JP2023066385A - Surface treatment agent - Google Patents

Abstract

To provide a compound capable of forming a surface treatment layer with higher durability.SOLUTION: The invention provides a compound represented by the formula (1) in the figure.SELECTED DRAWING: None

Description

The present disclosure relates to novel fluoropolyether group-containing acrylic compounds and surface treatment agents containing such compounds.

Certain fluoropolyether group-containing silane compounds are known to provide excellent water repellency, oil repellency, antifouling properties, etc. when used for surface treatment of substrates. A layer obtained from a surface treatment agent containing a fluoropolyether group-containing silane compound (hereinafter also referred to as a "surface treatment layer") is a so-called functional thin film, for example, glass, plastic, fiber, sanitary goods, building materials, etc. (Patent Document 1).

Japanese Patent Application Laid-Open No. 2003-238577

Although the fluoropolyether group-containing silane compound described in Patent Document 1 can provide a surface treatment layer having excellent functions, a surface treatment layer having higher durability is desired.

An object of the present disclosure is to provide a fluoropolyether group-containing compound capable of providing a surface treatment layer with excellent durability.

［式中：
Ｒ^Ｆ２は、それぞれ独立して、－Ｒｆ^２ _ｐ－Ｒ^Ｆ－Ｏ_ｑ－であり、
Ｒｆ^２は、１個又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、二価のフルオロポリエーテル基であり、
ｐは、０又は１であり、
ｑは、０又は１であり、
Ｒ^ａは、それぞれ独立して、（ｍ＋２）価の有機基であり、
ｍは、１～４の整数であり、
Ｒ^ｂは、それぞれ独立して、Ｒ^Ｓｉ、Ｒ^Ａｃ、又はＲ^ｃであり、
Ｒ^Ｓｉは、それぞれ独立して、－Ｘ^Ｃ－ＳｉＲ^１ _ｎ’Ｒ^２ _３－ｎ’であり、
Ｘ^Ｃは、炭素数１～１０の二価の有機基であり、
Ｒ^１は、それぞれ独立して、水酸基又は加水分解性基であり、
Ｒ^２は、それぞれ独立して、水素原子又は一価の有機基であり、
ｎ’は、１～３の整数であり、
Ｒ^Ａｃは、それぞれ独立して、－Ｘ^Ｄ－Ｘ^Ｅ（－Ｘ^Ｆ－ＯＣＯ－ＣＲ^５＝ＣＨ_２）_ｍ’であり、
Ｘ^Ｄは、二価の有機基であり、
Ｘ^Ｅは、単結合、又は（ｍ’＋１）価の基であり、
Ｘ^Ｆは、それぞれ独立して、炭素数１～１０の二価の有機基であり、
Ｒ^５は、水素原子又は炭素数１～８の一価の有機基であり、
ｍ’は、１～１０の整数であり、
Ｒ^ｃは、それぞれ独立して、水素原子又はＣ_１－６アルキル基であり、
Ｒ^ｄは、それぞれ独立して、単結合、又は二価の有機基であり、
ｘは、１以上の整数である。］
で表される化合物。
［２］ Ｒ^Ｆは、それぞれ独立して、式：
－（ＯＣ_６Ｆ_１２）_ａ－（ＯＣ_５Ｆ_１０）_ｂ－（ＯＣ_４Ｆ_８）_ｃ－（ＯＣ_３Ｒ^Ｆａ _６）_ｄ－（ＯＣ_２Ｆ_４）_ｅ－（ＯＣＦ_２）_ｆ－
［式中、Ｒ^Ｆａは、それぞれ独立して、水素原子、フッ素原子又は塩素原子であり、
ａ、ｂ、ｃ、ｄ、ｅ及びｆは、それぞれ独立して、０～２００の整数であって、ａ、ｂ、ｃ、ｄ、ｅ及びｆの和は１以上であり、ａ、ｂ、ｃ、ｄ、ｅ又は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り、ただし、すべてのＲ^Ｆａが水素原子又は塩素原子である場合、ａ、ｂ、ｃ、ｅ及びｆの少なくとも１つは、１以上である。］
で表される基である、上記［１］に記載の化合物。
［３］ Ｒ^Ｆａは、フッ素原子である、上記［１］又は［２］に記載の化合物。
［４］ Ｒ^Ｆは、それぞれ独立して、下記式（ｆ１）、（ｆ２）、（ｆ３）、（ｆ４）、（ｆ５）又は（ｆ６）：
－（ＯＣ_３Ｆ_６）_ｄ－（ＯＣ_２Ｆ_４）_ｅ－ （ｆ１）
［式中、ｄは１～２００の整数であり、ｅは、０～２の整数であり、
添字ｃ、ｄ、ｅ又は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_４Ｆ_８）_ｃ－（ＯＣ_３Ｆ_６）_ｄ－（ＯＣ_２Ｆ_４）_ｅ－（ＯＣＦ_２）_ｆ－ （ｆ２）
［式中、ｃ及びｄは、それぞれ独立して、０～３０の整数であり；
ｅ及びｆは、それぞれ独立して、１～２００の整数であり；
ｃ、ｄ、ｅ及びｆの和は、１０～２００の整数であり；
添字ｃ、ｄ、ｅ又は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－Ｒ^９－ （ｆ３）
［式中、Ｒ^６は、ＯＣＦ_２又はＯＣ_２Ｆ_４であり；
Ｒ^７は、ＯＣ_２Ｆ_４、ＯＣ_３Ｆ_６、ＯＣ_４Ｆ_８、ＯＣ_５Ｆ_１０及びＯＣ_６Ｆ_１２から選択される基であるか、あるいは、これらの基から選択される２又は３つの基の組み合わせであり；
Ｒ^９は、単結合、又は、ＯＣＦ_２、ＯＣ_２Ｆ_４、ＯＣ_３Ｆ_６、ＯＣ_４Ｆ_８、ＯＣ_５Ｆ_１０及びＯＣ_６Ｆ_１２から選択される基であり；
ｇは、２～１００の整数である。］、
－（Ｒ^６－Ｒ^７）_ｇ－Ｒ^ｒ－（Ｒ^７’－Ｒ^６’）_ｇ’－ （ｆ４）
［式中、Ｒ^６は、ＯＣＦ_２又はＯＣ_２Ｆ_４であり、
Ｒ^７は、ＯＣ_２Ｆ_４、ＯＣ_３Ｆ_６、ＯＣ_４Ｆ_８、ＯＣ_５Ｆ_１０及び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又は３つの基の組み合わせであり、
Ｒ^６’は、ＯＣＦ_２又はＯＣ_２Ｆ_４であり、
Ｒ^７’は、ＯＣ_２Ｆ_４、ＯＣ_３Ｆ_６、ＯＣ_４Ｆ_８、ＯＣ_５Ｆ_１０及び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又は３つの基の組み合わせであり、
ｇは、２～１００の整数であり、
ｇ’は、２～１００の整数であり、
Ｒ^ｒは、

（式中、＊は、結合位置を示す。）
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、ｅは、１以上２００以下の整数であり、ａ、ｂ、ｃ、ｄ及び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及びｆの和は少なくとも１であり、また、ａ、ｂ、ｃ、ｄ、ｅ又は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－ （ｆ６）
［式中、ｆは、１以上２００以下の整数であり、ａ、ｂ、ｃ、ｄ及び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及びｆの和は少なくとも１であり、また、ａ、ｂ、ｃ、ｄ、ｅ又は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、上記［１］～［３］のいずれか１項に記載の化合物。
［５］ Ｒｆ^２は、それぞれ独立して、Ｃ_１－６パーフルオロアルキレン基である、
上記［１］～［４］のいずれか１項に記載の化合物。
［６］ Ｒ^ａは、それぞれ独立して、下記式：
－Ｒ^９－（Ｒ^ａ’－Ｒ^９）_ｋ－
［式中：
Ｒ^９は、それぞれ独立して、Ｃ_１－６アルキレン基であり、
Ｒ^ａ’は、それぞれ独立して、ｍ＋２価の有機基であり、
ｋは、０～４の整数である。］
で表される基である、上記［１］～［５］のいずれか１項に記載の化合物。
［７］ Ｒ^ａ’は、それぞれ独立して、Ｎ原子又はＯ原子を含むｍ＋２価の有機基である、上記［６］に記載の化合物。
［８］ Ｒ^ａ’は、それぞれ独立して、炭素－炭素原子間に、アミノ結合、アミド結合、ウレタン結合、ウレア結合、エーテル結合、又はエステル結合を含んでもよい３価の有機基である、上記［６］に記載の化合物。
［９］ Ｒ^ａ’は、それぞれ独立して、下記の基：

［式中、Ｒ^８は、水素原子、又はＣ_１－６アルキル基である。］
である、上記［６］～［８］のいずれか１項に記載の化合物。
［１０］ Ｒ^ａ’は、Ｎである、上記［６］～［９］のいずれか１項に記載の化合物。
［１１］ ｋは、１である、上記［６］～［１０］のいずれか１項に記載の化合物。
［１２］ ｋは、２である、上記［６］～［１０］のいずれか１項に記載の化合物。
［１３］ 少なくとも１つのＲ^ｂは、Ｒ^Ｓｉである、上記［１］～［１２］のいずれか１項に記載の化合物。
［１４］ 各末端に位置するＮ原子に結合するＲ^ｂの１つはＲ^Ｓｉであり、他方はＲ^ｃである、上記［１］～［１３］のいずれか１項に記載の化合物。
［１５］ 各末端に位置するＮ原子に結合するＲ^ｂの１つはＲ^Ｓｉであり、他方はＲ^Ａｃである、上記［１］～［１３］のいずれか１項に記載の化合物。
［１６］ Ｘ^Ｃは、
Ｃ_１－６アルキレン基、
－（ＣＨ_２）_ｚ１－Ｏ－（ＣＨ_２）_ｚ２－（式中、ｚ１は、０～６の整数であり、ｚ２は、０～６の整数である）、又は、
－（ＣＨ_２）_ｚ３－フェニレン－（ＣＨ_２）_ｚ４－（式中、ｚ３は、０～６の整数であり、ｚ４は、０～６の整数である）
である、上記［１］～［１５］のいずれか１項に記載の化合物。
［１７］ Ｘ^Ｃは、Ｃ_１－６アルキレン基である、上記［１］～［１６］のいずれか１項に記載の化合物。
［１８］ ｎ’は、２、または３である、上記［１］～［１７］のいずれか１項に記載の化合物。
［１９］ ｎ’は３である、上記［１］～［１８］のいずれか１項に記載の化合物。
［２０］ Ｘ^Ｄは、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯＮＨ－、－ＮＨＣＯ－、－ＯＣＯＮＨ－、－ＮＨＣＯＯ－、－ＮＨ－ＣＯ－ＮＨ－、－ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２－、又は－ＣＨ（ＣＨ_２ＯＨ）ＣＨ_２－である、上記［１］～［１９］のいずれか１項に記載の化合物。
［２１］ Ｘ^Ｄは、－ＣＯＮＨ－、－ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２－、又は－ＣＨ（ＣＨ_２ＯＨ）ＣＨ_２－である、上記［１］～［２０］のいずれか１項に記載の化合物。
［２２］ Ｘ^Ｄは、－ＣＯＮＨ－である、上記［１］～［２１］のいずれか１項に記載の化合物。
［２３］ Ｘ^Ｅは、単結合である、上記［１］～［２２］のいずれか１項に記載の化合物。
［２４］ Ｘ^Ｅは、－Ｘ^Ｇ－Ｘ^Ｈであり、
Ｘ^Ｇは、
単結合、
Ｃ_１－６アルキレン基、
－（ＣＨ_２）_ｚ９－Ｏ－（ＣＨ_２）_ｚ１０－（式中、ｚ９は、０～６の整数であり、ｚ１０は、０～６の整数である）、又は、
－（ＣＨ_２）_ｚ１１－フェニレン－（ＣＨ_２）_ｚ１２－（式中、ｚ１１は、０～６の整数であり、ｚ１２は、０～６の整数である）
であり、
Ｘ^Ｈは、下記

であり、
Ｒ^８は、水素原子、又はＣ_１－６アルキル基である、
上記［１］～［２３］のいずれか１項に記載の化合物。
［２５］ Ｘ^Ｆは、
Ｃ_１－６アルキレン基、
－（ＣＨ_２）_ｚ５－Ｏ－（ＣＨ_２）_ｚ６－（式中、ｚ５は、０～６の整数であり、ｚ６は、０～６の整数である）、又は、
－（ＣＨ_２）_ｚ７－フェニレン－（ＣＨ_２）_ｚ８－（式中、ｚ７は、０～６の整数であり、ｚ８は、０～６の整数である）
である、上記［１］～［２４］のいずれか１項に記載の化合物。
［２６］ Ｒ^ｃは、それぞれ独立して、水素原子又はＣ_１－６アルキル基である、上記［１］～［２５］のいずれか１項に記載の化合物。
［２７］ Ｒ^ｄは、それぞれ独立して、単結合、又は－（ＣＨ_２）_ｚ１７－ＮＲ^１０－（ＣＨ_２）_ｚ１８－（式中、Ｒ^１０は、水素原子又はＣ_１－６アルキル基であり、ｚ１７は、０～６の整数であり、ｚ１８は、０～６の整数である）である、上記［１］～［２６］のいずれか１項に記載の化合物。
［２８］ ｘは、１以上５以下の整数である、上記［１］～［２７］のいずれか１項に記載の化合物。
［２９］ 上記［１］～［２８］のいずれか１項に記載の化合物を含有する、表面処理剤。
［３０］ 含フッ素オイル、シリコーンオイル、及び触媒から選択される１種又はそれ以上の他の成分をさらに含有する、上記［２９］に記載の表面処理剤。
［３１］ 防汚性コーティング剤又は防水性コーティング剤として使用される、上記［２９］又は［３０］に記載の表面処理剤。
［３２］ 基材と、該基材の表面に、上記［１］～［２８］のいずれか１項に記載の化合物又は上記［２９］～［３１］のいずれかに記載の表面処理剤より形成された層とを含む物品。 The present disclosure includes the following aspects.
[1] Formula (1) below:

[In the formula:
each R ^F2 is independently -Rf ² _p -R ^F -O _q -;
Rf ² is a C _1-6 alkylene group optionally substituted by one or more fluorine atoms,
^RF is a divalent fluoropolyether group,
p is 0 or 1,
q is 0 or 1;
each R ^a is independently a (m+2)-valent organic group;
m is an integer from 1 to 4,
each R ^b is independently R ^Si , R ^Ac , or R ^c ;
each R ^Si is independently -X ^C -SiR ¹ _n' R ² _3-n' ;
X ^C is a divalent organic group having 1 to 10 carbon atoms,
each R ¹ is independently a hydroxyl group or a hydrolyzable group;
each R ² is independently a hydrogen atom or a monovalent organic group;
n' is an integer of 1 to 3,
each R ^Ac is independently -X ^D -X ^E (-X ^F -OCO-CR ⁵ =CH ₂ ) _m' ;
X ^D is a divalent organic group,
X ^E is a single bond or a (m'+1) valent group,
each X ^F is independently a divalent organic group having 1 to 10 carbon atoms,
R ⁵ is a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms,
m' is an integer from 1 to 10,
each R ^c is independently a hydrogen atom or a C _1-6 alkyl group,
each R ^d is independently a single bond or a divalent organic group;
x is an integer of 1 or more. ]
A compound represented by
[2] R ^F is each independently represented by the formula:
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ R ^Fa ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f -
[Wherein, each R ^Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom,
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, provided that when all ^RFa are hydrogen atoms or chlorine atoms, a, b, At least one of c, e and f is 1 or more. ]
The compound according to the above [1], which is a group represented by
[3] The compound according to the above [1] or [2], wherein R ^Fa is a fluorine atom.
[4] R ^F each independently represents the following formula (f1), (f2), (f3), (f4), (f5) or (f6):
-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)
[Wherein, d is an integer of 1 to 200, e is an integer of 0 to 2,
The order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula. ],
-(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 to 30;
e and f are each independently an integer from 1 to 200;
the sum of c, d, e and f is an integer from 10 to 200;
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 —R ⁹ — (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 two or three groups selected from these groups. is a combination of groups;
^R9 _{is a} single bond _{or a} group selected from _OCF2 , _OC2F4 , _OC3F6 , _OC4F8 , _OC5F10 and _{OC6F12 ;}
g is an integer from 2 to 100; ],
—(R ⁶ —R ⁷ ) _g —R ^r —(R ^7′ —R ^6′ ) _g′ − (f4)
[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,
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 independently selected from these groups a combination of two or three groups,
g is an integer from 2 to 100,
g' is an integer from 2 to 100,
^Rr is

(In the formula, * indicates the binding position.)
is. ];
- (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, 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 - (f6)
[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. ]
The compound according to any one of [1] to [3] above, which is a group represented by
[5] each Rf ² is independently a C _1-6 perfluoroalkylene group;
The compound according to any one of [1] to [4] above.
[6] R ^a is each independently represented by the following formula:
—R ⁹ —(R ^a′ —R ⁹ ) _k —
[In the formula:
each R ⁹ is independently a C _1-6 alkylene group;
each R ^a' is independently an m+2 valent organic group,
k is an integer from 0 to 4; ]
The compound according to any one of [1] to [5] above, which is a group represented by
[7] The compound according to [6] above, wherein each R ^a′ is independently an m+2 valent organic group containing an N atom or an O atom.
[8] Each R ^a' is independently a trivalent organic group which may contain an amino bond, an amide bond, a urethane bond, a urea bond, an ether bond, or an ester bond between carbon atoms. The compound described in [6] above.
[9] R ^a′ is each independently one of the following groups:

[In the formula, R ⁸ is a hydrogen atom or a C _1-6 alkyl group. ]
The compound according to any one of [6] to [8] above.
[10] The compound according to any one of [6] to [9] above, wherein R ^a' is N.
[11] The compound according to any one of [6] to [10] above, wherein k is 1.
[12] The compound according to any one of [6] to [10] above, wherein k is 2.
[13] The compound according to any one of [1] to [12] above, wherein at least one R ^b is R ^Si .
[14] The compound according to any one of [1] to [13] above, wherein one of R ^{2 b} bonded to N atoms located at each terminal is R 3 ^Si and the other is R 3 ^c .
[15] The compound according to any one of the above [1] to [13], wherein one of R ^{2 b} bonded to the terminal N atom is R 2 ^Si and the other is R 3 ^Ac .
[16] X ^C is
a C _1-6 alkylene group,
-(CH ₂ ) _z1 -O-(CH ₂ ) _z2 - (wherein z1 is an integer from 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 an integer from 0 to 6)
The compound according to any one of [1] to [15] above.
[17] The compound according to any one of [1] to [16] above, wherein X ^C is a C _1-6 alkylene group.
[18] The compound according to any one of [1] to [17] above, wherein n' is 2 or 3.
[19] The compound according to any one of [1] to [18] above, wherein n' is 3.
[20] X ^D is -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -OCONH-, -NHCOO-, -NH-CO-NH-, _-CH The compound according to any one of [1] to [19] above, which is CH(OH)CH ₂ - or -CH(CH ₂ OH)CH ₂ -.
[21] Any one of [1] to [20] above, wherein X ^D is -CONH-, -CH ₂ CH(OH)CH ₂ -, or -CH(CH ₂ OH)CH ₂ - Compound as described.
[22] The compound according to any one of [1] to [21] above, wherein ^XD is -CONH-.
[23] The compound according to any one of [1] to [22] above, wherein X ^E is a single bond.
[24] X ^E is -X ^G -X ^H ;
^XG is
single bond,
a C _1-6 alkylene group,
-(CH ₂ ) _z9 -O-(CH ₂ ) _z10 - (wherein z9 is an integer of 0 to 6 and z10 is an integer of 0 to 6), or
-(CH ₂ ) _z11 -phenylene-(CH ₂ ) _z12 - (wherein z11 is an integer from 0 to 6 and z12 is an integer from 0 to 6)
and
X ^H is the following

and
R ⁸ is a hydrogen atom or a C _1-6 alkyl group,
The compound according to any one of [1] to [23] above.
[25] X ^F is
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 and z8 is an integer from 0 to 6)
The compound according to any one of [1] to [24] above.
[26] The compound according to any one of [1] to [25] above, wherein each R ^c is independently a hydrogen atom or a C _1-6 alkyl group.
[27] Each R ^d is independently a single bond or —(CH ₂ ) _z17 —NR ¹⁰ —(CH ₂ ) _z18 — (wherein R ¹⁰ is a hydrogen atom or a C _1-6 alkyl group; , z17 is an integer of 0 to 6, and z18 is an integer of 0 to 6), the compound according to any one of [1] to [26] above.
[28] The compound according to any one of [1] to [27] above, wherein x is an integer of 1 or more and 5 or less.
[29] A surface treatment agent containing the compound according to any one of [1] to [28] above.
[30] The surface treatment agent according to [29] above, which further contains one or more other components selected from fluorine-containing oils, silicone oils, and catalysts.
[31] The surface treatment agent according to [29] or [30] above, which is used as an antifouling coating agent or a waterproof coating agent.
[32] A base material and, on the surface of the base material, the compound according to any one of [1] to [28] or the surface treatment agent according to any one of [29] to [31] above an article comprising a formed layer;

According to the present disclosure, it is possible to provide a fluoropolyether group-containing acrylic compound capable of providing a highly durable surface treatment layer.

As used herein, "monovalent organic radical" means a monovalent radical containing carbon. The monovalent organic group is not particularly limited, but may be a hydrocarbon group or 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.

As used herein, "hydrolyzable group" means a group capable of undergoing a hydrolysis reaction, ie, a group capable of being detached from the backbone 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.

［式中：
Ｒ^Ｆ２は、それぞれ独立して、－Ｒｆ^２ _ｐ－Ｒ^Ｆ－Ｏ_ｑ－であり、
Ｒｆ^２は、１個又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、二価のフルオロポリエーテル基であり、
ｐは、０又は１であり、
ｑは、０又は１であり、
Ｒ^ａは、それぞれ独立して、（ｍ＋２）価の有機基であり、
ｍは、１～４の整数であり、
Ｒ^ｂは、それぞれ独立して、Ｒ^Ｓｉ、Ｒ^Ａｃ、又はＲ^ｃであり、
Ｒ^Ｓｉは、それぞれ独立して、－Ｘ^Ｃ－ＳｉＲ^１ _ｎ’Ｒ^２ _３－ｎ’であり、
Ｘ^Ｃは、炭素数１～１０の二価の有機基であり、
Ｒ^１は、それぞれ独立して、水酸基又は加水分解性基であり、
Ｒ^２は、それぞれ独立して、水素原子又は一価の有機基であり、
ｎ’は、１～３の整数であり、
Ｒ^Ａｃは、それぞれ独立して、－Ｘ^Ｄ－Ｘ^Ｅ（－Ｘ^Ｆ－ＯＣＯ－ＣＲ^５＝ＣＨ_２）_ｍ’であり、
Ｘ^Ｄは、二価の有機基であり、
Ｘ^Ｅは、単結合、又は（ｍ’＋１）価の基であり、
Ｘ^Ｆは、それぞれ独立して、炭素数１～１０の二価の有機基であり、
Ｒ^５は、水素原子又は炭素数１～８の一価の有機基であり、
ｍ’は、１～１０の整数であり、
Ｒ^ｃは、それぞれ独立して、水素原子又はＣ_１－６アルキル基であり、
Ｒ^ｄは、それぞれ独立して、単結合、又は二価の有機基であり、
ｘは、１以上の整数である。］
で表されるフルオロポリエーテル基含有アクリル化合物である。 The fluoropolyether group-containing acrylic compound of the present disclosure has the following formula (1):

[In the formula:
each R ^F2 is independently -Rf ² _p -R ^F -O _q -;
Rf ² is a C _1-6 alkylene group optionally substituted by one or more fluorine atoms,
^RF is a divalent fluoropolyether group,
p is 0 or 1,
q is 0 or 1;
each R ^a is independently a (m+2)-valent organic group;
m is an integer from 1 to 4,
each R ^b is independently R ^Si , R ^Ac , or R ^c ;
each R ^Si is independently -X ^C -SiR ¹ _n' R ² _3-n' ;
X ^C is a divalent organic group having 1 to 10 carbon atoms,
each R ¹ is independently a hydroxyl group or a hydrolyzable group;
each R ² is independently a hydrogen atom or a monovalent organic group;
n' is an integer of 1 to 3,
each R ^Ac is independently -X ^D -X ^E (-X ^F -OCO-CR ⁵ =CH ₂ ) _m' ;
X ^D is a divalent organic group,
X ^E is a single bond or a (m'+1) valent group,
each X ^F is independently a divalent organic group having 1 to 10 carbon atoms,
R ⁵ is a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms,
m' is an integer from 1 to 10,
each R ^c is independently a hydrogen atom or a C _1-6 alkyl group,
each R ^d is independently a single bond or a divalent organic group;
x is an integer of 1 or more. ]
is a fluoropolyether group-containing acrylic compound represented by

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

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, each q is 0 or 1 independently. In one aspect, q is zero. In another aspect q is 1.

In formula (1) above, each R ^F is independently a divalent fluoropolyether group.

R ^F is preferably:
- (OC _h1 R ^Fa _2h1 ) _h3 - (OC _h2 R ^Fa _2h2-2 ) _h4 -
[In the formula:
R ^Fa is independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom;
h1 is an integer from 1 to 6,
h2 is an integer from 4 to 8,
h3 is an integer of 0 or more,
h4 is an integer of 0 or more,
However, the composition of h3 and h4 is 1 or more, preferably 2 or more, more preferably 5 or more, and the order of existence of each repeating unit bracketed with h3 and h4 is Optional. ]
It may contain a group represented by

In one aspect, R ^F can be linear or branched. R ^F preferably has the formula:
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ R ^Fa ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f -
[In the formula:
each R ^Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom,
a, b, c, d, e and f are each independently integers from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of existence of each repeating unit bracketed with a, b, c, d, e or f is arbitrary in the formula. However, when all ^RFa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more. ]
is a group represented by

^RFa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom. However, when all ^RFa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more.

a, b, c, d, e and f may preferably each independently be an integer from 0 to 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. _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 ))- and the like. -( _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 ))- and the like. -( _OC4F8 )- is -( _{OCF2CF2CF2CF2 ) -} , -(OCF( _CF3 ) _CF2CF2 )- _, -( _OCF2CF ( _CF3 ) _{CF2 ) -} , -( _OCF2CF2CF ( _CF3 ))-, - ₍ OC( _CF3 ) _2CF2 )-, -( _OCF2C ( _CF3 ) ₂ ) _- , -(OCF( _CF3 )CF( CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- and -(OCF ₂ CF(C ₂ F ₅ ))-. -(OC ₃ F ₆ )- (that is, in the above formula, R 3 ^Fa is a fluorine atom) is represented by -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- and -( OCF ₂ CF(CF ₃ ))—. -(OC ₂ F ₄ )- may be either -(OCF ₂ CF ₂ )- or -(OCF(CF ₃ ))-.

In one aspect, the repeating unit is linear. By making the repeating unit linear, the surface lubricity, abrasion resistance, etc. of the surface-treated layer can be improved.

In one aspect, the repeat unit is branched. By branching the repeating unit, the dynamic friction coefficient of the surface treatment layer can be increased.

In one aspect, R ^F can include a ring structure.

［式中、＊は、結合位置を示す。］ The ring structure may be the following three-membered ring, four-membered ring, five-membered ring, or six-membered ring.

[In the formula, * indicates a binding position. ]

The ring structure can be preferably a four-, five- or six-membered ring, more preferably a four- or six-membered ring.

［式中、＊は、結合位置を示す。］ The repeating unit having a ring structure can preferably be the following units.

[In the formula, * indicates a binding position. ]

（式中、＊は、結合位置を示す。）
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、ｅは、１以上２００以下の整数であり、ａ、ｂ、ｃ、ｄ及びｆは、それぞれ独立して０以上２００以下の整数であって、また、ａ、ｂ、ｃ、ｄ、ｅ又は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－ （ｆ６）
［式中、ｆは、１以上２００以下の整数であり、ａ、ｂ、ｃ、ｄ及びｅは、それぞれ独立して０以上２００以下の整数であって、また、ａ、ｂ、ｃ、ｄ、ｅ又は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。］ In one embodiment, each R 1 ^F is independently a group represented by any one of the following formulas (f1) to (f6).
-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)
[Wherein, d is an integer of 1 to 200, e is an integer of 0 to 2,
The order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula. ];
-(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 —R ⁹ — (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,
^R9 _{is a} single bond _{or a} group selected from _OCF2 , _OC2F4 , _OC3F6 , _OC4F8 , _OC5F10 and _{OC6F12 ;}
g is an integer from 2 to 100; ];
—(R ⁶ —R ⁷ ) _g —R ^r —(R ^7′ —R ^6′ ) _g′ − (f4)
[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,
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 independently selected from these groups a combination of two or three groups,
g is an integer from 2 to 100,
g' is an integer from 2 to 100,
^Rr is

(In the formula, * indicates a binding position.)
is. ];
- (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, 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 or f in parentheses may be present in any order 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 - (f6)
[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 or f in parentheses may be present in any order 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 one aspect, e is one. In another aspect, e is zero. In yet another aspect, e is two. In one embodiment, the above formula (f1) is -(OCF ₂ CF ₂ CF ₂ ) _d -(OCF ₂ CF ₂ ) _e - or -(OCF(CF ₃ )CF ₂ ) _d -(OCF(CF ₃ ) ) is a group represented by _e- . In another embodiment, the above formula (f1) is -(OC ₃ F ₆ ) _d1 -(OC ₂ F ₄ ) _e1 -(OC ₃ F ₆ ) _d2 -(OC ₂ F ₄ ) _e2 - (wherein d1 and d2 are each independently an integer of 1 to 200, the sum of d1 and d2 is 200 or less, and e1 and e2 are each independently 0 or 1.) is.

_In one embodiment _, formula ₍ f1) is -( _{OCF2CF2CF2 ) d-} ( _OCF2CF2 ) _e- , preferably _{-(OCF2CF2CF2 ) d-} ( _{OCF2CF 2} ) is -.

In another embodiment, formula (f1) is a group represented by -(OCF(CF ₃ )CF ₂ ) _d -(OCF(CF ₃ )) _e -, preferably -(OCF(CF ₃ )CF ₂ ) _d- (OCF(CF ₃ ))-.

In another embodiment, formula (f1) is -(OC ₃ F ₆ ) _d1 -(OC ₂ F ₄ ) _e1 -(OC ₃ F ₆ ) _d2 -(OC ₂ F ₄ ) _e2 -, preferably - (OC ₃ F ₆ ) _d1 -(OC ₂ F ₄ )-(OC ₃ F ₆ ) _d2 -(OC ₂ F ₄ )-, more preferably -(OCF(CF ₃ )CF ₂ ) _d1 -(OCF ₂ CF ₂ )-(OCF(CF ₃ )CF ₂ ) _d2 -(OCF(CF ₃ ))-.

In the above formula (f2), e and f are each independently an integer of preferably 5-200, 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 one aspect, ^R9 is a single bond. In another aspect _, ^R9 is _{a group} selected from _{OCF2 , OC2F4} , _OC3F6 , _{OC4F8 , OC5F10} and _OC6F12 . 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, (R ⁶ -R ⁷ ) _g is preferably -(OC ₂ F ₄ -OC ₃ F ₆ ) _g - or -(OC ₂ F ₄ -OC ₄ F ₈ ) _g -.

［式中、＊は、結合位置を示す。］
であり、より好ましくは

［式中、＊は、結合位置を示す。］
である。 In formula (f4) above, R ⁶ , R ⁷ and g have the same meanings as in formula (f3) above, and have the same aspects. R ^6′ , R ^7′ and g′ have the same meanings as R ⁶ , R ⁷ and g in formula (f3) above, respectively, and have the same aspects. R ^r is preferably

[In the formula, * indicates a binding position. ]
and more preferably

[In the formula, * indicates a binding position. ]
is.

In the above formula (f5), 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 (f6), 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 embodiment, R ^F is a group represented by formula (f1) or (f2).

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, R ^F is a group represented by the formula (f6).

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, still more preferably 0.2 to 0.85. By setting the e/f ratio to 10 or less, the slipperiness, wear resistance and chemical resistance (for example, durability against artificial perspiration) 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 abrasion resistance 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.

In one aspect, the e/f ratio is preferably 0.2 to 0.95, more preferably 0.2 to 0.9.

In one aspect, from the viewpoint of heat resistance, the e/f ratio is preferably 1.0 or more, more preferably 1.0 to 2.0.

In the fluoropolyether group-containing acrylic compound, the number average molecular weight of the ^RF2 portion is not particularly limited, but is for example 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000. 000 to 10,000. In this specification, the number average molecular weight of R ^F2 is a value measured by ¹⁹ F-NMR.

In the above formula (1), each R ^a is independently an (m+2)-valent organic group.

In one aspect, R ^a has the formula:
—R ⁹ —(R ^a′ —R ⁹ ) _k —
[In the formula:
each R ⁹ is independently a C _1-6 alkylene group;
each R ^a' is independently a trivalent organic group,
k is an integer from 1 to 4; ]
It is a group represented by In such groups:

R ⁹ is preferably a C _1-4 alkylene group, more preferably a C _2-4 alkylene group.

In preferred embodiments, k is an integer from 1-2.

In one aspect, k is one.

In one aspect, k is two.

In one aspect, each R ^a' is independently a trivalent group containing an N atom or an O atom.

In a preferred embodiment, each R ^a' is independently a trivalent organic group which may contain an amino bond, an amide bond, a urethane bond, a urea bond, an ether bond, or an ester bond between carbon atoms.

［式中、Ｒ^８は、水素原子、又はＣ_１－６アルキル基（好ましくはメチル基又はエチル基、より好ましくはメチル基）である。］
である。上記－ＣＲ^８（－Ｏ－）－は、ＯがＲ^Ａｃに結合する。 In one aspect, each R ^a' is independently selected from the following groups:

[In the formula, R ⁸ is a hydrogen atom or a C _1-6 alkyl group (preferably a methyl group or an ethyl group, more preferably a methyl group). ]
is. In -CR ⁸ (-O-)- above, O binds to R ^Ac .

In one aspect, R ^a' is N.

In one aspect, R ^a' is -CR ⁸ (-O-)-.

In the above formula (1), m is an integer of 1-4.

In preferred embodiments, m is 1 or 2.

In one aspect, m is one.

In one aspect, m is two.

In formula (1) above, each R ^b is independently R ^Si , R ^Ac , or R ^c .

In formula (1) above, at least one R ^b is R ^Si .

In a preferred embodiment, at least one of the ^Rb 's attached to each terminal N atom of formula (1) is ^RSi .

In one embodiment, one of the ^Rb 's attached to each terminal N atom of formula (1) is ^RSi and the other is ^Rc .

In another embodiment, one of the ^Rb 's attached to each terminal N atom of formula (1) is ^RSi and the other is ^RAc .

Each R 1 ^Si is independently -X ^C -SiR ¹ _n' R ² _3-n' .

X ^C is a divalent organic group having 1 to 10 carbon atoms.

In one aspect, X ^C is
a C _1-6 alkylene group,
—(CH ₂ ) _z1 —O—(CH ₂ ) _z2 —, wherein z1 is an integer of 0 to 6, such as an integer of 1 to 6, z2 is an integer of 0 to 6, such as 1 to 6 is an integer of ), or
—(CH ₂ ) _z3 —phenylene-(CH ₂ ) _z4 —, wherein z3 is an integer of 0-6, such as an integer of 1-6, z4 is an integer of 0-6, such as 1-6 is an integer of
is. 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. These groups are attached to Si on the right side.

The above C _1-6 alkylene group may be linear or branched, but is preferably linear.

In a preferred embodiment, X ^C is a C _1-6 alkylene group, preferably a C _2-4 alkylene group.

Each R ¹ above is independently a hydroxyl group or a hydrolyzable group.

R ¹ is preferably each independently a hydrolyzable group.

R ¹ is preferably each independently -OR ^h , -OCOR ^h , -ON=CR ^h ₂ , -NR ^h ₂ , -NHR ^h , -NCO, 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 R ² 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 ² , 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.

In the above formula, n' is an integer of 1 to 3, preferably 2 or 3, more preferably 3, independently for each (SiR ¹ _n' R ² _3-n' ) unit. .

In formula (1) above, each R ^Ac is independently -X ^D -X ^E (-X ^F -OCO-CR ⁵ =CH ₂ ) _m' .

X ^D above is a divalent organic group.

X ^D is preferably -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -OCONH-, -NHCOO-, -NH-CO-NH-, -CH ₂ CH(OH)CH ₂ - or -CH(CH ₂ OH)CH ₂ -, more preferably -CONH-, -CH ₂ CH(OH)CH ₂ - or -CH(CH ₂ OH)CH ₂ -, more preferably -CONH-. These groups are attached to X ^E on the right side.

X ^E above is a single bond or a (m'+1) valent group.

In one aspect, X ^E is a single bond.

であり、
Ｒ^８は、水素原子、又はＣ_１－６アルキル基である。］
で表される三又は四価の基である。 In one aspect, X ^E is
-X ^G -X ^H
[In the formula:
^XG is
single bond,
a C _1-6 alkylene group,
—(CH ₂ ) _z9 —O—(CH ₂ ) _z10 —, wherein z9 is an integer of 0-6, such as an integer of 1-6, z10 is an integer of 0-6, such as 1-6 is an integer of), or
—(CH ₂ ) _z11 —phenylene-(CH ₂ ) _z12 —, wherein z11 is an integer of 0-6, such as an integer of 1-6, z12 is an integer of 0-6, such as 1-6 is an integer of
and
X ^H is the following

and
R ⁸ is a hydrogen atom or a C _1-6 alkyl group. ]
is a trivalent or tetravalent group represented by

The above C _1-6 alkylene group may be linear or branched, but is preferably linear.

In a preferred embodiment, said C _1-6 alkylene group is a C _2-4 alkylene group.

The C _1-6 alkyl group is preferably a C _1-3 alkyl group, more preferably a methyl group.

Each X ^F is independently a divalent organic group having 1 to 10 carbon atoms.

In one aspect, X ^F is
a C _1-6 alkylene group,
—(CH ₂ ) _z5 —O—(CH ₂ ) _z6 —, wherein z5 is an integer of 0-6, such as an integer of 1-6, z6 is an integer of 0-6, such as 1-6 is an integer of ), or
—(CH ₂ ) _z7 —phenylene-(CH ₂ ) _z8 —, wherein z7 is an integer of 0-6, such as an integer of 1-6, z8 is an integer of 0-6, such as 1-6 is an integer of
is. 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. These groups are attached to X ^E on the left side.

The C _1-6 alkylene group may be linear or branched. In one aspect, the C _1-6 alkylene group is straight chain. In another aspect, a C _1-6 alkylene group is branched.

In a preferred embodiment, X ^F is a C _1-6 alkylene group, preferably a C _2-4 alkylene group.

In another preferred embodiment, X ^F is -O-(CH ₂ ) _z6 -, preferably -O-(CH ₂ ) _2-4 -.

R ⁵ above is a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms.

The monovalent organic group is preferably a C _1-8 alkyl group, a C _3-8 cycloalkyl group, or a C _5-8 aryl group, more preferably a C _1-6 alkyl group or a phenyl group, A C _1-3 alkyl group is more preferred, and a methyl group is particularly preferred.

In one aspect, ^R5 is a hydrogen atom.

In one aspect, ^R5 is a methyl group.

The above m' is an integer of 1 to 10, preferably an integer of 1 to 3, more preferably 1.

In a preferred embodiment, R ^Ac is -CONH-X ^F -OCO-CR ⁵ =CH ₂ .

In formula (1) above, each R ^c is independently a hydrogen atom or a C _1-6 alkyl group.

The C _1-6 alkyl group is preferably a C _1-3 alkyl group, particularly preferably a methyl group. A C _1-6 alkyl group may be straight or branched.

In one aspect, R ^c is a hydrogen atom.

In one aspect, R ^c is a methyl group.

In formula (1) above, each R ^d is independently a single bond or a divalent organic group.

In one aspect, R ^d is a single bond.

In another aspect, R ^d is a divalent organic group.

The divalent organic group in R ^d is
a C _1-10 alkylene group, preferably a C _2-6 alkylene group,
—(CH ₂ ) _z13 —O—(CH ₂ ) _z14 —, wherein z13 is an integer of 0-6, such as an integer of 1-6, z14 is an integer of 0-6, such as 1-6 is an integer of ),
—(CH ₂ ) _z15 —phenylene-(CH ₂ ) _z16 —, wherein z15 is an integer of 0-6, such as an integer of 1-6, z16 is an integer of 0-6, such as 1-6 ), or —(CH ₂ ) _z17 —NR ¹⁰ —(CH ₂ ) _z18 — (wherein R ¹⁰ is a hydrogen atom or a C _1-6 alkyl group, and z17 is 0 to 6 is an integer and z18 is an integer from 0 to 6),
is. 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. These groups are attached to the CO on the left side.

The divalent organic group in R ^d is preferably —(CH ₂ ) _z17 —NR ¹⁰ —(CH ₂ ) _z18 — (wherein R ¹⁰ is a hydrogen atom or a C _1-6 alkyl group, and z17 is , an integer of 0 to 6, and z18 is an integer of 0 to 6), more preferably —NR ¹⁰ —(CH ₂ ) _z18 — (wherein R ¹⁰ is a hydrogen atom or C _1-6 alkyl and z18 is an integer from 1 to 6).

The C _1-10 alkylene group may be linear or branched, but is preferably linear.

In the above formula (1), x is an integer of 1 or more.

In one aspect, x is preferably an integer of 1 or more and 100 or less, more preferably an integer of 1 or more and 10 or less, still more preferably an integer of 1 or more and 5 or less, such as an integer of 2 or more and 10 or less, further preferably 2 or more. It is an integer of 5 or less.

The fluoropolyether group-containing acrylic compound represented by formula (1) is not particularly limited, but may have a number average molecular weight of 5×10 ² to 2×10 ⁵ . Among these ranges, a number average molecular weight of 2×10 ³ to 1×10 ⁵ , more preferably 3×10 ³ to 2×10 ⁴ is preferable from the viewpoint of abrasion resistance. The "number average molecular weight" is a value measured by ¹⁹ F-NMR.

In one aspect, the fluoropolyether group-containing acrylic compound represented by the above formula (1) has the following formula:
^R21 OOC-R ^F2 - ^COOR21
[In the formula, R ²¹ is a hydrogen atom or a methyl group, and R ^F2 has the same meaning as described for formula (1). ]
and a compound represented by the following formula:
_NH2 - ^R9- (NH- ^R9 ) _k - _NH2
[In the formula, R ⁹ and k have the same meanings as described for formula (1). ]
and react with
R ²¹ OOC-(R ^F2 -CONH-R ⁹ -(NH-R ⁹ ) _k -NHCO) _x -R ^F2 -COOR ²¹
[In the formula, R ²¹ is a hydrogen atom or a methyl group, and R ^F2 , R ⁹ and k have the same meanings as those described for formula (1). ]
get then the resulting compound and
NR ²³ _m H _2-m -R ²² -SiR ¹ _n' R ² _3-n'
[wherein R ²³ is a C _1-6 alkyl group or a phenyl group, m is 0 or 1, R ²² is a divalent group, and R ¹ , R ² and n′ are It has the same meaning as described in relation to formula (1). ]
is reacted with a compound represented by the following formula:
R ² _3-n′ R ¹ _n′ Si—R ²² —HNOC—(R ^F2 —CONH—R ⁹ —(NH—R ⁹ ) _k —NHCO) _x —R ^F2 —CONH—R ²² —SiR ¹ _n′ R ² _3-n′
A compound represented by is obtained. Then, the obtained compound and the following formula:
R ³⁴ -R ³⁵ -OCOCH=CH ₂
[Wherein, R ³⁴ is a reactive group such as —NCO, —COOH,
R ³⁵ is a divalent group. ]
The compound represented by the formula (1) can be obtained by reacting with the compound represented by.

In one aspect, the fluoropolyether group-containing acrylic compound represented by the above formula (1) has the following formula:
^R21 OOC-R ^F2 - ^COOR21
[In the formula, R ²¹ is a hydrogen atom or a methyl group, and R ^F2 has the same meaning as described for formula (1). ]
and a compound represented by the following formula:
_NH2- ^R9- (CH(OH) ^-R9 ) _k - _NH2
[In the formula, R ⁹ and k have the same meanings as described for formula (1). ]
and react with
R ²¹ OOC-(R ^F2 -CONH-R ⁹ -(CH(OH)-R ⁹ ) _k -NHCO) _x -R ^F2 -COOR ²¹
[In the formula, R ²¹ is a hydrogen atom or a methyl group, and R ^F2 , R ⁹ and k have the same meanings as those described for formula (1). ]
get then the resulting compound and
NR ²³ _m H _2-m -R ²² -SiR ¹ _n' R ² _3-n'
[wherein R ²³ is a C _1-6 alkyl group or a phenyl group, m is 0 or 1, R ²² is a divalent group, and R ¹ , R ² and n′ are It has the same meaning as described in relation to formula (1). ]
is reacted with a compound represented by the following formula:
R ² _3-n′ R ¹ _n′ Si—R ²² —HNOC—(R ^F2 —CONH—R ⁹ —(CH(OH)—R ⁹ ) _k —NHCO) _x —R ^F2 —CONH—R ²² —SiR ¹ _n' R ² _3-n'
A compound represented by is obtained. Then, the obtained compound and the following formula:
R ³⁴ -R ³⁵ -OCOCH=CH ₂
[Wherein, R ³⁴ is a reactive group such as —NCO, —COOH,
R ³⁵ is a divalent group. ]
The compound represented by the formula (1) can be obtained by reacting with the compound represented by.

In one aspect, the fluoropolyether group-containing acrylic compound represented by the above formula (1) has the following formula:
^R21 OOC-R ^F2 - ^COOR21
[In the formula, R ²¹ is a hydrogen atom or a methyl group, and R ^F2 has the same meaning as described for formula (1). ]
and a compound represented by the following formula:
_NH2 - ^R9- (NH- ^R9 ) _k - _NH2
[In the formula, R ⁹ and k have the same meanings as described for formula (1). ]
and react with
R ²¹ OOC-(R ^F2 -CONH-R ⁹ -(NH-R ⁹ ) _k -NHCO) _x -R ^F2 -COOR ²¹
[In the formula, R ²¹ is a hydrogen atom or a methyl group, and R ^F2 , R ⁹ and k have the same meanings as those described for formula (1). ]
get then the resulting compound and
_NH2 - ^R9' - _NH2
[In the formula, R9 ^' has the same meaning as described for ^R9 . ]
and a compound represented by the following formula: R ²¹ OOC-(R ^F2 -CONH-R ⁹ -(NH-R ⁹ ) _k -NHCO) _x -(R ^F2 -CONH-R ⁹ '-NHCO) _{x '} ^-RF2 -COOR ²¹
[In the formula, R ²¹ is a hydrogen atom or a methyl group, R ^F2 , R ⁹ and k have the same meanings as described for formula (1), and R ^9′ has the same meanings as described for R ⁹ ]
get then the resulting compound and
NR ²³ _m H _2-m -R ²² -SiR ¹ _n' R ² _3-n'
[wherein R ²³ is a C _1-6 alkyl group or a phenyl group, m is 0 or 1, R ²² is a divalent group, and R ¹ , R ² and n′ are It has the same meaning as described in relation to formula (1). ]
is reacted with a compound represented by the following formula:
R ² _3-n′ R ¹ _n′ Si—R ²² —HNOC—(R ^F2 —CONH-R ⁹ —(NH—R ⁹ ) _k —NHCO) _x —(R ^F2 —CONH—R ^9′ —NHCO) _x' - ^RF2 -CONH- ^R22 - ^SiR1n'R23 _{- n} ^'
A compound represented by is obtained. Then, the obtained compound and the following formula:
R ³⁴ -R ³⁵ -OCOCH=CH ₂
[Wherein, R ³⁴ is a reactive group such as —NCO, —COOH,
R ³⁵ is a divalent group. ]
The compound represented by the formula (1) can be obtained by reacting with the compound represented by.

The reaction conditions for each step of the above reaction can be appropriately set by those skilled in the art.

Next, the surface treatment agent of the present disclosure will be explained.

The surface treatment agent of the present disclosure contains at least one fluoropolyether group-containing acrylic compound represented by formula (1).

In one aspect, the fluoropolyether group-containing acrylic compound in the surface treatment agent of the present disclosure is a compound represented by Formula (1).

The content of the compound represented by the above formula (1) is preferably 0.1 to 50.0% by mass, more preferably 1.0 to 30.0% by mass, and more preferably 1.0 to 30.0% by mass, based on the total surface treatment agent. Preferably 5.0 to 25.0% by weight, particularly preferably 10.0 to 20.0% by weight. By setting the content of the fluoropolyether group-containing acrylic compound within the above range, higher water/oil repellency and friction durability can be obtained.

The surface treatment agent of the present disclosure is a solvent, a (non-reactive) fluoropolyether compound, preferably a perfluoro(poly)ether compound, which can be understood as a solvent, a fluorine-containing oil (hereinafter collectively referred to as "fluorine-containing oil"). , a (non-reactive) silicone compound that can be understood as silicone oil (hereinafter referred to as “silicone oil”), alcohols, catalysts, surfactants, polymerization inhibitors, sensitizers, and the like.

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, CF ₃ CH ₂ OH, CF ₃ CF ₂ CH ₂ OH, (CF ₃ ) ₂ CHOH and other fluorine-containing solvents. mentioned. 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 contained 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 surface treatment agent of the present disclosure. In one aspect, the surface treatment agent of the present disclosure is substantially free of fluorine-containing oil. “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.

In one aspect, the average molecular weight of the fluorine-containing oil may be larger than the average molecular weight of the fluoropolyether group-containing acrylic compound. With such an average molecular weight, particularly when the surface treatment layer is formed by a vacuum deposition method, it is possible to obtain more excellent abrasion resistance and surface lubricity.

In one aspect, the average molecular weight of the fluorine-containing oil may be smaller than the average molecular weight of the fluoropolyether group-containing acrylic compound. With such an average molecular weight, it is possible to form a cured product having high abrasion resistance and high surface slipperiness while suppressing deterioration of the transparency of the surface treatment layer obtained from such a compound.

The fluorine-containing oil contributes to improving the surface lubricity of the layer formed by the 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 surface treatment agent of the present disclosure, such a silicone oil is added to a total of 100 parts by mass of the fluoropolyether group-containing acrylic compound of the present disclosure (the sum of these when two or more types, the same applies hereinafter), for example It can be contained in an amount of 0 to 300 parts by weight, preferably 50 to 200 parts by weight.

Silicone oil contributes to improving the surface lubricity of the surface treatment layer.

Examples of the alcohols include alcohols having 1 to 6 carbon atoms which may be substituted with one or more fluorine atoms, such as methanol, ethanol, iso-propanol, tert-butanol, CF ₃ CH ₂ OH, CF ₃ CF ₂ CH ₂ OH, (CF ₃ ) ₂ CHOH. By adding these alcohols to the surface treating agent, the stability of the surface treating agent is improved, and the compatibility between the perfluoropolyether group-containing acrylic compound and the solvent is improved.

The alcohol is preferably 2,2,3,3,3-pentafluoro-1-propanol or 2,2,2-trifluoroethanol.

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, dehydration condensation, or polymerization of the fluoropolyether group-containing acrylic compound of the present disclosure and promotes formation of the layer formed by the 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 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.

In addition to the components described above, the surface treatment agent of the present disclosure contains trace amounts of impurities such as Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, and silane condensates. obtain.

Articles of the present disclosure are described below.

The article of the present disclosure includes a base material and a layer (surface treatment layer) formed on the surface of the base material from the surface treatment agent of the present disclosure.

Substrates that can be used in the present disclosure include, for example, glass, resins (natural or synthetic resins, such as common plastic materials), metals, ceramics, semiconductors (silicon, germanium, etc.), fibers (woven fabrics, non-woven fabrics etc.), fur, leather, wood, ceramics, stone, etc., construction members, etc., sanitary products, and any suitable material.

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 , Ta3O5 .} , Nb ₂ O ₅ , HfO ₂ , Si ₃ N ₄ , CeO ₂ , MgO, Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO ₃ and the like. These inorganic substances may be used alone or in combination of two or more (for example, as a mixture). In the case of a multi-layer 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, the insulating layer, adhesive layer, protective layer, decorative frame layer (I-CON), atomized film layer, hard coating film layer, polarizing film, phase retardation film, and a liquid crystal display module.

The shape of the substrate is not particularly limited, and may be, for example, plate-like, film, or other shapes. Moreover, the surface region of the base material on which the surface treatment layer is to be formed may be at least part of the surface of the base material, and can be appropriately determined according to the application and specific specifications of the article to be manufactured.

In one embodiment, such a substrate may consist of a material that originally has hydroxyl groups, at least at its surface portion. 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 comprise, at least a portion of its surface, another reactive group, such as a silicone compound having one or more Si—H groups, or a material comprising an alkoxysilane. .

In a preferred embodiment, the substrate is glass. As such glass, sapphire glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are preferable, and chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glasses are particularly preferred.

The article of the present disclosure is produced by forming a layer of the surface treatment agent of the present disclosure on the surface of the substrate, and post-treating this layer as necessary, thereby forming a layer from the surface treatment agent of the present disclosure. It can be manufactured by forming.

Layer formation of the surface treatment agent of the present disclosure can be carried out by applying the 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 can be diluted with a solvent prior to application to the substrate surface. From the viewpoint of the stability of the composition of the present disclosure and the volatility of the solvent, the following solvents are preferably used: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (for example, 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, Asahi Glass Asahiklin (registered trademark) AC-6000 manufactured by 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. Novec™ ₇₀₀₀ from Sumitomo 3M), perfluorobutyl _methyl ether ( _{C4F9OCH3 )} ) (e.g. Novec (trademark) 7100 manufactured by Sumitomo 3M), perfluorobutyl ethyl ether ( _C4F9OC2H5 ) (e.g. Novec ( _trademark ) ₇₂₀₀ manufactured by Sumitomo 3M), _{perfluoro Alkyl} perfluoroalkyl ethers ( _{perfluoroalkyl} groups _and alkyl _{groups are} directly may be chain or branched), or CF ₃ CH ₂ OCF ₂ CHF ₂ (eg Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), etc. These solvents may be used alone or , can be used as a mixture of two or more, among which hydrofluoroethers are preferred, and perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and/or perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ 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.

The surface treatment layer included in the articles of the present disclosure has both high abrasion resistance. In addition to high abrasion resistance, the surface treatment layer has water repellency, oil repellency, and antifouling properties (for example, it prevents the adhesion of stains such as fingerprints), depending on the composition of the surface treatment agent used. Waterproofness (prevents water from penetrating into electronic parts, etc.), surface slipperiness (or lubricity, such as wiping off of fingerprints and other stains, excellent touch feeling on fingers), chemical resistance, etc. It can be suitably used as a functional thin film.

Therefore, the present disclosure further relates to an optical material having the surface treatment layer 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 of the present disclosure are not particularly limited, but may be 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 of the present disclosure may also be medical devices or medical materials. An article having a layer obtained by the present disclosure may also be an automobile interior or exterior member. Examples of exterior materials include: windows, light covers, exterior camera covers. Examples of interior materials include: instrument panel covers, navigation system touch panels, decorative interior materials.

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, abrasion resistance and antifouling properties.

The articles of the present disclosure have been described above in detail. Note that the article, the method for manufacturing the article, and the like of the present disclosure are not limited to the examples given above.

The compounds of the present disclosure will be described below in Examples, but the present disclosure is not limited to the following Examples. In this example, the order of existence of the repeating units constituting the fluoropolyether is arbitrary, and the chemical formula shown below indicates the average composition.

Synthesis example 1
A 100 mL 3 _- necked flask equipped with a reflux _condenser , _thermometer and stirrer was charged with permeate of average composition _CH3OCOCF2O ( _CF2O ) ₁₂ ( _CF2CF2O ) _{12CF2COOCH3 .} 10.0 g of fluoropolyether-modified ester, 5.0 g of 1,3-bis(trifluoromethyl)benzene, and 0.20 g of diethylenetriamine were charged and stirred at 25° C. for 1 hour under a nitrogen stream. Subsequently, after adding 0.68 g of 3-aminopropyltrimethoxysilane, the mixture was stirred at 25° C. for 1 hour. Then, the volatile matter was distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (A) represented by the following formula.

_{( CH3O ) 3SiCH2CH2CH2NHCOCF2O ( CF2CF2O ) 12 ( CF2O ) 12CF2CONHCH2CH2NHCH2CH2NHCOCF2O ( CF2CF2O ) 12 _ _ _ _ ( CF2O ) 12CF2CONHCH2CH2CH2Si ( OCH3 ) 3}

Synthesis example 2
10.0 g of the perfluoropolyether group-containing silane compound (A) obtained in Synthesis Example 1 and 2-isocyanatoethyl acrylate ( 0.27 g of Karenz (registered trademark) AOI manufactured by Showa Denko K.K. was charged and stirred at 25° C. for 1 hour under a nitrogen stream to obtain a perfluoropolyether group-containing silane compound (B) represented by the following formula. .

_{( CH3O ) 3SiCH2CH2CH2NHCOCF2O ( CF2CF2O ) 12 ( CF2O ) 12CF2CONHCH2CH2N ( X ) CH2CH2NHCOCF2O ( CF2CF 2O ) 12 ( CF2O} ) _{12CF2CONHCH2CH2CH2Si ( OCH3 ) 3}
-X= _{-CONHCH2CH2OCOCH = CH2}

Synthesis example 3
10.0 g of the perfluoropolyether group-containing silane compound (A) obtained in Synthesis Example 1 and 1,1-(bisacryloyl 0.46 g of oxymethyl)ethyl isocyanate (Kalenz (registered trademark) BEI manufactured by Showa Denko Co., Ltd.) was charged and stirred at 25° C. for 1 hour under a nitrogen stream to obtain a perfluoropolyether group-containing silane compound represented by the following formula. (C) was obtained.

_{( CH3O ) 3SiCH2CH2CH2NHCOCF2O ( CF2CF2O ) 12 ( CF2O ) 12CF2CONHCH2CH2N ( X ) CH2CH2NHCOCF2O ( CF2CF 2O ) 12 ( CF2O} ) _{12CF2CONHCH2CH2CH2Si ( OCH3 ) 3}
-X=-CONHC( _CH3 )( _CH2OCOCH = _CH2 ) ₂

Synthesis example 4
A 100 mL 3 _- necked flask equipped with a reflux _condenser , _thermometer and stirrer was charged with permeate of average composition _CH3OCOCF2O ( _CF2O ) ₁₂ ( _CF2CF2O ) _{12CF2COOCH3 .} 10.0 g of fluoropolyether-modified ester, 5.0 g of 1,3-bis(trifluoromethyl)benzene, and 0.28 g of triethylenetetramine were charged and stirred at 25° C. for 1 hour under a nitrogen stream. Subsequently, after adding 0.68 g of 3-aminopropyltrimethoxysilane, the mixture was stirred at 25° C. for 1 hour. Then, the volatile matter was distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (D) represented by the following formula.

_{( CH3O ) 3SiCH2CH2CH2NHCOCF2O ( CF2CF2O ) 12 ( CF2O ) 12CF2CONHCH2CH2NHCH2CH2NHCH2CH2NHCOCF2O ( CF2CF _ _ _ _ _ _ 2O ) 12 ( CF2O} ) _{12CF2CONHCH2CH2CH2Si ( OCH3 ) 3}

Synthesis example 5
10.0 g of the perfluoropolyether group-containing silane compound (D) obtained in Synthesis Example 4, 2-isocyanatoethyl acrylate (Showa 0.54 g of Karenz (registered trademark) AOI manufactured by Denko Co., Ltd. was charged and stirred at 25° C. for 1 hour under a nitrogen stream to obtain a perfluoropolyether group-containing silane compound (E) represented by the following formula.

_{( CH3O ) 3SiCH2CH2CH2NHCOCF2O ( CF2CF2O ) 12 ( CF2O ) 12CF2CONHCH2CH2N (} X) _{CH2CH2N (} X _{) CH2CH 2NHCOCF2O ( CF2CF2O ) 12 ( CF2O ) 12CF2CONHCH2CH2CH2Si ( OCH3 ) 3}
-X= _{-CONHCH2CH2OCOCH = CH2}

Synthesis example 6
A 100 mL 3-neck flask equipped with a reflux condenser, thermometer and _stirrer was charged _with the average composition _CH3OCOCF ( _CF3 ){ _OCF2CF ( _CF3 )} _mOCF2CF2O {CF( _CF3 ). CF ₂ O} _n CF(CF ₃ )COOCH ₃ (m+n≈34) perfluoropolyether-modified ester 10.0 g, hexafluorobenzene 5.0 g, and diethylenetriamine 0.085 g were charged and placed under a nitrogen stream. , and 70° C. for 13 hours. Subsequently, after adding 0.29 g of 3-aminopropyltrimethoxysilane, the mixture was stirred at 70° C. for 12 hours. After that, the volatile matter was distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (F) represented by the following formula.

(CH3O _{) 3SiCH2CH2CH2NHCOCF} ( _{CF3 )} { _OCF2CF ( _{CF3 )} } _{mOCF2CF2O { CF} ( _{CF3 )} CF2O} _n CF( _{CF3 ) CONHCH2 CH2NHCH2CH2NHCOCF ( CF3} ) _{{ OCF2CF} (CF3 _{) } mOCF2CF2O} {CF( _CF3 )CF2O _{} nCF ( CF3 ) CONHCH2CH2CH2Si (} OCH ₃ ) ₃

Synthesis example 7
10.0 g of the perfluoropolyether group-containing silane compound (F) obtained in Synthesis Example 6 and 2-isocyanatoethyl acrylate ( 0.12 g of Karenz (registered trademark) AOI manufactured by Showa Denko K.K. was charged and stirred at 25° C. for 1 hour under a nitrogen stream to obtain a perfluoropolyether group-containing silane compound (G) represented by the following formula. .

(CH3O _{) 3SiCH2CH2CH2NHCOCF} ( _{CF3 )} { _OCF2CF ( _{CF3 )} } _{mOCF2CF2O { CF} ( _{CF3 )} CF2O} _n CF( _{CF3 ) CONHCH2 CH2N} ( _X ) _CH2CH2NHCOCF ( _CF3 ) _{{ OCF2CF} (CF3) _{} mOCF2CF2O {} CF( _{CF3 )} CF2O} _{nCF ( CF3} ) _{CONHCH2CH2 CH2Si} ( _OCH3 ) ₃
-X= _{-CONHCH2CH2OCOCH = CH2}

Synthesis example 8
A 100 mL three-neck flask equipped with a reflux condenser, a thermometer and a stirrer was charged with 10.0 g of the perfluoropolyether group-containing silane compound (A) obtained in Synthesis Example 1 and 4-hydroxybutyl acrylate glycidyl ether. (Mitsubishi Chemical Co., Ltd. 4HBAGE) 0.38 g was charged and stirred at 50° C. for 3 hours under a nitrogen stream to obtain a perfluoropolyether group-containing silane compound (H) represented by the following formula.

_{( CH3O ) 3SiCH2CH2CH2NHCOCF2O ( CF2CF2O ) 12 ( CF2O ) 12CF2CONHCH2CH2N ( X ) CH2CH2NHCOCF2O ( CF2CF 2O ) 12 ( CF2O} ) _{12CF2CONHCH2CH2CH2Si ( OCH3 ) 3}
-X is a mixture of -X ¹ and -X ² below (X ¹ : X ² = 80: 20)
—X ¹ = —CH ₂ CH(OH)CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCOCH=CH ₂
^-X2 _{= -CH ( CH2OH} ) _{CH2OCH2CH2CH2CH2OCOCH = CH2}

Synthesis example 9
A 100 mL 3 _- necked flask equipped with a reflux _condenser , _thermometer and stirrer was charged with permeate of average composition _CH3OCOCF2O ( _CF2O ) ₁₂ ( _CF2CF2O ) _{12CF2COOCH3 .} 10.0 g of fluoropolyether-modified ester, 5.0 g of 1,3-bis(trifluoromethyl)benzene, and 0.20 g of 1,3-diamino-2-propanol were charged and heated at 25° C. for 1 hour under a nitrogen stream. Stirred. Subsequently, after adding 0.68 g of 3-aminopropyltrimethoxysilane, the mixture was stirred at 25° C. for 1 hour. After that, the volatile matter was distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (I) represented by the following formula.

_{( CH3O ) 3SiCH2CH2CH2NHCOCF2O ( CF2CF2O ) 12 ( CF2O ) 12CF2CONHCH2CH (} OH) _{CH2NHCOCF2O ( CF2CF2O ) 12 ( CF2O ) 12CF2CONHCH2CH2CH2Si ( OCH3 ) 3}

Synthesis example 10
10.0 g of the perfluoropolyether group-containing silane compound (I) obtained in Synthesis Example 9, 2-isocyanatoethyl acrylate (Showa 0.27 g of Karenz (registered trademark) AOI manufactured by Denko Co., Ltd. and 0.012 g of dibutyltin dilaurate were charged and stirred at 50° C. for 2 hours under a nitrogen stream to obtain a perfluoropolyether group-containing silane compound represented by the following formula. (J) was obtained.

_{( CH3O ) 3SiCH2CH2CH2NHCOCF2O ( CF2CF2O ) 12 ( CF2O ) 12CF2CONHCH2CH (} OX ₎ CH2NHCOCF2O _{( CF2CF2O ) 12 ( CF2O ) 12CF2CONHCH2CH2CH2Si ( OCH3 ) 3}
-X= _{-CONHCH2CH2OCOCH = CH2}

Synthesis Example 11
A 100 mL 3 _- necked flask equipped with a reflux _condenser , _thermometer and stirrer was charged with permeate of average composition _CH3OCOCF2O ( _CF2O ) ₁₂ ( _CF2CF2O ) _{12CF2COOCH3 .} 10.0 g of fluoropolyether-modified ester, 5.0 g of 1,3-bis(trifluoromethyl)benzene, and 0.20 g of diethylenetriamine were charged and stirred at 25° C. for 1 hour under a nitrogen stream. Subsequently, 0.85 g of 3-(2-aminoethylamino)propyltrimethoxysilane was added, and the mixture was stirred at 25° C. for 1 hour. After that, the volatile matter was distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (K) represented by the following formula.

_{( CH3O ) 3SiCH2CH2CH2NHCH2CH2NHCOCF2O ( CF2CF2O ) 12 ( CF2O ) 12CF2CONHCH2CH2NHCH2CH2NHCOCF2O ( CF2CF _ _ _ _ _ _ 2O ) 12 ( CF2O ) 12CF2CONHCH2CH2NHCH2CH2CH2Si ( OCH3 ) 3 _}

Synthesis Example 12
10.0 g of the perfluoropolyether group-containing silane compound (K) obtained in Synthesis Example 11 and 2-isocyanatoethyl acrylate ( 0.81 g of Karenz (registered trademark) AOI manufactured by Showa Denko K.K. was charged and stirred at 25° C. for 2 hours under a nitrogen stream to obtain a perfluoropolyether group-containing silane compound (L) represented by the following formula. .

( _{CH3O ) 3SiCH2CH2CH2N (} X _{) CH2CH2NHCOCF2O ( CF2CF2O ) 12 ( CF2O ) 12CF2CONHCH2CH2N ( X} ) _{CH2CH 2NHCOCF2O ( CF2CF2O ) 12 ( CF2O ) 12CF2CONHCH2CH2N ( X} ) _CH2CH2CH2Si ( _{OCH3 ) 3}
-X= _{-CONHCH2CH2OCOCH = CH2}

Synthesis Example 13
_A 100 mL 3- _{necked flask} equipped with _a reflux condenser, _thermometer and stirrer was charged with a permeate of average _{composition CH3OCOCF2CF2O} ( _CF2CF2CF2O ) _{16CF2CF2COOCH3 .} 10.0 g of fluoropolyether-modified ester, 5.0 g of 1,3-bis(trifluoromethyl)benzene, and 0.17 g of diethylenetriamine were charged and stirred at 25° C. for 1 hour under a nitrogen stream. Subsequently, after adding 0.60 g of 3-aminopropyltrimethoxysilane, the mixture was stirred at 25° C. for 1 hour. After that, the volatile matter was distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (M) represented by the following formula.

_{( CH3O ) 3SiCH2CH2CH2NHCOCF2CF2O ( CF2CF2CF2O ) 16CF2CF2CONHCH2CH2NHCH2CH2NHCOCF2CF2O ( CF2CF2CF _ _ _ _ _ _ _ _ _ _ _ 2O ) 16CF2CF2CONHCH2CH2CH2Si ( OCH3 ) 3 _ _}

Synthesis Example 14
10.0 g of the perfluoropolyether group-containing silane compound (M) obtained in Synthesis Example 13 and 2-isocyanatoethyl acrylate ( 0.24 g of Karenz (registered trademark) AOI manufactured by Showa Denko K.K. was charged and stirred at 25° C. for 1 hour under a nitrogen stream to obtain a perfluoropolyether group-containing silane compound (N) represented by the following formula. .

_{( CH3O ) 3SiCH2CH2CH2NHCOCF2CF2O ( CF2CF2CF2O ) 16CF2CF2CONHCH2CH2N ( X ) CH2CH2NHCOCF2CF2O ( CF _ _ _ _ _ 2CF2CF2O ) 16CF2CF2CONHCH2CH2CH2Si ( OCH3 ) 3 _ _ _ _}
-X= _{-CONHCH2CH2OCOCH = CH2}

Example 1
The compound (B) obtained in Synthesis Example 2 was dissolved in Novec 7200 (manufactured by 3M) to a concentration of 20 wt % to prepare a surface treatment agent.

Each of the surface treatment agents prepared above was vacuum-deposited on a chemically strengthened glass (manufactured by Corning, "Gorilla" glass, thickness 0.7 mm). The conditions of the vacuum deposition method were a resistance heating deposition machine chamber size of 1,900 mmφ, a degree of vacuum of 5.0E-05, a current value of 240 A, a voltage of 10 V, and a substrate temperature of 40°C. Next, the vapor-deposited chemically strengthened glass was allowed to stand in an atmosphere at a temperature of 150° C. for 30 minutes, and then allowed to cool to room temperature. Subsequently, the vapor-deposited chemically strengthened glass was irradiated with a light beam containing UV light of 365 nm in an air atmosphere at an intensity of 1000 mJ/cm ² to form a surface treatment layer on the glass substrate.

Example 2
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1, except that the compound (C) obtained in Synthesis Example 3 was used instead of the compound (B).

Example 3
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1, except that the compound (E) obtained in Synthesis Example 5 was used instead of the compound (B).

Example 4
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1, except that the compound (G) obtained in Synthesis Example 7 was used instead of the compound (B).

Example 5
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1, except that the compound (H) obtained in Synthesis Example 8 was used instead of the compound (B).

Example 6
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1, except that compound (J) obtained in Synthesis Example 10 was used instead of compound (B).

Example 7
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1, except that the compound (L) obtained in Synthesis Example 12 was used instead of the compound (B).

Example 8
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1, except that the compound (N) obtained in Synthesis Example 14 was used instead of the compound (B).

Comparative example 1
A surface treatment agent was prepared by dissolving the following compound (O) in Novec 7200 (manufactured by 3M) to a concentration of 20 wt %.

_{( CH3O ) 3SiCH2CH2CH2NHCOCF2O ( CF2CF2O ) 12 ( CF2O ) 12CF2CONHCH2CH2CH2Si ( OCH3 ) 3 _}

Each of the surface treatment agents prepared above was vacuum-deposited on a chemically strengthened glass (manufactured by Corning, "Gorilla" glass, thickness 0.7 mm). The conditions of the vacuum deposition method were a resistance heating deposition machine chamber size of 1,900 mmφ, a degree of vacuum of 5.0E-05, a current value of 240 A, a voltage of 10 V, and a substrate temperature of 40°C. Next, the vapor-deposited chemically strengthened glass was allowed to stand in an atmosphere at a temperature of 150° C. for 30 minutes, and then allowed to cool to room temperature to form a surface treatment layer on the glass substrate.

Comparative example 2
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Comparative Example 1, except that the following compound (P) was used instead of the compound (O).

_{( CH3O ) 3SiCH2CH2CH2NHCOCF2CF2O ( CF2CF2CF2O ) 16CF2CF2CONHCH2CH2CH2Si ( OCH3 ) 3 _ _ _ _ _ _}

Comparative example 3
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Comparative Example 1, except that the following compound (Q) was used instead of the compound (O).

_{( CH3O ) 3SiCH2CH2CH2NHCOCF2O ( CF2CF2O ) 12 ( CF2O ) 12CF2CONHCH2CH2CH2NHCOCF2O ( CF2CF2O ) 12 ( CF _ 2O ) 12CF2CONHCH2CH2CH2Si ( OCH3 ) 3 _}

Comparative example 4
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Comparative Example 1, except that the following compound (R) was used instead of the compound (O).

(CH3O _{) 3SiCH2CH2CH2NHCOCF} ( _{CF3 )} { _OCF2CF ( _{CF3 )} } _{mOCF2CF2O { CF} ( _{CF3 )} CF2O} _n CF( _{CF3 ) CONHCH2 CH2CH2Si} ( _{OCH3 ) 3}

<Evaluation>
For each of the glass substrates with a surface treatment layer obtained above, the water contact angle was measured and the alkali test was evaluated as follows.

(Alkaline immersion test)
A PTFE O-ring with a diameter of 1 cm was placed on the surface of the base material surface-treated in Examples 1 to 8 and Comparative Examples 1 to 4, and an 8N NaOH solution (alkaline aqueous solution) was dropped into the O-ring. , the surface of the surface treatment layer was brought into contact with an alkaline aqueous solution and subjected to an alkaline immersion test. After 20 to 300 minutes of the alkali immersion test, the alkaline aqueous solution was wiped off, and after washing with pure water and ethanol, the contact angle with water was measured. In addition, the static contact angle of water was determined by placing a 2 μL drop of pure water on the surface of the glass substrate after the above alkali immersion test, and using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.: automatic contact angle meter). The contact angle to water was measured using DropMaster 701). The static contact angle of water after the alkali immersion test was measured at five points. The alkaline immersion test was stopped prematurely if the measured static contact angle of water decreased within 300 minutes. The following table shows the relationship between the immersion time and the average value of contact angles at five locations.

(Abrasion durability test)
A sample article on which a surface treatment layer is formed is placed horizontally, the following friction element is brought into contact with the surface of the surface treatment layer (the contact surface is a circle with a diameter of 1 cm), a load of 5 N is applied thereon, and then the load is applied. was applied, the friction element was reciprocated at a speed of 40 mm/sec. The friction element was reciprocated up to 4000 times, and the static contact angle (°) of water was measured every 1000 reciprocations (friction times). The test was stopped when the measured static contact angle of water was less than 60°. The static contact angle of water was measured in the same manner as the alkali test described above. The results are shown in the table below.

Friction element A surface (1 cm in diameter) of a silicone rubber product shown below was covered with cotton immersed in artificial sweat having the composition shown below, and this was used as a friction element.
Composition of artificial sweat:
Anhydrous disodium hydrogen phosphate: 2 g
Sodium chloride: 20g
85% lactic acid: 2g
Histidine hydrochloride: 5g
Distilled water: 1 kg
Silicone rubber products:
A silicone rubber plug SR-51 manufactured by Tigers Polymer was processed into a cylindrical shape with a diameter of 1 cm and a thickness of 1 cm.

The fluoropolyether group-containing acrylic compound 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 friction durability.

Claims (33)

Formula (1) below:

[In the formula:
each R ^F2 is independently -Rf ² _p -R ^F -O _q -;
Rf ² is a C _1-6 alkylene group optionally substituted by one or more fluorine atoms,
^RF is a divalent fluoropolyether group,
p is 0 or 1,
q is 0 or 1;
each R ^a is independently a (m+2)-valent organic group;
m is an integer from 1 to 4,
each R ^b is independently R ^Si , R ^Ac , or R ^c ;
each R ^Si is independently -X ^C -SiR ¹ _n' R ² _3-n' ;
X ^C is a divalent organic group having 1 to 10 carbon atoms,
each R ¹ is independently a hydroxyl group or a hydrolyzable group;
each R ² is independently a hydrogen atom or a monovalent organic group;
n' is an integer of 1 to 3,
each R ^Ac is independently -X ^D -X ^E (-X ^F -OCO-CR ⁵ =CH ₂ ) _m' ;
X ^D is a divalent organic group,
X ^E is a single bond or a (m'+1) valent group,
each X ^F is independently a divalent organic group having 1 to 10 carbon atoms,
R ⁵ is a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms,
m' is an integer from 1 to 10,
each R ^c is independently a hydrogen atom or a C _1-6 alkyl group,
each R ^d is independently a single bond or a divalent organic group;
x is an integer of 1 or more. ]
A compound represented by Each R ^F is independently of the formula:
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ R ^Fa ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f -
[Wherein, each R ^Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom,
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, provided that when all ^RFa are hydrogen atoms or chlorine atoms, a, b, At least one of c, e and f is 1 or more. ]
The compound according to claim 1, which is a group represented by: 2. The compound of claim 1, wherein ^RFa is a fluorine atom. R ^F each independently represents the following formula (f1), (f2), (f3), (f4), (f5) or (f6):
-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)
[Wherein, d is an integer of 1 to 200, e is an integer of 0 to 2,
The order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula. ],
-(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 to 30;
e and f are each independently an integer from 1 to 200;
the sum of c, d, e and f is an integer from 10 to 200;
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 —R ⁹ — (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 two or three groups selected from these groups. is a combination of groups;
^R9 _{is a} single bond _{or a} group selected from _OCF2 , _OC2F4 , _OC3F6 , _OC4F8 , _OC5F10 and _{OC6F12 ;}
g is an integer from 2 to 100; ],
—(R ⁶ —R ⁷ ) _g —R ^r —(R ^7′ —R ^6′ ) _g′ − (f4)
[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,
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 independently selected from these groups a combination of two or three groups,
g is an integer from 2 to 100,
g' is an integer from 2 to 100,
^Rr is

(In the formula, * indicates the binding position.)
is. ];
- (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, 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 - (f6)
[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. ]
The compound according to claim 1, which is a group represented by: each Rf ² is independently a C _1-6 perfluoroalkylene group;
A compound according to claim 1 . Each R ^a is independently represented by the following formula:
—R ⁹ —(R ^a′ —R ⁹ ) _k —
[In the formula:
each R ⁹ is independently a C _1-6 alkylene group;
each R ^a' is independently a trivalent organic group,
k is an integer from 1 to 4; ]
The compound according to claim 1, which is a group represented by: 7. The compound of claim 6, wherein each R ^a' is independently a trivalent organic group containing an N atom or an O atom. Claim 6, wherein each R ^a' is independently a trivalent organic group which may contain an amino bond, an amide bond, a urethane bond, a urea bond, an ether bond, or an ester bond between carbon atoms. The compound described in . Each R ^a' is independently selected from the following groups:

[In the formula, R ⁸ is a hydrogen atom or a C _1-6 alkyl group. ]
7. The compound of claim 6, which is 7. The compound of claim 6, wherein R ^a' is N. 7. The compound of claim 6, wherein k is 1. 7. The compound of claim 6, wherein k is two. 2. The compound of claim 1, wherein at least one ^Rb is ^RSi . 2. The compound of claim 1, wherein one of the ^Rb 's attached to each terminal N atom is ^RSi and the other is ^Rc . 2. The compound of claim 1, wherein one of the ^Rb 's attached to each terminal N atom is ^RSi and the other is ^RAc . X ^C is
a C _1-6 alkylene group,
-(CH ₂ ) _z1 -O-(CH ₂ ) _z2 - (wherein z1 is an integer from 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 an integer from 0 to 6)
2. The compound of claim 1, which is The compound of claim 1, wherein X ^C is a C _1-6 alkylene group. 2. The compound of claim 1, wherein n' is 2 or 3. 2. The compound of claim 1, wherein n' is 3. X ^D is -O-, -CO-, -COO-, -OCO- _, -CONH-, -NHCO-, -OCONH-, -NHCOO-, -NH-CO-NH-, -CH CH(OH )CH ₂ -, or -CH(CH ₂ OH)CH ₂ -. 2. The compound of claim 1, wherein X ^D is -CONH-, -CH ₂ CH(OH)CH ₂ -, or -CH(CH ₂ OH)CH ₂ -. 2. The compound of claim 1, wherein X ^D is -CONH-. 2. The compound of claim 1, wherein X ^E is a single bond. X ^E is -X ^G -X ^H ;
^XG is
single bond,
a C _1-6 alkylene group,
-(CH ₂ ) _z9 -O-(CH ₂ ) _z10 - (wherein z9 is an integer of 0 to 6 and z10 is an integer of 0 to 6), or
-(CH ₂ ) _z11 -phenylene-(CH ₂ ) _z12 - (wherein z11 is an integer from 0 to 6 and z12 is an integer from 0 to 6)
and
X ^H is the following

and
R ⁸ is a hydrogen atom or a C _1-6 alkyl group,
A compound according to claim 1 . ^XF is
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 and z8 is an integer from 0 to 6)
2. The compound of claim 1, which is 2. The compound according to claim 1, wherein each R ^c is independently a hydrogen atom or a C _1-6 alkyl group. Each R ^d is independently a single bond or —(CH ₂ ) _z17 —NR ¹⁰ —(CH ₂ ) _z18 — (wherein R ¹⁰ is a hydrogen atom or a C _1-6 alkyl group, z17 is an integer from 0 to 6 and z18 is an integer from 0 to 6). 2. The compound according to claim 1, wherein x is an integer of 1 or more and 5 or less. A surface treatment agent containing the compound according to any one of claims 1 to 28. 30. The surface treatment agent according to claim 29, further comprising one or more other components selected from fluorine-containing oils, silicone oils, and catalysts. 30. The surface treatment agent according to claim 29, which is used as an antifouling coating agent or a waterproof coating agent. An article comprising a substrate and a layer formed from the compound according to any one of claims 1 to 28 on the surface of the substrate. An article comprising a base material and a layer formed from the surface treating agent according to claim 29 on the surface of the base material.