atoms .

3. Organosilicon compound (C)
The organosilicon compound (C) is represented by the following formula (c1).

In the above formula (c1),
^{R x1, R x2, R x3} , and R ^x4 are each independently a hydrogen atom or a carbon number from 1 to 4 alkyl groups, if R ^x1 there exist a plurality different plurality of R ^x1, respectively 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 If multiple ^Rx4s may be different from each other,
Rf ^x1 , R f ^x2 , R f ^x3 and R f ^x4 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with a fluorine atom or a fluorine atom, and R f ^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, 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 X are present, the plurality of X may be different from each other,
Y is -O-, -NH-, or -S-, and when there are a plurality of Y, a plurality of Y may be different from each other,
Z is a vinyl group, an α-methyl vinyl 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 each independently an integer of 0 to 10, and p5 is an integer of 0 to 10,
p6 is an integer of 1 to 3,
_{Z -, - Si (X)} p6 (R x5) 3-p6, p1 amino ^{- {C (R x1) (} R x2)} -, p2 amino ^{- {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 ^{x 5} ) _3-p6 is terminated, and so long as -O- is not linked to -O-, they are linked in any order.

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

Each of Rf ^x1 , Rf ^x2 , Rf ^x3 and Rf ^x4 is preferably independently an alkyl group having 1 to 10 carbons in which one or more hydrogen atoms are substituted by a fluorine atom, or a fluorine atom.

It is preferable that ^Rx5 is a C1-C5 alkyl group.

  X is preferably an alkoxy group, a halogeno group, a cyano group or an isocyanate group, more preferably an alkoxy group, still 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 still more preferably an amino group.

  1 to 15 are preferable, More preferably, it is 2-10.

  Each of p2, p3 and p4 is independently preferably 0-5, more preferably all 0-2.

  1-5 are preferable and, as for p5, 1-3 are more preferable.

  2-3 are preferable and, as for p6, 3 are more preferable.

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

When N-2- (aminoethyl) -3-aminopropyltrimethoxysilane used as 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 In all, a hydrogen atom, 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—, —CH ₂ — or —O—
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.

Y ¹ is preferably -NH-.

Z ¹ is preferably an amino group.

R ^{x 51} 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, more preferably 3.

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

  The content of the organosilicon compound (A) is, for example, 0.01% by mass or more, preferably 0.05% by mass or more, and 0.5% by mass or less in 100% by mass of the composition of the present invention. It is preferable that the amount be 0.3% by mass or less.

  The content of the organosilicon compound (B) is, for example, 0.01% by mass or more, preferably 0.03% by mass or more, and 0.3% by mass or less in 100% by mass of the composition of the present invention. Is preferably 0.2% by mass or less.

  The content of the organosilicon compound (C) is, for example, 0.1% by mass or more, preferably 0.2% by mass or more, and 1% by mass or less in 100% by mass of the composition of the present invention. Is more preferably 0.6% by mass or less and still more preferably 0.4% by mass or less.

  The total amount of the organosilicon compounds (A), (B) and (C) is preferably 0.15% by mass or more, more preferably 0.3% by mass or more in 100% by mass of the composition of the present invention, Moreover, 1.5 mass% or less is preferable, More preferably, it is 0.7 mass% or less, and 0.6 mass% or less is still more preferable.

  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 .

  The total mass ratio of the organosilicon compound (A) and the organosilicon compound (B) to the organosilicon compound (C) is preferably 0.1 or more, more preferably 0.2 or more, and 1.5 or less. Preferably, it is 1 or less, more preferably 0.75 or less.

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

  As the fluorine-based solvent, in addition to the above, hydrochlorofluorocarbons such as ASAHIKLIN (registered trademark) AK 225 (manufactured by Asahi Glass Co., Ltd.) and hydrofluorocarbons such as ASAHIKLIN (registered trademark) AC 2000 (manufactured by Asahi Glass Co., Ltd.) Can.

  It is preferable to use at least a fluorinated amine solvent as the solvent (D). The solvent (D) preferably contains two or more fluorinated solvents, and contains a fluorinated amine solvent and a fluorinated hydrocarbon solvent (especially a fluorinated aliphatic hydrocarbon solvent). Is preferred.

  The composition of the present invention is a silanol condensation catalyst, an antioxidant, a rust inhibitor, an ultraviolet absorber, a light stabilizer, an antifungal agent, an antibacterial agent, an antibiofouling agent, an extinction agent, as long as the effects of the present invention are not impaired. Various additives such as odorants, pigments, flame retardants and antistatic agents may be contained.

  The composition of the present invention can be applied to a substrate and dried to form a film on the substrate. Examples of the method of applying the composition of the present invention include dip coating, roll coating, bar coating, spin coating, spray coating, die coating, and gravure coating.

  The conditions after the composition of the present invention is applied to a substrate are not particularly limited, and for example, it may be left standing for 1 hour or more in normal temperature and air. In the present invention, the normal temperature is 5 to 60 ° C., preferably by leaving at a temperature range of 15 to 40 ° C., a film can be formed. Thereafter, it may be heated (baked) for about 10 to 60 minutes at a temperature of 50 to 300 ° C., preferably 100 to 200 ° C.

  The thickness of the film formed from the composition of the present invention is, for example, 0.1 to 100 nm. The film has water repellency, and a water contact angle (initial contact angle) measured at a liquid volume of 3 μL by a droplet method (analysis method: θ / 2 method) is, for example, 105 ° or more. More preferably, it is 110 ° or more, and for example, 120 ° or less. In addition, after conducting the chemical resistance test carried out in the examples described later, the water contact angle (contact angle after chemical resistance test) measured at a liquid volume of 3 μL by the droplet method (analysis method: θ / 2 method) For example, it is 82.0 ° or more, preferably 90 ° or more, more preferably 100 ° or more (particularly 106 ° or more), and the upper limit may be 115 ° or less and 110 ° or less.

  The material of the substrate to which the composition of the present invention is applied is not particularly limited, and any of organic materials and inorganic materials may be used, and the shape of the substrate may be flat or curved, It may be a combined shape. As an organic material, 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 resin Thermoplastic resins such as alcohol, etc .; thermosetting resins such as phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester, silicone resin, urethane resin etc. may be mentioned. Examples of the inorganic material include metals such as iron, silicon, copper, zinc and aluminum, or alloys containing these metals, ceramics, glass and the like. Among these, organic materials are particularly preferable, and a surface-treated resin substrate having a film made of the composition of the present invention on the surface of the resin substrate is also included in the present invention. Among 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 substrate to which the composition of the present invention is applied may be subjected to easy adhesion treatment. Examples of the easy adhesion treatment include hydrophilic treatment such as corona treatment, plasma treatment, and ultraviolet treatment. A functional group such as an OH group (especially when the substrate is an epoxy resin) or a COOH group (especially when the substrate is an acrylic resin) is formed on the surface of the substrate by carrying out an easy adhesion treatment such as plasma treatment. When such a functional group is formed on the surface of the substrate, the adhesion between the film formed from the composition of the present invention and the substrate can be further improved.

  In a preferred embodiment, the composition of the present invention is provided on a protective layer (hereinafter sometimes referred to as a hard coat layer) provided to protect an article from scratches in applications requiring wear resistance such as displays of electronic devices. An article can be applied to form a film, and a laminate of a hard coat layer and a film layer formed from the composition of the present invention can be constructed.

  The above-described hard coat layer is a layer having a surface hardness, and the hardness is, for example, 2 H or more in pencil hardness. The hard coat layer may have a single layer structure or a multilayer structure. The hard coat layer contains a hard coat layer resin, and examples of the hard coat layer resin include acrylic resins, epoxy resins, urethane resins, vinyl benzyl chloride resins, vinyl resins or silicone resins, or the like. Examples thereof include ultraviolet curable resins such as mixed resins, electron beam curable resins, and thermosetting resins. In particular, the hard coat layer preferably contains an acrylic resin in order to develop high hardness. It is preferable to contain an epoxy-based resin because it tends to improve the adhesion with the film layer formed from the composition of the present invention.

  The hard coat layer may further contain an ultraviolet absorber, or may contain a metal oxide such as silica or alumina, or an inorganic filler such as polyorganosiloxane. By including such an inorganic filler, the adhesion with the film layer formed from the composition of the present invention can be improved. The thickness of the hard coat layer is, for example, 1 to 100 μm.

  The laminate of the hard coat layer and the film layer formed of the composition of the present invention preferably further includes a resin layer, and a film formed of the composition of the present invention in order from the surface of the laminate. The layer, the hard coat layer, and the resin layer may be in this order. Although the resin component of the resin layer is not particularly limited, polyacrylate resins, polyamide resins, polyimide resins, polyamideimide resins, polyurethane resins, polyester resins, polycarbonate resins, polyether sulfone resins, acetyl cellulose resins Resins, cycloolefin resins, polyvinyl alcohol resins and the like are preferable because they can easily improve the adhesion to the hard coat layer, and polyimide resins and polyamideimide resins are particularly preferable. The thickness of the resin layer is, for example, 10 to 500 μm. In addition, a laminate of a hard coat layer and an antireflective layer may be used, or the hard coat layer may have the function of an antireflective layer.

  A primer layer may be provided between the resin layer and the hard coat layer. As a primer agent, there are, for example, a primer agent such as an ultraviolet curing type, a thermosetting type, or a two-component curing 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 or the silicon material optionally contained. Moreover, you may use a polyamic acid as a primer agent and can improve the adhesiveness of a resin layer and a hard-coat layer. Furthermore, a silane coupling agent may be mentioned as a primer agent, and it may be chemically bonded to the silicon material optionally contained in the resin substrate by a condensation reaction. The thickness of the primer layer is, for example, 0.1 to 20 μm.

  Hereinafter, the present invention will be more specifically described by way of examples. The present invention is not limited by the following examples, and it is of course possible to implement with appropriate modifications as long as it can conform to the above-mentioned and the following effects, and all of them can be technical of the present invention. It is included in the scope.

Example 1
As the organosilicon compound (A), a compound represented by the following formula (1) (hereinafter, compound a), and as the organosilicon compound (B), FAS ₁₃ E (C ₆ F ₁₃ -C ₂ H ₄ -Si (OC ₂ H _{5) 3} ) Tokyo Chemical Industry Co., Ltd.), FC-3283 (C ₉ F ₂₁ N, Fluorinert, 3M) as solvent (D), mixed, stirred at room temperature for a predetermined time, and then an organosilicon compound (C As KBM-603 (N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) relative to the total amount of compounds (A), (B) and solvent (D) It dripped so that it might become 0.125 mass%. Then, it stirred at room temperature for a predetermined time, and obtained the solution for film formation. In the solution, the proportion of the compound (A) is 0.085% by mass, and the proportion of the compound (B) is 0.05% by mass. The solution obtained was activated using an atmospheric pressure plasma apparatus (Fuji Machine Mfg. Co., Ltd.) on a substrate having an acrylic hard coat layer activated using a spray coater manufactured by Apiros Co., Ltd. Applied. Then, it baked at 120 degreeC for 20 minutes, and obtained the transparent film on the acryl-type hard-coat layer. The spray coating conditions are: scan speed: 600 mm / sec, pitch: 5 mm, liquid volume: 6 cc / min, atomizing air: 350 kPa, gap: 70 mm.

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

Example 2
Acrylic hard as in Example 1 except that the proportion of the added compound (C) is 0.25 mass% with respect to the total amount of the compounds (A), (B) and the solvent (D) A transparent film was obtained on the coated substrate.

Example 3
Acrylic hard as in Example 1 except that the proportion of the added compound (C) is 0.5 mass% with respect to the total amount of the compounds (A), (B) and the solvent (D) A transparent film was obtained on the coated substrate.

Example 4
An acrylic hard coat group is prepared in the same manner as in Example 1 except that the proportion of the added compound (C) is 1 mass% with respect to the total amount of the compounds (A), (B) and the solvent (D). A transparent film was obtained on the material.

Comparative Example 1
Compound a as the organosilicon compound (A), FAS ₁₃ E (C ₆ F ₁₃ -C ₂ H ₄ -Si (OC ₂ H ₅ ) ₃ , manufactured by Tokyo Chemical Industry Co., Ltd.) as the organosilicon compound (B), solvent (D) FC-3283 (C ₉ F ₂₁ N, Fluorinert, manufactured by 3M) was mixed as the solution, and stirred at room temperature for a predetermined time to obtain a solution for forming a film. In the solution, the proportion of the compound (A) is 0.085% by mass, and the proportion of the compound (B) is 0.05% by mass. The obtained solution was applied on a hard coat whose surface was activated using an atmospheric pressure plasma apparatus (manufactured by Fuji Machine Mfg. Co., Ltd.) using a spray coater manufactured by Apiros Corporation. Then, it baked at 120 degreeC for 20 minutes, and obtained the transparent film on the acryl-type hard coat base material.

  The following measurement was performed about the film | membrane obtained by the said Example and comparative example.

(1) Measurement of water contact angle (initial contact angle)
A 3 μL water droplet is dropped on the obtained film, and the contact angle of water is measured by a droplet method (analysis method: θ / 2 method) using a contact angle measuring device (DM700 manufactured by Kyowa Interface Science Co., Ltd.) 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 a minoan eraser, with the eraser in contact with the film. About 2.5 ml of ethanol was dropped thereto, and the eraser was reciprocated on the film at a speed of 40 r / min (a speed of 40 reciprocations per minute) to conduct 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.

  All of Examples 1 to 4 using the organosilicon compounds (A), (B) and (C) of the present invention were good when the water contact angle after the chemical resistance test was 82 ° or more, whereas In the comparative example 1 which does not contain a silicon compound (C), the water contact angle after a chemical resistance test fell.

  The composition of the present invention is a display device such as a touch panel display, an optical element, a semiconductor element, a building material, a nanoimprint technology, a solar cell, a window glass of a car or building, a metal product such as a cooker, a ceramic product such as a dish, plastic The film can be suitably formed on manufactured automobile parts and the like, which is industrially useful. Moreover, it is preferably used also for articles of each member around a kitchen, a bathroom, a wash basin, a mirror, a toilet, goggles, glasses and the like.

Claims (6)

A composition comprising an organosilicon compound (A) represented by the formula (a1), an organosilicon compound (B) represented by the formula (b1) and an organosilicon compound (C) represented by the formula (c1).

In the above formula (a1),
Rf ^a1 is 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 from each other,
G ¹ and G ² are each independently a di- to 10-valent organosiloxane group having a siloxane bond,
J ¹ , J ² and J ³ are each independently a hydrolyzable group or — (CH ₂ ) _{e 6} —Si (OR ¹⁴ ) ₃ , e 6 is 1 to 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 If present, multiple J ³ may be different from each other,
L ¹ and L ² each independently represent an oxygen atom, a nitrogen atom, or a divalent C 1-12 linking group which may contain a fluorine atom, and a plurality of L ^{1 s} may be present when a plurality of L ^{1 s} are present. 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 to 9,
d12 is 0 to 9,
a10 and a14 are each independently 0 to 10,
a11 and a15 are each independently 0 or 1, and
a12 and a16 are each independently 0 to 9,
a13 is 0 or 1;
and a21, a22 and a23 are each independently 0 to 2;
Each of e1, e2 and e3 is independently 1 to 3.

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 by a fluorine atom,
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 And R ^{b14 's} may be different from each other,
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 In the case of multiple Rf ^b11 may be different from each other, when multiple R f ^b12 are present, multiple R f ^b12 may be different from each other, and when multiple R f ^b13 is present, multiple R f ^b13 are different from each other 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—, —O—C (= 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 each independently an integer of 0 to 100,
c is an integer of 1 to 3,
^{Rf b10 -, - Si (A} 2) c (R b15) 3-c, b11 amino ^{- {C (R b11) (} R b12)} -, b12 amino ^{- {C (Rf b11) (} Rf b12) }-, B13 pieces of-{Si (R ^b13 ) (R ^b14 )}-, b14 pieces of-{Si (Rf ^b13 ) (Rf ^b14 )}-, b15 pieces of -A ¹ -are Rf ^b10- , As long as -Si (A ² ) _c (R ^b15 ) _3-c is terminated to form a perfluoropolyether structure and -O- is not linked to -O- to -F, they may be arranged in any order. Join.

In the above formula (c1),
^{R x1, R x2, R x3} , R x4 are each independently a hydrogen atom or a carbon number from 1 to 4 alkyl groups, if R ^x1 there exist a plurality differ plurality of R ^x1, respectively 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 And each R ^{x 4} may be different from each other,
Rf ^x1 , R f ^x2 , R f ^x3 and R f ^x4 are each independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted by fluorine atoms or a fluorine atom, and a plurality of R f ^x1 are present 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, 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 X are present, the plurality of X may be different from each other,
Y is -O-, -NH-, or -S-, and when there are a plurality of Y, a plurality of Y may be different from each other,
Z is a vinyl group, an α-methyl vinyl 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 each independently an integer of 0 to 10, and p5 is an integer of 0 to 10,
p6 is an integer of 1 to 3,
_{Z -, - Si (X)} p6 (R x5) 3-p6, p1 amino ^{- {C (R x1) (} R x2)} -, p2 amino ^{- {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 ^{x 5} ) _3-p6 is terminated, and so long as -O- is not linked to -O-, they are linked in any order.   The composition according to claim 1, wherein the organosilicon compound (C) is 0.1% by mass or more and 1% by mass or less in the total mass of the composition. The composition according to claim 1, wherein the organosilicon compound (C) 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—, —CH ₂ — or —O—
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.   The surface treatment resin base material which has a film which consists of a composition in any one of Claims 1-3 on the surface of a resin base material.   The surface-treated resin substrate according to claim 4, wherein the resin substrate is an acrylic resin substrate.   The manufacturing method of the surface treatment resin base material which apply | coats the composition in any one of Claims 1-3 to the surface of a resin base material, and hardens it at normal temperature.