JP2021088551A - Fluoropolyether group-containing silane compound - Google Patents

Abstract

To provide a new fluoropolyether group-containing silane compound that can be used as a surface treatment agent.SOLUTION: A fluoropolyether group-containing silane compound is represented by formula (1a) or formula (1b). In the formulae, the symbols are as defined in the description.SELECTED DRAWING: None

Description

The present disclosure relates to fluoropolyether group-containing silane compounds.

It is known that certain fluorine-containing silane compounds can provide excellent water repellency, oil repellency, antifouling property, etc. when used for surface treatment of a base material. The layer obtained from the surface treatment agent containing a fluorine-containing silane compound (hereinafter, also referred to as “surface treatment layer”) is applied as a so-called functional thin film to various base materials such as glass, plastic, fiber, and building materials. ing.

As such a fluorine-containing compound, a perfluoropolyether group-containing silane compound having a perfluoropolyether group in the main chain of the molecule and a hydrolyzable group bonded to a Si atom at the end or end of the molecule is known. (Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2014-218369 Japanese Unexamined Patent Publication No. 2017-082194

A further new structure may be required for the fluoropolyether group-containing silane compound that can be used as the above-mentioned surface treatment agent.

［式中：
Ｒ^Ｆ１は、各出現においてそれぞれ独立して、Ｒｆ^１−Ｒ^Ｆ−Ｏ_ｑ−であり；
Ｒ^Ｆ２は、−Ｒｆ^２ _ｐ−Ｒ^Ｆ−Ｏ_ｑ−であり；
Ｒｆ^１は、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよいＣ_１−１６アルキル基であり；
Ｒｆ^２は、１個またはそれ以上のフッ素原子により置換されていてもよいＣ_１−６アルキレン基であり；
Ｒ^Ｆは、各出現においてそれぞれ独立して、２価のフルオロポリエーテル基であり；
ｐは、０または１であり；
ｑは、各出現においてそれぞれ独立して、０または１であり；
αは、１〜９の整数であり；
βは、１〜９の整数であり；
γは、それぞれ独立して、１〜９の整数であり；
Ｘ^Ａは、各出現においてそれぞれ独立して、２以上のアミド結合を有する２〜１０価の有機基であり；
Ｒ^Ｓｉは、各出現においてそれぞれ独立して、水酸基、加水分解性基、水素原子または１価の有機基が結合したＳｉ原子を含む１価の基である。］
で表されるフルオロポリエーテル基含有シラン化合物。
［２］ Ｒ^Ｆは、各出現においてそれぞれ独立して、式：
−（ＯＣ_６Ｆ_１２）_ａ−（ＯＣ_５Ｆ_１０）_ｂ−（ＯＣ_４Ｆ_８）_ｃ−（ＯＣ_３Ｆ_６）_ｄ−（ＯＣ_２Ｆ_４）_ｅ−（ＯＣＦ_２）_ｆ−
［式中：
ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して、０〜２００の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は１以上であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。］
で表される基である、［１］に記載のフルオロポリエーテル基含有シラン化合物。
［３］ Ｒ^Ｆは、各出現においてそれぞれ独立して、下記式（ｆ１）、（ｆ２）、（ｆ３）、（ｆ４）または（ｆ５）で表される、［１］または［２］に記載のフルオロポリエーテル基含有シラン化合物。
−（ＯＣ_３Ｆ_６）_ｄ−（ＯＣ_２Ｆ_４）_ｅ− （ｆ１）
［式中、ｄは、１〜２００の整数であり、ｅは１である。］
−（ＯＣ_４Ｆ_８）_ｃ−（ＯＣ_３Ｆ_６）_ｄ−（ＯＣ_２Ｆ_４）_ｅ−（ＯＣＦ_２）_ｆ− （ｆ２）
［式中、ｃおよびｄは、それぞれ独立して０以上３０以下の整数であり、ｅおよびｆは、それぞれ独立して１以上２００以下の整数であり、
ｃ、ｄ、ｅおよびｆの和は２以上であり、
添字ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。］
−（Ｒ^６−Ｒ^７）_ｇ− （ｆ３）
［式中、Ｒ^６は、ＯＣＦ_２またはＯＣ_２Ｆ_４であり、
Ｒ^７は、ＯＣ_２Ｆ_４、ＯＣ_３Ｆ_６、ＯＣ_４Ｆ_８、ＯＣ_５Ｆ_１０およびＯＣ_６Ｆ_１２から選択される基であるか、あるいは、これらの基から独立して選択される２または３つの基の組み合わせであり、
ｇは、２〜１００の整数である。］
−（ＯＣ_６Ｆ_１２）_ａ−（ＯＣ_５Ｆ_１０）_ｂ−（ＯＣ_４Ｆ_８）_ｃ−（ＯＣ_３Ｆ_６）_ｄ−（ＯＣ_２Ｆ_４）_ｅ−（ＯＣＦ_２）_ｆ− （ｆ４）
［式中、ｅは、１以上２００以下の整数であり、ａ、ｂ、ｃ、ｄおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、また、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。］
−（ＯＣ_６Ｆ_１２）_ａ−（ＯＣ_５Ｆ_１０）_ｂ−（ＯＣ_４Ｆ_８）_ｃ−（ＯＣ_３Ｆ_６）_ｄ−（ＯＣ_２Ｆ_４）_ｅ−（ＯＣＦ_２）_ｆ− （ｆ５）
［式中、ｆは、１以上２００以下の整数であり、ａ、ｂ、ｃ、ｄおよびｅは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、また、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。］
［４］ Ｘ^Ａは、各出現においてそれぞれ独立して、
−（Ｘ^２１）_ｓ２１−［（Ｘ^Ｎ）−（Ｘ^２２）］_ｓ１１−（Ｘ^Ｎ）−（Ｘ^２１）_ｓ２２−
で表される基である、［１］〜［３］のいずれか１つに記載のフルオロポリエーテル基含有シラン化合物。
［式中：
Ｘ^Ｎは、アミド結合を表し；
ｓ１１は、１〜３の整数であり；
Ｘ^２１は、それぞれ独立して、２〜１０価の有機基であり；
Ｘ^２２は、各出現においてそれぞれ独立して、２価の有機基であり；
ｓ２１は、それぞれ独立して、０または１であり；
ｓ２２は、それぞれ独立して、０または１である。］
［５］ Ｘ^Ａは、２価の有機基であり、各出現においてそれぞれ独立して、
−（Ｘ^２１）_ｓ２１−［（Ｘ^Ｎ）−（Ｘ^２２）］_ｓ１１−（Ｘ^Ｎ）−（Ｘ^２１）_ｓ２２−
で表される基である、［１］〜［４］のいずれか１つに記載のフルオロポリエーテル基含有シラン化合物。
［式中：
Ｘ^Ｎは、アミド結合を表し；
ｓ１１は、１〜３の整数であり；
Ｘ^２１は、それぞれ独立して、２価の有機基であり；
Ｘ^２２は、各出現においてそれぞれ独立して、２価の有機基であり；
ｓ２１は、それぞれ独立して、０または１であり；
ｓ２２は、それぞれ独立して、０または１である。］
［６］ Ｘ^２２は、各出現においてそれぞれ独立して、
−Ｒ^２２１−、または、
−（Ｒ^２２１）_ｓ３１−Ｘ^３１−（Ｒ^２２２）_ｓ３２−
である、［４］または［５］に記載のフルオロポリエーテル基含有シラン化合物。
［式中：
Ｒ^２２１およびＲ^２２２は、それぞれ独立して、Ｃ_１−１０アルキレン基であり；
前記Ｃ_１−１０アルキレン基の水素原子は、置換されていてもよく；
Ｘ^３１は、−Ｏ−、または−ＮＲ^５４−であり；
Ｒ^５４は、水素原子、フェニル基またはＣ_１−６アルキル基であり；
ｓ３１は、０または１であり；
ｓ３２は、０または１である。］
［７］ α、βおよびγが、それぞれ１である、［１］〜［６］のいずれか１つに記載のフルオロポリエーテル基含有シラン化合物。
［８］ Ｒ^Ｓｉは、各出現においてそれぞれ独立して、式（Ｓ１）、（Ｓ２）、（Ｓ３）または（Ｓ４）で表される、［１］〜［７］のいずれか１つに記載のフルオロポリエーテル基含有シラン化合物。

［式中：
Ｒ^１１は、各出現においてそれぞれ独立して、水酸基または加水分解性基であり；
Ｒ^１２は、各出現においてそれぞれ独立して、水素原子または１価の有機基であり；
ｎ１は、（ＳｉＲ^１１ _ｎ１Ｒ^１２ _３−ｎ１）単位毎にそれぞれ独立して、０〜３の整数であり；
Ｘ^１１は、各出現においてそれぞれ独立して、単結合または２価の有機基であり；
Ｒ^１３は、各出現においてそれぞれ独立して、水素原子または１価の有機基であり；
ｔは、各出現においてそれぞれ独立して、２以上の整数であり；
Ｒ^１４は、各出現においてそれぞれ独立して、水素原子、ハロゲン原子または−Ｘ^１１−ＳｉＲ^１１ _ｎ１Ｒ^１２ _３−ｎ１であり；
Ｒ^１５は、各出現においてそれぞれ独立して、単結合、酸素原子、炭素数１〜６のアルキレン基または炭素数１〜６のアルキレンオキシ基であり；
Ｒ^ａ１は、各出現においてそれぞれ独立して、−Ｚ^１−ＳｉＲ^２１ _ｐ１Ｒ^２２ _ｑ１Ｒ^２３ _ｒ１であり；
Ｚ^１は、各出現においてそれぞれ独立して、酸素原子または２価の有機基であり；
Ｒ^２１は、各出現においてそれぞれ独立して、−Ｚ^１’−ＳｉＲ^２１’ _ｐ１’Ｒ^２２’ _ｑ１’Ｒ^２３’ _ｒ１’であり；
Ｒ^２２は、各出現においてそれぞれ独立して、水酸基または加水分解性基であり；
Ｒ^２３は、各出現においてそれぞれ独立して、水素原子または１価の有機基であり；
ｐ１は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｑ１は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｒ１は、各出現においてそれぞれ独立して、０〜３の整数であり；
Ｚ^１’は、各出現においてそれぞれ独立して、酸素原子または２価の有機基であり；
Ｒ^２１’は、各出現においてそれぞれ独立して、−Ｚ^１”−ＳｉＲ^２２” _ｑ１”Ｒ^２３” _ｒ１”であり；
Ｒ^２２’は、各出現においてそれぞれ独立して、水酸基または加水分解性基であり；
Ｒ^２３’は、各出現においてそれぞれ独立して、水素原子または１価の有機基であり；
ｐ１’は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｑ１’は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｒ１’は、各出現においてそれぞれ独立して、０〜３の整数であり；
Ｚ^１”は、各出現においてそれぞれ独立して、酸素原子または２価の有機基であり；
Ｒ^２２”は、各出現においてそれぞれ独立して、水酸基または加水分解性基であり；
Ｒ^２３”は、各出現においてそれぞれ独立して、水素原子または１価の有機基であり；
ｑ１”は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｒ１”は、各出現においてそれぞれ独立して、０〜３の整数であり；
Ｒ^ｂ１は、各出現においてそれぞれ独立して、水酸基または加水分解性基であり；
Ｒ^ｃ１は、各出現においてそれぞれ独立して、水素原子または１価の有機基であり；
ｋ１は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｌ１は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｍ１は、各出現においてそれぞれ独立して、０〜３の整数であり；
Ｒ^ｄ１は、各出現においてそれぞれ独立して、−Ｚ^２−ＣＲ^３１ _ｐ２Ｒ^３２ _ｑ２Ｒ^３３ _ｒ２であり；
Ｚ^２は、各出現においてそれぞれ独立して、単結合、酸素原子または２価の有機基であり；
Ｒ^３１は、各出現においてそれぞれ独立して、−Ｚ^２’−ＣＲ^３２’ _ｑ２’Ｒ^３３’ _ｒ２’であり；
Ｒ^３２は、各出現においてそれぞれ独立して、−Ｚ^３−ＳｉＲ^３４ _ｎ２Ｒ^３５ _３−ｎ２であり；
Ｒ^３３は、各出現においてそれぞれ独立して、水素原子、水酸基または１価の有機基であり；
ｐ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｑ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｒ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
Ｚ^２’は、各出現においてそれぞれ独立して、単結合、酸素原子または２価の有機基であり；
Ｒ^３２’は、各出現においてそれぞれ独立して、−Ｚ^３−ＳｉＲ^３４ _ｎ２Ｒ^３５ _３−ｎ２であり；
Ｒ^３３’は、各出現においてそれぞれ独立して、水素原子、水酸基または１価の有機基であり；
ｑ２’は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｒ２’は、各出現においてそれぞれ独立して、０〜３の整数であり；
Ｚ^３は、各出現においてそれぞれ独立して、単結合、酸素原子または２価の有機基であり；
Ｒ^３４は、各出現においてそれぞれ独立して、水酸基または加水分解性基であり；
Ｒ^３５は、各出現においてそれぞれ独立して、水素原子または１価の有機基であり；
ｎ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
Ｒ^ｅ１は、各出現においてそれぞれ独立して、−Ｚ^３−ＳｉＲ^３４ _ｎ２Ｒ^３５ _３−ｎ２であり；
Ｒ^ｆ１は、各出現においてそれぞれ独立して、水素原子、水酸基または１価の有機基であり；
ｋ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｌ２は、各出現においてそれぞれ独立して、０〜３の整数であり；
ｍ２は、各出現においてそれぞれ独立して、０〜３の整数である。］
［９］ ｎ１は、３である、［８］に記載のフルオロポリエーテル基含有シラン化合物。
［１０］ ｋ１は、３であり、ｑ１は１〜３の整数である、［８］または［９］に記載のフルオロポリエーテル基含有シラン化合物。
［１１］ ｌ２は、３であり、ｎ２は１〜３の整数である、［８］〜［１０］のいずれか１つに記載のフルオロポリエーテル基含有シラン化合物。
［１２］ ［１］〜［１１］のいずれか１つに記載の式（１ａ）または式（１ｂ）で表される少なくとも１種のフルオロポリエーテル化合物を含有する、表面処理剤。
［１３］ 含フッ素オイル、シリコーンオイル、および触媒から選択される１種またはそれ以上の他の成分をさらに含有する、［１２］に記載の表面処理剤。
［１４］ さらに溶媒を含む、［１２］または［１３］に記載の表面処理剤。
［１５］ 防汚性コーティング剤または防水性コーティング剤として使用される、［１２］〜［１４］のいずれか１つに記載の表面処理剤。
［１６］ 真空蒸着用である、［１２］〜［１５］のいずれか１つに記載の表面処理剤。
［１７］ 湿潤被覆処理用である、［１２］〜［１５］のいずれか１つに記載の表面処理剤。
［１８］ ［１２］〜［１６］のいずれか１つに記載の表面処理剤を含有するペレット。
［１９］ 基材と、該基材の表面に、［１］〜［１１］のいずれか１つに記載のフルオロポリエーテル基含有シラン化合物、または、［１２］〜［１７］のいずれか１つに記載の表面処理剤より形成された層とを含む物品。
［２０］ 光学部材である、［１９］に記載の物品。 The present disclosure provides the following [1] to [20].
[1] Equation (1a) or Equation (1b):

[During the ceremony:
R ^{F1 is Rf 1-} R ^F- O _q- independently at each appearance;
R ^F2 is −Rf ² _p −R ^F −O _q −;
Rf ¹ _{is a C 1-16} alkyl group that may be independently substituted with one or more fluorine atoms at each appearance;
Rf ² _{is a C 1-6} alkylene group that may be substituted with one or more fluorine atoms;
^RF is a divalent fluoropolyether group independently at each appearance;
p is 0 or 1;
q is 0 or 1 independently at each appearance;
α is an integer from 1 to 9;
β is an integer from 1 to 9;
γ is an integer of 1 to 9 independently of each other;
X ^A is a 2-10 valent organic group with two or more amide bonds, each independently at each appearance;
R ^Si is a monovalent group containing a Si atom to which a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group is bonded independently at each appearance. ]
A fluoropolyether group-containing silane compound represented by.
[2] ^RF is independent of each appearance, and the formula:
− (OC ₆ F ₁₂ ) _a − (OC ₅ F ₁₀ ) _b − (OC ₄ F ₈ ) _c − (OC ₃ F ₆ ) _d − (OC ₂ F ₄ ) _e − (OCF ₂ ) _f −
[During the ceremony:
a, b, c, d, e and f are independently integers from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more, and a, b, The order of existence of each repeating unit in parentheses with c, d, e or f is arbitrary in the equation. ]
The fluoropolyether group-containing silane compound according to [1], which is a group represented by.
[3] ^{R F} are each independently at each occurrence, the following formula (f1), (f2), (f3), represented by (f4) or (f5), according to [1] or [2] Fluoropolyether group-containing silane compound.
-(OC ₃ F ₆ ) _d- (OC ₂ F ₄ ) _e- (f1)
[In the formula, d is an integer of 1 to 200 and e is 1. ]
− (OC ₄ F ₈ ) _c − (OC ₃ F ₆ ) _d − (OC ₂ F ₄ ) _e − (OCF ₂ ) _f − (f2)
[In the formula, c and d are independently integers of 0 or more and 30 or less, and e and f are independently integers of 1 or more and 200 or less.
The sum of c, d, e and f is 2 or more,
The order of existence of each repeating unit with the subscripts c, d, e or f in parentheses is arbitrary in the equation. ]
-(R ^6- R ⁷ ) _g- (f3)
[In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ and
R ⁷ is _{a group selected from OC 2} F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or is selected independently of these groups 2 Or a combination of three groups,
g is an integer of 2 to 100. ]
− (OC ₆ F ₁₂ ) _a − (OC ₅ F ₁₀ ) _b − (OC ₄ F ₈ ) _c − (OC ₃ F ₆ ) _d − (OC ₂ F ₄ ) _e − (OCF ₂ ) _f − (f4)
[In the formula, e is an integer of 1 or more and 200 or less, and a, b, c, d and f are independently integers of 0 or more and 200 or less, and a, b, c, d and e. The sum of and f is at least 1, and the order of existence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the equation. ]
− (OC ₆ F ₁₂ ) _a − (OC ₅ F ₁₀ ) _b − (OC ₄ F ₈ ) _c − (OC ₃ F ₆ ) _d − (OC ₂ F ₄ ) _e − (OCF ₂ ) _f − (f5)
[In the formula, f is an integer of 1 or more and 200 or less, and a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and a, b, c, d and e. The sum of and f is at least 1, and the order of existence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the equation. ]
[4] X ^A is independent of each appearance.
-(X ²¹ ) _s21 -[(X ^N )-(X ²² )] _s11- (X ^N )-(X ²¹ ) _s22-
The fluoropolyether group-containing silane compound according to any one of [1] to [3], which is a group represented by.
[During the ceremony:
X ^N represents an amide bond;
s11 is an integer from 1 to 3;
Each of X ²¹ is an independently 2-10 valent organic group;
X ²² is a divalent organic group independently at each appearance;
s21 is 0 or 1 independently of each other;
s22 is 0 or 1 independently of each other. ]
[5] X ^A is a divalent organic group, and each appearance is independent.
-(X ²¹ ) _s21 -[(X ^N )-(X ²² )] _s11- (X ^N )-(X ²¹ ) _s22-
The fluoropolyether group-containing silane compound according to any one of [1] to [4], which is a group represented by.
[During the ceremony:
X ^N represents an amide bond;
s11 is an integer from 1 to 3;
Each of X ²¹ is a divalent organic group independently;
X ²² is a divalent organic group independently at each appearance;
s21 is 0 or 1 independently of each other;
s22 is 0 or 1 independently of each other. ]
[6] X ²² is independent of each appearance.
-R ^221- or
_{^{- (R 221) s31 -X 31}} - (R 222) s32 -
The fluoropolyether group-containing silane compound according to [4] or [5].
[During the ceremony:
R ²²¹ and R ²²² are independently C _1-10 alkylene groups;
The hydrogen atom of the C _1-10 alkylene group may be substituted;
X ³¹ is, -O-, or ^{-NR 54} - and is;
R ⁵⁴ is a hydrogen atom, a phenyl group or a C _1-6 alkyl group;
s31 is 0 or 1;
s32 is 0 or 1. ]
[7] The fluoropolyether group-containing silane compound according to any one of [1] to [6], wherein α, β and γ are 1 each.
[8] R ^Si is described in any one of [1] to [7] represented by the formulas (S1), (S2), (S3) or (S4) independently at each appearance. Fluoropolyether group-containing silane compound.

[During the ceremony:
R ¹¹ is an independent hydroxyl group or hydrolyzable group at each appearance;
R ¹² is an independent hydrogen atom or monovalent organic group at each appearance;
n1 is an integer of 0 to 3 independently for each unit ^{(SiR 11} _n1 R ¹² _3-n1);
X ¹¹ is an independent, single-bonded or divalent organic group at each appearance;
R ¹³ is an independent hydrogen atom or monovalent organic group at each appearance;
t is an integer greater than or equal to 2 independently for each occurrence;
R ¹⁴ is independently a hydrogen atom, a halogen atom or -X ^11- SiR ¹¹ _n1 R ¹² _3-n1 at each appearance;
R ¹⁵ is independently at each occurrence, a single bond, an oxygen atom, an alkylene group or alkyleneoxy group having 1 to 6 carbon atoms having from 1 to 6 carbon atoms;
R ^{a1 is -Z 1-} SiR ²¹ _p1 R ²² _q1 R ²³ _r1 independently in each appearance;
Z ¹ is an oxygen atom or a divalent organic group, independently of each appearance;
R ²¹ is independently at each occurrence, be a _{^{-Z 1 '-SiR 21' p1 '}} R 22' q1 'R 23' r1 ';
R ²² is an independent hydroxyl group or hydrolyzable group at each appearance;
R ²³ is an independent hydrogen atom or monovalent organic group at each appearance;
p1 is an integer from 0 to 3 independently for each occurrence;
q1 is an integer from 0 to 3 independently for each occurrence;
r1 is an integer from 0 to 3 independently for each occurrence;
Z 1 ^'are each independently at each occurrence, an oxygen atom or a divalent organic group;
R ^{21 'are} each independently at each ^occurrence, be a _{^{-Z 1 "-SiR 22" q1 "}} R 23" r1 ";
R ^{22 'are} each independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R ^23'is a hydrogen atom or monovalent organic group independently at each appearance;
p1'is an integer from 0 to 3 independently for each occurrence;
q1'is an integer from 0 to 3 independently for each occurrence;
r1'is an integer from 0 to 3 independently for each occurrence;
Z ^{1 "} is an oxygen atom or a divalent organic group, independently of each appearance;
R ^{22 "} is an independent hydroxyl group or hydrolyzable group at each appearance;
R ^{23 "} is an independent hydrogen atom or monovalent organic group at each appearance;
q1 ”is an integer from 0 to 3 independently for each occurrence;
"r1" is an integer from 0 to 3 independently for each occurrence;
R ^b1 is independently a hydroxyl group or a hydrolyzable group at each appearance;
R ^c1 is an independent hydrogen atom or monovalent organic group at each appearance;
k1 is an integer from 0 to 3 independently for each occurrence;
l1 is an integer from 0 to 3 independently for each occurrence;
m1 is an integer from 0 to 3 independently for each occurrence;
R ^{d1 is -Z 2-} CR ³¹ _p2 R ³² _q2 R ³³ _r2 independently at each appearance;
Z ² is an independent, single bond, oxygen atom or divalent organic group at each appearance;
R ³¹ is independently at each occurrence, be a _{^{-Z 2 '-CR 32' q2 '}} R 33' r2 ';
R ^{32 is -Z 3-} SiR ³⁴ _n2 R ³⁵ _3-n2 independently at each appearance;
R ³³ is an independent hydrogen atom, hydroxyl group or monovalent organic group at each appearance;
p2 is an integer from 0 to 3 independently for each occurrence;
q2 is an integer from 0 to 3 independently for each occurrence;
r2 is an integer from 0 to 3 independently for each occurrence;
Z 2 ^'are each independently at each occurrence, a single bond, an oxygen atom or a divalent organic group;
R ^{32 'are} each independently at each ^occurrence, be a _{^{-Z 3 -SiR 34 n2 R 35 3}} -n2;
R ^33'is a hydrogen atom, a hydroxyl group or a monovalent organic group independently at each appearance;
q2'is an integer from 0 to 3 independently for each occurrence;
r2'is an integer from 0 to 3 independently for each occurrence;
Z ³ is an independent, single bond, oxygen atom or divalent organic group at each appearance;
R ³⁴ is an independent hydroxyl group or hydrolyzable group at each appearance;
R ³⁵ is an independent hydrogen atom or monovalent organic group at each appearance;
n2 is an integer from 0 to 3 independently for each occurrence;
R ^{e1 is -Z 3-} SiR ³⁴ _n2 R ³⁵ _3-n2 independently at each appearance;
R ^f1 is a hydrogen atom, a hydroxyl group or a monovalent organic group independently at each appearance;
k2 is an integer from 0 to 3 independently for each occurrence;
l2 is an integer from 0 to 3 independently for each occurrence;
m2 is an integer from 0 to 3 independently for each appearance. ]
[9] The fluoropolyether group-containing silane compound according to [8], wherein n1 is 3.
[10] The fluoropolyether group-containing silane compound according to [8] or [9], wherein k1 is 3 and q1 is an integer of 1 to 3.
[11] The fluoropolyether group-containing silane compound according to any one of [8] to [10], wherein l2 is 3 and n2 is an integer of 1 to 3.
[12] A surface treatment agent containing at least one fluoropolyether compound represented by the formula (1a) or the formula (1b) according to any one of [1] to [11].
[13] The surface treatment agent according to [12], which further contains one or more other components selected from a fluorine-containing oil, a silicone oil, and a catalyst.
[14] The surface treatment agent according to [12] or [13], which further contains a solvent.
[15] The surface treatment agent according to any one of [12] to [14], which is used as an antifouling coating agent or a waterproof coating agent.
[16] The surface treatment agent according to any one of [12] to [15], which is used for vacuum vapor deposition.
[17] The surface treatment agent according to any one of [12] to [15], which is used for a wet coating treatment.
[18] Pellets containing the surface treatment agent according to any one of [12] to [16].
[19] On the base material and the surface of the base material, the fluoropolyether group-containing silane compound according to any one of [1] to [11], or any one of [12] to [17]. Articles comprising a layer formed from the surface treatment agent according to one.
[20] The article according to [19], which is an optical member.

According to the present disclosure, a novel fluoropolyether group-containing silane compound that can be used as a surface treatment agent is provided.

As used herein, "monovalent organic group" means a carbon-containing monovalent group. The monovalent organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A hydrocarbon group derivative is a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. in the terminal or molecular chain of the hydrocarbon group. Means. When simply referred to as "organic group", it means a monovalent organic group.

Further, the "divalent organic group" means a divalent group containing carbon. The divalent organic group is not particularly limited, and examples thereof include a divalent group obtained by desorbing one hydrogen atom from the organic group.

As used herein, "hydrocarbon group" means a group containing carbon and hydrogen, from which one hydrogen atom has been desorbed from the hydrocarbon. Such hydrocarbon groups are not particularly limited, but may be substituted with one or more substituents _{, such as C 1-20} hydrocarbon groups, eg, aliphatic hydrocarbon groups, aromatics. Hydrocarbon groups and the like can be mentioned. The "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. In addition, the hydrocarbon group may contain one or more ring structures.

As used herein, the substituent of the "hydrocarbon group" is not particularly limited, but may be substituted with, for example, a halogen atom, one or more halogen atoms, C _1-6 alkyl. Group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, 5-10 member heterocyclyl group, 5-10 member unsaturated heterocyclyl Groups include _{one or more groups selected from C 6-10} aryl groups and 5-10 membered heteroaryl groups.

(Fluoropolyether group-containing silane compound)
The fluoropolyether group-containing silane compound of the present embodiment is represented by the following formula (1a) or formula (1b).

In formula (1a), R ^{F1 is Rf 1 −} R ^F− O _q − independently at each appearance.

In formula (1b), R ^F2 is −Rf ² _p −R ^F −O _q −.

In the above formula, Rf ¹ _{is a C 1-16} alkyl group that may be independently substituted with one or more fluorine atoms at each appearance.

The "C _{1-16 alkyl group" in the C 1-16} alkyl group which may be substituted with one or more fluorine atoms may be a straight chain or a branched chain, and is preferable. Is a linear or branched C _1-6 alkyl group, particularly a C _1-3 alkyl group, more preferably a linear C _1-6 alkyl group, particularly a C _1-3 alkyl group.

The Rf ¹ is preferably a one or more _{C 1-16} alkyl group substituted by fluorine atoms, more preferably _CF 2 _{H-C 1-15} perfluoroalkylene group, more preferably Is a C _1-16 perfluoroalkyl group.

The C _1-16 perfluoroalkyl group may be linear or branched, preferably a straight or branched C _1-6 perfluoroalkyl group, particularly C _{1-. A 3} perfluoroalkyl group, more preferably a linear C _1-6 perfluoroalkyl group, particularly a C _1-3 perfluoroalkyl group, specifically -CF ₃ , -CF ₂ CF ₃ , or -CF. ₂ CF ₂ CF ₃ .

In the above formula, Rf ² _{is a C 1-6} alkylene group which may be substituted with one or more fluorine atoms.

The "C _{1-6 alkylene group" in the C 1-6} alkylene group which may be substituted with one or more fluorine atoms may be a straight chain or a branched chain, and is preferable. Is a linear or branched C _1-3 alkylene group, more preferably a linear C _1-3 alkylene group.

The Rf ² is preferably a one or more C _1-6 alkylene group substituted with a fluorine atom, more preferably a C _1-6 perfluoroalkylene group, more preferably C _{1- 3} Perfluoroalkylene group.

The C _1-6 perfluoroalkylene group may be a straight chain or a branched chain, preferably a straight chain or a branched C _1-3 perfluoroalkylene group, and more preferably. Is a linear C _1-3 perfluoroalkyl group, specifically −CF ₂ −, _{−CF 2} CF ₂ −, or −CF ₂ CF ₂ CF ₂ −.

In the above formula, p is 0 or 1. In one embodiment, p is 0. In another embodiment p is 1.

In the above equation, q is 0 or 1 independently at each occurrence. In one embodiment, q is 0. In another embodiment q is 1.

In the above formula (1a) and (1b), ^{R F} is independently at each occurrence, is a divalent perfluoropolyether group.

^RF is preferably the formula:
− (OC ₆ F ₁₂ ) _a − (OC ₅ F ₁₀ ) _b − (OC ₄ F ₈ ) _c − (OC ₃ F ₆ ) _d − (OC ₂ F ₄ ) _e − (OCF ₂ ) _f −
It is a fluoropolyether group represented by.
In the above formula:
a, b, c, d, e and f are independently integers from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more, and a, b, The order of existence of each repeating unit in parentheses with c, d, e or f is arbitrary in the equation.

a, b, c, d, e and f may preferably be independently integers from 0 to 100.

The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. The sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, still more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

These repeating units may be linear or branched, but are preferably linear. For example,-(OC ₆ F ₁₂ )-is-(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ CF ₂ CF ₂ CF ₂ )-,-(OCF) ₂ CF (CF ₃ ) CF ₂ CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF (CF ₃ ) CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ CF (CF ₃ ) CF ₂ )- ,-(OCF ₂ CF ₂ CF ₂ CF ₂ CF (CF ₃ ))-etc., But preferably-(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₅ F ₁₀ )-is-(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ CF ₂ CF ₂ )-,-(OCF ₂ CF (CF ₃ )) CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF (CF ₃ ) CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ CF (CF ₃ ))-etc., But preferably-( OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₄ F ₈ )-is-(OCF ₂ CF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ CF ₂ )-,-(OCF ₂ CF (CF ₃ ) CF ₂ )- ,-(OCF ₂ CF ₂ CF (CF ₃ ))-,-(OC (CF ₃ ) ₂ CF ₂ )-,-(OCF ₂ C (CF ₃ ) ₂ )-,-(OCF (CF ₃ ) CF ( CF ₃ ))-,-(OCF (C ₂ F ₅ ) CF ₂ )-and-(OCF ₂ CF (C ₂ F ₅ ))-may be any of-(OCF ₂ CF _2). CF ₂ CF ₂ )-. -(OC ₃ F ₆ )-is either-(OCF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ )-and-(OCF ₂ CF (CF ₃ ))- It is good, but preferably − (OCF ₂ CF ₂ CF ₂ ) −. Further, − (OC ₂ F ₄ ) − may be any of − (OCF ₂ CF ₂ ) − and − (OCF (CF ₃ )) −, but − (OCF ₂ CF ₂ ) − is preferable. is there.

In one embodiment, ^RF is independently represented by the following formulas (f1), (f2), (f3), (f4) or (f5) in each appearance.
-(OC ₃ F ₆ ) _d- (OC ₂ F ₄ ) _e- (f1)
[In the formula, d is an integer of 1 to 200 and e is 1. ]
− (OC ₄ F ₈ ) _c − (OC ₃ F ₆ ) _d − (OC ₂ F ₄ ) _e − (OCF ₂ ) _f − (f2)
[In the formula, c and d are independently integers of 0 or more and 30 or less, and e and f are independently integers of 1 or more and 200 or less.
The sum of c, d, e and f is 2 or more,
The order of existence of each repeating unit with the subscripts c, d, e or f in parentheses is arbitrary in the equation. ]
-(R ^6- R ⁷ ) _g- (f3)
[In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ and
R ⁷ is _{a group selected from OC 2} F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or is selected independently of these groups 2 Or a combination of three groups,
g is an integer of 2 to 100. ]
− (OC ₆ F ₁₂ ) _a − (OC ₅ F ₁₀ ) _b − (OC ₄ F ₈ ) _c − (OC ₃ F ₆ ) _d − (OC ₂ F ₄ ) _e − (OCF ₂ ) _f − (f4)
[In the formula, e is an integer of 1 or more and 200 or less, and a, b, c, d and f are independently integers of 0 or more and 200 or less, and a, b, c, d and e. The sum of and f is at least 1, and the order of existence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the equation. ]
− (OC ₆ F ₁₂ ) _a − (OC ₅ F ₁₀ ) _b − (OC ₄ F ₈ ) _c − (OC ₃ F ₆ ) _d − (OC ₂ F ₄ ) _e − (OCF ₂ ) _f − (f5)
[In the formula, f is an integer of 1 or more and 200 or less, and a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and a, b, c, d and e. The sum of and f is at least 1, and the order of existence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the equation. ]

In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, still more preferably 15 to 50, for example 25 to 35. In the above formula (f1), − (OC ₃ F ₆ ) _d − is preferably a group represented by _{− (OCF 2} CF ₂ CF ₂ ) _d − or − (OCF (CF ₃ ) CF ₂ ) _{d −.} Yes, more preferably a group represented by _{− (OCF 2} CF ₂ CF ₂ ) _{d −.}

In the above formula (f2), e and f are each independently an integer of preferably 5 or more and 200 or less, more preferably 10 to 200. The sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably − (OCF ₂ CF ₂ CF ₂ CF ₂ ) _c − (OCF ₂ CF ₂ CF ₂ ) _d − (OCF ₂ CF ₂ ) _e − (OCF ₂ ). It is a group represented by _{f −.} In another embodiment, the formula (f2) may be a group represented by _{− (OC 2} F ₄ ) _e − (OCF ₂ ) _{f −.}

In the above formula (f3), R ⁶ is preferably OC ₂ F ₄ . In (f3) above, R ⁷ is preferably _{a group selected from OC 2} F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , or 2 or independently selected from these groups. It is a combination of three groups, more preferably a group selected from _{OC 3} F ₆ and OC ₄ F _8. The combination of two or three groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited, but is, for example, -OC ₂ F ₄ OC ₃ F _6- , -OC. _{2 F 4 OC 4 F 8 -} , - OC 3 F 6 OC 2 F 4 -, - OC 3 F 6 OC 3 F 6 -, - OC 3 F 6 OC 4 F 8 -, - OC 4 F 8 OC 4 F _{8 -, - OC 4 F 8} OC 3 F 6 -, - OC 4 F 8 OC 2 F 4 -, - OC 2 F 4 OC 2 F 4 OC 3 F 6 -, - OC 2 F 4 OC 2 F 4 OC _{4 F 8 -, - OC 2} F 4 OC 3 F 6 OC 2 F 4 -, - OC 2 F 4 OC 3 F 6 OC 3 F 6 -, - OC 2 F 4 OC 4 F 8 OC 2 F 4 -, _{-OC 3 F 6 OC 2 F 4} OC 2 F 4 -, - OC 3 F 6 OC 2 F 4 OC 3 F 6 -, - OC 3 F 6 OC 3 F 6 OC 2 F 4 -, and _-OC 4 F ₈ OC ₂ F ₄ OC ₂ F ₄ -etc. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ may be either linear or branched, preferably straight. It is a chain. In this embodiment, the above formula (f3) is preferably − (OC ₂ F ₄ −OC ₃ F ₆ ) _g − or − (OC ₂ F ₄ −OC ₄ F ₈ ) _g −.

In the above formula (f4), e is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.

In the above formula (f5), f is preferably an integer of 1 or more and 100 or less, and more preferably 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.

In one embodiment, the R ^F is a group represented by the formula (f1).

In one embodiment, the R ^F is a group represented by the formula (f2).

In one embodiment, the R ^F is a group represented by the formula (f3).

In one embodiment, the R ^F is a group represented by the above formula (f4).

In one embodiment, the R ^F is a group represented by the above formula (f5).

In one embodiment, the ^RF is
-(OC ₃ F ₆ ) _d-
[In the formula, d is an integer from 1 to 200].

In the ^{R F,} the ratio of e for f (hereinafter, referred to as "e / f ratio") is 0.1 to 10, preferably from 0.2 to 5, more preferably 0.2 to 2 Yes, more preferably 0.2 to 1.5. By setting the e / f ratio to 10 or less, the slipperiness, friction durability and chemical resistance (for example, durability against (human) sweat) of the surface treatment layer obtained from this compound are further improved. The smaller the e / f ratio, the better the slipperiness and friction durability of the surface treatment layer. On the other hand, by setting the e / f ratio to 0.1 or more, the stability of the compound can be further enhanced. The larger the e / f ratio, the better the stability of the compound. Here, f is an integer of 1 or more.

In one embodiment, the e / f ratio is preferably 0.2 to 0.9, more preferably 0.2 to 0.85, and even more preferably 0.2 to 0.8.

In one embodiment, from the viewpoint of heat resistance, the e / f ratio is preferably 0.9 or more, and more preferably 0.9 to 1.5.

The number average molecular weight of the ^{R F1} and ^{R F2} portion, is not particularly limited, for example 500 to 30,000, preferably 1,500～30,000, more preferably 2,000 to 10,000 is there. In the present ^{specification,} the number average molecular weight of ^{R F1} and ^{R F2 is} a value measured by 19 F-NMR.

In another ^embodiment, the number average molecular weight of ^{R F1} and ^{R F2} portion, 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, even more preferably 2, It can be 000 to 10,000, for example 3,000 to 9,000, for example 3,000 to 8,000.

In the above formula (1a), α is an integer of 1 to 9, and β is an integer of 1 to 9. These α and β can vary depending on the valence of ^{X A.} The sum of α and β is the same as the valence of ^{X A.} For example, when X ^A is a 10-valent organic group, the sum of α and β is 10, for example, α is 9 and β is 1, α is 5 and β is 5, or α is 1 and β is 9. obtain. When X ^A is a divalent organic group, α and β are 1.

In the above equation (1b), γ is an integer of 1-9. γ can vary depending on the valence of ^{X A.} That is, γ is a value obtained by subtracting 1 from the valence of ^{X A.}

In the above formula (1a) and (1b), ^{X A} is mainly to provide the binding ability of the fluoropolyether part for providing water repellency and surface sliding property, etc. and ^{(R F1} and ^{R F2)} and base section ( It is understood as a linker that connects R ^Si). The structure which is described as ^{X A} has left the ^{R F1} or ^{R F2,} the right side is attached respectively ^{R Si.} The X ^A are those compounds of formula (1a) and (1b) can exist stably.

X ^A is a 2-10 valent organic group having two or more amide bonds independently at each appearance. In the amide bond, the hydrogen atom bonded to the nitrogen atom may be substituted. In other words, an amide ^{bond, -NR N C (= O)} -, or -C (= O) NR ^N - is represented by, ^{R N} is, for example, a hydrogen atom, a phenyl group or a _{C 1-6} alkyl group ( It is preferably a methyl group), and is preferably a hydrogen atom.
The fluoropolyether group-containing silane compound of the present disclosure has such a structure, and thus has friction durability (for example, skin friction durability, woven fabric friction durability, eraser friction durability, steel wool friction durability) and resistance. Chemical properties (for example, durability against solvents, resistance to artificial sweat, durability against acids and alkalis), water repellency, oil repellency, stain resistance (for example, preventing the adhesion of stains such as fingerprints), waterproof properties (electronics) Prevents water from entering parts, etc.), waterproof (for example, prevents water from entering electronic parts, etc.), or surface slipperiness (or lubricity, for example, wiping off stains such as fingerprints, and against fingers It can contribute to the formation of a good cured layer (for example, a surface-treated layer) such as (excellent tactile sensation). It is considered that this is because having two or more amide bonds enhances the affinity between the fluoropolyether group-containing silane compound and the base material, and a tighter and stronger bond can be formed.

2-10 monovalent organic groups represented by ^{X A} is preferably a 2-8 monovalent organic group. In one embodiment, the 2-10 valent organic group is preferably a 2-4 valent organic group, more preferably a divalent organic group. In another embodiment, the 2-10 valent organic group is preferably a 3-8 valent organic group, more preferably a 3-6 valent organic group.

In one embodiment, ^{X A} is a 2-10 monovalent organic group, each independently in each occurrence formula (L1):
_{^{- (X N) s10 - (}} X 2) s12 - (L1)
It is represented by.

In formula (L1), X ^N represents an amide bond. Here, amide ^{bond, -NR N C (= O)} -, or -C (= O) NR ^N - represented by. ^RN is, for example, a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group), preferably a hydrogen atom.

In formula (L1), X ² is a divalent or higher valent organic group independently at each appearance. The valence of X ² can vary depending on the valence of the group represented by the above formula (L1). For example, when the group represented by the formula (L1) is divalent, all X ² are divalent organic groups, and when the group represented by the formula (L1) is trivalent, any one X 2 is used. ² is a trivalent organic group, and the other X ² is a divalent organic group.

In formula (L1), s10 is an integer of 2-4, preferably 2 or 3. In one embodiment, s10 is 2.

In the formula (L1), s12 is an integer of 1 to 7, may be an integer of 1 to 5, or may be an integer of 1 to 3.

However, in the formula (L1), the order of existence of each repeating unit with the subscript s10 or r12 and enclosed in parentheses is arbitrary in the formula.

In one embodiment, ^{X A} are each independently at each occurrence, formula (L2):
-(X ²¹ ) _s21 -[(X ^N )-(X ²² )] _s11- (X ^N )-(X ²¹ ) _s22-
(L2)
It is a group represented by.
During the ceremony:
X ^N represents an amide bond;
s11 is an integer from 1 to 3;
Each of X ²¹ is an independently 2-10 valent organic group;
X ²² is a divalent organic group independently at each appearance;
s21 is 0 or 1 independently of each other;
s22 is 0 or 1 independently of each other.

^{The part represented by − (X 21} ) _s21 −, − (X ²² ) −, and (X ²¹ ) _s22 − of the above equation (L2) is represented by − (X ² ) _s12 − of the equation (L1). Corresponds to the part. That is, the sum of s21, s11 and s22 is equivalent to ^s12, the structure of ^{X 21} and ^{X 22} corresponds to the structure of ^{X 2.} The value obtained by adding 1 to s11 in the formula (L2) is s10 in the formula (L1).

In formula (L2), X ²¹ is an independently 2 to 10 valent organic group.

In one embodiment, X ²¹ is a divalent organic group. In this aspect, X ²¹ may have the same meaning as the structure described as a divalent organic group in ^{X 22} , which will be described later.

In one embodiment, the X ²¹ is independent of each appearance.
-R ^211- or
− (R ²¹¹ ) _s31 −X ³¹ − (R ²¹² ) _s32 −
Is. In one embodiment, X ²¹ is −R ²¹¹⁻ . In one embodiment, X ²¹ is − (R ²¹¹ ) _s31 −X ³¹ − (R ²¹² ) _s32 −.

Each of the above R ²¹¹ and R ²¹² is independently a C _1-10 alkylene group, preferably a C _1-5 alkylene group, more preferably a C _1-3 alkylene group, for example, C _1-2. It is an alkylene group. The hydrogen atoms of these alkylene groups may be substituted.
When the hydrogen atom of the alkylene group is substituted, the substituent may be a C _1-6 alkyl group or a C _2-6 alkenyl group substituted with one or more halogen atoms. , C _2-6 alkynyl group, C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, 5-10 member heterocyclyl group, 5-10 member unsaturated heterocyclyl group, C _6-10 aryl group And one or more groups selected from 5-10 membered heteroaryl groups, such as halogen atoms, preferably fluorine atoms.

For ^{example, R 211} and ^{R 212} are each _{independently, -CH 2 -, - CH 2} CH 2 -, CH 2 CF 2 -, - CF 2 CH 2 -, or _-CF 2 CF ₂ - is a also Good.

In the present ^{embodiment, X 31} are each independently at each occurrence, -O-, or ^{-NR 54} - is. Here, R ⁵⁴ represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group), and is preferably a hydrogen atom.

In this embodiment, s31 is 0 or 1 independently at each appearance. In one embodiment, s31 is 0. In one embodiment, s31 is 1.

In this embodiment, s32 is 0 or 1 independently at each appearance. In one embodiment, s32 is 0. In one embodiment, s32 is 1.

In this embodiment, the sum of s31 and s32 is preferably 1 or more.

In this embodiment, for example, s31 is 1 and s32 is 1, and in one embodiment, s31 is 1 and s32 is 0. In one embodiment, s31 is 0 and s32 is 1.

［式中、Ｒ^２５、Ｒ^２６およびＲ^２７は、それぞれ独立して２〜６価の有機基である。］ In one embodiment, X ²¹ includes the following groups:

[In the formula, R ²⁵ , R ²⁶ and R ²⁷ are independently 2 to 6 valent organic groups, respectively. ]

In one embodiment, the ^{R 25} is a single _{bond, C 1-20} alkylene _{group, C 3-20} cycloalkylene _{groups, C 5-20} arylene ^{group, -R 57 -X 58 -R 59 -} , - X 58 - R ⁵⁹ − or − R ⁵⁷ −X ⁵⁸ −. The R ⁵⁷ and R ⁵⁹ described above are each independently a single bond, a C _1-20 alkylene group, a C _3-20 cycloalkylene group, or a C _5-20 arylene group. The X ⁵⁸ is −O−, −S−, −CO−, −O—CO− or −COO−.

In one embodiment, the R ²⁶ and R ²⁷ are each independently a hydrocarbon, or a group having at least one atom selected from N, O and S in the end or backbone of the hydrocarbon. _{preferably, C 1-6} alkylene ^{group, -R 36 -R 37 -R 36 -} , - R 36 -CHR 38 2 - and the like. Here, R ³⁶ is independently a single bond or an alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms. R ³⁷ is N, O or S, preferably N or O. R ³⁸ is −R ⁴⁵ −R ⁴⁶ −R ⁴⁵ −, ^{−R 46} −R ⁴⁵ − or −R ⁴⁵ −R ⁴⁶ −. Here, R ⁴⁵ is an alkyl group having 1 to 6 carbon atoms independently. R ⁴⁶ is N, O or S, preferably O.

In this embodiment ^{, each of X 21} can be an organic group having a valence of 3 to 10 independently.

In formula (L2), X ^N represents an amide bond. Here, amide ^{bond, -NR N C (= O)} -, or -C (= O) NR ^N - represented by. ^RN is, for example, a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group), preferably a hydrogen atom.

In formula (L2), X ²² is a divalent organic group independently at each appearance.

In one embodiment, the X ²² is, for example, the following equation:
-(R ⁵¹ ) _p5- (X ⁵¹ ) _q5-
[During the ceremony:
R ⁵¹ represents a single bond, − (CH ₂ ) _s5- or o-, m- or p-phenylene group, preferably − (CH ₂ ) _s5- .
s5 is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
X ⁵¹ represents − (X ⁵² ) _l5 −
X ⁵² is an independent -O-, -S-, o-, m- or p-phenylene group, -C (O) O-, -Si (R ⁵³ ) ₂ -,-( _{^{Si (R 53) 2 O)}} m5 -Si (R 53) 2 -, - NR 54 - and - _{(CH 2) n5} - represents a group selected from the group consisting of, ^{however, X 52} is an amide bond Is not included,
R ⁵³ independently represents a phenyl group, a C _1-6 alkyl group or a C _1-6 alkoxy group at each appearance, preferably a phenyl group or a C _1-6 alkyl group, more preferably a methyl group. And
R ⁵⁴ independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group) at each appearance.
m5 is an integer of 1 to 100, preferably an integer of 1 to 20, independently of each occurrence.
n5 is an integer of 1 to 20, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3, independently of each occurrence.
l5 is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3.
p5 is 0 or 1 and
q5 is 0 or 1 and
Here, at least one of p5 and q5 is 1, and the order of existence of each repeating unit in parentheses with p5 or q5 is arbitrary].
Examples thereof include a divalent organic group represented by. Here, X ²² (typically ^{the hydrogen atom of X 22} ) is substituted with one or more substituents selected from fluorine atoms, C _1-3 alkyl groups and C _{1-3 fluoroalkyl groups.} May be. In one embodiment, X ²² is not substituted by these groups.

In a preferred embodiment, the X ^22s are independent of each other.
-(R ⁵¹ ) _p5- (X ⁵¹ ) _q5- R ^52-
Is.
R ⁵² represents a single bond, − (CH ₂ ) _t5- or o-, m- or p-phenylene group, preferably − (CH ₂ ) _t5- . t5 is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. Here, R ⁵² (typically ^{the hydrogen atom of R 52} ) is substituted with one or more substituents selected from fluorine atoms, C _1-3 alkyl groups and C _{1-3 fluoroalkyl groups.} May be. In a preferred embodiment, R ⁵² is not substituted with these groups.

X ²² is preferably
-R ^221- or
_{^{- (R 221) s31 -X 31}} - (R 222) s32 -
Is.

R ²²¹ and R ²²² _{are independently C 1-10} alkylene groups, preferably C _1-7 alkylene groups, respectively, at each appearance. The hydrogen atoms of these alkylene groups may be substituted.
When the hydrogen atom of the alkylene group is substituted, the substituent may be a C _1-6 alkyl group or a C _2-6 alkenyl group substituted with one or more halogen atoms. , C _2-6 alkynyl group, C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, 5-10 member heterocyclyl group, 5-10 member unsaturated heterocyclyl group, C _6-10 aryl group And one or more groups selected from 5-10 membered heteroaryl groups, such as halogen atoms, preferably fluorine atoms. For example, all the hydrogen atoms of the alkylene group may be substituted, and preferably all the hydrogen atoms of the alkylene group may be substituted with fluorine atoms.

In one embodiment, the hydrogen atoms of the alkylene group in ^{R 221} and R ^{222 are at least partially substituted.}

In one embodiment, the hydrogen atom of the alkylene group in ^{R 221} and R ^{222 is unsubstituted.}

X ³¹ are each independently at each occurrence, -O-, or ^{-NR 54} - is. Here, R ⁵⁴ represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group), and is preferably a hydrogen atom.

s31 is 0 or 1 independently at each appearance. In one embodiment, s31 is 0. In one embodiment, s31 is 1.

s32 is 0 or 1 independently at each appearance. In one embodiment, s32 is 0. In one embodiment, s32 is 1.

Preferably, the sum of s31 and s32 is 1 or more.

In one embodiment, s31 is 1 and s32 is 1. In one embodiment, s31 is 1 and s32 is 0. In one embodiment, s31 is 0 and s32 is 1.

In one embodiment, X ²² is represented by ^{−R 221 −.}

In one embodiment, X ²² is represented by − (R ²²¹ ) _s31 −X ³¹ − (R ²²² ) _s32 −.

In formula (L2), s21 is 0 or 1 independently of each other. In one embodiment, s21 is 1. In one embodiment, s21 is 0.

In formula (L2), s22 is 0 or 1, respectively. In one embodiment, s22 is 1. In one embodiment, s22 is 0.

In one embodiment, s21 is 1 and s22 is 1.

In one embodiment, s21 is 1 and s22 is 0.

In one embodiment, s21 is 0 and s22 is 1.

In one embodiment, s21 is 0 and s22 is 0.

In one embodiment, s11 is an integer of 1-3, preferably 1 or 2. In one embodiment, s11 is 1. In one embodiment, s11 is 2.

In one embodiment, X ²² is ^{represented by −R 221} − and s11 is 2 or 3, preferably 2. That is, in the present embodiment, a plurality of ^{-R 221} - are present. In other words, in this ^embodiment, -X N ^{-X 22} - group represented by the presence of a plurality. In the present embodiment, -R 221 ^- is partly an alkylene group substituted with may be a hydrogen atom; may be an alkylene group part of which is the replacement of a hydrogen atom and an unsubstituted alkylene group, It may be only an unsubstituted alkylene group. For example, s11 is ^{2, -R 221} - if the present two are two ^{-R 221} - are both may be an alkylene group partially substituted for hydrogen atoms; one of A part of the hydrogen atom may be an substituted alkylene group and the other may be an unsubstituted alkylene group; both may be an unsubstituted alkylene group.

In one embodiment, X ^A is a divalent organic group, each independently in each occurrence,
-(X ²¹ ) _s21 -[(X ^N )-(X ²² )] _s11- (X ^N )-(X ²¹ ) _s22-
It is a group represented by.
During the ceremony:
X ^N represents an amide bond;
s11 is an integer from 1 to 3;
s21 is 0 or 1 independently of each other;
s22 is 0 or 1 independently of each other;
X ²¹ and X ²² are each independently divalent organic group at each appearance, and specifically can be the divalent organic group described above as ^{X 21} or X ^22.

In this embodiment, preferably, X ²¹ or X ²² is independent of each appearance.
-(R ⁵¹ ) _p5- (X ⁵¹ ) _q5- R ^52-
In the represented, more preferably -R ²²¹ -, or,
_{^{- (R 221) s31 -X 31}} - (R 222) s32 -
It is represented by. R ⁵¹ , X ⁵¹ , R ⁵² , p5, q5, R ²²¹ and R ²²² , X ³¹ , s31 and s32 have the same meanings as described above, respectively.

In one embodiment, for example
− (X ²¹ ) _s21 − is a single bond, and − (X ²¹ ) _s22 − is −R ²²¹ −, or − (X ²¹ ) _s21 − is − (R ²²¹ ) _s31 −X ³¹ −. ^{and, -} (X _{21) s22} ^- it is ^{-R 221} -
It may be.

When expressed by the formula (L2), X ^A is, for example,
^{-X N -X 22 -X N -X 21} -,
−X ²¹ −X ^N −X ²² −X ^N −X ²¹ −,
^{-X N -X 22 -X N -X 22} -X N -X 21 -,
−X ²¹ −X ^N −X ²² −X ^N −X ²² −X ^N −X ²¹ −,
-X ^N- X ^22- X ^N- X ^22- X ^N- X ^22- X ^N- X ^21- or-X ^21- X ^N- X ^22- X ^N- X ^22- X ^N- X ^22- X ^N -X ²¹ -
It can be a group represented by.

As a specific structure of X ^A, is not particularly limited, examples thereof include the following groups. In the following, n31 is an integer of 1 to 3 independently at each occurrence, and n32 is an integer of 1 to 10 (preferably an integer of 1 to 7).
-CONH-NHCO- (CH ₂ ) _n31- ,
_{-CONH- (CH 2) n32 -CONH- (} CH 2) n31 -,
_{-CONH- (CH 2) n32 -NHCO- (} CH 2) n31 -,
_{-CONH- (CH 2) n32 -O-} CONH- (CH 2) n31 -,
_{-CONH- (CH 2) n32 -NHCO-} O- (CH 2) n31 -,
_{-CONH- (CH 2) n32 -NH-} CONH- (CH 2) n31 -,
-(CH ₂ ) _n31 -CONH-NHCO- (CH ₂ ) _n31- ,
_{- (CH 2) n31 -CONH- (} CH 2) n32 -CONH- (CH 2) n31 -,
_{- (CH 2) n31 -CONH- (} CH 2) n32 -NHCO- (CH 2) n31 -,
_{- (CH 2) n31 -O-} CONH- (CH 2) n32 -CONH- (CH 2) n31 -,
_{- (CH 2) n31 -O-} CONH- (CH 2) n32 -NHCO- (CH 2) n31 -,
_{- (CH 2) n31 -O-} CONH- (CH 2) n32 -NHCONH- (CH 2) n31 -,
_{- (CH 2) n31 -NH-} CONH- (CH 2) n32 -CONH- (CH 2) n31 -,
_{- (CH 2) n31 -NH-} CONH- (CH 2) n32 -NHCO- (CH 2) n31 -,
_{- (CH 2) n31 -CONH- (} CH 2) n32 -O-CONH- (CH 2) n31 -,
_{- (CH 2) n31 -CONH- (} CH 2) n32 -NHCO-O- (CH 2) n31 -,
_{- (CH 2) n31 -CONH- (} CH 2) n32 -NH-CONH- (CH 2) n31 -,
_{-CONH- (CH 2) n32 -NHCO- (} CF 2) n32 -CONH- (CH 2) n31 -,
_{- (CH 2) n31 -CONH- (} CH 2) n32 -NHCO- (CF 2) n32 -CONH- (CH 2) n31 -
-CF ₂ CF ₂ -CONH-NHCO- (CH ₂ ) _n31- ,
_{-CF 2 CF 2 -CONH- (CH 2} ) n32 -CONH- (CH 2) n31 -,
_{-CF 2 CF 2 -CONH- (CH 2} ) n32 -NHCO- (CH 2) n31 -,
_{-CF 2 CF 2 -CONH- (CH 2} ) n32 -O-CONH- (CH 2) n31 -,
_{-CF 2 CF 2 -CONH- (CH 2} ) n32 -NHCO-O- (CH 2) n31 -,
_{-CF 2 CF 2 -CONH- (CH 2} ) n32 -NH-CONH- (CH 2) n31 -,
-CF ₂ CF _2- (CH ₂ ) _n31 -CONH-NHCO- (CH ₂ ) _n31- ,
_{-CF 2 CF 2 - (CH 2} ) n31 -CONH- (CH 2) n32 -CONH- (CH 2) n31 -,
_{-CF 2 CF 2 - (CH 2} ) n31 -CONH- (CH 2) n32 -NHCO- (CH 2) n31 -,
_{-CF 2 CF 2 - (CH 2} ) n31 -O-CONH- (CH 2) n32 -CONH- (CH 2) n31 -,
_{-CF 2 CF 2 - (CH 2} ) n31 -O-CONH- (CH 2) n32 -NHCO- (CH 2) n31 -,
_{-CF 2 CF 2 - (CH 2} ) n31 -NH-CONH- (CH 2) n32 -CONH- (CH 2) n31 -,
_{-CF 2 CF 2 - (CH 2} ) n31 -NH-CONH- (CH 2) n32 -NHCO- (CH 2) n31 -,
_{-CF 2 CF 2 - (CH 2} ) n31 -CONH- (CH 2) n32 -O-CONH- (CH 2) n31 -,
_{-CF 2 CF 2 - (CH 2} ) n31 -CONH- (CH 2) n32 -NHCO-O- (CH 2) n31 -,
_{-CF 2 CF 2 - (CH 2} ) n31 -CONH- (CH 2) n32 -NH-CONH- (CH 2) n31 -,
_{-CF 2 CF 2 -CONH- (CH 2} ) n31 -NHCO- (CF 2) n32 -CONH- (CH 2) n31 -,
_{-CF 2 CF 2 - (CH 2} ) n31 -CONH- (CH 2) n32 -NHCO- (CF 2) n32 -CONH- (CH 2) n31 -
-OCF ₂ CF ₂ -CONH-NHCO- (CH ₂ ) _n31- ,
_{-OCF 2 CF 2 -CONH- (CH 2} ) n32 -CONH- (CH 2) n31 -,
_{-OCF 2 CF 2 -CONH- (CH 2} ) n32 -NHCO- (CH 2) n31 -,
_{-OCF 2 CF 2 -CONH- (CH 2} ) n32 -O-CONH- (CH 2) n31 -,
_{-OCF 2 CF 2 -CONH- (CH 2} ) n32 -NHCO-O- (CH 2) n31 -,
_{-OCF 2 CF 2 -CONH- (CH 2} ) n32 -NH-CONH- (CH 2) n31 -,
-OCF ₂ CF _2- (CH ₂ ) _n31 -CONH-NHCO- (CH ₂ ) _n31- ,
_{-OCF 2 CF 2 - (CH 2} ) n31 -CONH- (CH 2) n32 -CONH- (CH 2) n31 -,
_{-OCF 2 CF 2 - (CH 2} ) n31 -CONH- (CH 2) n32 -NHCO- (CH 2) n31 -,
_{-OCF 2 CF 2 - (CH 2} ) n31 -O-CONH- (CH 2) n32 -CONH- (CH 2) n31 -,
_{-OCF 2 CF 2 - (CH 2} ) n31 -O-CONH- (CH 2) n32 -NHCO- (CH 2) n31 -,
_{-OCF 2 CF 2 - (CH 2} ) n31 -NH-CONH- (CH 2) n32 -CONH- (CH 2) n31 -,
_{-OCF 2 CF 2 - (CH 2} ) n31 -NH-CONH- (CH 2) n32 -NHCO- (CH 2) n31 -,
_{-OCF 2 CF 2 - (CH 2} ) n31 -CONH- (CH 2) n32 -O-CONH- (CH 2) n31 -,
_{-OCF 2 CF 2 - (CH 2} ) n31 -CONH- (CH 2) n32 -NHCO-O- (CH 2) n31 -,
_{-OCF 2 CF 2 - (CH 2} ) n31 -CONH- (CH 2) n32 -NH-CONH- (CH 2) n31 -,
_{-OCF 2 CF 2 -CONH- (CH 2} ) n31 -NHCO- (CF 2) n32 -CONH- (CH 2) n31 -,
_{-OCF 2 CF 2 - (CH 2} ) n31 -CONH- (CH 2) n32 -NHCO- (CF 2) n32 -CONH- (CH 2) n31 -

In one embodiment, alpha is 1, beta is 2-5, the ^{X A} is a trivalent to hexavalent organic group.

In one embodiment, gamma is 2-5, the ^{X A} is a trivalent to hexavalent organic group.

In one embodiment, α is 1, β is 2, and X ^A is a trivalent organic group.

In one embodiment, γ is 2 and X ^A is a trivalent organic group.

In one embodiment, α is 1, β is 1, and X ^A is a divalent organic group.

R ^Si is a monovalent group containing a Si atom to which a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group is bonded independently at each appearance.

Here, the "hydrolyzable group" means a group capable of undergoing a hydrolysis reaction, that is, a group capable of being eliminated from the main skeleton of the compound by the hydrolysis reaction. Examples of hydrolyzable _{^{groups, -OR h, -OCOR h, -O}} -N = CR h 2, -NR h 2, -NHR h, halogen (in these formulas, ^{R h} is a substituted or unsubstituted C _1-4 alkyl group is shown) and the like.

R ^Si is preferably a group represented by the formulas (S1), (S2), (S3) or (S4) independently at each appearance.

R ¹¹ is a hydroxyl group or a hydrolyzable group independently at each appearance.

R ¹¹ is preferably a hydrolyzable group, each independently at each appearance.

R ¹¹ is preferably independently of each appearance, -OR ^h , -OCOR ^h , -ON = CR ^h ₂ , -NR ^h ₂ , -NHR ^h , or halogen (in these formulas, R ^h). Indicates a substituted or unsubstituted C _1-4 alkyl group), more preferably −OR ^h (ie, an alkoxy group). ^Examples of R h include an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. In one embodiment, R ^h is a methyl group and in another embodiment, R ^h is an ethyl group.

R ¹² is a hydrogen atom or a monovalent organic group independently at each appearance. The monovalent organic group is a monovalent organic group excluding the hydrolyzable group.

In R ¹² , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and even more preferably a methyl group.

n1 is an integer of 0 to 3 independently for each unit ^{(SiR 11} _n1 R ¹² _3-n1).
However, when R ^Si is a group represented by the formula (S1) or (S2), the R ^Si portion at the end of the formula (1a) and the formula (1b) (hereinafter, simply the formula (1a) and the formula (1b)). There is at least one unit in which n1 is 1-3 (SiR ¹¹ _n1 R ¹² _3-n1). That is, not all n1s become 0 at the same time at such an end portion. In other words, at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded is present at the terminal portions of the formulas (1a) and (1b).

n1 is an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3 independently for each unit ^{(SiR 11} _n1 R ¹² _3-n1).

X ¹¹ is a single bond or divalent organic group independently at each appearance. Such divalent organic group is preferably _{^{-R 28 - (O) x -R}} 29 - is. In the formula, R ²⁸ and R ²⁹ are independently single-bonded or C _1-20 alkylene groups at each appearance, where x is 0 or 1. The C _1-20 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain. Such a C _1-20 alkylene group is preferably a C _1-10 alkylene group, more preferably a C _1-6 alkylene group, and even more preferably a C _1-3 alkylene group.

In one embodiment, X ¹¹ _{is -C 1-6} alkylene-OC _1-6 alkylene- or -O-C _1-6 alkylene-, independently of each appearance.

In a preferred embodiment, X ¹¹ is an independently single-bonded or straight-chain C _1-6 alkylene group at each appearance, preferably a single-bonded or straight-chain C _1-3 alkylene group, more preferably a single. It is a bonded or straight C _1-2 alkylene group, more preferably a straight C _1-2 alkylene group.

R ¹³ is a hydrogen atom or a monovalent organic group independently at each appearance. Such a monovalent organic group is preferably a C _1-20 alkyl group. Such a C _1-20 alkyl group may be a straight chain or a branched chain, but is preferably a straight chain.

In a preferred embodiment, R ¹³ is independently a hydrogen atom or a linear C _1-6 alkyl group at each appearance, preferably a hydrogen atom or a linear C _1-3 alkyl group, preferably a hydrogen atom. Or it is a methyl group.

t is an integer greater than or equal to 2 independently at each occurrence.

In a preferred embodiment, t is an integer of 2-10, preferably an integer of 2-6, independently of each occurrence.

R ¹⁴ is independently a hydrogen atom, a halogen atom or -X ^11- SiR ¹¹ _n1 R ¹² _3-n1 at each appearance. Such a halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, and more preferably a fluorine atom. In a preferred embodiment, R ¹⁴ is a hydrogen atom.

R ¹⁵ is a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group having 1 to 6 carbon atoms independently at each appearance.

In one embodiment, R ¹⁵ is independently at each occurrence, is an oxygen atom, an alkylene group having 1-6 alkylene group or a carbon number of 1 to 6 carbon atoms.

In a preferred ^{embodiment, R 15} is a single bond.

［式中、
Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｘ^１１、およびｎ１は、上記式（Ｓ１）の記載と同意義であり；
ｔ１およびｔ２は、各出現においてそれぞれ独立して、１以上の整数である。］ In one embodiment, the formula (S1) is the following formula (S1-a).

[During the ceremony,
R ¹¹ , R ¹² , R ¹³ , X ¹¹ , and n1 have the same meaning as the description in the above formula (S1);
t1 and t2 are integers of 1 or more independently at each occurrence. ]

［式中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｘ^１１、ｎ１およびｔは、上記式（Ｓ１）の記載と同意義である］ In a preferred embodiment, the formula (S1) is the following formula (S1-b).

[In the formula, R ¹¹ , R ¹² , R ¹³ , X ¹¹ , n1 and t have the same meaning as the description in the above formula (S1)].

R ^{a1 is −Z 1 −} SiR ²¹ _p1 R ²² _q1 R ²³ _r1 independently in each appearance.

Z ¹ is an oxygen atom or a divalent organic group independently at each appearance. In the structure described below as Z ¹ , the right side is coupled to ^{(SiR 21} _p1 R ²² _q1 R ²³ _r1).

In a preferred embodiment, Z ¹ is a divalent organic group.

In a preferred embodiment, Z ¹ does not include those that form a siloxane bond with the Si atom to which Z ^{1 is attached.} That is, in the formula (S3), (Si-Z ¹ -Si) does not contain a siloxane bond.

Z ¹ is preferably a C _1-6 alkylene group, − (CH ₂ ) _z1 −O− (CH ₂ ) _z2 − (in the formula, z1 is an integer of 0 to 6, for example, an integer of 1 to 6). Yes, z2 is an integer from 0 to 6, for example an integer from 1 to 6) _{or- (CH 2} ) z3-phenylene- (CH ₂ ) _z4- (in the formula, z3 is an integer from 0 to 6, For example, it is an integer of 1 to 6, and z4 is an integer of 0 to 6, for example, an integer of 1 to 6). The C _1-6 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain. These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _{2-6 alkynyl group.} However, it is preferably unsubstituted.

In a preferred embodiment, Z ¹ is a C _1-6 alkylene group or − (CH ₂ ) _{z3 −phenylene} − (CH ₂ ) _z4 −, preferably _{−phenylene − (CH 2} ) _z4 −. When Z ¹ is such a group, light resistance, especially UV resistance, can be higher.

In another preferred embodiment, the Z ¹ is a C _1-3 alkylene group. In one embodiment, Z ¹ can be −CH ₂ CH ₂ CH _2- . In another embodiment, Z ¹ can be −CH ₂ CH ₂₋ .

R ^{21 is −Z 1 ′} −SiR ^{21 ′} _{p1 ′} R ^{22 ′} _{q1 ′} R ^{23 ′} _{r1 ′} independently in each appearance.

The Z ^{1 'are} each independently at each occurrence, is an oxygen atom or a divalent organic group. In the following Z ^{1 'structure} described as the right side (SiR ^21' binds to _{^{p1 'R 22' q1 'R}} 23' r1 ').

In a preferred embodiment, Z 1 ^'is a divalent organic group.

In a preferred embodiment, Z 1 ^'is, Z ^1' do not include those that form a siloxane bond and Si atoms are bonded. That is, in the formula (S3), (Si-Z 1 '-Si) do not include siloxane bond.

The Z ^{1 'are} _{preferably, C 1-6} alkylene _{group, - (CH 2) z1'} -O- (CH 2) z2 '- ( wherein, z1' is an integer of 0 to 6, for example 1 It is an integer of 6, and z2'is an integer of 0 to 6, for example, an integer of 1 to 6) _{or-(CH 2 ) z3'-} phenylene- (CH ₂ ) _z4' -(in the formula, z3'. Is an integer of 0 to 6, for example, an integer of 1 to 6, and z4'is an integer of 0 to 6, for example, an integer of 1 to 6). The C _1-6 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain. These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _{2-6 alkynyl group.} However, it is preferably unsubstituted.

In a preferred embodiment, Z 1 'is, C 1-6 alkylene group or - (CH 2) z3' - phenylene - (CH 2) z4 '- , preferably - phenylene - (CH 2) z4' - a. When Z 1'is such a group, light resistance, especially UV resistance, can be higher.

In another preferred embodiment, the Z ^{1 _'is} a _{C 1-3} alkylene group. In one embodiment, Z ^{1 _'is,} -CH 2 _CH 2 CH ₂ - may be. In another embodiment, Z ^{1 'is,} _{-CH 2} CH 2 - may be.

The ^{R 21 'are} each independently at each ^occurrence, is _{^{-Z 1 "-SiR 22" q1 "}} R 23" r1 ".

The above Z ^{1 "} is an oxygen atom or a divalent organic group independently at each appearance. In ^{the structure described below as Z 1"} , the right side is (SiR ^{22 "} _q1" R ^{23 "} _r1". ).

In a preferred embodiment, Z ^{1 "} is a divalent organic group.

In a preferred embodiment, Z ^{1 "} does not include those forming a siloxane bond with the Si atom to which Z ^{1" is attached.} That is, in the formula (S3), (Si-Z ^{1 "} -Si) does not contain a siloxane bond.

The above Z ^{1 "} is preferably a C _1-6 alkylene group,-(CH ₂ ) _z1" -O- (CH ₂ ) _{z2 "} -(in the formula, z1" is an integer of 0 to 6, for example, 1 to 1. It is an integer of 6, and z2 "is an integer of 0 to 6, for example, an integer of 1 to 6) _{or-(CH 2 ) z3" -phenylene-} (CH ₂ ) _{z4 "} -(in the formula, z3". Is an integer from 0 to 6, for example an integer from 1 to 6, and z4 "is an integer from 0 to 6, for example, an integer from 1 to 6). Such a C _1-6 alkylene group is a straight chain. It may be a branched chain or a branched chain, but it is preferably a straight chain. These groups are, for example, a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2- It may be substituted with one or more substituents selected from the _{6 alkynyl groups, but is preferably unsubstituted.}

In a preferred embodiment, Z ^{1 "} is a C _1-6 alkylene group _{or- (CH 2} ) z 3" -phenylene- (CH ₂ ) _{z 4 "} -, preferably _{-phenylene- (CH 2} ) _{z 4"} -. When the ^{group is Z 1 ”} , light resistance, especially UV resistance, can be higher.

In another preferred embodiment, the Z ^{1 "} is a C _1-3 alkylene group. In one embodiment, the Z ^1" can be -CH ₂ CH ₂ CH _2- . In another embodiment, Z ^{1 "} can be -CH ₂ CH _2- .

The R ^{22 "} is an hydroxyl group or a hydrolyzable group independently at each appearance.

The R ^{22 "} is preferably an independently hydrolyzable group at each appearance.

The above R ^{22 ”} is preferably independently of each appearance, −OR ^h , −OCOR ^h , −ON = CR ^h ₂ , −NR ^h ₂ , −NHR ^h , or halogen (in these equations, R ^h indicates a substituted or unsubstituted C _1-4 alkyl group), more preferably −OR ^h (that is, an alkoxy group). R ^h includes a methyl group, an ethyl group, a propyl group, and the like. Unsubstituted alkyl groups such as isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group are mentioned. Among them, alkyl groups, particularly unsubstituted alkyl groups are preferable, and methyl group or ethyl group is preferable. More preferred. In one embodiment, R ^h is a methyl group and in another embodiment, R ^h is an ethyl group.

The R ^{23 ″} is a hydrogen atom or a monovalent organic group independently at each appearance. The monovalent organic group is a monovalent organic group excluding the hydrolyzable group.

In the above R ^{23 "} , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and even more preferably a methyl group.

The q1 "is an integer of 0 to 3 independently at each appearance, and the r1" is an integer of 0 to 3 independently at each appearance. The total of q1 "and r1" is 3 in the unit of ^{(SiR 22 "} _q1" R ^{23 "} _r1").

The above q1 ”is an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3 independently for each unit ^{(SiR 22”} _{q1 ”} R ^23” _{r1 ”).}

The R ^{22 'are} each independently at each occurrence, it is a hydroxyl group or a hydrolyzable group.

R ^22'is preferably a hydrolyzable group, independently of each appearance.

R ^{22 'are} preferably each independently at each _{^{occurrence, -OR h, -OCOR h, -O}} -N = CR h 2, -NR h 2, -NHR h or halogen (in these formulas,, R ^h is a substituted or unsubstituted C _1-4 alkyl group), more preferably −OR ^h (ie, an alkoxy group). ^Examples of R h include an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. In one embodiment, R ^h is a methyl group and in another embodiment, R ^h is an ethyl group.

The R ^23'is a hydrogen atom or a monovalent organic group independently at each appearance. The monovalent organic group is a monovalent organic group excluding the hydrolyzable group.

In R ^23' , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and even more preferably a methyl group.

The above p1'is an integer of 0 to 3 independently in each appearance, q1'is an integer of 0 to 3 independently in each appearance, and r1'is an independent integer in each appearance. Then, it is an integer of 0 to 3. Incidentally, p1 ', q1' and r1 'sum of, (SiR ^21' at _{^{p1 'R 22' q1 'R}} 23' r1 ') units, is 3.

In one embodiment, p1'is 0.

In one embodiment, p1 _{^{'is, (SiR 21' p1 'R}} 22' q1 'R 23' r1 ') independently for each unit, the integer of 1 to 3, 2-3 integer or 3, met You may. In a preferred embodiment, p1'is 3.

In one embodiment, q1 _{^{'is, (SiR 21' p1 'R}} 22' q1 'R 23' r1 ') independently for each unit, an integer of 1 to 3, preferably 2-3 integer, More preferably, it is 3.

In one embodiment, p1 'is 0, q1' _{^{is, (SiR 21 'p1' R}} 22 'q1' R 23 'r1') independently for each unit, a is an integer from 1 to 3, preferably Is an integer of 2-3, more preferably 3.

The R ²² is a hydroxyl group or a hydrolyzable group independently at each appearance.

R ²² is preferably an independently hydrolyzable group at each appearance.

R ²² is preferably independently of each appearance, -OR ^h , -OCOR ^h , -ON = CR ^h ₂ , -NR ^h ₂ , -NHR ^h , or halogen (in these formulas, R ^h). Indicates a substituted or unsubstituted C _1-4 alkyl group), more preferably −OR ^h (ie, an alkoxy group). ^Examples of R h include an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. In one embodiment, R ^h is a methyl group and in another embodiment, R ^h is an ethyl group.

The R ²³ is a hydrogen atom or a monovalent organic group independently at each appearance. The monovalent organic group is a monovalent organic group excluding the hydrolyzable group.

In R ²³ , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and even more preferably a methyl group.

The above p1 is an integer of 0 to 3 independently in each appearance, q1 is an integer of 0 to 3 independently in each appearance, and r1 is an integer of 0 to 3 independently in each appearance. It is an integer from 0 to 3. The total of p1, q1 and r1 is 3 in the unit of ^{(SiR 21} _p1 R ²² _q1 R ²³ _r1).

In one embodiment, p1 is 0.

In one embodiment, p1 may be an integer of 1-3, an integer of 2-3, or 3 independently for each unit ^{(SiR 21} _p1 R ²² _q1 R ²³ _r1). In a preferred embodiment, p1 is 3.

In one embodiment, q1 is an integer of 1-3, preferably an integer of 2-3, more preferably 3 independently for each unit ^{(SiR 21} _p1 R ²² _q1 R ²³ _r1).

In one embodiment, p1 is 0 and q1 is an integer of 1-3, preferably an integer of 2-3, independently for each unit ^{(SiR 21} _p1 R ²² _q1 R ²³ _r1). It is preferably 3.

In the above formula, R ^b1 is a hydroxyl group or a hydrolyzable group independently at each appearance.

The R ^b1 is preferably a hydrolyzable group independently at each appearance.

The R ^{b1 is preferably -OR h} , -OCOR ^h , -ON = CR ^h ₂ , -NR ^h ₂ , -NHR ^h , or halogen (in these formulas, R) independently at each appearance. ^h is a substituted or unsubstituted C _1-4 alkyl group), more preferably −OR ^h (ie, an alkoxy group). ^Examples of R h include an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. In one embodiment, R ^h is a methyl group and in another embodiment, R ^h is an ethyl group.

In the above formula, R ^c1 is a hydrogen atom or a monovalent organic group independently at each appearance. The monovalent organic group is a monovalent organic group excluding the hydrolyzable group.

In R ^c1 , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and even more preferably a methyl group.

The above k1 is an integer of 0 to 3 independently in each appearance, l1 is an integer of 0 to 3 independently in each appearance, and m1 is an independent integer in each appearance. It is an integer from 0 to 3. The total of k1, l1 and m1 is 3 in the unit of ^{(SiR a1} _k1 R ^b1 _l1 R ^c1 _m1).

In one embodiment, k1 is an integer of 1-3, preferably 2 or 3, more preferably 3, independently of each unit ^{(SiR a1} _k1 R ^b1 _l1 R ^c1 _m1). In a preferred embodiment, k1 is 3.

In the above formulas (1a) and (1b), when R ^Si is a group represented by the formula (S3), a hydroxyl group or a hydrolyzable group is preferably at the terminal portion of the formulas (1a) and (1b). There are at least two Si atoms bonded to.

In a preferred embodiment, the group represented by the formula (S3) is −Z ¹ −SiR ²² _q1 R ²³ _r1 (where q1 is an integer 1-3, preferably 2 or 3, more preferably 3). (R1 is an integer of 0 to 2), −Z ^{1 ′ −SiR 22 ′} _{q1 ′} ^{R 23 ′} _{r1 ′} (in the equation, q1 ′ is an integer of 1 to 3, preferably 2 Or 3, more preferably 3, r1'is an integer of 0 to 2), or -Z ^{1 "} -SiR ^22" _{q1 "} R ^23" _{r1 "} (in the formula, q1" is 1 to It is an integer of 3, preferably 2 or 3, more preferably 3, and r1 ”is an integer of 0 to 2).) Here, the sum of q1 and r1. be q1 'and r1' sum -Z ¹ with _{^{'-SiR 22' q1 'R 23}} ' r1 '3 for each unit; is ^-Z 1 ^-SiR ₂₂ q1 ^R _{23 r1} each unit to be 3 q1 The sum of "and r1" is -Z ^{1 "} -SiR ^22" _{q1 "} R ^23" _{r1 "for} each unit.

In a preferred embodiment, in Formula (S3), ^'if there is at least one, preferably all of ^{R 21' R 21} in, q1 "is an integer of 1 to 3, preferably 2 or 3, more It is preferably 3.

In a preferred embodiment, ^{where R 21} is present in formula (S3), p1'is 0 and q1'is an integer of 1-3, preferably in at least one, preferably all R ^21,. Is 2 or 3, more preferably 3.

In a preferred embodiment, in formula (S3), when ^Ra1 is present, in at least one, preferably all ^Ra1 , p1 is 0 and q1 is an integer of 1-3, preferably 2. Or 3, more preferably 3.

In a preferred embodiment, in formula (S3), k1 is 2 or 3, preferably 3, p1 is 0, and q1 is 2 or 3, preferably 3.

R ^{d1 is -Z 2-} CR ³¹ _p2 R ³² _q2 R ³³ _r2 independently at each appearance.

Z ² is an independent, single bond, oxygen atom or divalent organic group at each appearance. In the structure described below as Z ² , the right side is coupled to ^{(CR 31} _p2 R ³² _q2 R ³³ _r2).

In a preferred embodiment, Z ² is a divalent organic group.

Z ² is preferably a C _1-6 alkylene group, − (CH ₂ ) _z5 −O− (CH ₂ ) _z6- (in the formula, z5 is an integer of 0 to 6, for example, an integer of 1 to 6). _Yes , z6 is an integer from 0 to 6, for example an integer from 1 to 6) _{or-(CH 2} ) z7-phenylene- (CH ₂ ) _z8- (in the formula, z7 is an integer from 0 to 6, For example, it is an integer of 1 to 6, and z8 is an integer of 0 to 6, for example, an integer of 1 to 6). The C _1-6 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain. These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _{2-6 alkynyl group.} However, it is preferably unsubstituted.

In a preferred embodiment, Z ² is a C _1-6 alkylene group or − (CH ₂ ) _{z7 −phenylene} − (CH ₂ ) _z8 −, preferably _{−phenylene − (CH 2} ) _z8 −. When Z ² is such a group, light resistance, especially UV resistance, can be higher.

In another preferred embodiment, the Z ² is a C _1-3 alkylene group. In one embodiment, Z ² can be −CH ₂ CH ₂ CH ₂ −. In another embodiment, Z ² can be −CH ₂ CH ₂₋ .

R ^{31 is −Z 2 ′} −CR ^{32 ′} _{q2 ′} R ^{33 ′} _{r2 ′} independently in each appearance.

Z 2 ^'are each independently at each occurrence, a single bond, an oxygen atom or a divalent organic group. In the following Z ^{2 'structure} described as the right side ^{(CR 32'} binds to _{^{q2 'R 33' r2 ')}} .

Said Z ^{2 'are} _{preferably, C 1-6} alkylene _{group, - (CH 2) z5'} -O- (CH 2) z6 '- ( wherein, z5' is an integer of 0 to 6, for example 1 It is an integer of 6, and z6'is an integer of 0 to 6, for example, an integer of 1 to 6) _{or-(CH 2 ) z7'-} phenylene- (CH ₂ ) _z8' -(in the formula, z7'. Is an integer of 0 to 6, for example, an integer of 1 to 6, and z8'is an integer of 0 to 6, for example, an integer of 1 to 6). The C _1-6 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain. These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _{2-6 alkynyl group.} However, it is preferably unsubstituted.

In a preferred embodiment, Z 2 'is, C 1-6 alkylene group or - (CH 2) z7' - phenylene - (CH 2) z8 '- , preferably - phenylene - (CH 2) z8' - a. When Z 2'is such a group, light resistance, especially UV resistance, can be higher.

In another preferred embodiment, the Z ^{2 _'is} a _{C 1-3} alkylene group. In one embodiment, Z ^{2 _'is,} -CH 2 _CH 2 CH ₂ - may be. In another embodiment, Z ^{2 'is,} _{-CH 2} CH 2 - may be.

The ^{R 32 'are} each independently at each ^occurrence, is _{^{-Z 3 -SiR 34 n2 R 35 3}} -n2.

Z ³ is a single bond, an oxygen atom or a divalent organic group independently at each appearance. In the structure described below as Z ³ , the right side is coupled to ^{(SiR 34} _n2 R ³⁵ _3-n2).

In one embodiment, Z ³ is an oxygen atom.

In one embodiment, Z ³ is a divalent organic group.

The above Z ³ is preferably a C _1-6 alkylene group, − (CH ₂ ) _{z5 ″} −O− (CH ₂ ) _{z6 ″} − (in the formula, z5 ”is an integer of 0 to 6, for example, 1 to 6. an integer, z6 "is an integer of 0 to 6, such as an integer from 1 to 6) _{or, - (CH 2) z7"} - phenylene _{- (CH 2) z8 "-} ( wherein, z7" is , 0-6 integers, for example 1-6 integers, and z8 "is 0-6 integers, eg 1-6 integers). The C _1-6 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain. These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _{2-6 alkynyl group.} However, it is preferably unsubstituted.

In preferred embodiments, ^{Z 3} _{is, C 1-6} alkylene group or - _{(CH 2) z7 "-} phenylene _{- (CH 2) z8" -} , preferably - phenylene - _{(CH 2) z8 "-} a .Z ³ The light resistance, especially the UV resistance, can be higher if the group is such a group.

In another preferred embodiment, the Z ³ is a C _1-3 alkylene group. In one embodiment, Z ³ can be −CH ₂ CH ₂ CH _2- . In another embodiment, Z ³ can be −CH ₂ CH ₂₋ .

The R ³⁴ is a hydroxyl group or a hydrolyzable group independently at each appearance.

R ³⁴ is preferably a hydrolyzable group, each independently at each appearance.

R ³⁴ is preferably independently of each appearance, -OR ^h , -OCOR ^h , -ON = CR ^h ₂ , -NR ^h ₂ , -NHR ^h , or halogen (in these formulas, R ^h). Indicates a substituted or unsubstituted C _1-4 alkyl group), more preferably −OR ^h (ie, an alkoxy group). ^Examples of R h include an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. In one embodiment, R ^h is a methyl group and in another embodiment, R ^h is an ethyl group.

The R ³⁵ is a hydrogen atom or a monovalent organic group independently at each appearance. The monovalent organic group is a monovalent organic group excluding the hydrolyzable group.

In ^R35 , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and even more preferably a methyl group.

In the above formula, n2 is an integer of 0 to 3 independently for each unit ^{(SiR 34} _n2 R ³⁵ _3-n2). However, when R ^Si is a group represented by the formula (S4), n2 is 1 to 3 (SiR ³⁴ _n2 R ³⁵ _3-n2 ) in the terminal portions of the formulas (1a) and (1b). There is at least one. That is, not all n2s become 0 at the same time at such an end portion. In other words, at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded is present at the terminal portions of the formulas (1a) and (1b).

n2 is an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3 independently for each unit ^{(SiR 34} _n2 R ³⁵ _3-n2).

The R ^33'is a hydrogen atom, a hydroxyl group or a monovalent organic group independently at each appearance. The monovalent organic group is a monovalent organic group excluding the hydrolyzable group.

In the above R ^33' , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and even more preferably a methyl group.

In one embodiment, R ^33'is a hydroxyl group.

In another embodiment, ^{R 33 'represents} a monovalent organic group, preferably a _{C 1-20} alkyl group, more preferably a _{C 1-6} alkyl group.

The q2'is an integer of 0 to 3 independently at each appearance, and the r2'is an integer of 0 to 3 independently at each appearance. Incidentally, the sum of q2 'and r2' are the _{^{(CR 32 'q2' R 33}} 'r2') units, it is 3.

q2 _{^{'is, (CR 32' q2 'R}} 33' r2 ') independently for each unit, and preferably is an integer of 1 to 3, more preferably 2 to 3, more preferably 3.

R ^{32 is -Z 3-} SiR ³⁴ _n2 R ³⁵ _3-n2 independently at each appearance. Such −Z ^3- SiR ³⁴ _n2 R ³⁵ _3-n2 has the same meaning as the description in ^{R 32 ′ above.}

The R ³³ is a hydrogen atom, a hydroxyl group or a monovalent organic group independently at each appearance. The monovalent organic group is a monovalent organic group excluding the hydrolyzable group.

In R ³³ , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and even more preferably a methyl group.

In one embodiment, R ³³ is a hydroxyl group.

In another embodiment, the monovalent organic group of ^{R 33} _{is preferably a C 1-20} alkyl group, more preferably a C _1-6 alkyl group.

The above p2 is an integer of 0 to 3 independently in each appearance, q2 is an integer of 0 to 3 independently in each appearance, and r2 is an integer of 0 to 3 independently in each appearance. It is an integer from 0 to 3. The total of p2, q2 and r2 is 3 in the unit of ^{(CR 31} _p2 R ³² _q2 R ³³ _r2).

In one embodiment, p2 is 0.

In one embodiment, p2 may be an integer of 1-3, an integer of 2-3, or 3 independently for each unit ^{(CR 31} _p2 R ³² _q2 R ³³ _r2). In a preferred embodiment, p2'is 3.

In one embodiment, q2 is an integer of 1-3, preferably an integer of 2-3, more preferably 3 independently for each unit ^{(CR 31} _p2 R ³² _q2 R ³³ _r2).

In one embodiment, p2 is 0 and q2 is an integer of 1-3, preferably an integer of 2-3, independently for each unit ^{(CR 31} _p2 R ³² _q2 R ³³ _r2). It is preferably 3.

The ^{Re1 is -Z 3-} SiR ³⁴ _n2 R ³⁵ _3-n2 independently at each appearance. Such −Z ^3- SiR ³⁴ _n2 R ³⁵ _3-n2 has the same meaning as the description in ^{R 32 ′ above.}

The R ^f1 is a hydrogen atom, a hydroxyl group or a monovalent organic group independently at each appearance. The monovalent organic group is a monovalent organic group excluding the hydrolyzable group.

In the above R ^f1 , the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, and even more preferably a methyl group.

In one embodiment, R ^f1 is a hydroxyl group.

In another embodiment, the monovalent organic group of ^{R f1} _{is preferably a C 1-20} alkyl group, more preferably a C _1-6 alkyl group.

The above k2 is an integer of 0 to 3 independently in each appearance, l2 is an integer of 0 to 3 independently in each appearance, and m2 is an independent integer in each appearance. It is an integer from 0 to 3. The total of k2, l2 and m2 is 3 in the unit of ^{(CR d1} _k2 ^Re1 _l2 R ^f1 _m2).

In one embodiment, when R ^Si is the group represented by the formula (S4), n2 is 1-3, preferably 2 or 3, more preferably 3 (SiR ³⁴ _n2 R ³⁵ _3-n2 ) units. In each terminal portion of the formula (1a) and the formula (1b), two or more, for example, 2 to 27, preferably 2 to 9, more preferably 2 to 6, still more preferably 2 to 3. Especially preferably, there are three.

^{In a preferred embodiment, where R 32'is} present in formula (S4), in at least one, preferably all R ^32' , n2 is an integer of 1-3, preferably 2 or 3, more preferably. Is 3.

^{In a preferred embodiment, where R 32} is present in formula (S4), in at least one, preferably all R ³² , n2 is an integer of 1-3, preferably 2 or 3, more preferably 3. Is.

In a preferred embodiment, in formula (S4), when ^Re1 is present, in at least one, preferably all ^Ra1 , n2 is an integer of 1-3, preferably 2 or 3, more preferably 3. Is.

In a preferred embodiment, in formula (S4), k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.

In one embodiment, R ^Si is a group represented by the formula (S2), (S3) or (S4). These compounds can form a surface treatment layer having high surface slipperiness.

In one embodiment, R ^Si is a group represented by the formula (S1), (S3) or (S4). Since these compounds have a plurality of hydrolyzable groups at one end, they can strongly adhere to the substrate and form a surface treatment layer having high friction durability.

In one embodiment, R ^Si is a group represented by the formula (S3) or (S4). Since these compounds may have a plurality of hydrolyzable groups branched from one Si atom or C atom at one end, a surface treatment layer having higher friction durability can be formed.

In one embodiment, R ^Si is a group represented by the formula (S1).

In one embodiment, R ^Si is a group represented by the formula (S2).

In one embodiment, R ^Si is a group represented by the formula (S3).

In one embodiment, R ^Si is a group represented by the formula (S4).

(Composition)
Hereinafter, the composition of the present disclosure (for example, a surface treatment agent) will be described.

The compositions of the present disclosure (eg, surface treatment agents) contain at least one fluoropolyether group-containing silane compound represented by formula (1a) or formula (1b).

In one embodiment, the compositions of the present disclosure (eg, surface treatment agents) may comprise fluoropolyether group-containing silane compounds represented by formulas (1a) and (1b).

In one embodiment, it is represented by the formula (1a) with respect to the fluoropolyether group-containing silane compound represented by the formulas (1a) and (1b) contained in the composition of the present disclosure (for example, a surface treatment agent). The lower limit of the ratio (molar ratio) of the fluoropolyether group-containing silane compound is preferably 0.001, more preferably 0.002, still more preferably 0.005, still more preferably 0.01, and particularly preferably. It can be 0.02, especially 0.05. The upper limit of the ratio (molar ratio) of the fluoropolyether group-containing silane compound represented by the formula (1b) to the fluoropolyether group-containing silane compound represented by the formulas (1a) and (1b) is preferably. It can be 0.35, more preferably 0.30, even more preferably 0.20, even more preferably 0.15 or 0.10. The ratio (molar ratio) of the fluoropolyether group-containing silane compound represented by the formula (1b) to the fluoropolyether group-containing silane compound represented by the formulas (1a) and (1b) is preferably 0.001. 0.30 or less, more preferably 0.001 or more and 0.20 or less, still more preferably 0.002 or more and 0.20 or less, still more preferably 0.005 or more and 0.20 or less, particularly preferably 0.01 or more. It is 0.20 or less, for example, 0.02 or more and 0.20 or less (specifically, 0.15 or less) or 0.05 or more and 0.20 or less (specifically, 0.15 or less). By including in the above range, the composition of the present disclosure can contribute to the formation of a cured layer having good friction durability.

The composition of the present disclosure (for example, a surface treatment agent) can impart water repellency, oil repellency, stain resistance, surface slipperiness, and friction durability to a substrate, and is not particularly limited. However, it can be suitably used as an antifouling coating agent or a waterproof coating agent.

The compositions of the present disclosure (eg, surface treatment agents) are solvent, fluoropolyether compounds that can be understood as fluorine-containing oils, preferably perfluoro (poly) ether compounds (hereinafter collectively referred to as "containing". It may further contain a (referred to as "fluorinated oil"), a (non-reactive) silicone compound (hereinafter referred to as "silicone oil") that can be understood as a silicone oil, a catalyst, a surfactant, a polymerization inhibitor, a sensitizer, and the like. ..

Examples of the solvent include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane and mineral spirit; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene and solvent naphtha. Methyl acetate, ethyl acetate, propyl acetate, -n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate , Ethylacetacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate and other esters; acetone, methyl ethyl ketone, Ketones such as methylisobutylketone, 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; ethylcellsolve, methylcellosolve, methylcellosolve acetate, ethylcellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Glycol ethers such as monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, ethylene glycol monoalkyl ether; methanol, ethanol, iso-propanol, n-butanol, Alcohols such as isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, tert-amyl alcohol; glycols such as ethylene glycol and propylene glycol; tetrahydrofuran, tetrahydro Cyclic ethers such as pyran and dioxane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve and diethylene glycol monomethyl ether; diethylene glycol monoethyl ether Acetate; 1,1,2-trichloro-1,2,2-trifluoroethan, 1,2-dichloro-1,1,2,2-tetrafluo Examples thereof include fluorine-containing solvents such as loetane, dimethyl sulfoxide, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), Zeolola H, HFE7100, HFE7200, and HFE7300. Alternatively, a mixed solvent of two or more of these may be mentioned.

The fluorine-containing oil is not particularly limited, and examples thereof include a compound represented by the following general formula (3) (perfluoro (poly) ether compound).
Rf ^5- (OC ₄ F ₈ ) _a' -(OC ₃ F ₆ ) _b' -(OC ₂ F ₄ ) _c' -(OCF ₂ ) _d'- ^{Rf 6} ... (3)
In the formula, Rf ⁵ represents an alkyl group having 1 to 16 carbon atoms (preferably a perfluoroalkyl group of _{C 1-16} ^{) which may be substituted with one or more fluorine atoms, and Rf 6} is Represents a 1-16 alkyl group of carbon atoms (preferably a C _1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom which ^{may be substituted with one or more fluorine atoms, where Rf 5} and Rf ⁶ are. , More preferably, each independently is a C _1-3 perfluoroalkyl group.
a', b', c'and d'represent the number of four types of repeating units of perfluoro (poly) ether constituting the main skeleton of the polymer, and are integers of 0 or more and 300 or less independently of each other. , A', b', c'and d'are at least 1, preferably 1 to 300, more preferably 20 to 300. The order of existence of each repeating unit in parentheses with the subscripts a', b', c'or d'is arbitrary in the equation. Of these repeating units,-(OC ₄ F ₈ )-is-(OCF ₂ CF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ CF ₂ )-,-(OCF ₂ CF (CF) ₃ ) CF ₂ )-,-(OCF ₂ CF ₂ CF (CF ₃ ))-,-(OC (CF ₃ ) ₂ CF ₂ )-,-(OCF ₂ C (CF ₃ ) ₂ )-,-(OCF) (CF ₃ ) CF (CF ₃ ))-,-(OCF (C ₂ F ₅ ) CF ₂ )-and (OCF ₂ CF (C ₂ F ₅ ))-may be any of-, but preferably- (OCF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₃ F ₆ )-may be any of-(OCF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ )-and (OCF ₂ CF (CF ₃ ))-. , Preferably − (OCF ₂ CF ₂ CF ₂ ) −. − (OC ₂ F ₄ ) − may be any of − (OCF ₂ CF ₂ ) − and (OCF (CF ₃ )) −, but − (OCF ₂ CF ₂ ) − is preferable.

As an example of the perfluoro (poly) ether compound represented by the general formula (3), the compound represented by any of the following general formulas (3a) and (3b) (one or a mixture of two or more). It may be).
Rf ^5- (OCF ₂ CF ₂ CF ₂ ) _{b "} -Rf ⁶ ... (3a)
Rf ^5- (OCF ₂ CF ₂ CF ₂ CF ₂ ) _{a "} -(OCF ₂ CF ₂ CF ₂ ) _b" -(OCF ₂ CF ₂ ) _{c "} -(OCF ₂ ) _d" -Rf ⁶ ... (3b) )
In these equations, Rf ⁵ and Rf ⁶ are as described above; in equation (3a), b "is an integer between 1 and 100; in equation (3b), a" and b "are independent of each other. Is an integer of 0 or more and 30 or less, and c "and d" are independently integers of 1 or more and 300 or less. The subscripts a ", b", c ", and d" are added and enclosed in parentheses. The order of existence of each repeating unit is arbitrary in the equation.

From another point of view, the fluorine-containing oil may be a compound represented by ^{the general formula Rf 3-} F (in the formula, Rf ³ is a C _{5-16 perfluoroalkyl group).} Further, it may be a chlorotrifluoroethylene oligomer.

The fluorine-containing oil may have an average molecular weight of 500 to 10,000. The molecular weight of the fluorinated oil can be measured using GPC.

The fluorine-containing oil may be contained, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass with respect to the composition (for example, a surface treatment agent) of the present disclosure. In one embodiment, the compositions of the present disclosure are substantially free of fluorinated oils. Substantially free of fluorinated oil means that it may contain no fluorinated oil or may contain a very small amount of fluorinated oil.

The fluorinated oil contributes to improving the surface slipperiness of the layer formed by the composition of the present disclosure (for example, a surface treatment agent).

As the silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used. The linear silicone oil may be a so-called straight silicone oil or a modified silicone oil. Examples of the straight silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil. Examples of the modified silicone oil include those obtained by modifying straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like. Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.

In the composition of the present disclosure (for example, a surface treatment agent), such silicone oil is a total of 100 parts by mass of the above-mentioned fluoropolyether group-containing silane compound of the present disclosure (in the case of two or more kinds, the total of these, and so on. ), For example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass.

Silicone oils contribute to improving the surface slipperiness of the layers formed by the compositions of the present disclosure (eg, surface treatment agents).

Examples of the catalyst include acids (for example, acetic acid, trifluoroacetic acid, etc.), bases (for example, ammonia, triethylamine, diethylamine, etc.), transition metals (for example, Ti, Ni, Sn, etc.) and the like.

The catalyst promotes hydrolysis and dehydration condensation of the fluoropolyether group-containing silane compounds of the present disclosure and promotes the formation of layers formed by the compositions of the present disclosure (eg, surface treatment agents).

In addition to the above, examples of other components include tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, and the like.

The composition of the present disclosure can be used as a surface treatment agent for surface treatment of a base material.

The surface treatment agent of the present disclosure can be made into pellets by impregnating a porous material such as a porous ceramic material, a metal fiber, for example, steel wool into a cotton-like material. The pellet can be used, for example, for vacuum deposition.

(Article)
Hereinafter, the articles disclosed in the present disclosure will be described.

The article of the present disclosure is a surface treatment agent containing a base material and a fluoropolyether group-containing silane compound or a fluoropolyether group-containing silane compound of the present disclosure on the surface of the base material (hereinafter, simply "the present disclosure" on behalf of these. Includes a layer (surface treatment layer) formed from (referred to as "surface treatment agent").

The substrates that can be used in the present disclosure include, for example, glass, resin (natural or synthetic resin, for example, general plastic material, plate-like, film, or other form), metal, ceramics, and the like. It can be composed of any suitable material such as semiconductors (silicon, germanium, etc.), fibers (textiles, non-woven fabrics, etc.), fur, leather, wood, ceramics, stones, building materials, and the like.

For example, when the article to be manufactured is an optical member, the material constituting the surface of the base material may be a material for the optical member, for example, glass or transparent plastic. When the article to be manufactured is an optical member, some layer (or film), such as a hard coat layer or an antireflection layer, may be formed on the surface (outermost layer) of the base material. As the antireflection layer, either a single-layer antireflection layer or a multi-layer antireflection layer may be used. Examples of inorganic substances that can be used for the antireflection layer are SiO ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ , Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , MgO. , Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO _{3, and the} like. These inorganic substances may be used alone or in combination of two or more thereof (for example, as a mixture). In the case of a multi-layer antireflection layer, _{it is preferable to use SiO 2} and / or SiO as the outermost layer thereof. When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide is provided on a part of the surface of the base material (glass). May be. Further, the base material may be an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, etc., depending on the specific specifications thereof. And may have a liquid crystal display module and the like.

The shape of the base material is not particularly limited. Further, the surface region of the base material on which the layer formed by the surface treatment agent of the present disclosure should be formed may be at least a part of the surface of the base material, depending on the use of the article to be manufactured, specific specifications and the like. It can be determined as appropriate.

As such a base material, at least the surface portion thereof may be made of a material originally having a hydroxyl group. Examples of such a material include glass, and examples thereof include metals (particularly base metals) in which a natural oxide film or a thermal oxide film is formed on the surface, ceramics, semiconductors, and the like. Alternatively, when it is not sufficient to have a hydroxyl group such as a resin, or when it does not originally have a hydroxyl group, the hydroxyl group is introduced to the surface of the base material by applying some pretreatment to the base material. Can be increased or increased. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation. The plasma treatment can introduce or increase hydroxyl groups on the surface of the base material, and can also be suitably used for cleaning the surface of the base material (removing foreign substances and the like). Further, as another example of such pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bond group is previously subjected to a monomolecular film on the surface of the substrate by the LB method (Langmuir-Bloget method), the chemical adsorption method, or the like. Examples thereof include a method of forming the morphology and then cleaving the unsaturated bond in an atmosphere containing oxygen, nitrogen and the like.

Alternatively, the base material may have at least a surface portion thereof made of a silicone compound having one or more reactive groups, for example, a Si—H group, or a material containing an alkoxysilane.

Next, a layer of the above-mentioned surface treatment agent of the present disclosure is formed on the surface of such a base material, and this layer is post-treated as necessary to form a layer from the surface treatment agent of the present disclosure.

The layer formation of the surface treatment agent of the present disclosure can be carried out by applying the above surface treatment agent to the surface of the base material so as to cover the surface. The coating method is not particularly limited. For example, a wet coating method and a dry coating method can be used.

Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.

Examples of dry coating methods include vapor deposition (usually vacuum deposition), sputtering, CVD and similar methods. Specific examples of the vapor deposition method (usually a vacuum vapor deposition method) include resistance heating, high-frequency heating using an electron beam, a microwave, an ion beam, and a similar method. Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD and similar methods.

Further, coating by the atmospheric pressure plasma method is also possible.

When using the wet coating method, the surface treatment agents of the present disclosure can be diluted with a solvent before being applied to the surface of the substrate. From the viewpoint of the stability of the surface treatment agent of the present disclosure and the volatility of the solvent, the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (eg, perfluorohexane, perfluoromethylcyclohexane). and perfluoro-1,3-dimethylcyclohexane); polyfluoro aromatic hydrocarbons (e.g., bis (trifluoromethyl) benzene); polyfluoro aliphatic hydrocarbons _{(e.g., C 6 F 13 CH 2 CH} 3 ( e.g., Asahiclean (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd., 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeorora (registered trademark) H manufactured by Nippon Zeon Co., Ltd.) Hydrofluoroether (HFE) (for example, perfluoropropylmethyl ether (C ₃ F ₇ OCH ₃ )) (for example, Novec 7000 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl methyl ether (C ₄ F ₉ OCH). ₃ ) (For example, Novec ™ 7100 manufactured by Sumitomo 3M Co., Ltd.), Perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ) (For example, Novec ™ 7200 manufactured by Sumitomo 3M Co., Ltd.), Par. Alkyl perfluoroalkyl ethers (perfluoroalkyl groups and alkyl groups) such as fluorohexyl methyl ether (C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ ) (for example, Novec ™ 7300 manufactured by Sumitomo 3M Co., Ltd.) Can be linear or branched), or CF ₃ CH ₂ OCF ₂ CHF ₂ (eg, Asahiclean® AE-3000 manufactured by Asahi Glass Co., Ltd.), etc. These solvents can be used alone. Alternatively, it can be used as a mixture of two or more kinds. Among them, hydrofluoro ether is preferable, and perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and / or perfluoro butyl ethyl ether (C ₄ F ₉ OC _{2) are preferable.} H ₅ ) is particularly preferable.

When the dry coating method is used, the surface treatment agent of the present disclosure may be subjected to the dry coating method as it is, or may be diluted with the above-mentioned solvent and then subjected to the dry coating method.

Layer formation of the surface treatment agent is preferably carried out so that the surface treatment agent of the present disclosure is present in the layer together with a catalyst for hydrolysis and dehydration condensation. Conveniently, in the case of the wet coating method, a catalyst may be added to the diluted solution of the surface treatment agent of the present disclosure immediately after diluting the surface treatment agent of the present disclosure with a solvent and immediately before applying to the surface of the substrate. In the case of the dry coating method, the surface treatment agent of the present disclosure to which a catalyst is added is subjected to thin-film deposition (usually vacuum vapor deposition) as it is, or the surface treatment agent of the present disclosure is catalyst-added to a metal porous body such as iron or copper. A vapor deposition (usually vacuum vapor deposition) treatment may be performed using a pellet-like substance impregnated with.

Any suitable acid or base can be used as the catalyst. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used. Further, as the base catalyst, for example, ammonia, organic amines and the like can be used.

As described above, a layer derived from the surface treatment agent of the present disclosure is formed on the surface of the base material, and the article of the present disclosure is manufactured. The resulting layer has both high surface slipperiness and high friction durability. In addition to high friction durability, the above layer has water repellency, oil repellency, antifouling property (for example, prevents adhesion of stains such as fingerprints), and waterproofness, depending on the composition of the surface treatment agent used. It can have (preventing water from entering electronic parts, etc.), surface slipperiness (or lubricity, such as wiping off stains such as fingerprints, and excellent tactile sensation to fingers), and is suitable as a functional thin film. Can be used.

That is, the present disclosure further relates to an optical material having a layer derived from the surface treatment agent of the present disclosure as the outermost layer.

Examples of the optical material preferably include a wide variety of optical materials in addition to optical materials related to displays and the like as exemplified below: for example, cathode ray tubes (CRTs; for example, personal computer monitors), liquid crystal displays, plasma displays, organic EL. Display, inorganic thin film EL dot matrix display, rear projection type display, fluorescent display tube (VFD), electric field emission display (FED; Field Emission Display) and other displays or protective plates for those displays, or antireflection film on their surface. Processed.

The article having the layer obtained by the present disclosure is not particularly limited, but may be an optical member. Examples of optical components include: lenses such as spectacles; front protective plates for displays such as PDPs and LCDs, antireflection plates, polarizing plates, anti-glare plates; for devices such as mobile phones and mobile information terminals. Touch panel sheet; Blu-ray (registered trademark) disc, DVD disc, optical disc surface such as CD-R, MO; optical fiber; clock display surface, etc.

In addition, the article having a layer obtained by the present disclosure may be a medical device or a medical material.

Further, the article having the layer obtained by the present disclosure may be an interior / exterior of an automobile, for example, a headlight cover, a side mirror, a side window, an interior decorative film, a center console, an instrument panel, a camera lens cover, and the like.

The thickness of the layer is not particularly limited. In the case of an optical member, the thickness of the layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, preferably 1 to 15 nm from the viewpoint of optical performance, surface slipperiness, friction durability and antifouling property. ..

Although the embodiments have been described above, it will be understood that various modifications of the embodiments and details are possible without departing from the purpose and scope of the claims.

Hereinafter, the present disclosure will be described in Examples, but the present disclosure is not limited to the following Examples. In this example, all the chemical formulas shown below show the average composition. Further, the order of existence of the repeating units (OCF ₂ ) and (OCF ₂ CF _{2) constituting the polyether group is arbitrary.} In the following, "Me" is CH ₃ , "Boc" is a tert-butoxycarbonyl group, "BOP" is a benzotriazole-1-yloxy-trisdimethylaminophosphonium salt, and "mXHF" is a metaxylene hexafluorolide. Represent each.

２，２−ジアリル−４−ペンテニルアミン １．５ｇをジクロロメタン ２０ｍＬに溶解した後、Ｎ，Ｎ−ジイソプロピルエチルアミン（ＤＩＥＡ） ３．３ｍＬ、化合物１ａ １．７５ｇ、ＢＯＰ ４．８２ｇを添加し、室温で一晩撹拌した。炭酸水素ナトリウム水溶液で洗浄後、無水硫酸ナトリウムを用いて乾燥し、濃縮した。残渣をシリカゲルカラムクロマトグラフィにて精製し、化合物２ａを２．９３ｇ得た。

化合物２ａ
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ） δ: 1.45 (s, 9H), 2.00-2.05 (m, 6H), 3.17 (d, 2H), 3.74 (d, 2H), 5.05-5.15 (m, 6H), 5.75-5.90 (m, 3H), 6.36 (br s, 1H).
(Synthesis Example 1)
(Synthesis Example 1-1)

After dissolving 1.5 g of 2,2-diallyl-4-pentenylamine in 20 mL of dichloromethane, 3.3 mL of N, N-diisopropylethylamine (DIEA), 1.75 g of compound 1a and 4.82 g of BOP were added, and at room temperature. Stirred overnight. After washing with an aqueous sodium hydrogen carbonate solution, the mixture was dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to obtain 2.93 g of compound 2a.

Compound 2a
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ: 1.45 (s, 9H), 2.00-2.05 (m, 6H), 3.17 (d, 2H), 3.74 (d, 2H), 5.05-5.15 (m, 6H), 5.75-5.90 (m, 3H), 6.36 (br s, 1H).

合成例１−１で得た化合物２ａ １ｇをジクロロメタン １０ｍＬに溶解した後、氷浴に浸け、トリフルオロ酢酸（ＴＦＡ） ３．５ｍＬを添加して２時間撹拌した。水酸化ナトリウム水溶液を加え、水相を除去した後、無水硫酸ナトリウムを用いて乾燥し、濃縮乾固した。シリカゲルカラムクロマトグラフィにて精製し、化合物３ａを０．６９ｇ得た。

化合物３ａ
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ） δ: 1.46 (br s, 2H), 2.00-2.08 (m, 6H), 3.18 (d, 2H), 3.30-3.60 (m, 2H), 5.05-5.15 (m, 6H), 5.75-5.90 (m, 3H), 7.50 (br s, 1H).
(Synthesis Example 1-2)

After dissolving 1 g of the compound 2a obtained in Synthesis Example 1-1 in 10 mL of dichloromethane, the mixture was immersed in an ice bath, 3.5 mL of trifluoroacetic acid (TFA) was added, and the mixture was stirred for 2 hours. An aqueous sodium hydroxide solution was added, the aqueous phase was removed, and the mixture was dried over anhydrous sodium sulfate and concentrated to dryness. Purification by silica gel column chromatography gave 0.69 g of compound 3a.

Compound 3a
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ: 1.46 (br s, 2H), 2.00-2.08 (m, 6H), 3.18 (d, 2H), 3.30-3.60 (m, 2H), 5.05-5.15 (m, 6H), 5.75-5.90 (m, 3H), 7.50 (br s, 1H).

ＣＦ_３ＣＦ_２ＣＦ_２（ＯＣＦ_２ＣＦ_２ＣＦ_２）_ｎＯＣＦ_２ＣＦ_２ＣＯ_２Ｍｅ（ｎ＝２５） ２．４ｇに対して、合成例１−２で得た化合物３ａ ０．２６７ｇとｍＸＨＦ ２ｍＬを入れ、室温で一晩撹拌した。パーフルオロヘキサン １０ｍＬを入れ、アセトン １０ｍＬで洗浄し、濃縮乾固することで、化合物４ａを２．４３５ｇ得た。

化合物４ａ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 2.30-2.45 (m, 6H), 3.61 (d, 2H), 4.36 (d, 2H), 5.38-5.45 (m, 6H), 6.10-6.26 (m, 3H), 6.30-6.34 (m, 1H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -84.1, -85.6, -86.5, -87.2, -125.2, -131.3, -132.4.
(Synthesis Example 1-3)

CF ₃ CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) _n OCF ₂ CF ₂ CO ₂ Me (n = 25) 2.4 g, compound 3a 0.267 g and mXHF 2 mL obtained in Synthesis Example 1-2 Was put in and stirred overnight at room temperature. To obtain 2.435 g of compound 4a by adding 10 mL of perfluorohexane, washing with 10 mL of acetone, and concentrating to dryness.

Compound 4a
^{1 1} H NMR (mXHF, 400MHz) δ: 2.30-2.45 (m, 6H), 3.61 (d, 2H), 4.36 (d, 2H), 5.38-5.45 (m, 6H), 6.10-6.26 (m, 3H) , 6.30-6.34 (m, 1H);
¹⁹ F NMR (mXHF, 400MHz) δ: -84.1, -85.6, -86.5, -87.2, -125.2, -131.3, -132.4.

合成例１−３で得た化合物４ａ １．３３ｇをｍＸＨＦ １ｍＬに溶解後、トリアセトキシメチルシラン ２．６１μｌ、トリクロロシラン ０．２５２ｍｌ、カールシュテット触媒 ３１．６μｌを添加し、６０℃で３時間撹拌した。濃縮乾固した後、残渣にｍＸＨＦ １ｍＬ、オルトギ酸トリメチル ０．９２ｍＬ、およびメタノール ５１μｌを滴下し、６０℃で３時間撹拌した。この液を濾過した後、濃縮乾固することで、化合物５ａ（ｎ＝２５）を１．０９ｇ得た。

化合物５ａ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 0.95-1.05 (m, 6H), 1.55-1.65 (m, 6H), 1.77-1.90 (m, 6H), 3.62 (d, 2H), 3.85-4.10 (m, 27H), 4.37 (d, 2H), 6.75-6.78 (m, 1H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -84.2, -85.5, -86.6, -124.4, -131.4, -132.4.
(Synthesis Example 1-4)

After dissolving 1.33 g of the compound 4a obtained in Synthesis Example 1-3 in 1 mL of mXHF, 2.61 μl of triacetoxymethylsilane, 0.252 ml of trichlorosilane, and 31.6 μl of Karstedt catalyst were added, and the temperature was 60 ° C. for 3 hours. Stirred. After concentration to dryness, 1 mL of mXHF, 0.92 mL of trimethyl orthoformate, and 51 μl of methanol were added dropwise to the residue, and the mixture was stirred at 60 ° C. for 3 hours. After filtering this liquid, it was concentrated to dryness to obtain 1.09 g of compound 5a (n = 25).

Compound 5a
^{1 1} H NMR (mXHF, 400MHz) δ: 0.95-1.05 (m, 6H), 1.55-1.65 (m, 6H), 1.77-1.90 (m, 6H), 3.62 (d, 2H), 3.85-4.10 (m, 27H), 4.37 (d, 2H), 6.75-6.78 (m, 1H);
¹⁹ F NMR (mXHF, 400MHz) δ: -84.2, -85.5, -86.6, -124.4, -131.4, -132.4.

２，２−ジアリル−４−ペンテニルアミン １．５ｇをジクロロメタン ２０ｍＬに溶解した後、Ｎ，Ｎ−ジイソプロピルエチルアミン ３．３２ｍＬ、化合物１ｂ １．７５ｇ、ＢＯＰ ４．８２ｇを添加し、室温で一晩撹拌した。炭酸水素ナトリウム水溶液で洗浄後、無水硫酸ナトリウムを用いて乾燥し、濃縮した。残渣をシリカゲルカラムクロマトグラフィにて精製することで、化合物２ｂを２．８１ｇ得た。

化合物２ｂ
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ） δ: 1.42 (s, 9H), 2.00-2.05 (m, 6H), 2.30-2.40 (m, 2H), 3.17-3.20 (m, 2H), 3.35-3.40 (m, 2H), 5.05-5.15 (m, 7H) , 5.65 (br s, 1H), 5.80-5.90 (m, 3H).
(Synthesis example 2)
(Synthesis Example 2-1)

After dissolving 1.5 g of 2,2-diallyl-4-pentenylamine in 20 mL of dichloromethane, add 3.32 mL of N, N-diisopropylethylamine, 1.75 g of compound 1b, and 4.82 g of BOP, and stir overnight at room temperature. did. After washing with an aqueous sodium hydrogen carbonate solution, the mixture was dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to obtain 2.81 g of compound 2b.

Compound 2b
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ: 1.42 (s, 9H), 2.00-2.05 (m, 6H), 2.30-2.40 (m, 2H), 3.17-3.20 (m, 2H), 3.35-3.40 (m) , 2H), 5.05-5.15 (m, 7H), 5.65 (br s, 1H), 5.80-5.90 (m, 3H).

合成例２−１で得た化合物２ｂ １．０９ｇをジクロロメタン ３ｍＬに溶解した後、氷浴に浸け、トリフルオロ酢酸 ３．０ｍＬを添加して４時間撹拌した。水酸化ナトリウム水溶液を加え、水相を除去した後、無水硫酸ナトリウムを用いて乾燥し、濃縮した。残渣をシリカゲルカラムクロマトグラフィにて精製することで、化合物３ｂを０．５９７ｇ得た。

化合物３ｂ
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ） δ: 1.41 (br s, 2H), 1.95-2.08 (m, 6H), 2.30 (t, 2H), 3.00 (t, 2H), 3.15-3.20 (m, 2H), 5.05-5.15 (m, 6H), 5.75-5.90 (m, 3H), 7.42 (br s, 1H).
(Synthesis Example 2-2)

After dissolving 1.09 g of the compound 2b obtained in Synthesis Example 2-1 in 3 mL of dichloromethane, the mixture was immersed in an ice bath, 3.0 mL of trifluoroacetic acid was added, and the mixture was stirred for 4 hours. An aqueous sodium hydroxide solution was added, the aqueous phase was removed, and the mixture was dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to obtain 0.597 g of compound 3b.

Compound 3b
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ: 1.41 (br s, 2H), 1.95-2.08 (m, 6H), 2.30 (t, 2H), 3.00 (t, 2H), 3.15-3.20 (m, 2H) , 5.05-5.15 (m, 6H), 5.75-5.90 (m, 3H), 7.42 (br s, 1H).

ＣＦ_３ＣＦ_２ＣＦ_２（ＯＣＦ_２ＣＦ_２ＣＦ_２）_ｎＯＣＦ_２ＣＦ_２ＣＯ_２Ｍｅ（ｎ＝２５） ２．１２ｇに対して、合成例２−２で得た化合物３ｂ ０．２５ｇとｍＸＨＦ ２ｍＬを入れ、室温で一晩撹拌した。パーフルオロヘキサン １０ｍＬを入れ、アセトンで洗浄した後、濃縮乾固後することで、化合物４ｂを２．２３ｇ得た。

化合物４ｂ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 2.30-2.50 (m, 8H), 3.17-3.20 (m, 2H), 3.55-3.65 (m, 2H), 5.38-5.50 (m, 6H), 6.10-6.28 (m, 3H), 6.30-6.40 (br s, 1H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -84.1, -85.6, -86.5, -87.2, -125.2, -131.3, -132.4.
(Synthesis Example 2-3)

CF ₃ CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) _n OCF ₂ CF ₂ CO ₂ Me (n = 25) 2.12 g, compound 3b 0.25 g and mXHF 2 mL obtained in Synthesis Example 2-2. Was put in and stirred overnight at room temperature. To obtain 2.23 g of compound 4b by adding 10 mL of perfluorohexane, washing with acetone, and then concentrating to dryness.

Compound 4b
^{1 1} H NMR (mXHF, 400MHz) δ: 2.30-2.50 (m, 8H), 3.17-3.20 (m, 2H), 3.55-3.65 (m, 2H), 5.38-5.50 (m, 6H), 6.10-6.28 ( m, 3H), 6.30-6.40 (br s, 1H);
¹⁹ F NMR (mXHF, 400MHz) δ: -84.1, -85.6, -86.5, -87.2, -125.2, -131.3, -132.4.

合成例２−３で得た化合物４ｂ １．５２ｇをｍＸＨＦ １ｍＬに溶解後、室温下、トリアセトキシメチルシラン ２．９８μｌ、トリクロロシラン ０．４７９ｍｌ、カールシュテット触媒 ３６．１μｌを添加し、６０℃で３時間撹拌した。濃縮乾固した後、その残渣にｍＸＨＦ １ｍＬ、オルトギ酸トリメチル １．１０ｍＬ、およびメタノール ５８μｌ滴下し、６０℃で３時間撹拌した。この液を濾過した後、濃縮乾固することで、化合物５ｂ（ｎ＝２５）を１．２９ｇ得た。

化合物５ｂ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 0.95-1.05 (m, 6H), 1.55-1.65 (m, 6H), 1.77-1.90 (m, 6H), 2.30-2.40 (m, 2H), 3.17-3.20 (m, 2H), 3.62 (d, 2H), 3.85-4.10 (m, 27H), 6.75-6.78 (m, 1H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -84.2, -85.5, -86.6, -124.4, -131.4, -132.4.
(Synthesis Example 2-4)

After dissolving 1.52 g of the compound 4b obtained in Synthesis Example 2-3 in 1 mL of mXHF, 2.98 μl of triacetoxymethylsilane, 0.479 ml of trichlorosilane, and 36.1 μl of Karstedt catalyst were added at room temperature to 60 ° C. Was stirred for 3 hours. After concentration to dryness, 1 mL of mXHF, 1.10 mL of trimethyl orthoformate, and 58 μl of methanol were added dropwise to the residue, and the mixture was stirred at 60 ° C. for 3 hours. After filtering this liquid, it was concentrated to dryness to obtain 1.29 g of compound 5b (n = 25).

Compound 5b
^{1 1} H NMR (mXHF, 400MHz) δ: 0.95-1.05 (m, 6H), 1.55-1.65 (m, 6H), 1.77-1.90 (m, 6H), 2.30-2.40 (m, 2H), 3.17-3.20 ( m, 2H), 3.62 (d, 2H), 3.85-4.10 (m, 27H), 6.75-6.78 (m, 1H);
¹⁹ F NMR (mXHF, 400MHz) δ: -84.2, -85.5, -86.6, -124.4, -131.4, -132.4.

２，２−ジアリル−４−ペンテニルアミン １．７９ｇをジクロロメタン ２０ｍＬに溶解した後、Ｎ，Ｎ−ジイソプロピルエチルアミン ３．６８ｍＬ、化合物１ｃ ２．０ｇ、ＢＯＰ ５．２２ｇを添加し、室温で一晩撹拌した。濃縮乾固後、シリカゲルカラムクロマトグラフィにて精製することで、化合物２ｃを３．４５ｇ得た。

化合物２ｃ
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ） δ: 1.42 (s, 9H), 1.75-1.80 (m, 2H), 2.00-2.05 (m, 6H), 2.15-2.20 (m, 2H), 3.15-3.20 (m, 4H), 4.74 (br s, 1H), 5.05-5.15 (m, 6H) , 5.80-5.90 (m, 3H), 6.33 (br s, 1H).
(Synthesis Example 3)
(Synthesis Example 3-1)

After dissolving 1.79 g of 2,2-diallyl-4-pentenylamine in 20 mL of dichloromethane, 3.68 mL of N, N-diisopropylethylamine, 2.0 g of compound 1c and 5.22 g of BOP are added, and the mixture is stirred overnight at room temperature. did. After concentration to dryness, purification by silica gel column chromatography gave 3.45 g of compound 2c.

Compound 2c
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ: 1.42 (s, 9H), 1.75-1.80 (m, 2H), 2.00-2.05 (m, 6H), 2.15-2.20 (m, 2H), 3.15-3.20 (m) , 4H), 4.74 (br s, 1H), 5.05-5.15 (m, 6H), 5.80-5.90 (m, 3H), 6.33 (br s, 1H).

合成例３−１で得た化合物２ｃ １．０７ｇをジクロロメタン ３ｍＬに溶解した後、氷浴に浸け、トリフルオロ酢酸 ４．０ｍＬを添加して４時間撹拌した。水酸化ナトリウム水溶液を加え、水相を除去した後、無水硫酸ナトリウム用いて乾燥し、濃縮した。残渣をシリカゲルカラムクロマトグラフィにて精製することで、化合物３ｃを０．６２ｇ得た。

化合物３ｃ
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ） δ: 1.21 (br s, 2H), 1.70-1.78 (m, 2H), 1.95-2.05 (m, 6H), 2.20-2.30 (m, 2H), 2.65-2.80 (m, 2H), 3.15-3.25 (m, 2H), 5.05-5.30 (m, 6H), 5.75-5.90 (m, 4H).
(Synthesis Example 3-2)

After dissolving 1.07 g of the compound 2c obtained in Synthesis Example 3-1 in 3 mL of dichloromethane, the mixture was immersed in an ice bath, 4.0 mL of trifluoroacetic acid was added, and the mixture was stirred for 4 hours. An aqueous sodium hydroxide solution was added, the aqueous phase was removed, and the mixture was dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to obtain 0.62 g of compound 3c.

Compound 3c
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ: 1.21 (br s, 2H), 1.70-1.78 (m, 2H), 1.95-2.05 (m, 6H), 2.20-2.30 (m, 2H), 2.65-2.80 ( m, 2H), 3.15-3.25 (m, 2H), 5.05-5.30 (m, 6H), 5.75-5.90 (m, 4H).

ＣＦ_３ＣＦ_２ＣＦ_２（ＯＣＦ_２ＣＦ_２ＣＦ_２）_ｎＯＣＦ_２ＣＦ_２ＣＯ_２Ｍｅ（ｎ＝２５） ２．２ｇに対して、合成例３−２で得た化合物３ｃ ０．２８ｇとｍＸＨＦ ３ｍＬを入れ、室温で一晩撹拌した。パーフルオロヘキサン １０ｍＬを入れ、アセトンで洗浄し、濃縮乾固することで、化合物４ｃを２．３２ｇ得た。

化合物４ｃ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 2.25-2.28 (m, 6H), 2.36-2.80 (m, 6H), 3.50-3.60 (m, 2H), 3.75-3.85 (m, 2H), 5.39-5.45 (m, 6H), 6.05-6.10 (m, 1H), 6.13-6.30 (m, 3H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -84.1, -85.6, -86.5, -87.2, -125.2, -131.3, -132.4.
(Synthesis Example 3-3)

CF ₃ CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) _n OCF ₂ CF ₂ CO ₂ Me (n = 25) 2.2 g, compound 3c 0.28 g and mXHF 3 mL obtained in Synthesis Example 3-2. Was put in and stirred overnight at room temperature. To obtain 2.32 g of compound 4c by adding 10 mL of perfluorohexane, washing with acetone, and concentrating to dryness.

Compound 4c
^{1 1} H NMR (mXHF, 400MHz) δ: 2.25-2.28 (m, 6H), 2.36-2.80 (m, 6H), 3.50-3.60 (m, 2H), 3.75-3.85 (m, 2H), 5.39-5.45 ( m, 6H), 6.05-6.10 (m, 1H), 6.13-6.30 (m, 3H);
¹⁹ F NMR (mXHF, 400MHz) δ: -84.1, -85.6, -86.5, -87.2, -125.2, -131.3, -132.4.

合成例３−３で得た化合物４ｃ １．１０ｇをｍＸＨＦ １ｍＬに溶解後、室温下、トリアセトキシメチルシラン ２．１６μｌ、トリクロロシラン ０．３４７ｍｌ、カールシュテット触媒 ３６．１μｌを添加し、６０℃で３時間撹拌した。濃縮乾固した後、ｍＸＨＦ １ｍＬ、オルトギ酸トリメチル ０．７６ｍＬ、およびメタノール ４２μｌを滴下し、６０℃で３時間撹拌した。この液を濾過した後、ろ液を濃縮乾固することで、化合物５ｃ（ｎ＝２５）を０．９２２ｇ得た。

化合物５ｃ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 0.95-1.05 (m, 6H), 1.55-1.65 (m, 6H), 1.77-1.90 (m, 6H), 2.30-2.40 (m, 2H), 2.76-2.78 (m, 2H), 3.53-3.55 (m, 2H), 3.84-3.86 (m, 2H), 3.85-4.10 (m, 27H), 6.75-6.78 (m, 1H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -84.2, -85.5, -86.6, -124.4, -131.4, -132.4.
(Synthesis Example 3-4)

After dissolving 1.10 g of the compound 4c obtained in Synthesis Example 3-3 in 1 mL of mXHF, 2.16 μl of triacetoxymethylsilane, 0.347 ml of trichlorosilane, and 36.1 μl of Karstedt catalyst were added at room temperature to 60 ° C. Was stirred for 3 hours. After concentration to dryness, 1 mL of mXHF, 0.76 mL of trimethyl orthoformate, and 42 μl of methanol were added dropwise, and the mixture was stirred at 60 ° C. for 3 hours. After filtering this solution, the filtrate was concentrated to dryness to obtain 0.922 g of compound 5c (n = 25).

Compound 5c
^{1 1} H NMR (mXHF, 400MHz) δ: 0.95-1.05 (m, 6H), 1.55-1.65 (m, 6H), 1.77-1.90 (m, 6H), 2.30-2.40 (m, 2H), 2.76-2.78 ( m, 2H), 3.53-3.55 (m, 2H), 3.84-3.86 (m, 2H), 3.85-4.10 (m, 27H), 6.75-6.78 (m, 1H);
¹⁹ F NMR (mXHF, 400MHz) δ: -84.2, -85.5, -86.6, -124.4, -131.4, -132.4.

ＣＦ_３ＣＦ_２ＣＦ_２（ＯＣＦ_２ＣＦ_２ＣＦ_２）_ｎＯＣＦ_２ＣＦ_２ＣＯ_２Ｍｅ（ｎ＝５０） ４．４ｇに対して、合成例３−２で得た化合物３ｃ ０．２８ｇとｍＸＨＦ ３ｍＬを入れ、室温で一晩撹拌した。パーフルオロヘキサン ２０ｍＬを入れ、アセトンで洗浄し、無水硫酸ナトリウムを用いて乾燥した後、濃縮乾固することで、化合物４ｃ’を４．６ｇ得た。

化合物４ｃ’
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 2.25-2.28 (m, 6H), 2.36-2.80 (m, 6H), 3.50-3.60 (m, 2H), 3.75-3.85 (m, 2H), 5.39-5.45 (m, 6H), 6.05-6.10 (m, 1H), 6.13-6.30 (m, 3H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -84.1, -85.6, -86.5, -87.2, -125.2, -131.3, -132.4.
(Synthesis Example 3-5)

CF ₃ CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) _n OCF ₂ CF ₂ CO ₂ Me (n = 50) 4.4 g, compound 3c 0.28 g and mXHF 3 mL obtained in Synthesis Example 3-2. Was put in and stirred overnight at room temperature. 20 mL of perfluorohexane was added, the mixture was washed with acetone, dried over anhydrous sodium sulfate, and then concentrated to dryness to obtain 4.6 g of compound 4c'.

Compound 4c'
^{1 1} H NMR (mXHF, 400MHz) δ: 2.25-2.28 (m, 6H), 2.36-2.80 (m, 6H), 3.50-3.60 (m, 2H), 3.75-3.85 (m, 2H), 5.39-5.45 ( m, 6H), 6.05-6.10 (m, 1H), 6.13-6.30 (m, 3H);
¹⁹ F NMR (mXHF, 400MHz) δ: -84.1, -85.6, -86.5, -87.2, -125.2, -131.3, -132.4.

合成例３−５で得た化合物４ｃ’ ２．２０ｇをｍＸＨＦ ２ｍＬに溶解後、室温下、トリアセトキシメチルシラン ２．１６μｌ、トリクロロシラン ０．３４７ｍｌ、カールシュテット触媒 ３６．１μｌを添加し、６０℃で３時間撹拌した。濃縮乾固した後、その残渣にｍＸＨＦ １ｍＬ、オルトギ酸トリメチル ０．７６ｍＬ、およびメタノール ４２μｌを滴下し、６０℃で３時間撹拌した。この液を濾過した後、ろ液を濃縮乾固することで、化合物５ｃ’（ｎ＝５０）を１．８２ｇ得た。

化合物５ｃ’
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 0.95-1.05 (m, 6H), 1.55-1.65 (m, 6H), 1.77-1.90 (m, 6H), 2.30-2.40 (m, 2H), 2.76-2.78 (m, 2H), 3.53-3.55 (m, 2H), 3.84-3.86 (m, 2H), 3.85-4.10 (m, 27H), 6.75-6.78 (m, 1H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -84.2, -85.5, -86.6, -124.4, -131.4, -132.4.
(Synthesis Example 3-6)

After dissolving 2.20 g of the compound 4c' obtained in Synthesis Example 3-5 in 2 mL of mXHF, 2.16 μl of triacetoxymethylsilane, 0.347 ml of trichlorosilane, and 36.1 μl of Karstedt catalyst were added at room temperature, and 60 The mixture was stirred at ° C. for 3 hours. After concentration to dryness, 1 mL of mXHF, 0.76 mL of trimethyl orthoformate, and 42 μl of methanol were added dropwise to the residue, and the mixture was stirred at 60 ° C. for 3 hours. After filtering this solution, the filtrate was concentrated to dryness to obtain 1.82 g of compound 5c'(n = 50).

Compound 5c'
^{1 1} H NMR (mXHF, 400MHz) δ: 0.95-1.05 (m, 6H), 1.55-1.65 (m, 6H), 1.77-1.90 (m, 6H), 2.30-2.40 (m, 2H), 2.76-2.78 ( m, 2H), 3.53-3.55 (m, 2H), 3.84-3.86 (m, 2H), 3.85-4.10 (m, 27H), 6.75-6.78 (m, 1H);
¹⁹ F NMR (mXHF, 400MHz) δ: -84.2, -85.5, -86.6, -124.4, -131.4, -132.4.

ＢＯＰ ５．３３ｇをジクロロメタン ２０ｍＬに溶解し、化合物１ｄ ２．５７ｇおよびトリエチルアミン １．７５ｍＬを添加し、２，２−ジアリル−４−ペンテニルアミン ２．１２ｍｌを加え、室温で一晩撹拌させた。濃縮乾固後、シリカゲルカラムクロマトグラフィにて精製することで、化合物２ｄを３．５２ｇ得た。

化合物２ｄ
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ） δ: 1.20-1.25 (m, 4H), 1.40-1.44 (m, 11H), 2.00-2.05 (m, 6H), 2.15-2.20 (m, 4H), 3.00-3.20 (m, 4H), 4.50 (br s, 1H), 5.05-5.15 (m, 6H) , 5.56 (br s, 1H), 5.75-5.90 (m, 3H).
(Synthesis Example 4)
(Synthesis Example 4-1)

5.33 g of BOP was dissolved in 20 mL of dichloromethane, 2.57 g of compound 1d and 1.75 mL of triethylamine were added, 2.12 ml of 2,2-diallyl-4-pentenylamine was added, and the mixture was stirred at room temperature overnight. After concentration to dryness, purification by silica gel column chromatography gave 3.52 g of compound 2d.

Compound 2d
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ: 1.20-1.25 (m, 4H), 1.40-1.44 (m, 11H), 2.00-2.05 (m, 6H), 2.15-2.20 (m, 4H), 3.00-3.20 (m, 4H), 4.50 (br s, 1H), 5.05-5.15 (m, 6H), 5.56 (br s, 1H), 5.75-5.90 (m, 3H).

合成例４−１で得た化合物２ｄ １．４０ｇをジクロロメタン ８ｍＬに溶解し、氷浴に浸け、トリフルオロ酢酸 ８．０ｍＬを添加して４時間撹拌した。濃縮乾固し、シリカゲルカラムクロマトグラフィにて精製することで、化合物３ｄを１．０４ｇ得た。

化合物３ｄ
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ） δ: 1.30-1.50 (m, 6H), 1.55-1.65 (m, 2H), 2.00-2.10 (m, 6H), 2.10-2.20 (m, 2H), 2.60-2.70 (m, 2H), 3.15-3.20 (m, 2H), 5.05-5.15 (m, 6H) , 5.51 (br s, 1H), 5.80-5.90 (m, 3H).
(Synthesis Example 4-2)

1.40 g of the compound 2d obtained in Synthesis Example 4-1 was dissolved in 8 mL of dichloromethane, immersed in an ice bath, 8.0 mL of trifluoroacetic acid was added, and the mixture was stirred for 4 hours. The mixture was concentrated to dryness and purified by silica gel column chromatography to obtain 1.04 g of compound 3d.

Compound 3d
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ: 1.30-1.50 (m, 6H), 1.55-1.65 (m, 2H), 2.00-2.10 (m, 6H), 2.10-2.20 (m, 2H), 2.60-2.70 (m, 2H), 3.15-3.20 (m, 2H), 5.05-5.15 (m, 6H), 5.51 (br s, 1H), 5.80-5.90 (m, 3H).

ＣＦ_３ＣＦ_２ＣＦ_２（ＯＣＦ_２ＣＦ_２ＣＦ_２）_ｎＯＣＦ_２ＣＦ_２ＣＯ_２Ｍｅ（ｎ＝２５） ２．３６ｇに対して、合成例４−２で得た化合物３ｄ ０．３４５ｇとｍＸＨＦ ３ｍＬを入れ、室温で一晩撹拌した。パーフルオロヘキサン １０ｍＬを入れ、アセトンで洗浄し、無水硫酸ナトリウムを用いて乾燥し、濃縮乾固後することで、化合物４ｄを２．４７ｇ得た。

化合物４ｄ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 1.60-1.80 (m, 4H), 1.90-1.95 (m, 2H), 2.00-2.10 (m, 2H), 2.35-2.39 (m, 6H), 2.50-2.57 (m, 6H), 3.50-3.61 (m, 2H), 3.72-3.75 (m, 2H), 5.30-5.45 (m, 6H), 5.90-5.95 (m, 1H), 6.15-6.35 (m, 3H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -84.1, -85.6, -86.5, -87.2, -125.2, -131.3, -132.4.
(Synthesis Example 4-3)

CF ₃ CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) _n OCF ₂ CF ₂ CO ₂ Me (n = 25) 2.36 g, the compound 3d 0.345 g and mXHF 3 mL obtained in Synthesis Example 4-2. Was put in and stirred overnight at room temperature. To obtain 2.47 g of compound 4d by adding 10 mL of perfluorohexane, washing with acetone, drying with anhydrous sodium sulfate, and concentrating to dryness.

Compound 4d
^{1 1} H NMR (mXHF, 400MHz) δ: 1.60-1.80 (m, 4H), 1.90-1.95 (m, 2H), 2.00-2.10 (m, 2H), 2.35-2.39 (m, 6H), 2.50-2.57 ( m, 6H), 3.50-3.61 (m, 2H), 3.72-3.75 (m, 2H), 5.30-5.45 (m, 6H), 5.90-5.95 (m, 1H), 6.15-6.35 (m, 3H);
¹⁹ F NMR (mXHF, 400MHz) δ: -84.1, -85.6, -86.5, -87.2, -125.2, -131.3, -132.4.

合成例４−３で得た化合物４ｄ １．６３ｇをｍＸＨＦ １ｍＬに溶解後、室温下、トリアセトキシメチルシラン ３．２０μｌ、トリクロロシラン ０．５１４ｍｌ、カールシュテット触媒 ３８．７μｌを添加し、６０℃で３時間撹拌した。濃縮乾固した後、その残渣にｍＸＨＦ １ｍＬ、オルトギ酸トリメチル １．１ｍＬおよびメタノール ６２μｌを滴下し、６０℃で３時間撹拌した。この液を濾過した後、ろ液を濃縮乾固することで、化合物５ｄ（ｎ＝２５）を１．４２ｇ得た。

化合物５ｄ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 0.95-1.05 (m, 6H), 1.55-1.88 (m, 14H), 1.91-1.95 (m, 2H), 2.00-2.10 (m, 2H), 2.50-2.57 (m, 6H), 3.50-3.61 (m, 2H), 3.72-3.75 (m, 2H), 3.85-4.10 (m, 27H), 5.90-5.95 (m, 1H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -84.2, -85.5, -86.6, -124.4, -131.4, -132.4.
(Synthesis Example 4-4)

After dissolving 1.63 g of the compound 4d obtained in Synthesis Example 4-3 in 1 mL of mXHF, 3.20 μl of triacetoxymethylsilane, 0.514 ml of trichlorosilane, and 38.7 μl of Karstedt catalyst were added at room temperature to 60 ° C. Was stirred for 3 hours. After concentration to dryness, 1 mL of mXHF, 1.1 mL of trimethyl orthoformate and 62 μl of methanol were added dropwise to the residue, and the mixture was stirred at 60 ° C. for 3 hours. After filtering this solution, the filtrate was concentrated to dryness to obtain 1.42 g of compound 5d (n = 25).

Compound 5d
^{1 1} H NMR (mXHF, 400MHz) δ: 0.95-1.05 (m, 6H), 1.55-1.88 (m, 14H), 1.91-1.95 (m, 2H), 2.00-2.10 (m, 2H), 2.50-2.57 ( m, 6H), 3.50-3.61 (m, 2H), 3.72-3.75 (m, 2H), 3.85-4.10 (m, 27H), 5.90-5.95 (m, 1H);
¹⁹ F NMR (mXHF, 400MHz) δ: -84.2, -85.5, -86.6, -124.4, -131.4, -132.4.

ＣＦ_３（ＯＣＦ_２）_ｍ（ＯＣＦ_２ＣＦ_２）_ｎＯＣＦ_２ＣＯ_２Ｍｅ（ｍ＝４０，ｎ＝２４） ４．０７ｇに対して、合成例１−２で得た化合物３ａ ０．２４５ｇとｍＸＨＦ ３ｍＬを入れ、室温で一晩撹拌した。パーフルオロヘキサン ２０ｍＬを入れ、アセトンで洗浄し、無水硫酸ナトリウムを用いて乾燥し、濃縮乾固することで、化合物６ａを３．７５ｇ得た。

化合物６ａ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 2.30-2.45 (m, 6H), 3.61 (d, 2H), 4.36 (d, 2H), 5.38-5.45 (m, 6H), 6.10-6.26 (m, 3H), 6.30-6.34 (m, 1H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -131.7, -127.9, -127.4, -117.7, -92.6, -91.0, -87.4, -87.3, -85.8, −85.6, -83.2, -81.6, -79.9, -74.5, -59.9, -58.2, -57.4, -55.6, -54.0.
(Synthesis Example 5-1)

CF ₃ (OCF ₂ ) _m (OCF ₂ CF ₂ ) _n OCF ₂ CO ₂ Me (m = 40, n = 24) 4.07 g, compound 3a 0.245 g and mXHF obtained in Synthesis Example 1-2 3 mL was added and stirred at room temperature overnight. 20 mL of perfluorohexane was added, washed with acetone, dried over anhydrous sodium sulfate, and concentrated to dryness to obtain 3.75 g of compound 6a.

Compound 6a
^{1 1} H NMR (mXHF, 400MHz) δ: 2.30-2.45 (m, 6H), 3.61 (d, 2H), 4.36 (d, 2H), 5.38-5.45 (m, 6H), 6.10-6.26 (m, 3H) , 6.30-6.34 (m, 1H);
¹⁹ F NMR (mXHF, 400MHz) δ: -131.7, -127.9, -127.4, -117.7, -92.6, -91.0, -87.4, -87.3, -85.8, -85.6, -83.2, -81.6, -79.9,- 74.5, -59.9, -58.2, -57.4, -55.6, -54.0.

合成例５−１で得た化合物６ａ ３．７５ｇをｍＸＨＦ ３ｍＬに溶解後、トリアセトキシメチルシラン ７．３５μｌ、トリクロロシラン １．１８ｍｌ、カールシュテット触媒 ８９．１μｌを添加し、６０℃で３時間撹拌した。濃縮乾固した後、その残渣にｍＸＨＦ ３ｍＬ、オルトギ酸トリメチル ２．６ｍＬ、およびメタノール １４０μｌを滴下し、６０℃で３時間撹拌した。この液を濾過した後、ろ液を濃縮乾固することで、化合物７ａ（ｍ＝４０，ｎ＝２４）を３．５４ｇ得た。

化合物７ａ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 0.95-1.05 (m, 6H), 1.55-1.65 (m, 6H), 1.77-1.90 (m, 6H), 3.62 (d, 2H), 3.85-4.10 (m, 27H), 4.37 (d, 2H), 6.75-6.78 (m, 1H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -131.7, -127.9, -127.4, -117.7, -92.6, -91.0, -87.4, -87.3, -85.8, −85.6, -83.2, -81.6, -79.9, -74.5, -59.9, -58.2, -57.4, -55.6, -54.0.
(Synthesis Example 5-2)

After dissolving 3.75 g of the compound 6a obtained in Synthesis Example 5-1 in 3 mL of mXHF, 7.35 μl of triacetoxymethylsilane, 1.18 ml of trichlorosilane, and 89.1 μl of Karstedt catalyst were added, and the temperature was 60 ° C. for 3 hours. Stirred. After concentration to dryness, 3 mL of mXHF, 2.6 mL of trimethyl orthoformate, and 140 μl of methanol were added dropwise to the residue, and the mixture was stirred at 60 ° C. for 3 hours. After filtering this liquid, the filtrate was concentrated to dryness to obtain 3.54 g of compound 7a (m = 40, n = 24).

Compound 7a
^{1 1} H NMR (mXHF, 400MHz) δ: 0.95-1.05 (m, 6H), 1.55-1.65 (m, 6H), 1.77-1.90 (m, 6H), 3.62 (d, 2H), 3.85-4.10 (m, 27H), 4.37 (d, 2H), 6.75-6.78 (m, 1H);
¹⁹ F NMR (mXHF, 400MHz) δ: -131.7, -127.9, -127.4, -117.7, -92.6, -91.0, -87.4, -87.3, -85.8, -85.6, -83.2, -81.6, -79.9,- 74.5, -59.9, -58.2, -57.4, -55.6, -54.0.

ＣＦ_３（ＯＣＦ_２）_ｍ（ＯＣＦ_２ＣＦ_２）_ｎＯＣＦ_２ＣＯ_２Ｍｅ（ｍ＝４０，ｎ＝２４） ２．０ｇに対して、合成例３−２で得た化合物３ｃ ０．１４７ｇをとｍＸＨＦ ２ｍＬを入れ、室温で一晩撹拌した。パーフルオロヘキサン ２０ｍＬを入れ、アセトンで洗浄し、無水硫酸ナトリウムを用いて乾燥した後、濃縮乾固することで、化合物６ｃを１．６８ｇ得た。

化合物６ｃ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 2.25-2.28 (m, 6H), 2.36-2.80 (m, 6H), 3.50-3.60 (m, 2H), 3.75-3.85 (m, 2H), 5.39-5.45 (m, 6H), 6.05-6.10 (m, 1H), 6.13-6.30 (m, 3H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -131.7, -127.9, -127.4, -117.7, -92.6, -91.0, -87.4, -87.3, -85.8, −85.6, -83.2, -81.6, -79.9, -74.5, -59.9, -58.2, -57.4, -55.6, -54.0.
(Synthesis Example 6-1)

To _{2.0 g of CF 3} (OCF ₂ ) _m (OCF ₂ CF ₂ ) _n OCF ₂ CO ₂ Me (m = 40, n = 24), 0.147 g of the compound 3c obtained in Synthesis Example 3-2 was added. 2 mL of mXHF was added and stirred at room temperature overnight. 20 mL of perfluorohexane was added, the mixture was washed with acetone, dried over anhydrous sodium sulfate, and then concentrated to dryness to obtain 1.68 g of compound 6c.

Compound 6c
^{1 1} H NMR (mXHF, 400MHz) δ: 2.25-2.28 (m, 6H), 2.36-2.80 (m, 6H), 3.50-3.60 (m, 2H), 3.75-3.85 (m, 2H), 5.39-5.45 ( m, 6H), 6.05-6.10 (m, 1H), 6.13-6.30 (m, 3H);
¹⁹ F NMR (mXHF, 400MHz) δ: -131.7, -127.9, -127.4, -117.7, -92.6, -91.0, -87.4, -87.3, -85.8, -85.6, -83.2, -81.6, -79.9,- 74.5, -59.9, -58.2, -57.4, -55.6, -54.0.

合成例６−１で得た化合物６ｃ １．６８ｇをｍＸＨＦ １ｍＬに溶解後、トリアセトキシメチルシラン ２．８２μｌ、トリクロロシラン ０．４５４ｍｌ、カールシュテット触媒 ３４．２μｌを添加し、６０℃で３時間撹拌した。濃縮乾固した後、その残渣にｍＸＨＦ １ｍＬ、オルトギ酸トリメチル ０．９９ｍＬ、およびメタノール ５５μｌを滴下し、６０℃で３時間撹拌した。この液を濾過した後、ろ液を濃縮乾固することで、化合物７ｃ（ｍ＝４０，ｎ＝２４）を１．６４ｇ得た。

化合物７ｃ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 0.95-1.05 (m, 6H), 1.55-1.65 (m, 6H), 1.77-1.90 (m, 6H), 2.30-2.40 (m, 2H), 2.76-2.78 (m, 2H), 3.53-3.55 (m, 2H), 3.84-3.86 (m, 2H), 3.85-4.10 (m, 27H), 6.75-6.78 (m, 1H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -131.7, -127.9, -127.4, -117.7, -92.6, -91.0, -87.4, -87.3, -85.8, −85.6, -83.2, -81.6, -79.9, -74.5, -59.9, -58.2, -57.4, -55.6, -54.0.
(Synthesis Example 6-2)

After dissolving 1.68 g of the compound 6c obtained in Synthesis Example 6-1 in 1 mL of mXHF, 2.82 μl of triacetoxymethylsilane, 0.454 ml of trichlorosilane, and 34.2 μl of Karstedt catalyst were added, and the temperature was 60 ° C. for 3 hours. Stirred. After concentration to dryness, 1 mL of mXHF, 0.99 mL of trimethyl orthoformate, and 55 μl of methanol were added dropwise to the residue, and the mixture was stirred at 60 ° C. for 3 hours. After filtering this solution, the filtrate was concentrated to dryness to obtain 1.64 g of compound 7c (m = 40, n = 24).

Compound 7c
^{1 1} H NMR (mXHF, 400MHz) δ: 0.95-1.05 (m, 6H), 1.55-1.65 (m, 6H), 1.77-1.90 (m, 6H), 2.30-2.40 (m, 2H), 2.76-2.78 ( m, 2H), 3.53-3.55 (m, 2H), 3.84-3.86 (m, 2H), 3.85-4.10 (m, 27H), 6.75-6.78 (m, 1H);
¹⁹ F NMR (mXHF, 400MHz) δ: -131.7, -127.9, -127.4, -117.7, -92.6, -91.0, -87.4, -87.3, -85.8, -85.6, -83.2, -81.6, -79.9,- 74.5, -59.9, -58.2, -57.4, -55.6, -54.0.

ＣＦ_３（ＯＣＦ_２）_ｍ（ＯＣＦ_２ＣＦ_２）_ｎＯＣＦ_２ＣＯ_２Ｍｅ（ｍ＝４０，ｎ＝２４） ３．５０ｇに対して、合成例４−２で得た化合物３ｄ ０．２７７ｇとｍＸＨＦ ３ｍＬを入れ、室温で一晩撹拌した。パーフルオロヘキサン ２０ｍＬを入れ、アセトンで洗浄し、無水硫酸ナトリウムを用いて乾燥し、濃縮乾固することで、化合物６ｄを３．３７ｇ得た。

化合物６ｄ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 1.60-1.80 (m, 4H), 1.90-1.95 (m, 2H), 2.00-2.10 (m, 2H), 2.35-2.39 (m, 6H), 2.50-2.57 (m, 6H), 3.50-3.61 (m, 2H), 3.72-3.75 (m, 2H), 5.30-5.45 (m, 6H), 5.90-5.95 (m, 1H), 6.15-6.35 (m, 3H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -131.7, -127.9, -127.4, -117.7, -92.6, -91.0, -87.4, -87.3, -85.8, −85.6, -83.2, -81.6, -79.9, -74.5, -59.9, -58.2, -57.4, -55.6, -54.0.
(Synthesis Example 7-1)

CF ₃ (OCF ₂ ) _m (OCF ₂ CF ₂ ) _n OCF ₂ CO ₂ Me (m = 40, n = 24) 3.50 g, the compound 3d 0.277 g and mXHF obtained in Synthesis Example 4-2. 3 mL was added and stirred at room temperature overnight. 20 mL of perfluorohexane was added, washed with acetone, dried over anhydrous sodium sulfate, and concentrated to dryness to obtain 3.37 g of compound 6d.

Compound 6d
^{1 1} H NMR (mXHF, 400MHz) δ: 1.60-1.80 (m, 4H), 1.90-1.95 (m, 2H), 2.00-2.10 (m, 2H), 2.35-2.39 (m, 6H), 2.50-2.57 ( m, 6H), 3.50-3.61 (m, 2H), 3.72-3.75 (m, 2H), 5.30-5.45 (m, 6H), 5.90-5.95 (m, 1H), 6.15-6.35 (m, 3H);
¹⁹ F NMR (mXHF, 400MHz) δ: -131.7, -127.9, -127.4, -117.7, -92.6, -91.0, -87.4, -87.3, -85.8, -85.6, -83.2, -81.6, -79.9,- 74.5, -59.9, -58.2, -57.4, -55.6, -54.0.

合成例７−１で得た化合物６ｄ ３．３７ｇをｍＸＨＦ ３ｍＬに溶解後、トリアセトキシメチルシラン ５．６６μｌ、トリクロロシラン ０．９１１ｍｌ、カールシュテット触媒 ６８．７μｌを添加し、６０℃で３時間撹拌した。濃縮乾固した後、その残渣にｍＸＨＦ ３ｍＬ、オルトギ酸トリメチル ２．００ｍＬ、およびメタノール １１０μｌを滴下、６０℃で３時間撹拌した。この液を濾過した後、ろ液を濃縮乾固することで、化合物７ｄ（ｍ＝４０，ｎ＝２４）を２．７７ｇ得た。

化合物７ｄ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 0.95-1.05 (m, 6H), 1.55-1.88 (m, 14H), 1.91-1.95 (m, 2H), 2.00-2.10 (m, 2H), 2.50-2.57 (m, 6H), 3.50-3.61 (m, 2H), 3.72-3.75 (m, 2H), 3.85-4.10 (m, 27H), 5.90-5.95 (m, 1H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -131.7, -127.9, -127.4, -117.7, -92.6, -91.0, -87.4, -87.3, -85.8, −85.6, -83.2, -81.6, -79.9, -74.5, -59.9, -58.2, -57.4, -55.6, -54.0.
(Synthesis Example 7-2)

After dissolving 3.37 g of the compound 6d obtained in Synthesis Example 7-1 in 3 mL of mXHF, 5.66 μl of triacetoxymethylsilane, 0.911 ml of trichlorosilane, and 68.7 μl of Karstedt catalyst were added, and the temperature was 60 ° C. for 3 hours. Stirred. After concentration to dryness, 3 mL of mXHF, 2.00 mL of trimethyl orthoformate, and 110 μl of methanol were added dropwise to the residue, and the mixture was stirred at 60 ° C. for 3 hours. After filtering this solution, the filtrate was concentrated to dryness to obtain 2.77 g of compound 7d (m = 40, n = 24).

Compound 7d
^{1 1} H NMR (mXHF, 400MHz) δ: 0.95-1.05 (m, 6H), 1.55-1.88 (m, 14H), 1.91-1.95 (m, 2H), 2.00-2.10 (m, 2H), 2.50-2.57 ( m, 6H), 3.50-3.61 (m, 2H), 3.72-3.75 (m, 2H), 3.85-4.10 (m, 27H), 5.90-5.95 (m, 1H);
¹⁹ F NMR (mXHF, 400MHz) δ: -131.7, -127.9, -127.4, -117.7, -92.6, -91.0, -87.4, -87.3, -85.8, -85.6, -83.2, -81.6, -79.9,- 74.5, -59.9, -58.2, -57.4, -55.6, -54.0.

化合物８ａ ５ｇをジクロロメタン １０ｍＬに溶解した後、氷浴に浸け、２，２−ジアリル−４−ペンテニルアミン ４．５５ｇを滴下した後、室温で一晩撹拌させた。濃縮乾固後、シリカゲルカラムクロマトグラフィにて精製することで、化合物９ａを４．４６ｇ得た。

化合物９ａ
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ） δ: 2.00-2.20 (m, 6H), 3.20-3.31 (m, 2H), 3.94 (s, 3H), 5.05-5.20 (m, 6H), 5.80-5.70 (m, 3H), 6.61 (br s, 0.5H), 6.84 (br s, 0.5H).
(Synthesis Example 8)
(Synthesis Example 8-1)

After dissolving 5 g of compound 8a in 10 mL of dichloromethane, the mixture was immersed in an ice bath, 4.55 g of 2,2-diallyl-4-pentenylamine was added dropwise, and the mixture was stirred overnight at room temperature. After concentration to dryness, purification by silica gel column chromatography gave 4.46 g of compound 9a.

Compound 9a
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ: 2.00-2.20 (m, 6H), 3.20-3.31 (m, 2H), 3.94 (s, 3H), 5.05-5.20 (m, 6H), 5.80-5.70 (m) , 3H), 6.61 (br s, 0.5H), 6.84 (br s, 0.5H).

合成例８−１で得た化合物９ａ １．５４ｇをテトラヒドロフラン（ＴＨＦ） ６ｍＬに溶解した後、Ｎ−Ｂｏｃ−エチレンジアミン １．７３ｍＬを滴下し、室温で３日間撹拌させた。濃縮乾固した後、シリカゲルカラムクロマトグラフィにて精製することで、化合物１０ａを２．１ｇ得た。

化合物１０ａ
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ） δ: 1.43 (s, 9H), 2.00-2.16 (m, 6H), 3.22 (d, 2H), 3.25-3.50 (m, 4H), 5.00-5.18 (m, 6H), 5.80-5.90 (m, 3H), 6.87 (br s, 1H), 7.50 (br s, 1H);
^１９Ｆ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ） δ: -119.56, -119.64, -120.08, -120.11.
(Synthesis Example 8-2)

After dissolving 1.54 g of the compound 9a obtained in Synthesis Example 8-1 in 6 mL of tetrahydrofuran (THF), 1.73 mL of N-Boc-ethylenediamine was added dropwise, and the mixture was stirred at room temperature for 3 days. After concentration to dryness, purification by silica gel column chromatography gave 2.1 g of compound 10a.

Compound 10a
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ: 1.43 (s, 9H), 2.00-2.16 (m, 6H), 3.22 (d, 2H), 3.25-3.50 (m, 4H), 5.00-5.18 (m, 6H) ), 5.80-5.90 (m, 3H), 6.87 (br s, 1H), 7.50 (br s, 1H);
¹⁹ F NMR (CDCl ₃ , 400 MHz) δ: -119.56, -119.64, -120.08, -120.11.

合成例８−２で得た化合物１０ａ １．１ｇをジクロロメタン １０ｍＬに溶解した後、氷浴に浸け、トリフルオロ酢酸 １０ｍＬを添加して５時間撹拌した。濃縮乾固した後、シリカゲルカラムにて精製することで、化合物１１ａを０．８７ｇ得た。

化合物１１ａ
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ） δ: 2.01-2.07 (m, 6H), 2.85-2.90 (m, 2H), 3.24-3.28 (m, 2H), 3.36-3.40 (m, 2H), 5.09-5.18 (m, 6H), 5.80-5.89 (m, 3H), 6.85 (br s, 1H), 7.12 (br s, 1H);
^１９Ｆ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ） δ: -119.33, -119.55.
(Synthesis Example 8-3)

After dissolving 1.1 g of the compound 10a obtained in Synthesis Example 8-2 in 10 mL of dichloromethane, the mixture was immersed in an ice bath, 10 mL of trifluoroacetic acid was added, and the mixture was stirred for 5 hours. After concentrating and drying, the mixture was purified on a silica gel column to obtain 0.87 g of compound 11a.

Compound 11a
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ: 2.01-2.07 (m, 6H), 2.85-2.90 (m, 2H), 3.24-3.28 (m, 2H), 3.36-3.40 (m, 2H), 5.09-5.18 (m, 6H), 5.80-5.89 (m, 3H), 6.85 (br s, 1H), 7.12 (br s, 1H);
¹⁹ F NMR (CDCl ₃ , 400 MHz) δ: -119.33, -119.55.

ＣＦ_３ＣＦ_２ＣＦ_２（ＯＣＦ_２ＣＦ_２ＣＦ_２）_ｎＯＣＦ_２ＣＦ_２ＣＯ_２Ｍｅ（ｎ＝２５） １．７ｇに対して、合成例８−３で得た化合物１１ａ ０．３７ｇとｍＸＨＦ ２ｍＬを入れ、室温で一晩撹拌した。パーフルオロヘキサン １０ｍＬを入れ、クロロホルムで洗浄し、無水硫酸ナトリウムを用いて乾燥し、濃縮乾固することで、化合物１２ａを１．６１ｇ得た。

化合物１２ａ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 2.36-2.51 (m, 6H), 3.18 (s, 2H), 3.36-3.40 (m, 4H), 5.41-5.45 (m, 6H), 6.13-6.20 (m, 3H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -84.14, -85.60 - -86.60, -87.00, -87.21 - -87.34, -123.22 - -123.40, -124.90 - -124.96, -125.78, -131.36 - -131.50, -132.41.
(Synthesis Example 8-4)

CF ₃ CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) _n OCF ₂ CF ₂ CO ₂ Me (n = 25) 1.7 g, the compound 11a 0.37 g and mXHF 2 mL obtained in Synthesis Example 8-3 Was put in and stirred overnight at room temperature. 10 mL of perfluorohexane was added, washed with chloroform, dried over anhydrous sodium sulfate, and concentrated to dryness to obtain 1.61 g of compound 12a.

Compound 12a
^{1 1} H NMR (mXHF, 400MHz) δ: 2.36-2.51 (m, 6H), 3.18 (s, 2H), 3.36-3.40 (m, 4H), 5.41-5.45 (m, 6H), 6.13-6.20 (m, 3H);
¹⁹ F NMR (mXHF, 400MHz) δ: -84.14, -85.60 --- 86.60, -87.00, -87.21 --- 87.34, -123.22 --- 123.40, -124.90 --- 124.96, -125.78, -131.36 --- 131.50,- 132.41.

合成例８−４で得た化合物１２ａ １．１２ｇをｍＸＨＦ ３ｍＬに溶解後、トリアセトキシメチルシラン ３μｌ、トリクロロシラン ０．２５２ｍｌ、カールシュテット触媒 ３４μｌを添加し、４時間撹拌した。濃縮乾固した後、ｍＸＨＦ ３ｍＬ、オルトギ酸トリメチル ０．９５ｍＬ、およびメタノール ６０μｌを滴下し、６０℃で３時間撹拌した。この液を濾過した後、濃縮乾固することで、化合物１３ａを１．２ｇ得た。

化合物１３ａ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 0.95-1.08 (m, 6H), 1.55-1.67 (m, 6H), 1.77-1.95 (m, 6H), 3.36-3.40 (m, 4H), 3.63 (s, 2H), 3.85-4.13 (m, 27H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -84.01 - -84.25, -84.50 - -86.00, -86.61, -87.12, -122.67, -124.79, -125.50, -131.20 - -131.73, -132.41.
(Synthesis Example 8-5)

After dissolving 1.12 g of the compound 12a obtained in Synthesis Example 8-4 in 3 mL of mXHF, 3 μl of triacetoxymethylsilane, 0.252 ml of trichlorosilane, and 34 μl of Karstedt catalyst were added, and the mixture was stirred for 4 hours. After concentration to dryness, 3 mL of mXHF, 0.95 mL of trimethyl orthoformate, and 60 μl of methanol were added dropwise, and the mixture was stirred at 60 ° C. for 3 hours. After filtering this liquid, it was concentrated to dryness to obtain 1.2 g of compound 13a.

Compound 13a
^{1 1} H NMR (mXHF, 400MHz) δ: 0.95-1.08 (m, 6H), 1.55-1.67 (m, 6H), 1.77-1.95 (m, 6H), 3.36-3.40 (m, 4H), 3.63 (s, 2H), 3.85-4.13 (m, 27H);
¹⁹ F NMR (mXHF, 400MHz) δ: -84.01 --- 84.25, -84.50 --- 86.00, -86.61, -87.12, -122.67, -124.79, -125.50, -131.20 --- 131.73, -132.41.

化合物８ｂ ６ｇをジクロロメタン １０ｍＬに溶解した後、氷浴に浸け、２，２−ジアリル−４−ペンテニルアミン ２．８５ｇを滴下した後、室温で一晩撹拌させた。濃縮乾固後、シリカゲルカラムクロマトグラフィにて精製することで、化合物９ｂを２．４３ｇ得た。

化合物９ｂ
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ） δ: 2.00-2.10 (m, 6H), 3.23-3.33 (m, 2H), 3.97 (s, 3H), 5.04-5.20 (m, 6H), 5.70-5.95 (m, 3H), 6.58 (br s, 1H).
(Synthesis Example 9)
(Synthesis Example 9-1)

After dissolving 6 g of compound 8b in 10 mL of dichloromethane, the mixture was immersed in an ice bath, 2.85 g of 2,2-diallyl-4-pentenylamine was added dropwise, and the mixture was stirred overnight at room temperature. After concentration to dryness, purification by silica gel column chromatography gave 2.43 g of compound 9b.

Compound 9b
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ: 2.00-2.10 (m, 6H), 3.23-3.33 (m, 2H), 3.97 (s, 3H), 5.04-5.20 (m, 6H), 5.70-5.95 (m) , 3H), 6.58 (br s, 1H).

合成例９−１で得た化合物９ｂ ２．９２ｇをＴＨＦ １２ｍＬに溶解した後、Ｎ−Ｂｏｃ−エチレンジアミン ４ｍＬを滴下し、５０℃で一晩撹拌した。濃縮乾固した後、シリカゲルカラムクロマトグラフィにて精製することで、化合物１０ｂを２．７４ｇ得た。

化合物１０ｂ
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ） δ: 1.43 (s, 9H), 2.00-2.16 (m, 6H), 3.27 (d, 2H), 3.30-3.50 (m, 4H), 5.00 (br s, 1H), 5.10-5.20 (m, 6H) , 5.75-5.90 (m, 3H), 6.81 (br s, 1H), 7.69 (br s, 1H).
(Synthesis Example 9-2)

After dissolving 2.92 g of the compound 9b obtained in Synthesis Example 9-1 in 12 mL of THF, 4 mL of N-Boc-ethylenediamine was added dropwise, and the mixture was stirred at 50 ° C. overnight. After concentration to dryness, purification by silica gel column chromatography gave 2.74 g of compound 10b.

Compound 10b
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ: 1.43 (s, 9H), 2.00-2.16 (m, 6H), 3.27 (d, 2H), 3.30-3.50 (m, 4H), 5.00 (br s, 1H) , 5.10-5.20 (m, 6H), 5.75-5.90 (m, 3H), 6.81 (br s, 1H), 7.69 (br s, 1H).

合成例９−２で得た化合物１０ｂ １．２ｇをジクロロメタン ５ｍＬに溶解した後、氷浴に付け、トリフルオロ酢酸 ５ｍＬを添加して５時間撹拌した。濃縮乾固した後、シリカゲルカラムクロマトグラフィにて精製することで、化合物１１ｂを０．８５３ｇ得た。

化合物１１ｂ
^１Ｈ ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ） δ: 2.00-2.10 (m, 6H), 2.80-2.92 (m, 2H), 3.20-3.30 (m, 2H), 3.40-3.50 (m, 2H), 5.00-5.18 (m, 6H), 5.75-5.90 (m, 3H), 6.82 (br s, 1H).
(Synthesis Example 9-3)

After dissolving 1.2 g of the compound 10b obtained in Synthesis Example 9-2 in 5 mL of dichloromethane, the mixture was placed in an ice bath, 5 mL of trifluoroacetic acid was added, and the mixture was stirred for 5 hours. After concentration to dryness, the product was purified by silica gel column chromatography to obtain 0.853 g of compound 11b.

Compound 11b
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ: 2.00-2.10 (m, 6H), 2.80-2.92 (m, 2H), 3.20-3.30 (m, 2H), 3.40-3.50 (m, 2H), 5.00-5.18 (m, 6H), 5.75-5.90 (m, 3H), 6.82 (br s, 1H).

ＣＦ_３ＣＦ_２ＣＦ_２（ＯＣＦ_２ＣＦ_２ＣＦ_２）_ｎＯＣＦ_２ＣＦ_２ＣＯ_２Ｍｅ（ｎ＝２５） ２．０ｇに対して、合成例８−３で得た化合物１１ｂ ０．４２９ｇとｍＸＨＦ ２ｍＬを入れ、室温で一晩撹拌した。パーフルオロヘキサン １０ｍＬを入れ、クロロホルムで洗浄し、無水硫酸ナトリウムを用いて乾燥した後、濃縮乾固することで、化合物１２ｂを２．２ｇ得た。

化合物１２ｂ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 2.39-2.48 (m, 6H), 3.70 (d, 2H), 3.80-4.00 (m, 4H), 5.40-5.52 (m, 6H), 6.13-6.26 (m, 3H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -84.13 - -84.17, -85.60 - -86.60, -87.29, -87.33 - -87.36, -121.82, -122.50, -125.11 - -125.15, -129.46, -131.35 - -131.40, -132.41.
(Synthesis Example 9-4)

CF ₃ CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) _n OCF ₂ CF ₂ CO ₂ Me (n = 25) 2.0 g, compound 11b 0.429 g and mXHF 2 mL obtained in Synthesis Example 8-3 Was put in and stirred overnight at room temperature. To obtain 2.2 g of compound 12b by adding 10 mL of perfluorohexane, washing with chloroform, drying with anhydrous sodium sulfate, and concentrating to dryness.

Compound 12b
^{1 1} H NMR (mXHF, 400MHz) δ: 2.39-2.48 (m, 6H), 3.70 (d, 2H), 3.80-4.00 (m, 4H), 5.40-5.52 (m, 6H), 6.13-6.26 (m, 3H);
¹⁹ F NMR (mXHF, 400MHz) δ: -84.13 --- 84.17, -85.60 --- 86.60, -87.29, -87.33 --- 87.36, -121.82, -122.50, -125.11 --- 125.15, -129.46, -131.35 --- 131.40, -132.41.

合成例９−４で得た化合物１２ｂ １．２５ｇをｍＸＨＦ １．５ｍＬに溶解後、トリアセトキシメチルシラン ３μｌ、トリクロロシラン ０．２５２ｍｌ、カールシュテット触媒 ３４μｌを添加し、４時間撹拌した。濃縮乾固した後、ｍＸＨＦ １．５ｍＬ、オルトギ酸トリメチル ０．９５ｍＬ、およびメタノール ６０μｌを滴下し、６０℃で３時間撹拌させた。この液を濾過した後、濃縮乾固することで、化合物１３ｂを１．１ｇ得た。

化合物１３ｂ
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 0.90-1.10 (m, 6H), 1.60-1.70 (m, 6H), 1.75-1.95 (m, 6H), 3.68 (d, 2H), 3.90-4.10 (m, 31H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -84.13 - -84.27, -85.10 - -85.76, -86.78, -87.36, -120.78, -121.86, -124.90, -128.85, -131.35 - -131.50, -132.40.
(Synthesis Example 9-5)

After dissolving 1.25 g of the compound 12b obtained in Synthesis Example 9-4 in 1.5 mL of mXHF, 3 μl of triacetoxymethylsilane, 0.252 ml of trichlorosilane, and 34 μl of Karstedt catalyst were added, and the mixture was stirred for 4 hours. After concentration to dryness, 1.5 mL of mXHF, 0.95 mL of trimethyl orthoformate, and 60 μl of methanol were added dropwise, and the mixture was stirred at 60 ° C. for 3 hours. After filtering this liquid, it was concentrated to dryness to obtain 1.1 g of compound 13b.

Compound 13b
^{1 1} H NMR (mXHF, 400MHz) δ: 0.90-1.10 (m, 6H), 1.60-1.70 (m, 6H), 1.75-1.95 (m, 6H), 3.68 (d, 2H), 3.90-4.10 (m, 31H);
¹⁹ F NMR (mXHF, 400MHz) δ: -84.13 --- 84.27, -85.10 --- 85.76, -86.78, -87.36, -120.78, -121.86, -124.90, -128.85, -131.35 --- 131.50, -132.40.

ＣＦ_３ＣＦ_２ＣＦ_２（ＯＣＦ_２ＣＦ_２ＣＦ_２）_ｎＯＣＦ_２ＣＦ_２ＣＯ_２Ｍｅ（ｎ＝２５） ３．０ｇに対して、２，２−ジアリル−４−ペンテニルアミン ０．２０７ｇとｍＸＨＦ ２ｍＬを入れ、室温で一晩撹拌した。パーフルオロヘキサン １０ｍＬを入れ、アセトンで洗浄し、無水硫酸ナトリウムを用いて乾燥した後、濃縮乾固することで、化合物１４を２．８９ｇ得た。

化合物１４
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 2.39 (d, 6H), 3.66 (d, 2H), 5.42-5.46 (m, 6H), 6.15-6.25 (m, 3H), 7.02 (brs, 1H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -84.2, -85.5, -86.6, -125.4, -131.4, -132.4.
(Comparative Example 1)
(Comparative Example 1-1)

CF ₃ CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) _n OCF ₂ CF ₂ CO ₂ Me (n = 25) 3.0 g, 2,2-diallyl-4-pentenylamine 0.207 g and mXHF 2 mL Was put in and stirred overnight at room temperature. To obtain 2.89 g of compound 14 by adding 10 mL of perfluorohexane, washing with acetone, drying with anhydrous sodium sulfate, and concentrating to dryness.

Compound 14
^{1 1} H NMR (mXHF, 400MHz) δ: 2.39 (d, 6H), 3.66 (d, 2H), 5.42-5.46 (m, 6H), 6.15-6.25 (m, 3H), 7.02 (brs, 1H);
¹⁹ F NMR (mXHF, 400MHz) δ: -84.2, -85.5, -86.6, -125.4, -131.4, -132.4.

比較例１−１で得た化合物１４ ２．８９ｇをｍＸＨＦ １．５ｍＬに溶解後、トリアセトキシメチルシラン ５．６７μｌ、トリクロロシラン ０．９１１ｍｌ、カールシュテット触媒 ６８．７μｌを添加し、４時間撹拌した。濃縮乾固した後、ｍＸＨＦ １．５ｍＬ、オルトギ酸トリメチル ２．０ｍＬ、およびメタノール １１０μｌを滴下し、６０℃で３時間撹拌させた。この液を濾過した後、濃縮乾固することで、化合物１５を２．５０ｇ得た。

化合物１５
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 0.96-1.02 (m, 6H), 1.58-1.67 (m, 6H),1.82-1.86 (m, 6H) 3.61 (d, 2H), 3.90-4.05 (m, 27H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -84.2, -85.5, -86.6, -124.4, -131.4, -132.4.
(Comparative Example 1-2)

After dissolving 2.89 g of the compound 14 obtained in Comparative Example 1-1 in 1.5 mL of mXHF, 5.67 μl of triacetoxymethylsilane, 0.911 ml of trichlorosilane, and 68.7 μl of Karstedt catalyst are added, and the mixture is stirred for 4 hours. did. After concentration to dryness, 1.5 mL of mXHF, 2.0 mL of trimethyl orthoformate, and 110 μl of methanol were added dropwise, and the mixture was stirred at 60 ° C. for 3 hours. After filtering this liquid, it was concentrated to dryness to obtain 2.50 g of compound 15.

Compound 15
^{1 1} H NMR (mXHF, 400MHz) δ: 0.96-1.02 (m, 6H), 1.58-1.67 (m, 6H), 1.82-1.86 (m, 6H) 3.61 (d, 2H), 3.90-4.05 (m, 27H) );
¹⁹ F NMR (mXHF, 400MHz) δ: -84.2, -85.5, -86.6, -124.4, -131.4, -132.4.

ＣＦ_３（ＯＣＦ_２）_ｍ（ＯＣＦ_２ＣＦ_２）_ｎＯＣＦ_２ＣＯ_２Ｍｅ（ｍ＝４０，ｎ＝２４） ２．０ｇに対して、２，２−ジアリル−４−ペンテニルアミン ０．１５８ｇとｍＸＨＦ ２ｍＬを入れ、室温で一晩撹拌した。パーフルオロヘキサン １０ｍＬを入れ、アセトンで洗浄し、無水硫酸ナトリウムを用いて乾燥した後、濃縮乾固することで、化合物１６を１．９１ｇ得た。

化合物１６
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 2.39 (d, 6H), 3.66 (d, 2H), 5.42-5.46 (m, 6H), 6.15-6.25 (m, 3H), 7.02 (brs, 1H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -131.7, -127.9, -127.4, -117.7, -92.6, -91.0, -87.4, -87.3, -85.8, −85.6, -83.2, -81.6, -79.9, -74.5, -59.9, -58.2, -57.4, -55.6, -54.0.
(Comparative Example 2)
(Comparative Example 2-1)

CF ₃ (OCF ₂ ) _m (OCF ₂ CF ₂ ) _n OCF ₂ CO ₂ Me (m = 40, n = 24) 2.0 g, 2,2-diallyl-4-pentenylamine 0.158 g and mXHF 2 mL was added and stirred at room temperature overnight. To obtain 1.91 g of compound 16 by adding 10 mL of perfluorohexane, washing with acetone, drying with anhydrous sodium sulfate, and concentrating to dryness.

Compound 16
^{1 1} H NMR (mXHF, 400MHz) δ: 2.39 (d, 6H), 3.66 (d, 2H), 5.42-5.46 (m, 6H), 6.15-6.25 (m, 3H), 7.02 (brs, 1H);
¹⁹ F NMR (mXHF, 400MHz) δ: -131.7, -127.9, -127.4, -117.7, -92.6, -91.0, -87.4, -87.3, -85.8, -85.6, -83.2, -81.6, -79.9,- 74.5, -59.9, -58.2, -57.4, -55.6, -54.0.

比較例２−１で得た化合物１６ １．９１ｇをｍＸＨＦ １．５ｍＬに溶解後、トリアセトキシメチルシラン ３．２１μｌ、トリクロロシラン ０．５１６ｍｌ、カールシュテット触媒 ３８．９μｌを添加し、４時間撹拌した。濃縮乾固した後、ｍＸＨＦ １．５ｍＬ、オルトギ酸トリメチル １．１ｍＬ、およびメタノール ６２μｌを滴下し、６０℃で３時間撹拌させた。この液を濾過した後、濃縮乾固することで、化合物１７を１．７７ｇ得た。

化合物１７
^１Ｈ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: 0.96-1.02 (m, 6H), 1.58-1.67 (m, 6H),1.82-1.86 (m, 6H) 3.61 (d, 2H), 3.90-4.05 (m, 27H);
^１９Ｆ ＮＭＲ（ｍＸＨＦ，４００ＭＨｚ） δ: -131.7, -127.9, -127.4, -117.7, -92.6, -91.0, -87.4, -87.3, -85.8, −85.6, -83.2, -81.6, -79.9, -74.5, -59.9, -58.2, -57.4, -55.6, -54.0.
(Comparative Example 2-2)

After dissolving 1.91 g of the compound 16 obtained in Comparative Example 2-1 in 1.5 mL of mXHF, 3.21 μl of triacetoxymethylsilane, 0.516 ml of trichlorosilane, and 38.9 μl of Karstedt catalyst were added, and the mixture was stirred for 4 hours. did. After concentration to dryness, 1.5 mL of mXHF, 1.1 mL of trimethyl orthoformate, and 62 μl of methanol were added dropwise, and the mixture was stirred at 60 ° C. for 3 hours. After filtering this liquid, it was concentrated to dryness to obtain 1.77 g of Compound 17.

Compound 17
^{1 1} H NMR (mXHF, 400MHz) δ: 0.96-1.02 (m, 6H), 1.58-1.67 (m, 6H), 1.82-1.86 (m, 6H) 3.61 (d, 2H), 3.90-4.05 (m, 27H) );
¹⁹ F NMR (mXHF, 400MHz) δ: -131.7, -127.9, -127.4, -117.7, -92.6, -91.0, -87.4, -87.3, -85.8, -85.6, -83.2, -81.6, -79.9,- 74.5, -59.9, -58.2, -57.4, -55.6, -54.0.

(Preparation of surface treatment agent)
The fluoropolyether group-containing silane compounds (5a, 5d, 7a, 7d, 15, 17) obtained in Synthesis Examples 1-4, 4-4, 5-2, 7-2, and Comparative Examples 1 and 2 were used. A surface treatment agent was prepared by dissolving each in hydrofluoroether (Novec HFE-7200, manufactured by 3M Japan Ltd.) so as to have a solid content concentration of 0.1% by mass.

(Formation of surface treatment layer)
The surface treatment agent was applied onto chemically tempered glass (Corning, "gorilla" glass, 0.7 mm thick) using a spin coater.
The conditions for spin coating were 300 rpm for 3 seconds and 2000 rpm for 30 seconds.
The coated glass was heated at 150 ° C. for 30 minutes in a constant temperature bath in the air to form a surface treatment layer.

(Characteristic evaluation of surface treatment layer)
The characteristics of the obtained surface treatment layer were evaluated as follows.

<Static contact angle>
(Initial evaluation)
First, as an initial evaluation, after the surface treatment layer was formed, the static contact angle of water was measured in a state where nothing was touched on the surface.

<Eraser wear resistance test>
The glass on which the surface treatment layer was formed was horizontally arranged, and an eraser loaded under the following conditions was reciprocated on the surface of the surface treatment layer using a rubbing tester (manufactured by Shinto Kagaku Co., Ltd.). The contact angle of water was measured every 2500 times of reciprocation (number of frictions), and the test was continued until the contact angle of water became less than 100 °. The test environmental conditions were 25 ° C. and a humidity of 40% RH.

Eraser: Raver Eraser (manufactured by Minoan)
Ground contact area: 6 mmφ
Travel distance (one way): 30 mm
Moving speed: 3,600 mm / min Load: 1 kg / 6 mmφ

The results are shown in the table below. In the table below, "-" indicates that the measurement is not performed.

The surface treatment agent of the present disclosure can be suitably used for forming a surface treatment layer on a wide variety of base materials, particularly the surface of an optical member that requires transparency.

Claims (20)

Equation (1a) or Equation (1b):

[During the ceremony:
R ^{F1 is Rf 1-} R ^F- O _q- independently at each appearance;
R ^F2 is −Rf ² _p −R ^F −O _q −;
Rf ¹ _{is a C 1-16} alkyl group that may be independently substituted with one or more fluorine atoms at each appearance;
Rf ² _{is a C 1-6} alkylene group that may be substituted with one or more fluorine atoms;
^RF is a divalent fluoropolyether group independently at each appearance;
p is 0 or 1;
q is 0 or 1 independently at each appearance;
α is an integer from 1 to 9;
β is an integer from 1 to 9;
γ is an integer of 1 to 9 independently of each other;
X ^A is a 2-10 valent organic group with two or more amide bonds, each independently at each appearance;
R ^Si is a monovalent group containing a Si atom to which a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group is bonded independently at each appearance. ]
A fluoropolyether group-containing silane compound represented by. ^RF is independent for each appearance and formula:
− (OC ₆ F ₁₂ ) _a − (OC ₅ F ₁₀ ) _b − (OC ₄ F ₈ ) _c − (OC ₃ F ₆ ) _d − (OC ₂ F ₄ ) _e − (OCF ₂ ) _f −
[During the ceremony:
a, b, c, d, e and f are independently integers from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more, and a, b, The order of existence of each repeating unit in parentheses with c, d, e or f is arbitrary in the equation. ]
The fluoropolyether group-containing silane compound according to claim 1, which is a group represented by. R ^F is, independently at each occurrence, the following formula (f1), (f2), (f3), represented by (f4) or (f5), fluoropolyether group according to claim 1 or 2 Containing silane compound.
− (OC ₃ F ₆ ) _d − − (OC ₂ F ₄ ) _e − (f1)
[In the formula, d is an integer of 1 to 200 and e is 1. ]
− (OC ₄ F ₈ ) _c − (OC ₃ F ₆ ) _d − (OC ₂ F ₄ ) _e − (OCF ₂ ) _f − (f2)
[In the formula, c and d are independently integers of 0 or more and 30 or less, and e and f are independently integers of 1 or more and 200 or less.
The sum of c, d, e and f is 2 or more,
The order of existence of each repeating unit with the subscripts c, d, e or f in parentheses is arbitrary in the equation. ]
-(R ^6- R ⁷ ) _g- (f3)
[In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ and
R ⁷ is _{a group selected from OC 2} F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or is selected independently of these groups 2 Or a combination of three groups,
g is an integer of 2 to 100. ]
− (OC ₆ F ₁₂ ) _a − (OC ₅ F ₁₀ ) _b − (OC ₄ F ₈ ) _c − (OC ₃ F ₆ ) _d − (OC ₂ F ₄ ) _e − (OCF ₂ ) _f − (f4)
[In the formula, e is an integer of 1 or more and 200 or less, and a, b, c, d and f are independently integers of 0 or more and 200 or less, and a, b, c, d and e. The sum of and f is at least 1, and the order of existence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the equation. ]
− (OC ₆ F ₁₂ ) _a − (OC ₅ F ₁₀ ) _b − (OC ₄ F ₈ ) _c − (OC ₃ F ₆ ) _d − (OC ₂ F ₄ ) _e − (OCF ₂ ) _f − (f5)
[In the formula, f is an integer of 1 or more and 200 or less, and a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and a, b, c, d and e. The sum of and f is at least 1, and the order of existence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the equation. ] X ^A is independent of each appearance,
-(X ²¹ ) _s21 -[(X ^N )-(X ²² )] _s11- (X ^N )-(X ²¹ ) _s22-
The fluoropolyether group-containing silane compound according to any one of claims 1 to 3, which is a group represented by.
[During the ceremony:
X ^N represents an amide bond;
s11 is an integer from 1 to 3;
Each of X ²¹ is an independently 2-10 valent organic group;
X ²² is a divalent organic group independently at each appearance;
s21 is 0 or 1 independently of each other;
s22 is 0 or 1 independently of each other. ] X ^A is a divalent organic group, which is independent of each appearance.
-(X ²¹ ) _s21 -[(X ^N )-(X ²² )] _s11- (X ^N )-(X ²¹ ) _s22-
The fluoropolyether group-containing silane compound according to any one of claims 1 to 4, which is a group represented by.
[During the ceremony:
X ^N represents an amide bond;
s11 is an integer from 1 to 3;
Each of X ²¹ is a divalent organic group independently;
X ²² is a divalent organic group independently at each appearance;
s21 is 0 or 1 independently of each other;
s22 is 0 or 1 independently of each other. ] The X- ²² is independent of each appearance,
-R ^221- or
_{^{- (R 221) s31 -X 31}} - (R 222) s32 -
The fluoropolyether group-containing silane compound according to claim 4 or 5.
[During the ceremony:
R ²²¹ and R ²²² are independently C _1-10 alkylene groups;
The hydrogen atom of the C _1-10 alkylene group may be substituted;
X ³¹ is, -O-, or ^{-NR 54} - and is;
R ⁵⁴ is a hydrogen atom, a phenyl group or a C _1-6 alkyl group;
s31 is 0 or 1;
s32 is 0 or 1. ] The fluoropolyether group-containing silane compound according to any one of claims 1 to 6, wherein α, β and γ are 1 each. The fluoropolyether group according to any one of claims 1 to 7, wherein R ^Si is independently represented by the formula (S1), (S2), (S3) or (S4) at each appearance. Containing silane compound.

[During the ceremony:
R ¹¹ is an independent hydroxyl group or hydrolyzable group at each appearance;
R ¹² is an independent hydrogen atom or monovalent organic group at each appearance;
n1 is an integer of 0 to 3 independently for each unit ^{(SiR 11} _n1 R ¹² _3-n1);
X ¹¹ is an independent, single-bonded or divalent organic group at each appearance;
R ¹³ is an independent hydrogen atom or monovalent organic group at each appearance;
t is an integer greater than or equal to 2 independently for each occurrence;
R ¹⁴ is independently a hydrogen atom, a halogen atom or -X ^11- SiR ¹¹ _n1 R ¹² _3-n1 at each appearance;
R ¹⁵ is independently at each occurrence, a single bond, an oxygen atom, an alkylene group or alkyleneoxy group having 1 to 6 carbon atoms having from 1 to 6 carbon atoms;
R ^{a1 is -Z 1-} SiR ²¹ _p1 R ²² _q1 R ²³ _r1 independently in each appearance;
Z ¹ is an oxygen atom or a divalent organic group, independently of each appearance;
R ²¹ is independently at each occurrence, be a _{^{-Z 1 '-SiR 21' p1 '}} R 22' q1 'R 23' r1 ';
R ²² is an independent hydroxyl group or hydrolyzable group at each appearance;
R ²³ is an independent hydrogen atom or monovalent organic group at each appearance;
p1 is an integer from 0 to 3 independently for each occurrence;
q1 is an integer from 0 to 3 independently for each occurrence;
r1 is an integer from 0 to 3 independently for each occurrence;
Z 1 ^'are each independently at each occurrence, an oxygen atom or a divalent organic group;
R ^{21 'are} each independently at each ^occurrence, be a _{^{-Z 1 "-SiR 22" q1 "}} R 23" r1 ";
R ^{22 'are} each independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R ^23'is a hydrogen atom or monovalent organic group independently at each appearance;
p1'is an integer from 0 to 3 independently for each occurrence;
q1'is an integer from 0 to 3 independently for each occurrence;
r1'is an integer from 0 to 3 independently for each occurrence;
Z ^{1 "} is an oxygen atom or a divalent organic group, independently of each appearance;
R ^{22 "} is an independent hydroxyl group or hydrolyzable group at each appearance;
R ^{23 "} is an independent hydrogen atom or monovalent organic group at each appearance;
q1 ”is an integer from 0 to 3 independently for each occurrence;
"r1" is an integer from 0 to 3 independently for each occurrence;
R ^b1 is independently a hydroxyl group or a hydrolyzable group at each appearance;
R ^c1 is an independent hydrogen atom or monovalent organic group at each appearance;
k1 is an integer from 0 to 3 independently for each occurrence;
l1 is an integer from 0 to 3 independently for each occurrence;
m1 is an integer from 0 to 3 independently for each occurrence;
R ^{d1 is -Z 2-} CR ³¹ _p2 R ³² _q2 R ³³ _r2 independently at each appearance;
Z ² is an independent, single bond, oxygen atom or divalent organic group at each appearance;
R ³¹ is independently at each occurrence, be a _{^{-Z 2 '-CR 32' q2 '}} R 33' r2 ';
R ^{32 is -Z 3-} SiR ³⁴ _n2 R ³⁵ _3-n2 independently at each appearance;
R ³³ is an independent hydrogen atom, hydroxyl group or monovalent organic group at each appearance;
p2 is an integer from 0 to 3 independently for each occurrence;
q2 is an integer from 0 to 3 independently for each occurrence;
r2 is an integer from 0 to 3 independently for each occurrence;
Z 2 ^'are each independently at each occurrence, a single bond, an oxygen atom or a divalent organic group;
R ^{32 'are} each independently at each ^occurrence, be a _{^{-Z 3 -SiR 34 n2 R 35 3}} -n2;
R ^33'is a hydrogen atom, a hydroxyl group or a monovalent organic group independently at each appearance;
q2'is an integer from 0 to 3 independently for each occurrence;
r2'is an integer from 0 to 3 independently for each occurrence;
Z ³ is an independent, single bond, oxygen atom or divalent organic group at each appearance;
R ³⁴ is an independent hydroxyl group or hydrolyzable group at each appearance;
R ³⁵ is an independent hydrogen atom or monovalent organic group at each appearance;
n2 is an integer from 0 to 3 independently for each occurrence;
R ^{e1 is -Z 3-} SiR ³⁴ _n2 R ³⁵ _3-n2 independently at each appearance;
R ^f1 is a hydrogen atom, a hydroxyl group or a monovalent organic group independently at each appearance;
k2 is an integer from 0 to 3 independently for each occurrence;
l2 is an integer from 0 to 3 independently for each occurrence;
m2 is an integer from 0 to 3 independently for each appearance. ] The fluoropolyether group-containing silane compound according to claim 8, wherein n1 is 3. The fluoropolyether group-containing silane compound according to claim 8 or 9, wherein k1 is 3 and q1 is an integer of 1 to 3. The fluoropolyether group-containing silane compound according to any one of claims 8 to 10, wherein l2 is 3 and n2 is an integer of 1 to 3. A surface treatment agent containing at least one fluoropolyether compound represented by the formula (1a) or the formula (1b) according to any one of claims 1 to 11. The surface treatment agent according to claim 12, further containing one or more other components selected from a fluorine-containing oil, a silicone oil, and a catalyst. The surface treatment agent according to claim 12 or 13, further comprising a solvent. The surface treatment agent according to any one of claims 12 to 14, which is used as an antifouling coating agent or a waterproof coating agent. The surface treatment agent according to any one of claims 12 to 15, which is used for vacuum vapor deposition. The surface treatment agent according to any one of claims 12 to 15, which is used for a wet coating treatment. A pellet containing the surface treatment agent according to any one of claims 12 to 16. The fluoropolyether group-containing silane compound according to any one of claims 1 to 11 or the surface treatment agent according to any one of claims 12 to 17 on the base material and the surface of the base material. Articles containing more formed layers. The article according to claim 19, which is an optical member.