JP7319242B2 - Fluoropolyether group silane-containing compound - Google Patents

Description

The present disclosure relates to silane compounds containing fluoropolyether groups.

Certain fluorine-containing silane compounds are known to provide excellent water repellency, oil repellency, and antifouling properties when used for surface treatment of substrates. A layer obtained from a surface treatment agent containing a fluorine-containing silane compound (hereinafter also referred to as a "surface treatment layer") is applied as a so-called functional thin film to various substrates 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 molecular main chain and a hydrolyzable group bonded to an Si atom at the molecular end or terminal portion is known. (Patent Documents 1 and 2).

JP 2014-218639 A JP 2017-082194 A

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

［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] Formula (1a) or Formula (1b):

[In the formula:
R ^F1 is independently at each occurrence Rf ¹ -R ^F -O _q -;
R ^F2 is -Rf ² _p -R ^F -O _q -;
Rf ¹ is independently at each occurrence a C _1-16 alkyl group optionally substituted by one or more fluorine atoms;
Rf ² is a C _1-6 alkylene group optionally substituted by one or more fluorine atoms;
R ^F is independently at each occurrence a divalent fluoropolyether group;
p is 0 or 1;
q is independently 0 or 1 at each occurrence;
α is an integer from 1 to 9;
β is an integer from 1 to 9;
each γ is independently an integer from 1 to 9;
X ^A is each independently at each occurrence a divalent to decavalent organic group having two or more amide bonds;
R ^Si is independently at each occurrence a monovalent group comprising a Si atom to which is attached a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group. ]
A fluoropolyether group-containing silane compound represented by
[2] R ^F is independently at each occurrence of 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 -
[In the formula:
a, b, c, d, e and f are each independently an integer of 0 to 200, the sum of a, b, c, d, e and f is 1 or more; The order of existence of each repeating unit bracketed with c, d, e or f is arbitrary in the formula. ]
The fluoropolyether group-containing silane compound according to [1], which is a group represented by
[3] R ^F is described in [1] or [2], wherein each occurrence is independently represented by the following formula (f1), (f2), (f3), (f4) or (f5) fluoropolyether group-containing silane compound.
-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)
[Wherein, 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)
[Wherein, c and d are each independently an integer of 0 or more and 30 or less, e and f are each independently an integer of 1 or more and 200 or less,
the sum of c, d, e and f is greater than or equal to 2;
The order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula. ]
-(R ⁶ -R ⁷ ) _g - (f3)
[wherein R ⁶ is OCF ₂ or OC ₂ F ₄ ;
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 2 independently selected from these groups or a combination of three groups,
g is an integer from 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)
[Wherein, e is an integer of 1 or more and 200 or less, a, b, c, d and f are each independently an integer of 0 or more and 200 or less, and a, b, c, d, e and f are at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in 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 - (f5)
[Wherein, f is an integer of 1 or more and 200 or less, a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and a, b, c, d, e and f are at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula. ]
[4] X ^A independently on each occurrence:
-(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
[In the formula:
X ^N represents an amide bond;
s11 is an integer from 1 to 3;
each X ²¹ is independently a divalent to decavalent organic group;
X ²² is independently at each occurrence a divalent organic group;
each s21 is independently 0 or 1;
s22 is 0 or 1 independently. ]
[5] X ^A is a divalent organic group, independently at each occurrence,
-(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
[In the formula:
X ^N represents an amide bond;
s11 is an integer from 1 to 3;
each X ²¹ is independently a divalent organic group;
X ²² is independently at each occurrence a divalent organic group;
each s21 is independently 0 or 1;
s22 is 0 or 1 independently. ]
[6] X ²² is independently at each occurrence:
-R ²²¹ -, or
-(R ²²¹ ) _s31 -X ³¹ -(R ²²² ) _s32 -
The fluoropolyether group-containing silane compound according to [4] or [5].
[In the formula:
R ²²¹ and R ²²² are each independently a C _1-10 alkylene group;
hydrogen atoms of said C _1-10 alkylene group may be substituted;
X ³¹ is —O—, or —NR ⁵⁴ —;
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 each 1.
[8] R ^Si according to any one of [1] to [7], wherein each occurrence of R Si is independently represented by formula (S1), (S2), (S3) or (S4) fluoropolyether group-containing silane compound.

[In the formula:
R ¹¹ is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ¹² is independently at each occurrence a hydrogen atom or a monovalent organic group;
n1 is an integer of 0 to 3 independently for each (SiR ¹¹ _n1 R ¹² _3-n1 ) unit;
X ¹¹ is independently at each occurrence a single bond or a divalent organic group;
R ¹³ is independently at each occurrence a hydrogen atom or a monovalent organic group;
t is independently at each occurrence an integer greater than or equal to 2;
R ¹⁴ is independently at each occurrence a hydrogen atom, a halogen atom or —X ¹¹ —SiR ¹¹ _n1 R ¹² _3-n1 ;
each occurrence of R ¹⁵ is independently 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;
R ^a1 is independently at each occurrence -Z ¹ -SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ;
Z ¹ is independently at each occurrence an oxygen atom or a divalent organic group;
R ²¹ is independently at each occurrence -Z ^1' -SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ;
R ²² is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ²³ is independently at each occurrence a hydrogen atom or a monovalent organic group;
p1 is independently at each occurrence an integer from 0 to 3;
q1 is independently at each occurrence an integer from 0 to 3;
r1 is independently at each occurrence an integer from 0 to 3;
Z ^1′ is independently at each occurrence an oxygen atom or a divalent organic group;
R ^21′ is independently at each occurrence —Z ^1″ —SiR ^22″ _q1″ R ^23″ _r1″ ;
R ^22′ is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ^23′ at each occurrence is independently a hydrogen atom or a monovalent organic group;
p1′ is independently at each occurrence an integer from 0 to 3;
q' is independently at each occurrence an integer from 0 to 3;
r' is independently at each occurrence an integer from 0 to 3;
Z ^1″ is independently at each occurrence an oxygen atom or a divalent organic group;
R ^22″ is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ^23″ is independently at each occurrence a hydrogen atom or a monovalent organic group;
q1″ is independently at each occurrence an integer from 0 to 3;
r1″ is independently at each occurrence an integer from 0 to 3;
R ^b1 is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ^c1 is independently at each occurrence a hydrogen atom or a monovalent organic group;
k1 is independently at each occurrence an integer from 0 to 3;
l1 is independently at each occurrence an integer from 0 to 3;
m1 is independently at each occurrence an integer from 0 to 3;
R ^d1 is independently at each occurrence -Z ² -CR ³¹ _p2 R ³² _q2 R ³³ _r2 ;
Z ² is independently at each occurrence a single bond, an oxygen atom or a divalent organic group;
R ³¹ is independently at each occurrence -Z ^2' -CR ^32' _q2' R ^33' _r2' ;
R ³² is independently at each occurrence -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 ;
each occurrence of R ³³ is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group;
p2 is independently at each occurrence an integer from 0 to 3;
q2 is independently at each occurrence an integer from 0 to 3;
r2 is independently at each occurrence an integer from 0 to 3;
Z ^2' is independently at each occurrence a single bond, an oxygen atom or a divalent organic group;
R ^32′ is independently at each occurrence —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 ;
R ^33′ is independently at each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group;
q2' is independently at each occurrence an integer from 0 to 3;
r2' is independently at each occurrence an integer from 0 to 3;
Z ³ is independently at each occurrence a single bond, an oxygen atom or a divalent organic group;
R ³⁴ is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ³⁵ is independently at each occurrence a hydrogen atom or a monovalent organic group;
n2 is independently at each occurrence an integer from 0 to 3;
R ^e1 is independently at each occurrence —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 ;
R ^f1 is independently at each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group;
k2 is independently at each occurrence an integer from 0 to 3;
l2 is independently at each occurrence an integer from 0 to 3;
m2 is independently an integer from 0 to 3 at each occurrence. ]
[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 1-3.
[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 1-3.
[12] A surface treatment agent containing at least one fluoropolyether compound represented by formula (1a) or (1b) according to any one of [1] to [11].
[13] The surface treatment agent of [12], further containing one or more other components selected from fluorine-containing oils, silicone oils, and catalysts.
[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 for vacuum deposition.
[17] The surface treatment agent according to any one of [12] to [15], which is for wet coating treatment.
[18] A pellet containing the surface treatment agent according to any one of [12] to [16].
[19] A substrate and, on the surface of the substrate, the fluoropolyether group-containing silane compound according to any one of [1] to [11], or any one of [12] to [17] and a layer formed from the surface treatment agent according to 1.
[20] The article according to [19], which is an optical member.

According to the present disclosure, new fluoropolyether group-containing silane compounds are provided that can be used as surface treatment agents.

As used herein, "monovalent organic radical" means a monovalent radical containing carbon. Although the monovalent organic group is not particularly limited, it may be a hydrocarbon group or a derivative thereof. A derivative of a hydrocarbon group is a group having one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain. means In addition, when it shows simply as an "organic group", it means a monovalent organic group.

Moreover, a "divalent organic group" means a divalent group containing carbon. Examples of such divalent organic groups include, but are not particularly limited to, divalent groups in which one hydrogen atom is further eliminated from an organic group.

As used herein, "hydrocarbon group" means a group containing carbon and hydrogen from which one hydrogen atom has been removed from a hydrocarbon. Such hydrocarbon groups include, but are not limited to, C _1-20 hydrocarbon groups optionally substituted by one or more substituents, such as aliphatic hydrocarbon groups, aromatic A hydrocarbon group etc. are mentioned. The above "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. Hydrocarbon groups may also contain one or more ring structures.

As used herein, the substituent of the "hydrocarbon group" is not particularly limited, but for example, a halogen atom, C _1-6 alkyl optionally substituted by one or more halogen atoms group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl groups, C _6-10 aryl groups and 5-10 membered heteroaryl groups.

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

In formula (1a), R ^F1 is independently at each occurrence Rf ¹ -R ^F -O _q -.

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

In the above formula, Rf ¹ at each occurrence is independently a C _1-16 alkyl group optionally substituted by one or more fluorine atoms.

The "C _1-16 alkyl group" in the C _1-16 alkyl group optionally substituted by one or more fluorine atoms may be linear or branched, preferably is a straight or branched C _1-6 alkyl group, especially a C _1-3 alkyl group, more preferably a straight chain C _1-6 alkyl group, especially a C _1-3 alkyl group.

Rf ¹ above is preferably a C _1-16 alkyl group substituted with one or more fluorine atoms, more preferably a CF ₂ H—C _1-15 perfluoroalkylene group, still more preferably is a C _1-16 perfluoroalkyl group.

The C _1-16 perfluoroalkyl group may be linear or branched, preferably a linear or branched C _1-6 perfluoroalkyl group, especially C _{1- 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 optionally substituted by one or more fluorine atoms.

The "C _1-6 alkylene group" in the C _1-6 alkylene group optionally substituted by one or more fluorine atoms may be linear or branched, preferably is a linear or branched C _1-3 alkylene group, more preferably a linear C _1-3 alkylene group.

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

The C _1-6 perfluoroalkylene group may be linear or branched, preferably a linear or branched C _1-3 perfluoroalkylene group, 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 aspect, p is zero. In another aspect, p is 1.

In the above formula, q is 0 or 1 independently at each occurrence. In one aspect, q is zero. In another aspect q is 1.

In formulas (1a) and (1b) above, R ^F is independently at each occurrence a divalent fluoropolyether group.

R ^F preferably has 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 -
is a fluoropolyether group represented by
In the above formula:
a, b, c, d, e and f are each independently an integer of 0 to 200, the sum of a, b, c, d, e and f is 1 or more; The order of existence of each repeating unit bracketed with c, d, e or f is arbitrary in the formula.

a, b, c, d, e and f may preferably each independently be an integer from 0-100.

The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, 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, -( _OC6F12 ) _{- is} -( _{OCF2CF2CF2CF2CF2CF2} ) _{- ,} - _{( OCF} ( _CF3 ) _CF2CF2CF2CF2 )-, - _{( 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 )-. -( _OC5F10 )- is -( _{OCF2CF2CF2CF2CF2 ) - ,} -( _{OCF ( CF3} ) _CF2CF2CF2 )-, _{- ( OCF2CF} ( _CF3 ) 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 )—. -( _OC4F8 )- is -( _{OCF2CF2CF2CF2 ) -} , -( _OCF ( _CF3 ) _CF2CF2 )- _, -( _OCF2CF ( _CF3 ) _CF2 ) _- , -( _OCF2CF2CF ( _CF3 ))-, - ₍ OC( _CF3 ) _2CF2 )-, -( _OCF2C ( _CF3 ) ₂ ) _- , -(OCF( _CF3 )CF( Any of CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- and -(OCF ₂ CF(C ₂ F ₅ ))-, preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₃ F ₆ )- is any of -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- and -(OCF ₂ CF(CF ₃ ))- but preferably -(OCF ₂ CF ₂ CF ₂ )-. -(OC ₂ F ₄ )- may be either -(OCF ₂ CF ₂ )- or -(OCF(CF ₃ ))-, but is preferably -(OCF ₂ CF ₂ )- be.

In one aspect, each occurrence of ^RF is independently represented by the following formula (f1), (f2), (f3), (f4) or (f5).
-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)
[Wherein, 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)
[Wherein, c and d are each independently an integer of 0 or more and 30 or less, e and f are each independently an integer of 1 or more and 200 or less,
the sum of c, d, e and f is greater than or equal to 2;
The order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula. ]
-(R ⁶ -R ⁷ ) _g - (f3)
[wherein R ⁶ is OCF ₂ or OC ₂ F ₄ ;
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 2 independently selected from these groups or a combination of three groups,
g is an integer from 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)
[Wherein, e is an integer of 1 or more and 200 or less, a, b, c, d and f are each independently an integer of 0 or more and 200 or less, and a, b, c, d, e and f are at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in 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 - (f5)
[Wherein, f is an integer of 1 or more and 200 or less, a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and a, b, c, d, e and f are at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula. ]

In the above formula (f1), d is preferably an integer of 5-200, more preferably 10-100, still more preferably 15-50, for example 25-35. 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 - and more preferably -(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 10-200. Also, 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 aspect, 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, formula (f2) may be a group represented by -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -.

In formula (f3) above, 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 independently selected from these groups, or 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 for example -OC ₂ F ₄ OC ₃ F ₆ -, -OC _{2F4OC4F8- , -OC3F6OC2F4- , -OC3F6OC3F6- , -OC3F6OC4F8- , -OC4F8OC4F _ _ _ _ _ _ _ _ _ _ 8- , -OC4F8OC3F6- , -OC4F8OC2F4- , -OC2F4OC2F4OC3F6- , -OC2F4OC2F4OC _ _ _ _ _ _ _ _ _ _ 4F8- , -OC2F4OC3F6OC2F4- , -OC2F4OC3F6OC3F6- , -OC2F4OC4F8OC2F4- , _ _ _ _ _ _ _ _ _ _ _ _ -OC3F6OC2F4OC2F4- , -OC3F6OC2F4OC3F6- , -OC3F6OC3F6OC2F4- , and -OC4F _ _ _ _ _ _ _ _ _ _ _ 8} OC ₂ F ₄ OC ₂ F ₄ - and the like. In the above formula (f3), g is an integer of preferably 3 or more, more preferably 5 or more. Said g is preferably an integer of 50 or less. In formula (f3) above, OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ may be linear or branched, preferably linear. is a chain. In this aspect, 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, 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 aspect, R ^F is a group represented by the formula (f1).

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

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

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

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

In one aspect, the R ^F is
-( _{OC3F6 ) d-}
where d is an integer of 1-200.

In the above ^RF , the ratio of e to f (hereinafter referred to as “e/f ratio”) is 0.1 to 10, preferably 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 more improved the sliding property 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 higher the e/f ratio, the more stable the compound. Here, f is an integer of 1 or more.

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

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

The number average molecular weight of the R ^F1 and R ^F2 moieties is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000. be. In this specification, the number average molecular weights of R ^F1 and R ^F2 are values measured by ¹⁹ F-NMR.

In another embodiment, the R ^F1 and R ^F2 moieties have a number average molecular weight of 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, even more preferably 2,000. 000 to 10,000, such as 3,000 to 9,000, such as 3,000 to 8,000.

In the above formula (1a), α is an integer of 1-9 and β is an integer of 1-9. These α and β can vary depending on the valence of ^XA . The sum of α and β is the same as the valence of ^XA . For example, if X ^A is a decavalent organic group, the sum of α and β is 10, such as α being 9 and β being 1, α being 5 and β being 5, or α being 1 and β being 9. obtain. Also, α and β are 1 when X ^A is a divalent organic group.

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

In the above formulas (1a) and (1b), X ^A is the fluoropolyether portion (R ^F1 and R ^F2 ) that mainly provides water repellency and surface slipperiness, etc., and the portion that provides bonding ability with the substrate ( R ^Si ) and the linker. In the structure described as X ^A , the left side is bonded to R ^F1 or R ^F2 , and the right side is bonded to R ^Si . The ^XA is such that the compounds represented by formulas (1a) and (1b) can exist stably.

Each occurrence of X ^A is independently a divalent to decavalent organic group having two or more amide bonds. A hydrogen atom bonded to a nitrogen atom in the amide bond may be substituted. In other words, the amide bond is represented by -NR ^N C(=O)- or -C(=O)NR ^N -, where R ^N is, for example, a hydrogen atom, a phenyl group or a C _1-6 alkyl group ( (preferably a methyl group), preferably a hydrogen atom.
By having such a structure, the fluoropolyether group-containing silane compound of the present disclosure has excellent friction durability (for example, skin friction durability, fabric friction durability, eraser friction durability, steel wool friction durability), resistance to Chemical properties (e.g. durability against solvents, durability against artificial perspiration, durability against acids and alkalis), water repellency, oil repellency, antifouling parts, etc.), waterproof (for example, to prevent water from entering electronic parts, etc.), or surface slipperiness (or lubricity, such as wiping off fingerprints and other stains, and It can contribute to the formation of a good cured layer (for example, a surface treatment layer) such as excellent touch. This is probably because having two or more amide bonds enhances the affinity between the fluoropolyether group-containing silane compound and the substrate, allowing formation of a tighter and stronger bond.

The divalent to decavalent organic group in X ^A above is preferably a divalent to octavalent organic group. In one aspect, such divalent to decavalent organic groups are preferably divalent to tetravalent organic groups, more preferably divalent organic groups. In another aspect, such divalent to decavalent organic groups are preferably trivalent to octavalent organic groups, more preferably trivalent to hexavalent organic groups.

In one aspect, X ^A is a divalent to decavalent organic group, each independently at each occurrence of formula (L1):
−(X ^N ) _s10 −(X ² ) _s12 − (L1)
is represented by

In Formula (L1), X ^N represents an amide bond. Here, the amide bond is represented by -NR ^N C(=O)- or -C(=O)NR ^N -. R ^N 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), each occurrence of X ² is independently a divalent or higher valent organic group. The valence of ^X2 may vary depending on the valence of the group represented by formula (L1) above. For example, when the group represented by formula (L1) is divalent, all X ² are divalent organic groups, and when the group represented by formula (L1) is trivalent, any one X 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 aspect, s10 is two.

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

In one aspect, X ^A is independently at each occurrence of formula (L2):
-(X ²¹ ) _s21 -[(X ^N )-(X ²² )] _s11 -(X ^N )-(X ²¹ ) _s22 -
(L2)
is a group represented by
In the formula:
X ^N represents an amide bond;
s11 is an integer from 1 to 3;
each X ²¹ is independently a divalent to decavalent organic group;
X ²² is independently at each occurrence a divalent organic group;
each s21 is independently 0 or 1;
s22 is 0 or 1 independently.

The portions represented by -(X ²¹ ) _s21 -, -(X ²² )-, and (X ²¹ ) _s22 - in formula (L2) are represented by -(X ² ) _s12 - in formula (L1) corresponds to the part That is, the sum of s21, s11 and s22 corresponds to s12, and the structure of ^X21 and ^X22 corresponds to the structure of ^X2 . The value obtained by adding 1 to s11 in formula (L2) is s10 in formula (L1).

In formula (L2), each X ²¹ is independently a divalent to decavalent organic group.

In one aspect, X ²¹ is a divalent organic group. In this embodiment, X ²¹ may have the same meaning as the structure described below as a divalent organic group for X ²² .

In one aspect, X ²¹ is independently at each occurrence:
-R ²¹¹ -, or
-(R ²¹¹ ) _s31 -X ³¹ -(R ²¹² ) _s32 -
is. In one aspect, X ²¹ is -R ²¹¹ -. In one aspect, X ²¹ is -(R ²¹¹ ) _s31 -X ³¹ -(R ²¹² ) _s32 -.

R ²¹¹ and R ²¹² above are each independently at each occurrence 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 halogen atom, a C _1-6 alkyl group optionally substituted by one or more halogen atoms, a C _2-6 alkenyl group , C _2-6 alkynyl group, C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl group, C _6-10 aryl group and one or more groups selected from 5- to 10-membered heteroaryl groups, such as halogen atoms, preferably fluorine atoms.

For example, R ²¹¹ and R ²¹² may each independently be -CH ₂ -, -CH ₂ CH ₂ -, CH ₂ CF ₂ -, -CF ₂ CH ₂ -, or -CF ₂ CF ₂ -. good.

In this embodiment, each occurrence of X ³¹ is independently —O— or —NR ⁵⁴ —. Here, R ⁵⁴ represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group), preferably a hydrogen atom.

In this aspect, s31 is independently 0 or 1 at each occurrence. In one aspect, s31 is zero. In one aspect, s31 is one.

In this aspect, s32 is independently 0 or 1 at each occurrence. In one aspect, s32 is zero. In one aspect, s32 is one.

In this aspect, 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 aspect, 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 aspect, X ²¹ includes the following groups:

[In the formula, R ²⁵ , R ²⁶ and R ²⁷ are each independently a divalent to hexavalent organic group. ]

In one embodiment, R ²⁵ above is a single bond, a C _1-20 alkylene group, a C _3-20 cycloalkylene group, a C _5-20 arylene group, -R ⁵⁷ -X ⁵⁸ -R ⁵⁹ -, -X ⁵⁸ - R ⁵⁹ -, or -R ⁵⁷ -X ⁵⁸ -. R ⁵⁷ and R ⁵⁹ 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. X ⁵⁸ above is -O-, -S-, -CO-, -O-CO- or -COO-.

In one embodiment, each of R ²⁶ and R ²⁷ above is independently a hydrocarbon or a group having at least one atom selected from N, O and S in the end or main chain of the hydrocarbon, Preferred are a C _1-6 alkylene group, -R ³⁶ -R ³⁷ -R ³⁶ -, -R ³⁶ -CHR ³⁸ ₂ - and the like. Here, each 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, each R ⁴⁵ is independently an alkyl group having 1 to 6 carbon atoms. R ⁴⁶ is N, O or S, preferably O.

In this aspect, each X ²¹ can independently be a trivalent to decavalent organic group.

In Formula (L2), X ^N represents an amide bond. Here, the amide bond is represented by -NR ^N C(=O)- or -C(=O)NR ^N -. R ^N 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 at each occurrence is independently a divalent organic group.

In one aspect, X ²² is, for example, the following formula:
-(R ⁵¹ ) _p5 -(X ⁵¹ ) _q5 -
[In the formula:
R ⁵¹ represents a single bond, —(CH ₂ ) _s5 — or an o-, m- or p-phenylene group, preferably —(CH ₂ ) _s5 —,
s5 is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, even more preferably 1 or 2;
X ⁵¹ represents -(X ⁵² ) _l5 -,
X ⁵² is independently at each occurrence -O-, -S-, o-, m- or p-phenylene group, -C(O)O-, -Si(R ⁵³ ) ₂ -, -( represents a group selected from the group consisting of Si(R ⁵³ ) ₂ O) _m5 —Si(R ⁵³ ) ₂ —, —NR ⁵⁴ — and —(CH ₂ ) _n5 —, provided that X ⁵² is an amide bond does not include
R ⁵³ at each occurrence independently represents a phenyl group, a C _1-6 alkyl group or a C _{1-6 alkoxy group, preferably a phenyl group or a C 1-6 alkyl} group, more preferably a methyl group and
each occurrence of R ⁵⁴ independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group);
m5 at each occurrence is independently an integer from 1 to 100, preferably an integer from 1 to 20;
n5 at each occurrence is independently an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3;
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;
q5 is 0 or 1;
Here, at least one of p5 and q5 is 1, and the order of existence of each repeating unit bracketed with p5 or q5 is arbitrary.]
A divalent organic group represented by is mentioned. wherein X ²² (typically a hydrogen atom of X ²² ) is substituted with one or more substituents selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group; may be In one aspect, X ²² is not substituted by these groups.

In a preferred embodiment, each of the above X ²² is independently
-(R ⁵¹ ) _p5 -(X ⁵¹ ) _q5 -R ⁵² -
is.
R ⁵² represents a single bond, -(CH ₂ ) _t5 - or an o-, m- or p-phenylene group, preferably -(CH ₂ ) _t5 -. t5 is an integer of 1-20, preferably an integer of 2-6, more preferably an integer of 2-3. wherein R ⁵² (typically the hydrogen atom of R ⁵² ) is substituted with one or more substituents selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group; may be In preferred embodiments, R ⁵² is not substituted by these groups.

X ²² is preferably
-R ²²¹ -, or
-(R ²²¹ ) _s31 -X ³¹ -(R ²²² ) _s32 -
is.

R ²²¹ and R ²²² are each independently at each occurrence a C _1-10 alkylene group, preferably a C _1-7 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 halogen atom, a C _1-6 alkyl group optionally substituted by one or more halogen atoms, a C _2-6 alkenyl group , C _2-6 alkynyl group, C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl group, C _6-10 aryl group and one or more groups selected from 5- to 10-membered heteroaryl groups, such as halogen atoms, preferably fluorine atoms. For example, all hydrogen atoms in the alkylene group may be substituted, preferably all hydrogen atoms in the alkylene group may be substituted with fluorine atoms.

In one aspect, the hydrogen atoms of the alkylene groups in R ²²¹ and R ²²² are at least partially substituted.

In one aspect, the hydrogen atoms of the alkylene groups in R ²²¹ and R ²²² are unsubstituted.

Each occurrence of X ³¹ is independently —O— or —NR ⁵⁴ —. Here, R ⁵⁴ represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group), preferably a hydrogen atom.

s31 is independently 0 or 1 at each occurrence. In one aspect, s31 is zero. In one aspect, s31 is one.

s32 is independently 0 or 1 at each occurrence. In one aspect, s32 is zero. In one aspect, s32 is one.

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

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

In one aspect, X ²² is represented by -R ²²¹ -.

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

In formula (L2), each s21 is 0 or 1 independently. In one aspect, s21 is one. In one aspect, s21 is zero.

In formula (L2), each s22 is 0 or 1 independently. In one aspect, s22 is one. In one aspect, s22 is zero.

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

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

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

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

In one aspect, s11 is an integer from 1 to 3, preferably 1 or 2. In one aspect, s11 is one. In one aspect, s11 is two.

In one aspect, X ²² is represented by -R ²²¹ - and s11 is 2 or 3, preferably 2. That is, in this embodiment, there are multiple -R ²²¹ -. In other words, in this aspect, there are a plurality of groups represented by -X ^N -X ²² -. In this embodiment, —R ²²¹ — may be an alkylene group in which some of the hydrogen atoms are substituted; an alkylene group in which some of the hydrogen atoms are substituted, and an unsubstituted alkylene group. ; it may be only an unsubstituted alkylene group. For example, when s11 is 2 and there are two -R ²²¹ -, the two -R ²²¹ - may both be alkylene groups in which a portion of the hydrogen atoms are substituted; Some of the hydrogen atoms may be substituted alkylene groups and the other may be unsubstituted alkylene groups; both may be unsubstituted alkylene groups.

In one aspect, X ^A is a divalent organic group, independently at each occurrence,
-(X ²¹ ) _s21 -[(X ^N )-(X ²² )] _s11 -(X ^N )-(X ²¹ ) _s22 -
is a group represented by
In the formula:
X ^N represents an amide bond;
s11 is an integer from 1 to 3;
each s21 is independently 0 or 1;
each s22 is independently 0 or 1;
X ²¹ and X ²² may each independently at each occurrence be a divalent organic group, specifically a divalent organic group as described above for X ²¹ or X ²² .

In this aspect, preferably each occurrence of X ²¹ or X ²² is independently
-(R ⁵¹ ) _p5 -(X ⁵¹ ) _q5 -R ⁵² -
and more preferably —R ²²¹ —, or
-(R ²²¹ ) _s31 -X ³¹ -(R ²²² ) _s32 -
is represented by R ⁵¹ , X ⁵¹ , R ⁵² , p5, q5, R ²²¹ , R ²²² , X ³¹ , s31 and s32 have the same meanings as above.

In one aspect, 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 - is -R ²²¹ -
may be

When represented by formula (L2), X ^A is, for example,
-X ^N -X ²² -X ^N -X ²¹ -,
^-X21 - ^XN - ^X22 - ^XN - ^X21- ,
-X ^N -X ²² -X ^N -X ²² -X ^N -X ²¹ -,
^-X21 - ^XN - ^X22 - ^XN - ^X22 - ^XN - ^X21- ,
-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 may be a group represented by

Although the specific structure of X ^A is not particularly limited, the following groups can be mentioned, for example. In the following n31 is independently at each occurrence an integer from 1 to 3 and n32 is an integer from 1 to 10 (preferably an integer from 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 -
_{-CF2CF2 -} CONH-NHCO-( _CH2 ) _n31- ,
—CF ₂ CF ₂ —CONH-(CH ₂ ) _n32 —CONH-(CH ₂ ) _n31 —,
_-CF2CF2 -CONH-( _CH2 ) _n32 -NHCO- _{( CH2} ) _n31- ,
—CF ₂ CF ₂ —CONH-(CH ₂ ) _n32 —O—CONH-(CH ₂ ) _n31 —,
_-CF2CF2 -CONH-( _CH2 ) _n32 -NHCO-O-( _CH2 ) _{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 —,
_-CF2CF2 -CONH-( _CH2 ) _n31 -NHCO-( _CF2 ) _n32 -CONH- _{( CH2} ) _n31- ,
-CF ₂ CF ₂ -(CH ₂ ) _n31 -CONH-(CH ₂ ) _n32 -NHCO-(CF ₂ ) _n32 -CONH-(CH ₂ ) _n31 -
_{-OCF2CF2 -} CONH-NHCO-( _CH2 ) _n31- ,
_{-OCF2CF2 -} CONH-( _CH2 ) _n32 -CONH-( _CH2 ) _n31- ,
_{-OCF2CF2 -} CONH-( _CH2 ) _n32 -NHCO-( _CH2 ) _n31- ,
_{-OCF2CF2 -} CONH-( _CH2 ) _n32 -O-CONH-( _CH2 ) _n31- ,
_{-OCF2CF2 -} CONH-( _CH2 ) _n32 -NHCO-O-( _CH2 ) _n31- ,
_{-OCF2CF2 -} CONH-( _CH2 ) _n32- NH-CONH-( _CH2 ) _n31- ,
—OCF ₂ CF ₂ —(CH ₂ ) _n31 —CONH—NHCO—(CH ₂ ) _n31 —,
_-OCF2CF2- ( _{CH2 ) n31} -CONH-( _CH2 ) _n32 -CONH-( _CH2 ) _n31- ,
—OCF ₂ CF ₂ —(CH ₂ ) _n31 —CONH—(CH ₂ ) _n32 —NHCO—(CH ₂ ) _n31 —,
_-OCF2CF2- ( _{CH2 ) n31} -O-CONH-( _CH2 ) _n32 -CONH-( _CH2 ) _n31- ,
—OCF ₂ CF ₂ —(CH ₂ ) _n31 —O—CONH—(CH ₂ ) _n32 —NHCO—(CH ₂ ) _n31 —,
_-OCF2CF2- ( _{CH2 ) n31} -NH-CONH-( _CH2 ) _n32 -CONH-( _CH2 ) _n31- ,
_-OCF2CF2- ( _{CH2 ) n31} -NH-CONH-( _CH2 ) _n32 -NHCO-( _CH2 ) _n31- ,
—OCF ₂ CF ₂ —(CH ₂ ) _n31 —CONH—(CH ₂ ) _n32 —O—CONH—(CH ₂ ) _n31 —,
_-OCF2CF2- ( _{CH2 ) n31} -CONH-( _CH2 ) _n32 -NHCO-O-( _CH2 ) _n31- ,
_-OCF2CF2- ( _{CH2 ) n31} -CONH-( _CH2 ) _n32 -NH-CONH-( _CH2 ) _n31- ,
_-OCF2CF2 -CONH-( _{CH2 ) n31} -NHCO-( _CF2 ) _n32 -CONH-( _CH2 ) _n31- ,
—OCF ₂ CF ₂ —(CH ₂ ) _n31 —CONH—(CH ₂ ) _n32 —NHCO—(CF ₂ ) _n32 —CONH—(CH ₂ ) _n31 —

In one embodiment, α is 1, β is 2-5, and X ^A is a tri- to hexavalent organic group.

In one embodiment, γ is 2-5 and X ^A is a tri- to hexavalent organic group.

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

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

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

R ^Si is independently at each occurrence a monovalent group comprising a Si atom to which is attached a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group.

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

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

Each occurrence of R ¹¹ is independently a hydroxyl group or a hydrolyzable group.

R ¹¹ is preferably independently at each occurrence a hydrolyzable group.

R ¹¹ is preferably independently at each occurrence -OR ^h , -OCOR ^h , -ON=CR ^h ₂ , -NR ^h ₂ , -NHR ^h , or halogen (wherein R ^h represents a substituted or unsubstituted C _1-4 alkyl group), more preferably —OR ^h (ie, an alkoxy group). Examples of R ^h include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as 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 aspect, R ^h is a methyl group, and in another aspect R ^h is an ethyl group.

R ¹² is independently at each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above 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, even more preferably a methyl group.

n1 is an integer of 0 to 3 independently for each (SiR ¹¹ _n1 R ¹² _3-n1 ) unit.
However, when R ^Si is a group represented by formula (S1) or (S2), the terminal R ^Si portion of formula (1a) and formula (1b) (hereinafter simply formula (1a) and formula (1b) (also referred to as the “terminal portion” of), there is at least one (SiR ¹¹ _n1 R ¹² _3-n1 ) unit where n1 is 1-3. That is, not all n1's are 0 at the same time. In other words, there is at least one Si atom to which a hydroxyl group or a hydrolyzable group is attached at the terminal portion of formulas (1a) and (1b).

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

X ¹¹ at each occurrence is independently a single bond or a divalent organic group. Such divalent organic groups are preferably -R ²⁸ -(O) _x -R ²⁹ -. wherein R ²⁸ and R ²⁹ are each independently at each occurrence a single bond or a C _1-20 alkylene group and x is 0 or 1; Such C _1-20 alkylene groups may be straight chain or branched, but are preferably straight chain. Such C _1-20 alkylene groups are preferably C _1-10 alkylene groups, more preferably C _1-6 alkylene groups, still more preferably C _1-3 alkylene groups.

In one aspect, X ¹¹ is independently at each occurrence -C _1-6 alkylene-O-C _1-6 alkylene- or -O-C _1-6 alkylene-.

In preferred embodiments, each occurrence of X ¹¹ is independently a single bond or a straight-chain C _1-6 alkylene group, preferably a single bond or a straight-chain C _1-3 alkylene group, more preferably a single It is a bond or straight chain C _1-2 alkylene group, more preferably a straight chain C _1-2 alkylene group.

Each occurrence of R ¹³ is independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are preferably C _1-20 alkyl groups. Such C _1-20 alkyl groups may be straight chain or branched, but are preferably straight chain.

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

t is independently an integer of 2 or greater at each occurrence.

In preferred embodiments, t is independently at each occurrence an integer from 2 to 10, preferably an integer from 2 to 6.

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

Each occurrence of R ¹⁵ is independently 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.

In one embodiment, each occurrence of R ¹⁵ is independently an oxygen atom, a C 1-6 alkylene group, or a C 1-6 alkyleneoxy group.

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 aspect, formula (S1) is the following formula (S1-a).

[In the formula,
R ¹¹ , R ¹² , R ¹³ , X ¹¹ , and n1 have the same meanings as described in formula (S1) above;
t1 and t2 are each independently at each occurrence an integer of 1 or greater. ]

［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, formula (S1) is the following formula (S1-b).

[Wherein, R ¹¹ , R ¹² , R ¹³ , X ¹¹ , n1 and t have the same meanings as described in formula (S1) above]

R ^a1 is independently at each occurrence -Z ¹ -SiR ²¹ _p1 R ²² _q1 R ²³ _r1 .

Z ¹ is independently at each occurrence an oxygen atom or a divalent organic group. The structure described below as Z ¹ is bound to (SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ) on the right side.

In preferred embodiments, 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 bonded. That is, in 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 — (wherein z1 is an integer of 0 to 6, for example an integer of 1 to 6 and z2 is an integer from 0 to 6, such as an integer from 1 to 6) or -(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 - (wherein z3 is an integer from 0 to 6, For example, it is an integer from 1 to 6, and z4 is an integer from 0 to 6, such as an integer from 1 to 6). Such C _1-6 alkylene groups may be linear or branched, but are preferably linear. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C _1-6 alkyl groups, C _2-6 alkenyl groups, and C _2-6 alkynyl groups. 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, higher light resistance, especially UV resistance, can be obtained.

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

R ²¹ is independently at each occurrence -Z ^1' -SiR ^21' _p1' R ^22' _q1' R ^23' _r1' .

Each occurrence of Z ^1′ above is independently an oxygen atom or a divalent organic group. In the structure described as Z ^1′ below, the right side is bound 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 bonded. That is, in 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′ — (wherein z1′ is an integer of 0 to 6, for example 1 to is an integer of 6 and z2' is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH ₂ ) _z3' -phenylene-(CH ₂ ) _z4' - (wherein z3' is an integer from 0 to 6, such as an integer from 1 to 6, and z4' is an integer from 0 to 6, such as an integer from 1 to 6). Such C _1-6 alkylene groups may be linear or branched, but are preferably linear. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C _1-6 alkyl groups, C _2-6 alkenyl groups, and C _2-6 alkynyl groups. 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, it can have higher light resistance, especially UV resistance.

In another preferred embodiment, Z ^1′ above is a C _1-3 alkylene group. In one aspect, Z ^1' can be -CH ₂ CH ₂ CH ₂ -. In another aspect, Z ^1' can be -CH ₂ CH ₂ -.

R ^21′ above is independently at each occurrence —Z ^1″ —SiR ^22″ _q1″ R ^23″ _r1″ .

Each occurrence ^of Z ^{1 ″} _above is independently an oxygen atom or _a ^divalent organic group. ).

In preferred embodiments, 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 bonded. That is, in 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″ — (wherein z1″ is an integer of 0 to 6, for example 1 to is an integer of 6, and z2″ is an integer of 0 to 6, such as an integer of 1 to 6) or —(CH ₂ ) _z3″ —phenylene-(CH ₂ ) _z4″ —, wherein z3″ is an integer from 0 to 6, such as an integer from 1 to 6, and z4″ is an integer from 0 to 6, such as an integer from 1 to 6). Such C _1-6 alkylene groups are linear or branched, but preferably straight-chain, these groups include, for example, fluorine atoms, C _1-6 alkyl groups, C _2-6 alkenyl groups, and C _2- It may be substituted with one or more substituents selected from ₆ alkynyl groups, but 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, it can be more light-resistant, especially UV-resistant.

In another preferred aspect, Z ^1″ is a C _1-3 alkylene group. In one aspect, Z ^1″ can be —CH ₂ CH ₂ CH ₂ —. In another aspect, Z ^1″ can be —CH ₂ CH ₂ —.

Each occurrence of R ^{22 ″} above is independently a hydroxyl group or a hydrolyzable group.

R ^{22 ″} above is preferably independently at each occurrence a hydrolyzable group.

R ^{22 ″} is preferably independently at each occurrence —OR ^h , —OCOR ^h , —ON=CR ^h ₂ , —NR ^h ₂ , —NHR ^h , or halogen (wherein R ^h represents 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, unsubstituted alkyl groups such as isopropyl group, n-butyl group, isobutyl group; More preferred, in one aspect R ^h is a methyl group, and in another aspect R ^h is an ethyl group.

Each occurrence of R ^{23 ″} above is independently a hydrogen atom or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above hydrolyzable groups.

In R ^23″ above, 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 q1″ is independently at each occurrence an integer from 0 to 3, and the at least one r1″ is independently at each occurrence an integer from 0 to 3. The sum of q1″ and r1″ is 3 in units of (SiR ^22″ _q1″ R ^23″ _r1″ ).

The above q1″ is an integer of preferably 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (SiR ^22″ _q1″ R ^23″ _r1″ ) unit.

Each occurrence of R ^22′ above is independently a hydroxyl group or a hydrolyzable group.

R ^22' is preferably independently at each occurrence a hydrolyzable group.

R ^22′ is preferably independently at each occurrence —OR ^h , —OCOR ^h , —ON═CR ^h ₂ , —NR ^h ₂ , —NHR ^h , or halogen (wherein R ^h represents a substituted or unsubstituted C _1-4 alkyl group), more preferably -OR ^h (ie, an alkoxy group). Examples of R ^h include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as 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 aspect, R ^h is a methyl group, and in another aspect R ^h is an ethyl group.

Each occurrence of R ^23′ above is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above 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, even more preferably a methyl group.

The above p1' is independently an integer of 0 to 3 at each occurrence, q1' is independently an integer from 0 to 3 at each occurrence, and r1' is independently at each occurrence. , and is an integer from 0 to 3. The sum of p1', q1' and r1' is 3 in the unit of (SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ).

In one aspect, p1' is zero.

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

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

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

Each occurrence of R ²² above is independently a hydroxyl group or a hydrolyzable group.

R ²² is preferably independently at each occurrence a hydrolyzable group.

R ²² is preferably independently at each occurrence -OR ^h , -OCOR ^h , -ON=CR ^h ₂ , -NR ^h ₂ , -NHR ^h , or halogen (wherein R ^h represents a substituted or unsubstituted C _1-4 alkyl group), more preferably —OR ^h (ie, an alkoxy group). Examples of R ^h include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as 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 aspect, R ^h is a methyl group, and in another aspect R ^h is an ethyl group.

Each occurrence of R ²³ above is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above 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, even more preferably a methyl group.

p1 above independently at each occurrence is an integer of 0 to 3, q1 is independently at each occurrence an integer from 0 to 3, r1 is independently at each occurrence, An integer from 0 to 3. The sum of p1, q1 and r1 is 3 in units of (SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ).

In one aspect, p1 is zero.

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

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

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

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

R ^b1 above is preferably independently at each occurrence a hydrolyzable group.

Preferably, each occurrence of R ^b1 is independently —OR ^h , —OCOR ^h , —ON=CR ^h ₂ , —NR ^h ₂ , —NHR ^h , or halogen (wherein R ^h represents a substituted or unsubstituted C _1-4 alkyl group), more preferably -OR ^h (ie, an alkoxy group). Examples of R ^h include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as 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 aspect, R ^h is a methyl group, and in another aspect R ^h is an ethyl group.

In the above formula, each occurrence of R ^c1 is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

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

k1 above independently at each occurrence is an integer of 0 to 3, l1 is independently at each occurrence an integer from 0 to 3, m1 is independently at each occurrence, An integer from 0 to 3. The sum of k1, l1 and m1 is 3 in units of (SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 ).

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

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

In a preferred embodiment, the group represented by formula (S3) is —Z ¹ —SiR ²² _q1 R ²³ _r1 (wherein q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3 and r1 is an integer of 0 to 2.), —Z ^1′ —SiR ^22′ _q1′ R ^23′ _r1′ (wherein q1′ is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1′ is an integer of 0 to 2), or —Z ^1″ —SiR ^22″ _q1″ R ^23″ _r1″ (wherein q1″ is 1 to is an integer of 3, preferably 2 or 3, more preferably 3, and r1″ is an integer of 0 to 2.) where the sum of q1 and r1 is 3 per -Z ¹ -SiR ²² _q1 R ²³ _r1 unit; the sum of q1' and r1' is 3 per -Z ^1' -SiR ^22' _q1' R ^23' _r1' unit; The sum of " and r1" is 3 for each -Z ^1" -SiR ^22" _q1" R ^23" _r1" unit.

In a preferred embodiment, in formula (S3), at least one, preferably all R ^{21′ ,} if present, q1″ is an integer from 1 to 3, preferably 2 or 3, or more 3 is preferred.

In a preferred embodiment, in formula (S3), if R ²¹ is present, at least one, preferably all R ²¹ , p1′ is 0 and q1′ is an integer of 1 to 3, preferably is 2 or 3, more preferably 3.

In a preferred embodiment, in formula (S3), if R ^a1 is present, at least one, preferably all R ^a1 , p1 is 0, q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3.

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

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

Z ² is independently at each occurrence a single bond, an oxygen atom or a divalent organic group. In the structure described below as Z ² , the right side is bound to (CR ³¹ _p2 R ³² _q2 R ³³ _r2 ).

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

The above Z ² is preferably a C _1-6 alkylene group, —(CH ₂ ) _z5 —O—(CH ₂ ) _z6 — (wherein z5 is an integer of 0 to 6, for example an integer of 1 to 6 and z6 is an integer from 0 to 6, such as an integer from 1 to 6) or -(CH ₂ ) _z7 -phenylene-(CH ₂ ) _z8 - (wherein z7 is an integer from 0 to 6, For example, an integer from 1 to 6, and z8 is an integer from 0 to 6, such as an integer from 1 to 6). Such C _1-6 alkylene groups may be linear or branched, but are preferably linear. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C _1-6 alkyl groups, C _2-6 alkenyl groups, and C _2-6 alkynyl groups. 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 ^Z2 is such a group, it can be more light-resistant, especially UV-resistant.

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

R ³¹ is independently at each occurrence -Z ^2' -CR ^32' _q2' R ^33' _r2' .

Z ^2' at each occurrence is independently a single bond, an oxygen atom or a divalent organic group. In the structure described as Z ^2′ below, the right side is bound to (CR ^32′ _q2′ R ^33′ _r2′ ).

The above Z ^2′ is preferably a C _1-6 alkylene group, —(CH ₂ ) _z5′ —O—(CH ₂ ) _z6′ — (wherein z5′ is an integer of 0 to 6, for example 1 to is an integer of 6 and z6' is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH ₂ ) _z7' -phenylene-(CH ₂ ) _z8' - (wherein z7' is an integer from 0 to 6, such as an integer from 1 to 6, and z8' is an integer from 0 to 6, such as an integer from 1 to 6). Such C _1-6 alkylene groups may be linear or branched, but are preferably linear. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C _1-6 alkyl groups, C _2-6 alkenyl groups, and C _2-6 alkynyl groups. 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, it can be more light-resistant, especially UV-resistant.

In another preferred embodiment, Z ^2′ above is a C _1-3 alkylene group. In one aspect, Z ^2' can be -CH ₂ CH ₂ CH ₂ -. In another aspect, Z ^2' can be -CH ₂ CH ₂ -.

Each occurrence of R ^32′ above is independently —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 .

Each occurrence of Z ³ above is independently a single bond, an oxygen atom or a divalent organic group. In the structure described below as Z ³ , the right side is bound to (SiR ³⁴ _n2 R ³⁵ _3-n2 ).

In one aspect, ^Z3 is an oxygen atom.

In one aspect, 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″ — (wherein z5″ is an integer of 0 to 6, such as 1 to 6 and z6″ is an integer of 0 to 6, such as an integer of 1 to 6) or —(CH ₂ ) _z7″ —phenylene-(CH ₂ ) _z8″ — (wherein z7″ is , an integer from 0 to 6, such as an integer from 1 to 6, and z8″ is an integer from 0 to 6, such as an integer from 1 to 6). Such C _1-6 alkylene groups may be linear or branched, but are preferably linear. These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C _1-6 alkyl groups, C _2-6 alkenyl groups, and C _2-6 alkynyl groups. is preferably unsubstituted.

In a preferred embodiment, Z ³ is a C _1-6 alkylene group or -(CH ₂ ) _z7″ -phenylene-(CH ₂ ) _z8″ -, preferably -phenylene-(CH ₂ ) _z8″ - ^. When is such a group, higher light resistance, especially UV resistance, can be obtained.

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

Each occurrence of R ³⁴ above is independently a hydroxyl group or a hydrolyzable group.

R ³⁴ is preferably independently at each occurrence a hydrolyzable group.

R ³⁴ is preferably independently at each occurrence -OR ^h , -OCOR ^h , -ON=CR ^h ₂ , -NR ^h ₂ , -NHR ^h , or halogen (wherein R ^h represents a substituted or unsubstituted C _1-4 alkyl group), more preferably —OR ^h (ie, an alkoxy group). Examples of R ^h include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as 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 aspect, R ^h is a methyl group, and in another aspect R ^h is an ethyl group.

Each occurrence of R ³⁵ above is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

In R ³⁵ above, the monovalent organic group is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group, still more preferably a methyl group.

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

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

Each occurrence of R ^33′ above is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

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

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

In another aspect, R ^33′ is a monovalent organic group, preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group.

Each occurrence of q2' is independently an integer from 0 to 3, and each occurrence of r2' is independently an integer from 0 to 3. The sum of q2' and r2' is 3 in the unit of (CR ^32' _q2' R ^33' _r2' ).

q2' is preferably an integer of 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (CR ^32' _q2' R ^33' _r2' ) unit.

R ³² is independently at each occurrence -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 . Such —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 has the same meaning as described for R ^32′ above.

Each occurrence of R ³³ above is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

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

In one aspect, R ³³ is a hydroxyl group.

In another aspect, R ³³ is a monovalent organic group, preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group.

p2 above independently at each occurrence is an integer of 0 to 3, q2 is independently at each occurrence an integer from 0 to 3, r2 is independently at each occurrence, An integer from 0 to 3. The sum of p2, q2 and r2 is 3 in the unit of (CR ³¹ _p2 R ³² _q2 R ³³ _r2 ).

In one aspect, p2 is zero.

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

In one aspect, q2 is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3 for each (CR ³¹ _p2 R ³² _q2 R ³³ _r2 ) unit.

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

Each occurrence of R ^e1 above is independently —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 . Such —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 has the same meaning as described for R ^32′ above.

Each occurrence of R ^f1 above is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

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

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

In another aspect, R ^f1 is a monovalent organic group, preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group.

k2 above independently at each occurrence is an integer of 0 to 3, l2 is independently at each occurrence an integer from 0 to 3, m2 is independently at each occurrence, An integer from 0 to 3. The sum of k2, l2 and m2 is 3 in units of (CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ).

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

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

In a preferred embodiment, in formula (S4), at least one, preferably all R ³² , if present, n2 is an integer from 1 to 3, ^preferably 2 or 3, more preferably 3 is.

In a preferred embodiment, in formula (S4), if R ^e1 is present, at least one, preferably all R ^a1 , n2 is an integer from 1 to 3, preferably 2 or 3, more preferably 3 is.

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

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

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

In one aspect, R ^Si is a group represented by formula (S3) or (S4). Since these compounds can have a plurality of hydrolyzable groups branched from one Si atom or C atom at one end, they can form a surface treatment layer with even higher friction durability.

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

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

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

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

(Composition)
Compositions (eg, surface treatment agents) of the present disclosure are described below.

The composition (eg, surface treatment agent) of the present disclosure contains at least one fluoropolyether group-containing silane compound represented by Formula (1a) or Formula (1b).

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

In one aspect, for the fluoropolyether group-containing silane compounds represented by formulas (1a) and (1b) contained in the composition (e.g., surface treatment agent) of the present disclosure, represented by formula (1a) 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, particularly preferably It may be 0.02, especially 0.05. The upper limit of the ratio (molar ratio) of the fluoropolyether group-containing silane compound represented by formula (1b) to the fluoropolyether group-containing silane compound represented by formulas (1a) and (1b) is preferably It can be 0.35, more preferably 0.30, 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 formula (1b) to the fluoropolyether group-containing silane compounds represented by 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 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 containing within the above range, the composition of the present disclosure can contribute to the formation of a cured layer with good friction durability.

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

The compositions (e.g., surface treatment agents) of the present disclosure include solvents, (non-reactive) fluoropolyether compounds, preferably perfluoro(poly)ether compounds (hereinafter collectively “containing fluorine oil"), a (non-reactive) silicone compound that can be understood as silicone oil (hereinafter referred to as "silicone oil"), a catalyst, a surfactant, a polymerization inhibitor, a sensitizer, etc. .

Examples of the solvent include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; 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 , ethyl acetoacetate, 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 methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve 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-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, dimethylsulfoxide, 1,1-dichloro-1,2 , 2,3,3-pentafluoropropane (HCFC225), Zeorola H, HFE7100, HFE7200, HFE7300 and other fluorine-containing solvents. Alternatively, a mixed solvent of two or more of these may be used.

Examples of the fluorine-containing oil include, but are not limited to, compounds represented by the following general formula (3) (perfluoro(poly)ether compounds).
^Rf5- ( _OC4F8 ) _a' -( _OC3F6 ) _b' -( _OC2F4 ) _{c '} -( _OCF2 ) _d'- ^Rf6 _{( 3} )
In the formula, Rf ⁵ represents a C 1-16 alkyl group (preferably a C _1-16 perfluoroalkyl group) optionally substituted with one or more fluorine atoms, and Rf ⁶ is represents a C 1-16 alkyl group optionally substituted with one or more fluorine atoms (preferably a C _1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom, and Rf ⁵ and Rf ⁶ , more preferably each independently a C _1-3 perfluoroalkyl group.
a', b', c' and d' each represent the number of four types of repeating units of perfluoro(poly)ether constituting the main skeleton of the polymer, and are independently integers of 0 or more and 300 or less, , a′, b′, c′ and d′ are at least 1, preferably 1-300, more preferably 20-300. The order of existence of each repeating unit enclosed in parentheses with subscript a', b', c' or d' is arbitrary in the formula. Among 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 ))-, 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 either -(OCF ₂ CF ₂ )- or (OCF(CF ₃ ))-, but is preferably -(OCF ₂ CF ₂ )-.

Examples of perfluoro(poly)ether compounds represented by the general formula (3) include compounds represented by any of the following general formulas (3a) and (3b) (one or a mixture of two or more) may be used).
Rf ⁵ -(OCF ₂ CF ₂ CF ₂ ) _b″ -Rf ⁶ (3a)
^Rf5- ( _{OCF2CF2CF2CF2 ) a"} -( _{OCF2CF2CF2 ) b" -} ( _{OCF2CF2 ) c "} -( _OCF2 ) _{d" -Rf6} ^... (3b )
In these formulas, Rf ⁵ and Rf ⁶ are as described above; in formula (3a), b″ is an integer of 1 or more and 100 or less; is an integer of 0 or more and 30 or less, and c" and d" are each independently an integer of 1 or more and 300 or less. The order of existence of each repeating unit is arbitrary in the formula.

From another point of view, the fluorine-containing oil may be a compound represented by the general formula Rf ³ —F (wherein Rf ³ is a C _5-16 perfluoroalkyl group). It may also be a chlorotrifluoroethylene oligomer.

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

The fluorine-containing oil may be included in an amount of, for example, 0 to 50% by mass, preferably 0 to 30% by mass, more preferably 0 to 5% by mass, based on the composition (eg, surface treatment agent) of the present disclosure. In one aspect, the compositions of the present disclosure are substantially free of fluorinated oils. “Substantially free of fluorine-containing oil” means that it does not contain fluorine-containing oil at all, or may contain a very small amount of fluorine-containing oil.

The fluorine-containing oil contributes to improving the surface lubricity of the layer formed by the composition (eg, surface treatment agent) of the present disclosure.

As the silicone oil, for example, linear or cyclic silicone oil having 2,000 or less siloxane bonds can be used. Linear silicone oils may be so-called straight silicone oils and modified silicone oils. Examples of straight silicone oils include dimethylsilicone oil, methylphenylsilicone oil, and methylhydrogensilicone oil. Modified silicone oils include those obtained by modifying straight silicone oils with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like. Cyclic silicone oil includes, for example, cyclic dimethylsiloxane oil.

In the composition (e.g., surface treatment agent) of the present disclosure, such silicone oil is a total of 100 parts by mass of the fluoropolyether group-containing silane compound of the present disclosure (if two or more, the total of these, the same below) ), for example 0 to 300 parts by weight, preferably 50 to 200 parts by weight.

Silicone oil contributes to improving the surface lubricity of the layer formed by the composition (eg, surface treatment agent) of the present disclosure.

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

The catalyst promotes hydrolysis and dehydration condensation of the fluoropolyether group-containing silane compound of the present disclosure and promotes formation of a layer formed by the composition (eg, surface treatment agent) of the present disclosure.

Other components include, in addition to the above, 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 substrates.

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

(Goods)
Articles of the present disclosure are described below.

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

Substrates that can be used in the present disclosure include, for example, glass, resins (natural or synthetic resins, such as common plastic materials, and may be in the form of plates, films, or other forms), metals, ceramics, It can be made of any suitable material, such as semiconductors (silicon, germanium, etc.), fibers (fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc., building materials, and the like.

For example, when the article to be manufactured is an optical member, the material forming the surface of the substrate may be a material for optical members, such as glass or transparent plastic. Moreover, 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 substrate. The antireflection layer may be either a single antireflection layer or a multi-layer antireflection layer. Examples of inorganic materials _that can be used for _the antireflection layer include _SiO2 , SiO, _ZrO2 , _TiO2 , _TiO , _Ti2O3 , _Ti2O5 , _Al2O3 , _Ta2O5 , _CeO2 , 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 (for example, as a mixture). In the case of a multilayer antireflection layer, it is preferable to use SiO ₂ and/or SiO for the outermost layer. 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 part of the surface of the substrate (glass). may be In addition, depending on the specific specifications of the base material, 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 retardation film, and a liquid crystal display module.

The shape of the substrate is not particularly limited. In addition, the surface region of the substrate on which the layer formed by the surface treatment agent of the present disclosure is to be formed may be at least a part of the substrate surface, depending on the application and specific specifications of the article to be manufactured. It can be determined as appropriate.

At least the surface portion of such a substrate may be made of a material that originally has hydroxyl groups. Examples of such materials include glass, metals (particularly base metals), ceramics, and semiconductors on which a natural oxide film or thermal oxide film is formed. Alternatively, in the case where the base material does not have sufficient hydroxyl groups or does not originally have hydroxyl groups, such as resins, hydroxyl groups are introduced onto the surface of the base material by subjecting the base material to some pretreatment. can be increased or increased. Examples of such pretreatment include plasma treatment (eg, corona discharge) and ion beam irradiation. Plasma treatment can introduce or increase hydroxyl groups on the substrate surface, and can also be suitably used to clean the substrate surface (remove foreign matter and the like). Further, as another example of such a pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bond group is preliminarily formed on the substrate surface by a monomolecular film by the LB method (Langmuir-Blodgett method), a chemical adsorption method, or the like. A method in which the unsaturated bond is cleaved in an atmosphere containing oxygen, nitrogen, or the like is exemplified.

Alternatively, such a substrate may consist, at least in its surface portion, of a material containing another reactive group, such as a silicone compound having one or more Si—H groups, or an alkoxysilane.

Next, a layer of the surface treating agent of the present disclosure is formed on the surface of such a substrate, and this layer is post-treated as necessary to form a layer from the surface treating agent of the present disclosure.

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 substrate so as to coat the surface. A coating method is not particularly limited. For example, wet coating methods and dry coating methods 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 vapor deposition methods (usually vacuum vapor deposition methods) include resistance heating, electron beams, high-frequency heating using microwaves, ion beams, and similar methods. Examples of CVD methods include plasma-CVD, optical CVD, thermal CVD and similar methods.

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

When using wet coating methods, the surface treatment agents of the present disclosure may be diluted with a solvent prior to application to the substrate surface. 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 (e.g., perfluorohexane, perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (eg C ₆ F ₁₃ CH ₂ CH ₃ (eg Asahiklin (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.) hydrofluoroethers ₍ HFE) (e.g., perfluoropropyl methyl ether ( _C3F7OCH3 ) (e.g., Sumitomo 3M Novec™ ₇₀₀₀ ), perfluorobutyl methyl ether ( _C4F9OCH ) _{; 3} ) (e.g. Novec (trademark) 7100 manufactured by Sumitomo 3M), perfluorobutyl ethyl ether ( _C4F9OC2H5 ) ( _{e.g. Novec} (trademark) ₇₂₀₀ manufactured by Sumitomo 3M), Per _Alkyl perfluoroalkyl _{ethers (} perfluoroalkyl _{groups and} alkyl groups are may be linear or branched), or CF ₃ CH ₂ OCF ₂ CHF ₂ (for example, Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), etc. These solvents alone are Alternatively, _it can be _used as _{a mixture} of two or _{more .} H ₅ ) is particularly preferred.

When using a dry coating method, the surface treatment agents of the present disclosure may be subjected to the dry coating method as is, or may be diluted with the solvents described above and then subjected to the dry coating method.

Layering of the surface treatment agent is preferably carried out such that the surface treatment agent of the present disclosure is present in the layer together with a catalyst for hydrolysis and dehydration condensation. Conveniently, when the wet coating method is used, the catalyst may be added to the diluted solution of the surface treatment agent of the present disclosure after the surface treatment agent of the present disclosure has been diluted with a solvent, just prior to application to the substrate surface. In the case of the dry coating method, the surface treatment agent of the present disclosure to which the catalyst has been added is vapor-deposited (usually, vacuum deposition) as it is, or the surface treatment agent of the present disclosure to which the catalyst is added is applied to a metal porous body such as iron or copper. A vapor deposition (usually vacuum vapor deposition) process may be performed using a pellet-shaped material impregnated with .

Any suitable acid or base can be used for the catalyst. Examples of acid catalysts that can be used include acetic acid, formic acid, and trifluoroacetic acid. Moreover, as a basic 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 substrate to produce the article of the present disclosure. The layer thus obtained has both high surface slipperiness and high friction durability. In addition to high friction durability, the layer has water repellency, oil repellency, antifouling properties (for example, to prevent the adhesion of stains such as fingerprints), and waterproof properties, depending on the composition of the surface treatment agent used. (prevents water from penetrating into electronic parts, etc.), surface lubricity (or lubricity, e.g., wiping off of fingerprints and other stains, excellent tactile sensation on fingers), etc., and is suitable as a functional thin film can be utilized.

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.

As optical materials, in addition to optical materials related to displays and the like as exemplified later, a wide variety of optical materials are preferably exemplified: for example, cathode ray tubes (CRT; e.g., personal computer monitors), liquid crystal displays, plasma displays, organic EL. Displays such as displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFD), field emission displays (FED; Field Emission Display), protective plates for these displays, or antireflection films on their surfaces processed.

Articles having layers obtained by the present disclosure may be, but are not limited to, optical members. Examples of optical members include the following: lenses for eyeglasses; front protective plates, antireflection plates, polarizing plates, anti-glare plates for displays such as PDP and LCD; touch panel sheets; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers;

Articles having layers provided by the present disclosure may also be medical devices or medical materials.

Furthermore, articles having layers obtained by the present disclosure may be automobile interior and exterior, such as headlight covers, side mirrors, side windows, interior decorative films, center consoles, meter panels, camera lens covers, and the like.

The thickness of the layer is not particularly limited. In the case of optical members, 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 properties. .

Although the embodiments have been described above, it will be appreciated that various changes in form and detail may be made without departing from the spirit 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 addition, in the present examples, all the chemical formulas shown below indicate average compositions. Moreover, 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 _CH3 , "Boc" is the tert-butoxycarbonyl group, "BOP" is benzotriazol-1-yloxy-trisdimethylaminophosphonium salt, and "mXHF" is meta-xylene hexafluoride. 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 the mixture was stirred at room temperature. Stir overnight. After washing with an aqueous sodium hydrogencarbonate solution, the extract was dried using 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 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 compound 2a obtained in Synthesis Example 1-1 in 10 mL of dichloromethane, the solution was immersed in an ice bath, added with 3.5 mL of trifluoroacetic acid (TFA), and stirred for 2 hours. An aqueous sodium hydroxide solution was added, and the aqueous phase was removed, 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 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) 0.267 g of compound 3a obtained in Synthesis Example 1-2 and 2 mL of mXHF are added to 2.4 g. was added and stirred overnight at room temperature. 2.435 g of compound 4a was obtained by adding 10 mL of perfluorohexane, washing with 10 mL of acetone, and concentrating to dryness.

Compound 4a
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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 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's catalyst were added, and the mixture was heated at 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. This liquid was filtered and then concentrated to dryness to obtain 1.09 g of compound 5a (n=25).

Compound 5a
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, 400 MHz) 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, 3.32 mL of N,N-diisopropylethylamine, 1.75 g of compound 1b, and 4.82 g of BOP were added and stirred overnight at room temperature. bottom. After washing with an aqueous sodium hydrogencarbonate solution, the extract was dried using 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 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 compound 2b obtained in Synthesis Example 2-1 in 3 mL of dichloromethane, the solution was immersed in an ice bath, added with 3.0 mL of trifluoroacetic acid, and stirred for 4 hours. Aqueous sodium hydroxide solution was added and the aqueous phase was removed, 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 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) 0.25 g of compound 3b obtained in Synthesis Example 2-2 and 2 mL of mXHF are added to 2.12 g. was added and stirred overnight at room temperature. After adding 10 mL of perfluorohexane, washing with acetone, and concentrating to dryness, 2.23 g of compound 4b was obtained.

Compound 4b
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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 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's catalyst were added at room temperature, and the mixture was heated to 60°C. and 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. This liquid was filtered and concentrated to dryness to obtain 1.29 g of compound 5b (n=25).

Compound 5b
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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 were added and stirred overnight at room temperature. bottom. 3.45g of compounds 2c were obtained by refine|purifying with silica gel column chromatography after concentration-drying.

Compound 2c
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 compound 2c obtained in Synthesis Example 3-1 in 3 mL of dichloromethane, the solution was immersed in an ice bath, added with 4.0 mL of trifluoroacetic acid, and stirred for 4 hours. An aqueous sodium hydroxide solution was added, the aqueous phase was removed, dried over anhydrous sodium sulfate, and concentrated. 0.62g of compound 3c was obtained by refine|purifying a residue with silica gel column chromatography.

Compound 3c
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) 0.28 g of compound 3c obtained in Synthesis Example 3-2 and 3 mL of mXHF are added to 2.2 g. was added and stirred overnight at room temperature. 2.32 g of compound 4c was obtained by adding 10 mL of perfluorohexane, washing with acetone, and concentrating to dryness.

Compound 4c
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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 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's catalyst were added at room temperature, and the mixture was heated to 60°C. and 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 liquid, the filtrate was concentrated to dryness to obtain 0.922 g of compound 5c (n=25).

Compound 5c
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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) 0.28 g of compound 3c obtained in Synthesis Example 3-2 and 3 mL of mXHF are added to 4.4 g. was added and stirred overnight at room temperature. 20 mL of perfluorohexane was added, washed with acetone, dried with anhydrous sodium sulfate, and concentrated to dryness to obtain 4.6 g of compound 4c'.

Compound 4c'
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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 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. 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 liquid, 1.82g of compounds 5c' (n=50) were obtained by concentrating and drying a filtrate.

Compound 5c'
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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 overnight at room temperature. 3.52g of compound 2d was obtained by refine|purifying with silica gel column chromatography after concentration-drying.

Compound 2d
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 compound 2d obtained in Synthesis Example 4-1 was dissolved in 8 mL of dichloromethane, immersed in an ice bath, added with 8.0 mL of trifluoroacetic acid, and stirred for 4 hours. 1.04g of compound 3d was obtained by concentration-drying and refine|purifying with silica gel column chromatography.

compound 3d
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) 0.345 g of compound 3d obtained in Synthesis Example 4-2 and 3 mL of mXHF are added to 2.36 g. was added and stirred overnight at room temperature. 2.47 g of compound 4d was obtained by adding 10 mL of perfluorohexane, washing with acetone, drying with anhydrous sodium sulfate, and concentrating to dryness.

Compound 4d
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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 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's catalyst were added at room temperature, and the mixture was heated to 60°C. and 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 liquid, the filtrate was concentrated to dryness to obtain 1.42 g of compound 5d (n=25).

compound 5d
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, 400 MHz) 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) 0.245 g of compound 3a obtained in Synthesis Example 1-2 and mXHF 3 mL was added and stirred overnight at room temperature. 3.75 g of compound 6a was obtained by adding 20 mL of perfluorohexane, washing with acetone, drying with anhydrous sodium sulfate, and concentrating to dryness.

Compound 6a
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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 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's catalyst were added, and the mixture was heated at 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 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, 400 MHz) 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)

0.147 g of compound 3c obtained in Synthesis Example 3-2 was added to 2.0 g of CF ₃ (OCF ₂ ) _m (OCF ₂ CF ₂ ) _n OCF ₂ CO ₂ Me (m=40, n=24). 2 mL of mXHF was added and stirred overnight at room temperature. After adding 20 mL of perfluorohexane, washing with acetone, drying with anhydrous sodium sulfate, and concentrating to dryness, 1.68 g of compound 6c was obtained.

Compound 6c
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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 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's catalyst were added, and the mixture was heated at 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 liquid, the filtrate was concentrated to dryness to obtain 1.64 g of compound 7c (m=40, n=24).

Compound 7c
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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) 0.277 g of compound 3d obtained in Synthesis Example 4-2 and mXHF 3 mL was added and stirred overnight at room temperature. 3.37 g of compound 6d was obtained by adding 20 mL of perfluorohexane, washing with acetone, drying with anhydrous sodium sulfate, and concentrating to dryness.

Compound 6d
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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 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's catalyst were added, and the mixture was heated at 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 liquid, the filtrate was concentrated to dryness to obtain 2.77 g of compound 7d (m=40, n=24).

Compound 7d
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, 400 MHz) 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 solution 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 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 1.54 g of compound 9a obtained in Synthesis Example 8-1 was dissolved in 6 mL of tetrahydrofuran (THF), 1.73 mL of N-Boc-ethylenediamine was added dropwise and 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 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 1.1 g of compound 10a obtained in Synthesis Example 8-2 was dissolved in 10 mL of dichloromethane, the solution was immersed in an ice bath, 10 mL of trifluoroacetic acid was added, and the mixture was stirred for 5 hours. After concentrating to dryness, 0.87 g of compound 11a was obtained by purifying with a silica gel column.

Compound 11a
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), 0.37 g of compound 11a obtained in Synthesis Example 8-3 and 2 mL of mXHF. was added and stirred overnight at room temperature. 10 mL of perfluorohexane was added, washed with chloroform, dried with anhydrous sodium sulfate, and concentrated to dryness to obtain 1.61 g of compound 12a.

Compound 12a
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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 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's catalyst were added and 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. This liquid was filtered and then concentrated to dryness to obtain 1.2 g of compound 13a.

Compound 13a
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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 6 g of compound 8b was dissolved in 10 mL of dichloromethane, the solution 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 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 2.92 g of the compound 9b obtained in Synthesis Example 9-1 was dissolved 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 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 solution was placed in an ice bath, 5 mL of trifluoroacetic acid was added, and the mixture was stirred for 5 hours. After concentrating to dryness, 0.853 g of compound 11b was obtained by purifying with silica gel column chromatography.

Compound 11b
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) 0.429 g of compound 11b obtained in Synthesis Example 8-3 and 2 mL of mXHF per 2.0 g was added and stirred overnight at room temperature. After adding 10 mL of perfluorohexane, washing with chloroform, drying with anhydrous sodium sulfate, and concentrating to dryness, 2.2 g of compound 12b was obtained.

Compound 12b
¹ H NMR (mXHF, 400 MHz) 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, -87.36, -87.36, -121.82, -122.50, -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 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's catalyst were added and 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 stirred at 60° C. for 3 hours. This liquid was filtered and concentrated to dryness to obtain 1.1 g of compound 13b.

Compound 13b
¹ H NMR (mXHF, 400 MHz) 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) Delta: -84.13 -84.27, -85.10 -85.76, -86.36, -120.78, -121.86, -121.86, -128.90, -132.40, -132.40, -132.40, -132.40, -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) 0.207 g 2,2-diallyl-4-pentenylamine 0.207 g and mXHF 2 mL was added and stirred overnight at room temperature. After adding 10 mL of perfluorohexane, washing with acetone, drying with anhydrous sodium sulfate, and concentrating to dryness, 2.89 g of compound 14 was obtained.

Compound 14
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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 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's catalyst were added and stirred for 4 hours. bottom. 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, 2.50g of compound 15 was obtained by concentrating and drying.

Compound 15
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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)

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

compound 16
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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 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's catalyst were added and stirred for 4 hours. bottom. 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, 1.77g of compounds 17 were obtained by concentrating and drying.

compound 17
¹ H NMR (mXHF, 400 MHz) 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, 400 MHz) 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 Each of these was dissolved in hydrofluoroether (Novec HFE-7200, manufactured by 3M Japan Ltd.) so as to have a solid content concentration of 0.1% by mass to prepare a surface treatment agent.

(Formation of surface treatment layer)
The surface treatment agent was applied onto a chemically strengthened glass (“Gorilla” glass manufactured by Corning, thickness 0.7 mm) using a spin coater.
The spin coating conditions 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 atmosphere to form a surface treatment layer.

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

<Static contact angle>
(Initial evaluation)
First, as an initial evaluation, after forming the surface treatment layer, the static contact angle of water was measured while nothing was touching the surface.

<Eraser abrasion resistance test>
The glass on which the surface treatment layer was formed was placed horizontally, and an eraser was reciprocated on the surface of the surface treatment layer using a rubbing tester (manufactured by Shinto Kagaku Co., Ltd.) under the following conditions. 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 40% RH.

Eraser: Rubber Eraser (manufactured by Minoan)
Contact area: 6mmφ
Travel distance (one way): 30mm
Movement speed: 3,600mm/min Load: 1kg/6mmφ

The results are shown in the table below. In the table below, "-" indicates not measured.

The surface treatment agent of the present disclosure can be suitably used to form a surface treatment layer on the surface of various substrates, particularly optical members that require transparency.

Claims (13)

Formula (1a) or Formula (1b):

[In the formula:
R ^F1 is independently at each occurrence Rf ¹ -R ^F -O _q -;
R ^F2 is -Rf ² _p -R ^F -O _q -;
Rf ¹ is independently at each occurrence a C _1-16 alkyl group optionally substituted by one or more fluorine atoms;
Rf ² is a C _1-6 alkylene group optionally substituted by one or more fluorine atoms;
R ^F is independently at each occurrence of formula (f1), (f2), or (f5):
-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)
[Wherein, 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)
[Wherein, c and d are each independently an integer of 0 or more and 30 or less, e and f are each independently an integer of 1 or more and 200 or less,
the sum of c, d, e and f is greater than or equal to 2;
The order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in 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 - (f5)
[Wherein, f is an integer of 1 or more and 200 or less, a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and a, b, c, d, e and f are at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula. ]
is a group represented by;
p is 0 or 1;
q is independently 0 or 1 at each occurrence;
α is 1;
β is 1;
γ is 1;
X ^A is independently at each occurrence -(X ²¹ ) _s21 -[(X ^N )-(X ²² )] _s11 -(X ^N )-(X ²¹ ) _s22 -;
X ^N represents an amide bond;
s11 is an integer from 1 to 3;
X ²¹ is independently at each occurrence -R ²¹¹ - or -(R ²¹¹ ) _s31 -X ³¹ -(R ²¹² ) _s32 -;
R ²¹¹ and R ²¹² are each independently a C _1-10 alkylene group;
hydrogen atoms of said C _1-10 alkylene group may be substituted;
each occurrence of X ³¹ is independently —O— or —NR ⁵⁴ —;
R ⁵⁴ is a hydrogen atom, a phenyl group or a C _1-6 alkyl group;
s31 is independently 0 or 1 at each occurrence ;
s32 is independently 0 or 1 at each occurrence ;
X ²² is independently at each occurrence -R ²²¹ - or -(R ²²¹ ) _s31 -X ³¹ -(R ²²² ) _s32 -;
R ²²¹ and R ²²² are each independently a C _1-10 alkylene group;
in at least one -R ²²¹ -, at least one hydrogen atom of said C _1-10 alkylene group is substituted with a halogen atom ;
each s 21 is independently 0 or 1;
each s22 is independently 0 or 1;
R ^Si is independently at each occurrence represented by formula (S1) , ( S3) or (S4):

[In the formula:
R ¹¹ is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ¹² is independently at each occurrence a hydrogen atom or a C _1-20 alkyl group;
n1 is an integer of 1 to 3 independently for each (SiR ¹¹ _n1 R ¹² _3-n1 ) unit;
X ¹¹ is independently at each occurrence a single bond or -R ²⁸ -(O) _x -R ²⁹ -;
R ²⁸ and R ²⁹ are each independently at each occurrence a single bond or a C _1-20 alkylene group;
x is 0 or 1;
R ¹³ is independently at each occurrence a hydrogen atom or a C _1-6 alkyl group;
t is independently at each occurrence an integer greater than or equal to 2;
R ¹⁴ is a hydrogen atom, a halogen atom or —X ¹¹ —SiR ¹¹ _n1 R ¹² _3-n1 ;
each occurrence of R ¹⁵ is independently 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;
R ^a1 is independently at each occurrence -Z ¹ -SiR ²² _q1 R ²³ _r1 ;
Z ¹ is independently at each occurrence an oxygen atom or a C _1-6 alkylene group, —(CH ₂ ) _z1 —O—(CH ₂ ) _z2 — (wherein z1 is an integer of 0 to 6 and z2 is an integer from 0 to 6) or -(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 - (wherein z3 is an integer from 0 to 6 and z4 is from 0 to is an integer of 6);
R ²² is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ²³ is independently at each occurrence a hydrogen atom or a C _1-20 alkyl group;
q1 is independently at each occurrence an integer from 1 to 3;
r1 is independently at each occurrence an integer from 0 to 2;
R ^b1 is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ^c1 is independently at each occurrence a hydrogen atom or a C _1-20 alkyl group;
k1 is an integer from 2 to 3;
l1 is an integer from 0 to 1;
m1 is an integer from 0 to 1;
R ^d1 is independently at each occurrence -Z ² -CR ³¹ _p2 R ³² _q2 R ³³ _r2 ;
Z ² is each independently at each occurrence a single bond, an oxygen atom, a C _1-6 alkylene group, —(CH ₂ ) _z5 —O—(CH ₂ ) _z6 — (wherein z5 is 0 to 6 z6 is an integer of 0 to 6) or -(CH ₂ ) _z7 -phenylene-(CH ₂ ) _z8 - (wherein z7 is an integer of 0 to 6 and z8 is an integer of 0 to 6 is an integer);
R ³¹ is independently at each occurrence -Z ^2' -CR ^32' _q2' R ^33' _r2' ;
Each occurrence of Z ^2′ is independently a single bond, an oxygen atom, a C _1-6 alkylene group, —(CH ₂ ) _z5′ —O—(CH ₂ ) _z6′ — (wherein z5′ is , an integer from 0 to 6, and z6′ is an integer from 0 to 6) or —(CH ₂ ) _z7′ —phenylene-(CH ₂ ) _z8′ —, wherein z7′ is an integer from 0 to 6 , z8′ is an integer from 0 to 6);
R ^32′ is independently at each occurrence —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 ;
Z ³ is a single bond, an oxygen atom, a C _1-6 alkylene group, —(CH ₂ ) _z5″ —O—(CH ₂ ) _z6″ — (wherein z5″ is an integer of 0 to 6, z6″ is an integer from 0 to 6) or —(CH ₂ ) _z7″ —phenylene-(CH ₂ ) _z8″ —, where z7″ is an integer from 0 to 6, z8″ is an integer from 0 to 6 is an integer);
R ³⁴ is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R ³⁵ is independently at each occurrence a hydrogen atom or a C _1-20 alkyl group;
n2 is an integer of 1 to 3 independently for each (SiR ³⁴ _n2 R ³⁵ _3-n2 ) unit;
R ^33′ at each occurrence is independently a hydrogen atom, a hydroxyl group or a C _1-20 alkyl group;
q2' is independently at each occurrence an integer from 0 to 3;
r2' is independently at each occurrence an integer from 0 to 3;
R ³² is independently at each occurrence -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 ;
R ³³ is independently at each occurrence a hydrogen atom, a hydroxyl group or a C _1-20 alkyl group;
p2 is independently at each occurrence an integer from 0 to 3;
q2 is independently at each occurrence an integer from 0 to 3;
r2 is independently at each occurrence an integer from 0 to 3;
R ^e1 is independently at each occurrence —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 ;
R ^f1 at each occurrence is independently a hydrogen atom, a hydroxyl group or a C _1-20 alkyl group;
k2 is 0;
l2 is an integer from 2 to 3;
m2 is an integer from 0 to 1; ]
is a group represented by ]
A fluoropolyether group-containing silane compound represented by 2. The fluoropolyether group-containing silane compound according to claim 1, wherein n1 is 3. 3. The fluoropolyether group-containing silane compound according to claim 1, wherein k1 is 3 and q1 is an integer of 1-3. The fluoropolyether group-containing silane compound according to any one of claims 1 to 3, wherein l2 is 3 and n2 is an integer of 1-3. A surface treatment agent containing at least one fluoropolyether group-containing silane compound represented by formula (1a) or (1b) according to any one of claims 1 to 4. 6. The surface treatment agent according to claim 5, further comprising one or more other components selected from fluorine-containing oils, silicone oils, and catalysts. The surface treatment agent according to claim 5 or 6, further comprising a solvent. The surface treatment agent according to any one of claims 5 to 7, which is used as an antifouling coating agent or a waterproof coating agent. The surface treatment agent according to any one of claims 5 to 8, which is for vacuum deposition. The surface treatment agent according to any one of claims 5 to 8, which is for wet coating treatment. A pellet containing the surface treatment agent according to any one of claims 5 to 9. A substrate and, on the surface of the substrate, the fluoropolyether group-containing silane compound according to any one of claims 1 to 4, or the surface treatment agent according to any one of claims 5 to 10. A layer formed from the article. 13. The article according to claim 12, which is an optical member.