WO2024253093A1 - Fluorosilicone compound - Google Patents

Abstract

The present invention provides a fluorosilicone compound represented by formula (I) (where the symbols in the formula are as defined in the description).

Description

Fluorosilicone Compounds

This disclosure relates to fluorosilicone compounds.

　Conventionally, silicone compounds having fluorine-containing groups have been known and are used, for example, as release agents for molding various rubbers and resins (see Patent Document 1).

Special Publication No. 2009-541498

The objective of this disclosure is to provide a fluorosilicone compound that has excellent release properties.

［式中：
　Ｒ^Ａは、ＣＦ_３－、ＣＦ_３Ｏ－、ＣＦ_３ＮＨ－、ＣＦ_３ＣＨ_２ＮＨ－、（ＣＦ_３）_２Ｎ－、（ＣＦ_３ＣＨ_２）_２Ｎ－、ＣＦ_３Ｓ－、ＣＦ_３Ｃ（＝Ｏ）－、ＣＦ_３ＣＨ_２Ｃ（＝Ｏ）－、ＣＦ_３Ｃ（＝Ｏ）Ｏ－、ＣＦ_３ＣＨ_２ＯＣ（＝Ｏ）－、ＣＦ_３ＣＯＮＨ－、ＣＦ_３ＣＨ_２ＣＯＮＨ－、ＣＦ_３ＮＨＣＯ－、ＣＦ_３ＣＨ_２ＮＨＣＯ－、ＣＦ_３ＣＯＮ（ＣＦ_３）－、ＣＦ_３ＣＨ_２ＣＯＮ（ＣＦ_３）－、ＣＦ_３ＣＯＮ（ＣＨ_２ＣＦ_３）－、ＣＦ_３ＣＨ_２ＣＯＮ（ＣＨ_２ＣＦ_３）－、（ＣＦ_３）_２ＮＣＯ－又は（ＣＦ_３ＣＨ_２）_２ＮＣＯ－であり、
　Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８およびＲ^９は、それぞれ独立して、置換または非置換のアルキル基、あるいは置換または非置換のアリール基であり、
　Ｒ^３およびＲ^１０は、それぞれ独立して、置換または非置換のアルキル基、置換または非置換のアリール基、Ｒ^Ａ－Ｘ－、またはＲ^Ｓｉ－Ｙ－であり、
　ＸおよびＹは、それぞれ独立して、２価の有機基であり、
　Ｒ^Ｓｉは、水酸基または加水分解性基が結合したＳｉ原子を含む１価の基であり、
　ｍは１～１００の整数であり、
　ｎは１～５０の整数であり、
　ｏは０～２００の整数であり、
　ｍ、ｎ、及びｏ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任意である。］
で表されるフルオロシリコーン化合物。
［２］　Ｒ^Ａは、ＣＦ_３Ｏ－、ＣＦ_３ＮＨ－、又は（ＣＦ_３）_２Ｎ－である、上記［１］に記載のフルオロシリコーン化合物。
［３］　Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８およびＲ^９は、それぞれ独立して、Ｃ_１－４アルキル基である、上記［１］または［２］に記載のフルオロシリコーン化合物。
［４］　Ｒ^３およびＲ^１０は、それぞれ独立して、Ｃ_１－４アルキル基である、上記［１］～［３］のいずれか１項に記載のフルオロシリコーン化合物。
［５］　Ｘは、
　　　－（Ａｒ）_ａ１－（ＣＦＨ）_ｂ１－（ＣＨ_２）_ｃ１－（Ｏ）_ｄ１－
［式中：
　Ａｒは、フッ素原子またはＲ^Ａにより置換されていてもよい２価の芳香族基であり、
　ａ１は、０～１０の整数であり、
　ｂ１は、０～２００の整数であり、
　ｃ１は、０～２００の整数であり、
　ｄ１は、０～１０の整数であり、
　符号ａ１、ｂ１、ｃ１、及びｄ１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任意である。］
で表される基である、上記［１］～［４］のいずれか１項に記載のフルオロシリコーン化合物。
［６］　Ｘは、
　　　－（Ａｒ）_ａ１－（Ｏ）_ｄ１－（ＣＨ_２）_ｃ１－
［式中：
　Ａｒは、フッ素原子またはＲ^Ａにより置換されていてもよい２価の芳香族基、好ましくは非置換の２価の芳香族基であり、
　ａ１は、０または１であり、
　ｃ１は、１～３６の整数であり、
　ｄ１は、０または１である。］
で表される基である、上記［１］～［５］のいずれか１項に記載のフルオロシリコーン化合物。
［７］　Ｙは、アルキレン基、またはアルキレンオキシアルキレン基である、上記［１］～［６］のいずれか１項に記載のフルオロシリコーン化合物。
［８］　Ｒ^Ｓｉは、下記式（Ｓ１）、（Ｓ２）、（Ｓ３）、（Ｓ４）または（Ｓ５）：

［式中：
　Ｒ^１１は、それぞれ独立して、水酸基または加水分解性基であり、
　Ｒ^１２は、それぞれ独立して、１価の有機基であり、
　ｎ１は、（ＳｉＲ^１１ _ｎ１Ｒ^１２ _３－ｎ１）単位毎にそれぞれ独立して、０～３の整数であり、
　Ｘ^１１は、それぞれ独立して、単結合または２価の有機基であり、
　Ｒ^１３は、それぞれ独立して、水素原子または１価の有機基であり、
　ｔは、それぞれ独立して、２以上の整数であり、
　Ｒ^１４は、それぞれ独立して、水素原子、ハロゲン原子または－Ｘ^１１－ＳｉＲ^１１ _ｎ１Ｒ^１２ _３－ｎ１であり、
　Ｒ^１５は、それぞれ独立して、単結合、酸素原子、炭素数１～６のアルキレン基または炭素数１～６のアルキレンオキシ基であり、
　Ｒ^ａ１は、それぞれ独立して、－Ｚ^１－ＳｉＲ^２１ _ｐ１Ｒ^２２ _ｑ１Ｒ^２３ _ｒ１であり； 
　Ｚ^１は、それぞれ独立して、２価の有機基であり、
　Ｒ^２１は、それぞれ独立して、－Ｚ^１’－ＳｉＲ^２１’ _ｐ１’Ｒ^２２’ _ｑ１’Ｒ^２３’ _ｒ１’であり； 
　Ｒ^２２は、それぞれ独立して、水酸基または加水分解性基であり、
　Ｒ^２３は、それぞれ独立して、１価の有機基であり、
　ｐ１は、それぞれ独立して、０～３の整数であり、
　ｑ１は、それぞれ独立して、０～３の整数であり、
　ｒ１は、それぞれ独立して、０～３の整数であり、
　Ｚ^１’は、それぞれ独立して、２価の有機基であり、
　Ｒ^２１’は、それぞれ独立して、－Ｚ^１”－ＳｉＲ^２２” _ｑ１”Ｒ^２３” _ｒ１”であり； 
　Ｒ^２２’は、それぞれ独立して、水酸基または加水分解性基であり、
　Ｒ^２３’は、それぞれ独立して、１価の有機基であり、
　ｐ１’は、それぞれ独立して、０～３の整数であり、
　ｑ１’は、それぞれ独立して、０～３の整数であり、
　ｒ１’は、それぞれ独立して、０～３の整数であり、
　Ｚ^１”は、それぞれ独立して、２価の有機基であり、
　Ｒ^２２”は、それぞれ独立して、水酸基または加水分解性基であり、
　Ｒ^２３”は、それぞれ独立して、１価の有機基であり、
　ｑ１”は、それぞれ独立して、０～３の整数であり、
　ｒ１”は、それぞれ独立して、０～３の整数であり、
　Ｒ^ｂ１は、それぞれ独立して、水酸基または加水分解性基であり、
　Ｒ^ｃ１は、それぞれ独立して、１価の有機基であり、
　ｋ１は、それぞれ独立して、０～３の整数であり、
　ｌ１は、それぞれ独立して、０～３の整数であり、
　ｍ１は、それぞれ独立して、０～３の整数であり、
　Ｒ^ｄ１は、それぞれ独立して、－Ｚ^２－ＣＲ^３１ _ｐ２Ｒ^３２ _ｑ２Ｒ^３３ _ｒ２であり、
　Ｚ^２は、それぞれ独立して、単結合、酸素原子または２価の有機基であり、
　Ｒ^３１は、それぞれ独立して、－Ｚ^２’－ＣＲ^３２’ _ｑ２’Ｒ^３３’ _ｒ２’であり、
　Ｒ^３２は、それぞれ独立して、－Ｚ^３－ＳｉＲ^３４ _ｎ２Ｒ^３５ _３－ｎ２であり、
　Ｒ^３３は、それぞれ独立して、水素原子、水酸基または１価の有機基であり、
　ｐ２は、それぞれ独立して、０～３の整数であり、
　ｑ２は、それぞれ独立して、０～３の整数であり、
　ｒ２は、それぞれ独立して、０～３の整数であり、
　Ｚ^２’は、それぞれ独立して、単結合、酸素原子または２価の有機基であり、
　Ｒ^３２’は、それぞれ独立して、－Ｚ^３－ＳｉＲ^３４ _ｎ２Ｒ^３５ _３－ｎ２であり、
　Ｒ^３３’は、それぞれ独立して、水素原子、水酸基または１価の有機基であり、
　ｑ２’は、それぞれ独立して、０～３の整数であり、
　ｒ２’は、それぞれ独立して、０～３の整数であり、
　Ｚ^３は、それぞれ独立して、単結合、酸素原子または２価の有機基であり； 
　Ｒ^３４は、それぞれ独立して、水酸基または加水分解性基であり、
　Ｒ^３５は、それぞれ独立して、１価の有機基であり、
　ｎ２は、それぞれ独立して、０～３の整数であり、
　Ｒ^ｅ１は、それぞれ独立して、－Ｚ^３－ＳｉＲ^３４ _ｎ２Ｒ^３５ _３－ｎ２であり、
　Ｒ^ｆ１は、それぞれ独立して、水素原子、水酸基または１価の有機基であり、
　ｋ２は、それぞれ独立して、０～３の整数であり、
　ｌ２は、それぞれ独立して、０～３の整数であり、
　ｍ２は、それぞれ独立して、０～３の整数である。
　Ｒ^ｇ１およびＲ^ｈ１は、それぞれ独立して、－Ｚ^４－ＳｉＲ^１１ _ｎ１Ｒ^１２ _３－ｎ１、－Ｚ^４－ＳｉＲ^ａ１ _ｋ１Ｒ^ｂ１ _ｌ１Ｒ^ｃ１ _ｍ１、または－Ｚ^４－ＣＲ^ｄ１ _ｋ２Ｒ^ｅ１ _ｌ２Ｒ^ｆ１ _ｍ２であり、
　Ｚ^４は、それぞれ独立して、単結合、酸素原子または２価の有機基であり、
　ｋ３は、１または２であり、
　ｌ３は、０または１であり、
　ただし、式（Ｓ１）、（Ｓ２）、（Ｓ３）、（Ｓ４）、または（Ｓ５）中、水酸基または加水分解性基が結合したＳｉ原子が少なくとも２つ存在する。］
で表される基である、上記［１］～［７］のいずれか１項に記載のフルオロシリコーン化合物。
［９］　上記［１］～［８］のいずれか１項に記載のフルオロシリコーン化合物を含む離型組成物。
［１０］　さらに、水および有機溶媒から選択された少なくとも１種である液状媒体を含む、上記［９］に記載の離型組成物。
［１１］　有機溶媒を含有する溶液またはエアゾール、あるいは水を含有する水系エマルションである、上記［９］または［１０］に記載の離型組成物。
［１２］　硬化促進触媒を、フルオロシリコーン化合物（Ｉ）１００重量部に基づいて０．０５重量部～１０重量部の量で更に含む、上記［９］～［１１］のいずれか１項に記載の離型組成物。
［１３］　シリコーン油、シリコーン樹脂、合成ワックス、天然ワックス、フッ素油およびフッ素樹脂から成る群から選ばれた少なくとも１つを、フルオロシリコーン化合物（Ｉ）１００部に基づいて０．１重量部～９９重量部の量で更に含む、上記［９］～［１２］のいずれか１項に記載の離型組成物。
［１４］　上記［９］～［１３］のいずれか１項に記載の離型組成物から得られる皮膜。
［１５］（ｉ）上記［９］～［１３］のいずれか１項に記載の離型組成物を成形型の内面に塗布して離型組成物の被膜を形成する工程
を含む、離型剤被膜の形成方法。
［１６］（ｉ）上記［９］～［１３］のいずれか１項に記載の離型組成物を成形型の内面に塗布して離型組成物の被膜を形成する工程、
（ｉｉ）離型組成物の被膜を有する成形型に成形用組成物を充填して成形体を得る工程；および
（ｉｉｉ）成形体を成形型から取り出す工程
を含む、成形体の製造方法。 [1] Formula (I):

[Wherein:
R ^A is CF ₃ -, CF ₃ O-, CF ₃ NH-, CF ₃ CH ₂ NH-, (CF ₃ ) ₂ N-, (CF ₃ CH ₂ ) ₂ N-, CF ₃ S-, CF ₃ C(=O)-, CF ₃ CH ₂ C(=O)-, CF ₃ C(=O)O-, CF ₃ CH ₂ OC(=O)-, CF ₃ CONH-, CF ₃ CH ₂ CONH-, CF ₃ NHCO-, CF ₃ CH ₂ NHCO-, CF ₃ CON(CF ₃ )-, CF ₃ CH ₂ CON(CF ₃ )-, CF ₃ CON(CH ₂ CF ₃ )-, CF _3CH2CON ( _{CH2CF3 )} -, _{( CF3} ) _{2NCO- or} ( _CF3CH2 ) _2NCO- ;
R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group;
R ³ and R ¹⁰ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, R ^A -X-, or R ^Si -Y-;
X and Y are each independently a divalent organic group;
R ^Si is a monovalent group containing a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto;
m is an integer from 1 to 100;
n is an integer from 1 to 50;
o is an integer from 0 to 200;
The repeating units enclosed in parentheses with m, n, and o may be present in any order.
A fluorosilicone compound represented by the formula:
[2] The fluorosilicone compound according to the above [1], wherein R ^A is CF ₃ O—, CF ₃ NH—, or (CF ₃ ) ₂ N—.
[3] The fluorosilicone compound according to the above [1] or [2], wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a C _1-4 alkyl group.
[4] The fluorosilicone compound according to any one of the above [1] to [3], wherein R ³ and R ¹⁰ are each independently a C _1-4 alkyl group.
[5] X is
-(Ar) _a1 -(CFH) _b1 -(CH ₂ ) _c1 -(O) _d1 -
[Wherein:
Ar is a divalent aromatic group optionally substituted by a fluorine atom or R ^A ;
a1 is an integer from 0 to 10,
b1 is an integer from 0 to 200,
c1 is an integer from 0 to 200,
d1 is an integer from 0 to 10,
The repeating units denoted by symbols a1, b1, c1, and d1 and enclosed in parentheses may be present in any order.]
The fluorosilicone compound according to any one of the above [1] to [4], wherein the fluorosilicone compound is a group represented by the formula:
[6] X is
-(Ar) _a1 -(O) _d1 -(CH ₂ ) _c1 -
[Wherein:
Ar is a divalent aromatic group which may be substituted by a fluorine atom or R ^A , preferably an unsubstituted divalent aromatic group;
a1 is 0 or 1;
c1 is an integer from 1 to 36,
d1 is 0 or 1.
The fluorosilicone compound according to any one of the above [1] to [5], wherein the fluorosilicone compound is a group represented by the formula:
[7] The fluorosilicone compound according to any one of the above [1] to [6], wherein Y is an alkylene group or an alkyleneoxyalkylene group.
[8] R ^Si is represented by the following formula (S1), (S2), (S3), (S4) or (S5):

[Wherein:
Each R ¹¹ is independently a hydroxyl group or a hydrolyzable group;
Each R ¹² is independently a monovalent organic group;
n1 is independently an integer of 0 to 3 for each (SiR ¹¹ _n1 R ¹² _3-n1 ) unit,
Each ^X11 independently represents a single bond or a divalent organic group;
Each R ¹³ is independently a hydrogen atom or a monovalent organic group.
Each t is independently an integer of 2 or more;
R ¹⁴ is each independently a hydrogen atom, a halogen atom or -X ¹¹ -SiR ¹¹ _n1 R ¹² _3-n1 ;
R ¹⁵ is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms;
Each R ^a1 is independently -Z ¹ -SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ;
^Each Z1 is independently a divalent organic group;
Each R ²¹ is independently -Z ^1' -SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ;
Each R ²² is independently a hydroxyl group or a hydrolyzable group;
Each R ²³ is independently a monovalent organic group;
Each p1 is independently an integer from 0 to 3;
Each q1 is independently an integer from 0 to 3,
Each r1 is independently an integer from 0 to 3;
Each Z ^1′ is independently a divalent organic group;
Each R ^21' is independently -Z ^1'' -SiR ^22'' _q1'' R ^23'' _r1'' ;
Each R ^22′ is independently a hydroxyl group or a hydrolyzable group;
Each R ^23′ is independently a monovalent organic group,
Each p1' is independently an integer of 0 to 3,
Each q1' is independently an integer of 0 to 3,
Each r1' is independently an integer of 0 to 3;
Each Z ^1″ is independently a divalent organic group;
Each R ^22″ is independently a hydroxyl group or a hydrolyzable group;
Each R ^{23 ″} is independently a monovalent organic group,
Each q1″ is independently an integer from 0 to 3,
Each r1″ is independently an integer from 0 to 3;
Each R ^b1 is independently a hydroxyl group or a hydrolyzable group;
Each R ^c1 is independently a monovalent organic group,
Each k1 is independently an integer from 0 to 3;
Each l1 is independently an integer from 0 to 3;
Each m1 is independently an integer of 0 to 3;
Each R ^d1 is independently -Z ² -CR ³¹ _p2 R ³² _q2 R ³³ _r2 ;
Each ^Z2 is independently a single bond, an oxygen atom, or a divalent organic group;
Each R ³¹ is independently -Z ^2' -CR ^32' _q2' R ^33' _r2' ;
Each R ³² is independently —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 ;
R ³³ is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group,
p2 is independently an integer of 0 to 3,
Each q2 is independently an integer from 0 to 3,
Each r2 is independently an integer from 0 to 3;
Each Z ^2′ is independently a single bond, an oxygen atom, or a divalent organic group;
Each R ^32' is independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 ;
Each R ^33′ is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group,
Each q2' is independently an integer of 0 to 3,
Each r2' is independently an integer of 0 to 3,
Each ^Z3 is independently a single bond, an oxygen atom, or a divalent organic group;
Each R ³⁴ is independently a hydroxyl group or a hydrolyzable group;
Each R ³⁵ is independently a monovalent organic group.
Each n2 is independently an integer from 0 to 3;
Each R ^e1 is independently —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 ;
Each R ^f1 is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group,
Each k2 is independently an integer from 0 to 3;
Each l2 is independently an integer from 0 to 3;
Each m2 independently represents an integer of 0 to 3.
R ^g1 and R ^h1 are each independently -Z ⁴ -SiR ¹¹ _n1 R ¹² _3-n1 , -Z ⁴ -SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 , or -Z ⁴ -CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ;
Each ^Z4 is independently a single bond, an oxygen atom, or a divalent organic group,
k3 is 1 or 2;
l3 is 0 or 1;
However, in formula (S1), (S2), (S3), (S4), or (S5), there are at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded.]
The fluorosilicone compound according to any one of the above [1] to [7], wherein the fluorosilicone compound is a group represented by the formula:
[9] A release composition comprising the fluorosilicone compound according to any one of the above [1] to [8].
[10] The release composition according to the above [9], further comprising a liquid medium which is at least one selected from water and an organic solvent.
[11] The release composition according to the above [9] or [10], which is a solution or aerosol containing an organic solvent, or an aqueous emulsion containing water.
[12] The release composition according to any one of the above items [9] to [11], further comprising a curing-accelerating catalyst in an amount of 0.05 parts by weight to 10 parts by weight based on 100 parts by weight of the fluorosilicone compound (I).
[13] The release composition according to any one of the above items [9] to [12], further comprising at least one selected from the group consisting of silicone oil, silicone resin, synthetic wax, natural wax, fluorine oil and fluorine resin in an amount of 0.1 parts by weight to 99 parts by weight based on 100 parts of the fluorosilicone compound (I).
[14] A coating obtained from the release composition according to any one of the above items [9] to [13].
[15] (i) A method for forming a release agent coating, comprising a step of applying the release composition according to any one of the above items [9] to [13] to an inner surface of a molding die to form a coating of the release composition.
[16] (i) a step of applying the mold release composition according to any one of the above items [9] to [13] to the inner surface of a molding die to form a coating of the mold release composition;
(ii) filling a molding composition into a mold having a coating of the mold release composition to obtain a molded body; and (iii) removing the molded body from the mold.

The fluorosilicone compound disclosed herein can provide excellent release properties.

As used herein, "monovalent organic group" refers to a monovalent group containing carbon. The monovalent organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A derivative of a hydrocarbon group refers to a group that has one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain.

As used herein, the term "divalent organic group" is not particularly limited, but includes divalent groups in which one hydrogen atom has been removed from a hydrocarbon group.

As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, with one hydrogen atom removed from the molecule. Such hydrocarbon groups are not particularly limited, but include hydrocarbon groups having 1 to 20 carbon atoms, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. Such a hydrocarbon group may be substituted with one or more substituents. The hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at its terminal or in the molecular chain.

As used herein, examples of substituents for a "hydrocarbon group" include, but are not limited to, one or more groups selected from a halogen atom; a C _1-6 alkyl group, a C _2-6 alkenyl group, a C 2-6 alkynyl group, a C _3-10 cycloalkyl group, a C _3-10 unsaturated cycloalkyl group, a _5-10 membered heterocyclyl group, a 5-10 membered unsaturated heterocyclyl group, a C _6-10 aryl group, and a 5-10 membered heteroaryl group, each of which is optionally substituted by one or more halogen atoms.

As used herein, the term "hydrolyzable group" refers to a group that can undergo hydrolysis, i.e., a group that can be removed from the main skeleton of a compound by hydrolysis. Examples of hydrolyzable groups include -OR ^h , -OCOR ^h , -O-N=CR ^h ₂ , -NR ^h ₂ , -NHR ^h , or -NCO (wherein R ^h is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), and preferably -OR ^h (i.e., an alkoxy group). Examples of R ^h include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred. In one embodiment, R ^h is a methyl group, and in another embodiment, R ^h is an ethyl group.

［式中：
　Ｒ^Ａは、ＣＦ_３－、ＣＦ_３Ｏ－、ＣＦ_３ＮＨ－、ＣＦ_３ＣＨ_２ＮＨ－、（ＣＦ_３）_２Ｎ－、（ＣＦ_３ＣＨ_２）_２Ｎ－、ＣＦ_３Ｓ－、ＣＦ_３Ｃ（＝Ｏ）－、ＣＦ_３ＣＨ_２Ｃ（＝Ｏ）－、ＣＦ_３Ｃ（＝Ｏ）Ｏ－、ＣＦ_３ＣＨ_２ＯＣ（＝Ｏ）－、ＣＦ_３ＣＯＮＨ－、ＣＦ_３ＣＨ_２ＣＯＮＨ－、ＣＦ_３ＮＨＣＯ－、ＣＦ_３ＣＨ_２ＮＨＣＯ－、ＣＦ_３ＣＯＮ（ＣＦ_３）－、ＣＦ_３ＣＨ_２ＣＯＮ（ＣＦ_３）－、ＣＦ_３ＣＯＮ（ＣＨ_２ＣＦ_３）－、ＣＦ_３ＣＨ_２ＣＯＮ（ＣＨ_２ＣＦ_３）－、（ＣＦ_３）_２ＮＣＯ－又は（ＣＦ_３ＣＨ_２）_２ＮＣＯ－であり、
　Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８およびＲ^９は、それぞれ独立して、置換または非置換のアルキル基、あるいは置換または非置換のアリール基であり、
　Ｒ^３およびＲ^１０は、それぞれ独立して、置換または非置換のアルキル基、置換または非置換のアリール基、Ｒ^Ａ－Ｘ－、またはＲ^Ｓｉ－Ｙ－であり、
　ＸおよびＹは、それぞれ独立して、２価の有機基であり、
　Ｒ^Ｓｉは、水酸基または加水分解性基が結合したＳｉ原子を含む１価の基であり、
　ｍは１～１００の整数であり、
　ｎは１～５０の整数であり、
　ｏは０～２００の整数であり、
　ｍ、ｎ、及びｏ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任意である。］
で表される。 The fluorosilicone compounds of the present disclosure have the formula (I):

[Wherein:
R ^A is CF ₃ -, CF ₃ O-, CF ₃ NH-, CF ₃ CH ₂ NH-, (CF ₃ ) ₂ N-, (CF ₃ CH ₂ ) ₂ N-, CF ₃ S-, CF ₃ C(=O)-, CF ₃ CH ₂ C(=O)-, CF ₃ C(=O)O-, CF ₃ CH ₂ OC(=O)-, CF ₃ CONH-, CF ₃ CH ₂ CONH-, CF ₃ NHCO-, CF ₃ CH ₂ NHCO-, CF ₃ CON(CF ₃ )-, CF ₃ CH ₂ CON(CF ₃ )-, CF ₃ CON(CH ₂ CF ₃ )-, CF _3CH2CON ( _{CH2CF3 )} -, _{( CF3} ) _{2NCO- or} ( _CF3CH2 ) _2NCO- ;
R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group;
R ³ and R ¹⁰ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, R ^A -X-, or R ^Si -Y-;
X and Y are each independently a divalent organic group;
R ^Si is a monovalent group containing a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto;
m is an integer from 1 to 100;
n is an integer from 1 to 50;
o is an integer from 0 to 200;
The repeating units enclosed in parentheses with m, n, and o may be present in any order.
It is expressed as:

R ^A is CF ₃ -, CF ₃ O-, CF ₃ NH-, CF ₃ CH ₂ NH-, (CF ₃ ) ₂ N-, (CF ₃ CH ₂ ) ₂ N-, CF ₃ S-, CF ₃ C(=O)-, CF ₃ CH ₂ C(=O)-, CF ₃ C(=O)O-, CF ₃ CH ₂ OC(=O)-, CF ₃ CONH-, CF ₃ CH ₂ CONH-, CF ₃ NHCO-, CF ₃ CH ₂ NHCO-, CF ₃ CON(CF ₃ ) -, CF ₃ CH ₂ CON (CF ₃ )-, CF ₃ CON(CH ₂ CF ₃ )-, CF _{R A} is _{preferably CF} ³ _{O— ,} CF _{3 NH— , ( CF 3} ) _2N- , _CF3S- , _CF3C (=O)-, _CF3C (=O)O-, _CF3OC (=O)-, _CF3CONH- , _CF3NHCO- , CF _{CF 3} CON(CF ₃ )-, or (CF ₃ ) ₂ NCO-, and more preferably CF ₃ O-, CF ₃ NH-, or (CF ₃ ) ₂ N-.

In one embodiment, R ^A can be CF ₃ O—.

In another embodiment, R ^A can be CF ₃ NH-- or (CF ₃ ) ₂ N--, preferably CF ₃ NH--.

R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

Substituents for the alkyl and aryl groups include halogen atoms, and one or more groups selected from a C _1-6 alkyl group, a C 2-6 alkenyl group, a C _2-6 alkynyl group, a C _3-10 cycloalkyl group, a C _3-10 unsaturated cycloalkyl group, a _5-10 membered heterocyclyl group, a 5-10 membered unsaturated heterocyclyl group, a C _6-10 aryl group, and a 5-10 membered heteroaryl group, each of which may be substituted by one or more halogen atoms. The halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a chlorine atom.

In one embodiment, the alkyl group may be an alkyl group that may be substituted with a halogen atom, such as a chlorine atom.

In one embodiment, the aryl group may be an aryl group that may be substituted with a halogen atom, such as a chlorine atom, or a C ₁ -C ₁₀ alkyl group, for example a methyl group.

The alkyl group may be preferably a C _1-20 alkyl group, more preferably a C _1-12 alkyl group, even more preferably a C _1-4 alkyl group, and even more preferably a methyl group.

The aryl group may be preferably a C _6-20 aryl group, more preferably a C _6-12 aryl group, and even more preferably a phenyl group.

In one embodiment, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ may each independently be an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, a hexyl group, or a dodecyl group; a substituted alkyl group such as a chloromethyl group, an unsubstituted aryl group such as a phenyl group or a naphthyl group; or a substituted aryl group such as a 4-chlorophenyl group or a 2-methylphenyl group. Among these, an alkyl group, particularly an unsubstituted alkyl group, is preferred, and a methyl group is more preferred.

R ³ and R ¹⁰ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, R ^A -X-, or R ^Si -Y-.

The substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group in ^R3 and ^R10 are the same as those described above for ^R1 and the like.

In one embodiment, ^R3 and ^R10 are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group.

In another embodiment, R ^A -X-, or R ^Si -Y-.

Each X is independently a divalent organic group.

In one embodiment, X is
-(Ar) _a1 -(CFH) _b1 -(CH ₂ ) _c1 -(O) _d1 -
[Wherein:
Ar is a divalent aromatic group optionally substituted by a fluorine atom or R ^A ;
R ^A is CF ₃ -, CF ₃ O-, CF ₃ NH-, CF ₃ CH ₂ NH-, (CF ₃ ) ₂ N-, (CF ₃ CH ₂ ) ₂ N-, CF ₃ S-, CF ₃ C(=O)-, CF ₃ CH ₂ C(=O)-, CF ₃ C(=O)O-, CF ₃ CH ₂ OC(=O)-, CF ₃ CONH-, CF ₃ CH ₂ CONH-, CF ₃ NHCO-, CF ₃ CH ₂ NHCO-, CF ₃ CON(CF ₃ )-, CF ₃ CH ₂ CON(CF ₃ )-, CF ₃ CON(CH ₂ CF ₃ )-, CF _3CH2CON ( _{CH2CF3 )} -, _{( CF3} ) _{2NCO- or} ( _CF3CH2 ) _2NCO- ;
a1 is an integer from 0 to 10,
b1 is an integer from 0 to 200,
c1 is an integer from 0 to 200,
d1 is an integer from 0 to 10,
The repeating units denoted by symbols a1, b1, c1, and d1 and enclosed in parentheses may be present in any order.]
In the formula, however, it is preferable that no consecutive oxygen atoms exist. In other words, it is preferable that no -O-O- bond exists. Note that the left side of X bonds to R ^A.

The above aromatic groups include aromatic rings containing only carbon as ring atoms (so-called arylenes), as well as aromatic rings containing nitrogen, oxygen or sulfur (so-called heteroarylenes), and groups having multiple aromatic rings.

The aromatic group preferably has a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a tetracene ring, a pentacene ring, a benzopyrene ring, a chrysene ring, a pyrene ring, a triphenylene ring, a corannulene ring, an ovalene ring, an indole ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a biphenyl ring, a terphenyl ring, a triphenylmethane ring, or a benzophenone ring.

In one embodiment, the aromatic group preferably has a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a tetracene ring, a pentacene ring, a benzopyrene ring, a chrysene ring, a pyrene ring, a triphenylene ring, a corannulene ring, or an ovalene ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.

In another embodiment, the aromatic group preferably has an indole ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, or a pyrazine ring, more preferably an indole ring.

In another embodiment, the aromatic group preferably has a biphenyl ring, a terphenyl ring, a triphenylmethane ring, or a benzophenone ring.

In one embodiment, Ar is an unsubstituted divalent aromatic group.

In another embodiment, Ar is a divalent aromatic group substituted with a fluorine atom or R 3 ^A.

In another embodiment, Ar is a divalent aromatic group substituted by R 3 ^A.

In another embodiment, Ar is a divalent aromatic group substituted with a fluorine atom.

The number of substituents on the aromatic group is not particularly limited, but may be, for example, 1 to 10, 1 to 5, 1 to 3, 1, 2, or 3. In one embodiment, the number of substituents on the aromatic group is 1 or more. In another embodiment, the aromatic group is fully substituted.

a1 is an integer from 0 to 10, preferably 0 or 1.

In one embodiment, a1 is 0.

In another embodiment, a1 is 1.

b1 is an integer from 0 to 200, preferably an integer from 0 to 6.

c1 is an integer between 0 and 200, preferably between 0 and 30.

d1 is an integer from 0 to 10, preferably an integer from 0 to 3.

In one embodiment, X is
-(Ar) _a1 -(O) _d1 -(CH ₂ ) _c1 -
[Wherein:
Ar is a divalent aromatic group which may be substituted by a fluorine atom or R ^A , preferably an unsubstituted divalent aromatic group;
a1 is 0 or 1;
c1 is an integer from 1 to 36, preferably an integer from 1 to 30, for example an integer from 1 to 9, an integer from 1 to 3, or an integer from 2 to 3;
d1 is 0 or 1.
It is a group represented by the following formula:

In one embodiment, X is
-(CH ₂ ) _c1 -
[In the formula, c1 is an integer from 1 to 36, preferably an integer from 1 to 30, and may be, for example, an integer from 1 to 9, or an integer from 1 to 3.]
It is a group represented by the following formula:

In one embodiment, X is
-Ar-O-(CH ₂ ) _c1 -
[Wherein:
Ar is a divalent aromatic group which may be substituted by a fluorine atom or R ^A , preferably an unsubstituted divalent aromatic group;
c1 is an integer from 1 to 36, preferably an integer from 1 to 30, and may be, for example, an integer from 1 to 9, an integer from 1 to 3, or an integer from 2 to 3.
It is a group represented by the following formula:

Each Y is independently a divalent organic group.

Y may be a divalent organic group preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms.

Y may preferably be an alkylene group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms), such as an ethylene group, a propylene group, a methylethylene group, an octylene group, and a decylene group, and an alkyleneoxyalkylene group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms), such as an ethyleneoxymethylene group, a propyleneoxymethylene group, a propyleneoxyethylene group, and an ethyleneoxybutylene group. Y may more preferably be -(CH ₂ ) _r -, where r is an integer of 2 to 200, preferably an integer of 2 to 12.

R 3 ^Si is a monovalent group containing a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto.

R 3 ^Si is preferably a group represented by formula (S1), (S2), (S3), (S4) or (S5).

Each R ¹¹ independently represents a hydroxyl group or a hydrolyzable group.

Preferably, each R ¹¹ is independently a hydrolyzable group.

Each R ¹² is independently a monovalent organic group, provided that R ¹² does not include a hydrolyzable group.

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

n1 is independently an integer of 0 to 3 for each (SiR ¹¹ _n1 R ¹² _3-n1 ) unit, provided that in formula (S1), there are at least two (SiR ¹¹ _n1 R ¹² _3-n1 ) units in which n1 is 1 to 3. In other words, in formula (S1), there are at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded.

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

In the above formula, each X ¹¹ is independently a single bond or a divalent organic group. Such a divalent organic group is preferably -R ²⁸ -O _x -R ²⁹ - (wherein R ²⁸ and R ²⁹ are independently a single bond or a C _1-20 alkylene group, and x is 0 or 1). Such a C _1-20 alkylene group may be linear or branched, but is preferably linear. Such a C _1-20 alkylene group is preferably a C _1-10 alkylene group, more preferably a C _1-6 alkylene group, and even more preferably a C _1-3 alkylene group.

In one embodiment, each X ¹¹ is independently —C _1-6 alkylene-O—C _1-6 alkylene- or —O—C _1-6 alkylene-.

In a preferred embodiment, each X ¹¹ is independently a single bond or a straight-chain C _1-6 alkylene group, preferably a single bond or a straight-chain C _1-3 alkylene group, more preferably a single bond or a straight-chain C _1-2 alkylene group, and even more preferably a straight-chain C _1-2 alkylene group.

Each R ¹³ is independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is preferably a C _1-20 alkyl group.

In a preferred embodiment, each R ¹³ is independently a hydrogen atom or a straight chain C _1-6 alkyl group, preferably a hydrogen atom or a straight chain C _1-3 alkyl group, preferably a hydrogen atom or a methyl group.

Each R ¹⁵ is independently a single bond, an oxygen atom, a C _1-6 alkylene group, or a C _1-6 alkyleneoxy group.

In one embodiment, each R ¹⁵ is independently an oxygen atom, a C _1-6 alkylene group, or a C _1-6 alkyleneoxy group.

In a preferred embodiment, R ¹⁵ is a single bond.

Each t is independently an integer of 2 or greater.

In a preferred embodiment, each t is independently an integer from 2 to 10, preferably an integer from 2 to 6.

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

［式中、
　Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｘ^１１、及びｎ１は、上記式（Ｓ１）の記載と同意義であり、
　ｔ１及びｔ２は、それぞれ独立して、１以上の整数、好ましくは１～１０の整数、より好ましくは２～１０の整数、例えば１～５の整数又は２～５の整数であり、
　ｔ１及びｔ２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, formula (S1) is formula (S1-a) below.

[Wherein,
R ¹¹ , R ¹² , R ¹³ , X ¹¹ and n1 are as defined above in formula (S1);
t1 and t2 each independently represent an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 2 to 10, for example, an integer of 1 to 5 or an integer of 2 to 5;
The order of occurrence of each repeating unit enclosed in parentheses with t1 and t2 is arbitrary in the formula.

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

[In the formula, R ¹¹ , R ¹² , R ¹³ , X ¹¹ , n1 and t are the same as defined in the above formula (S1)]

In a preferred embodiment, in formula (S2), the Si atom of --SiR ¹¹ _n1 R ¹² _3-n1 does not form a siloxane bond.

In one embodiment, in formula (S2), there are at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded.

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

The above Z1 ^'s are each independently an oxygen atom or a _divalent organic group _. In the structure hereinafter described as ^Z1 , the right side is ^{bonded to} ( ^{SiR21p1R22q1R23r1} ₎ .

In a preferred embodiment, ^Z1 is a divalent organic group.

In a preferred embodiment, Z ¹ does not include any that forms a siloxane bond with the Si atom to which Z ¹ is bonded. Preferably, in formula (S3), (Si-Z ¹ -Si) does not include a siloxane bond.

The above Z ¹ is preferably a C _1-6 alkylene group, -(CH ₂ ) _z1 -O-(CH ₂ ) _z2 - (wherein z1 is an integer of 0 to 6, for example an integer of 1 to 6, and z2 is an integer of 0 to 6, for example an integer of 1 to 6), or -(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 - (wherein z3 is an integer of 0 to 6, for example an integer of 1 to 6, and z4 is an integer of 0 to 6, for example an integer of 1 to 6). Such a C _1-6 alkylene group may be linear or branched, but is preferably linear. These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group, but are preferably unsubstituted.

In a preferred embodiment, Z ¹ is a C _1-6 alkylene group or -(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 -, preferably -phenylene-(CH ₂ ) _z4 -.

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

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

Each Z ^1' is independently an oxygen atom or a divalent organic group. In the structure hereinafter described as Z ^1' , the right side is bonded to (SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ).

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

In a preferred embodiment, Z ^{1 '} does not include any that forms a siloxane bond with the Si atom to which Z ^{1 '} is bonded. Preferably, in formula (S3), (Si-Z ^{1 '} -Si) does not include a siloxane bond.

The above Z ^1' is preferably a C _1-6 alkylene group, -(CH ₂ ) _z1' -O-(CH ₂ ) _z2' - (wherein z1' is an integer of 0 to 6, for example an integer of 1 to 6, and z2' is an integer of 0 to 6, for example an integer of 1 to 6), or -(CH ₂ ) _z3' -phenylene-(CH ₂ ) _z4' - (wherein z3' is an integer of 0 to 6, for example an integer of 1 to 6, and z4' is an integer of 0 to 6, for example an integer of 1 to 6). Such a C _1-6 alkylene group may be linear or branched, but is preferably linear. These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group, but are preferably unsubstituted.

In a preferred embodiment, Z ^1' is a C _1-6 alkylene group or -(CH ₂ ) _z3' -phenylene-(CH ₂ ) _z4' -, preferably -phenylene-(CH ₂ ) _z4' -.

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

Each R ^21' is independently -Z ^1'' -SiR ^22'' _q1'' R ^23'' _r1'' .

Z ^1″ is each independently an oxygen atom or a divalent organic group. In the structure hereinafter described as Z ^1″ , the right side is bonded to (SiR ^22″ _q1″ R ^23″ _r1″ ).

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

In a preferred embodiment, Z ^1″ does not include any that forms a siloxane bond with the Si atom to which Z ^1″ is bonded. Preferably, in formula (S3), (Si—Z ^1″ —Si) does not include a siloxane bond.

Z1 ^" is preferably a C _1-6 alkylene group, -(CH ₂ ) _z1" -O-(CH ₂ ) _z2" - (wherein z1" is an integer of 0 to 6, for example an integer of 1 to 6, and z2" is an integer of 0 to 6, for example an integer of 1 to 6) or -(CH ₂ ) _z3" -phenylene-(CH ₂ ) _z4" - (wherein z3" is an integer of 0 to 6, for example an integer of 1 to 6, and z4" is an integer of 0 to 6, for example an integer of 1 to 6). Such a C _1-6 alkylene group may be linear or branched, but is preferably linear. These groups may be substituted, but are preferably unsubstituted, by one or more substituents selected from, for example, a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group.

In a preferred embodiment, Z ^1" is a C _1-6 alkylene group or --(CH ₂ ) _z3" -phenylene-(CH ₂ ) _z4" --, preferably -phenylene-(CH ₂ ) _z4" --. When Z ^1" is such a group, light resistance, particularly ultraviolet resistance, may be improved.

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

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

Preferably, each R ^{22 ″} is independently a hydrolyzable group.

Each R ^{23 ″} is independently a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above-mentioned hydrolyzable groups.

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

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

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

Each R ^22' is independently a hydroxyl group or a hydrolyzable group.

Preferably, each R ^22′ is independently a hydrolyzable group.

Each R ^23′ is independently a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable groups.

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

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

In one embodiment, p1' is 0.

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

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

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

Each R ²² independently represents a hydroxyl group or a hydrolyzable group.

Preferably, each R ²² is independently a hydrolyzable group.

Each ^R23 is independently a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above-mentioned hydrolyzable group.

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

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

In one embodiment, p1 is 0.

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

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

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

Each R ^b1 independently represents a hydroxyl group or a hydrolyzable group.

Preferably, each R ^b1 is independently a hydrolyzable group.

Each R ^c1 is independently a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above-mentioned hydrolyzable groups.

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

Each k1 is independently an integer of 0 to 3, each l1 is independently an integer of 0 to 3, and each m1 is independently an integer of 0 to 3. The sum of k1, l1 and m1 is 3 in the (SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 ) unit.

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

In formula (S3), there are at least two Si atoms bonded to hydroxyl groups or hydrolyzable groups.

In a preferred embodiment, at least two Si atoms having hydroxyl groups or hydrolyzable groups bonded thereto are present in the terminal portion of formula (S3).

In a preferred embodiment, the group represented by formula (S3) has any one of -Z ¹ -SiR ²² _q1 R ²³ _r1 (wherein q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1 is an integer of 0 to 2); -Z ^1' -SiR ^22' _q1' R ^23' _r1' (wherein q1' is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1' is an integer of 0 to 2); or -Z ^1" -SiR ^22" _q1" R ^23" _r1" (wherein q1" is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1" is an integer of 0 to 2). Z ¹ , Z ^1' , Z ^1" , R ²² , R ²³ , R ^22' , R ^23' , R ^22'' , and R ^23'' are as defined above.

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

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

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

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

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

^Z2 's each independently represent a single bond, _an ^oxygen atom or a divalent ^organic group _. In the structure hereinafter described as ^Z2 , the right side is bonded to ( ^{CR31p2R32q2R33r2} ₎ .

In a preferred embodiment, ^Z2 is a divalent organic group.

In a preferred embodiment, ^Z2 does not contain a siloxane bond.

Z ² is preferably a C _1-6 alkylene group, -(CH ₂ ) _z5 -O-(CH ₂ ) _z6 - (wherein z5 is an integer of 0 to 6, for example an integer of 1 to 6, and z6 is an integer of 0 to 6, for example an integer of 1 to 6) or -(CH ₂ ) _z7 -phenylene-(CH ₂ ) _z8 - (wherein z7 is an integer of 0 to 6, for example an integer of 1 to 6, and z8 is an integer of 0 to 6, for example an integer of 1 to 6). Such a C _1-6 alkylene group may be linear or branched, but is preferably linear. These groups may be substituted by one or more substituents selected from, for example, a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group, but are preferably unsubstituted.

In a preferred embodiment, Z ² is a C _1-6 alkylene group or —(CH ₂ ) _z7 -phenylene-(CH ₂ ) _z8 —, preferably -phenylene-(CH ₂ ) _z8 —. When Z ² is such a group, light resistance, particularly ultraviolet resistance, may be improved.

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

Each R ³¹ is independently -Z ^2' -CR ^32' _q2' R ^33' _r2' .

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

In a preferred embodiment, Z ^2′ does not contain a siloxane bond.

Z ^2' is preferably a C _1-6 alkylene group, -(CH ₂ ) _z5' -O-(CH ₂ ) _z6' - (wherein z5' is an integer of 0 to 6, for example an integer of 1 to 6, and z6' is an integer of 0 to 6, for example an integer of 1 to 6), or -(CH ₂ ) _z7' -phenylene-(CH ₂ ) _z8' - (wherein z7' is an integer of 0 to 6, for example an integer of 1 to 6, and z8' is an integer of 0 to 6, for example an integer of 1 to 6). Such a C _1-6 alkylene group may be linear or branched, but is preferably linear. These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group, but are preferably unsubstituted.

In a preferred embodiment, Z ^2' is a C _1-6 alkylene group or -(CH ₂ ) _z7' -phenylene-(CH ₂ ) _z8' -, preferably -phenylene-(CH ₂ ) _z8' -. When Z ^2' is such a group, light resistance, particularly ultraviolet resistance, may be improved.

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

Each R ^32' is independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 .

^Z3 's are each independently a single bond, an oxygen atom or a divalent organic group. In the structure hereinafter described as ^Z3 , the right side is bonded to (SiR ³⁴ _n2 R ³⁵ _3-n2 ).

In one embodiment, ^Z3 is an oxygen atom.

In one embodiment, ^Z3 is a divalent organic group.

In a preferred embodiment, ^Z3 does not contain a siloxane bond.

^Z3 is preferably a C _1-6 alkylene group, -(CH ₂ ) _z5" -O-(CH ₂ ) _z6" - (wherein z5" is an integer of 0 to 6, for example an integer of 1 to 6, and z6" is an integer of 0 to 6, for example an integer of 1 to 6), or -(CH ₂ ) _z7" -phenylene-(CH ₂ ) _z8" - (wherein z7" is an integer of 0 to 6, for example an integer of 1 to 6, and z8" is an integer of 0 to 6, for example an integer of 1 to 6). Such a C _1-6 alkylene group may be linear or branched, but is preferably linear. These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group, but are preferably unsubstituted.

In a preferred embodiment, Z ³ is a C _1-6 alkylene group or --(CH ₂ ) _z7 " -phenylene-(CH ₂ ) _z8" --, preferably -phenylene-(CH ₂ ) _z8" --. When Z ³ is such a group, light resistance, particularly ultraviolet resistance, may be improved.

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

Each R ³⁴ is independently a hydroxyl group or a hydrolyzable group.

Preferably, each R ³⁴ is independently a hydrolyzable group.

Each R ³⁵ is independently a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable groups.

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

In the above formula, n2 is independently an integer of 0 to 3 for each (SiR ⁿ² R ³⁵ _3-n2 ) unit, provided that in the terminal portion of formula (S4), there are at least two (SiR _n2 R _{35 3-n2} ) units in which ⁿ² is 1 to 3. In other words, in the terminal portion of formula (S4), there are at least two Si atoms to ^which a hydroxyl group or a hydrolyzable group is bonded.

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

Each R ^33′ is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group, the monovalent organic group being a monovalent organic group other than the hydrolyzable groups.

In the above R ^33' , the monovalent organic group is preferably a C _1-20 alkyl group or -(C _s H _2s ) _t1 -(O-C _s H _2s ) _t2 (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably a C _1-20 alkyl group, still more preferably a C _1-6 alkyl group, and particularly preferably a methyl group.

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

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

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

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

Each _R ³² is independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _{3-n2 ,} which has the same meaning ^as described ^above for R ^{32' .}

Each R ³³ independently represents a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above-mentioned hydrolyzable groups.

In R ³³ , the monovalent organic group is preferably a C _1-20 alkyl group or -(C _s H _2s ) _t1 -(O-C _s H _2s ) _t2 -H (wherein each s is independently an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably a C _1-20 alkyl group, still more preferably a C _1-6 alkyl group, and particularly preferably a methyl group.

In one embodiment, R ³³ is a hydroxyl group.

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

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

In one embodiment, p2 is 0.

In one embodiment, p2 may be, independently at each (CR ³¹ _p2 R ³² _q2 R ³³ _r2 ) unit, an integer from 1 to 3, an integer from 2 to 3, or 3.

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

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

The R ^e1 's are each independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _{3-n2 , which} has the same meaning ^{as that} described above for ^{R 32'} .

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

In the above R ^f1 , the monovalent organic group is preferably a C _1-20 alkyl group or -(C _s H _2s ) _t1 -(O-C _s H _2s ) _t2 -H (wherein each s is independently an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably a C _1-20 alkyl group, still more preferably a C _1-6 alkyl group, and particularly preferably a methyl group.

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

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

Each k2 is independently an integer of 0 to 3, each l2 is independently an integer of 0 to 3, and each m2 is independently an integer of 0 to 3. The sum of k2, l2, and m2 is 3 in the (CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ) unit.

In one embodiment, the (SiR ³⁴ _n2 R ³⁵ _3-n2 ) units, where n2 is 1 to 3, preferably 2 or 3, more preferably 3, are present at each terminal portion of formula (S4) in an amount of 2 or more, for example 2 to 27, preferably 2 to 9, more preferably 2 to 6, even more preferably 2 to 3, and particularly preferably 3.

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

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

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

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

R ^g1 and R ^h1 are each independently -Z ⁴ -SiR ¹¹ _n1 R ¹² _3-n1 , -Z ⁴ -SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 , and -Z ⁴ -CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 , where R ¹¹ , R ¹² , R ^a1 , R ^b2 , R ^c1 , R d1 , R ^e1 , ^{R f1 ,} n1, k1, l1, m1, k2, l2, and m2 are the same as defined above.

In a preferred embodiment, R ^g1 and R ^h1 are each independently --Z ⁴ --SiR ¹¹ _n1 R ¹² _3-n1 .

The above ^Z4s are each independently a single bond, an oxygen atom or a divalent organic group. In the structure hereinafter described as ^Z4 , the right side is bonded to (SiR ¹¹ _n1 R ¹² _3-n1 ).

In one embodiment, ^Z4 is an oxygen atom.

In one embodiment, ^Z4 is a divalent organic group.

In a preferred embodiment, ^Z4 does not contain a siloxane bond.

Z ⁴ above is preferably a C _1-6 alkylene group, -(CH ₂ ) _z5" -O-(CH ₂ ) _z6" - (wherein z5" is an integer of 0 to 6, for example an integer of 1 to 6, and z6" is an integer of 0 to 6, for example an integer of 1 to 6), or -(CH ₂ ) _z7" -phenylene-(CH ₂ ) _z8" - (wherein z7" is an integer of 0 to 6, for example an integer of 1 to 6, and z8" is an integer of 0 to 6, for example an integer of 1 to 6). Such a C _1-6 alkylene group may be linear or branched, but is preferably linear. These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group, but are preferably unsubstituted.

In a preferred embodiment, Z ⁴ is a C _1-6 alkylene group or --(CH ₂ ) _z7 " -phenylene-(CH ₂ ) _z8" --, preferably -phenylene-(CH ₂ ) _z8" --. When Z ⁴ is such a group, light resistance, particularly ultraviolet resistance, may be improved.

In another preferred embodiment, Z ⁴ is a C _1-3 alkylene group. In one embodiment, Z ⁴ can be -CH ₂ CH ₂ CH ₂ -. In another embodiment, Z ⁴ can be -CH ₂ CH ₂ -.

In a preferred embodiment, formulas (S1), (S2), (S3), (S4) and (S5) do not contain a siloxane bond.

In one embodiment, R 3 ^Si is a group represented by formula (S3), (S4) or (S5).

In one embodiment, R 3 ^Si is a group represented by formula (S3) or (S4).

In one embodiment, R 3 ^Si is a group represented by formula (S4) or (S5).

In one embodiment, R ^Si is a group represented by formula (S1). In a preferred embodiment, formula (S1) is a group represented by formula (S1-b). In a preferred embodiment, in the formula, R ¹³ is a hydrogen atom, X ¹¹ is a single bond, or -R ²⁸ -O _x -R ²⁹ - (in the formula, R ²⁸ and R ²⁹ are each independently a single bond or a C _1-20 alkylene group, and x is 0 or 1), and n1 is 1 to 3, preferably 2 to 3, and more preferably 3.

In one embodiment, R 1 ^Si is a group represented by formula (S2): In a preferred embodiment, formula (S2) is -SiR ¹¹ ₂ R ¹² or -SiR ¹¹ ₃ .

In one embodiment, R 3 ^Si is a group represented by formula (S3). In a preferred embodiment, formula (S3) is -SiR ^a1 ₂ R ^c1 or -SiR ^a1 ₃ , R ^a1 is -Z ¹ -SiR ²² _q1 R ²³ _r1 , Z ¹ is a C _1-6 alkylene group, -(CH ₂ ) _z1 -O-(CH ₂ ) _z2 - (wherein z1 is an integer of 0 to 6, for example an integer of 1 to 6, and z2 is an integer of 0 to 6, for example an integer of 1 to 6), or -(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 - (wherein z3 is an integer of 0 to 6, for example an integer of 1 to 6, and z4 is an integer of 0 to 6, for example an integer of 1 to 6), preferably a C _1-6 alkylene group, and q1 is 1 to 3, preferably 2 to 3, more preferably 3.

In one embodiment, R ^Si is a group represented by formula (S4). In a preferred embodiment, formula (S4) is -CR ^e1 ₂ R ^f1 or -CR ^e1 ₃ , R ^e1 is -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 , Z ³ is a C _1-6 alkylene group, -(CH ₂ ) _z5" -O-(CH ₂ ) _z6" - (wherein z5" is an integer of 0 to 6, for example an integer of 1 to 6, and z6" is an integer of 0 to 6, for example an integer of 1 to 6), or -(CH ₂ ) _z7" -phenylene-(CH ₂ ) _z8" - (wherein z7" is an integer of 0 to 6, for example an integer of 1 to 6, and z8" is an integer of 0 to 6, for example an integer of 1 to 6), preferably C It is a _1-6 alkylene group, and n2 is 1 to 3, preferably 2 to 3, and more preferably 3.

In one embodiment, R ^Si is a group represented by formula (S5). In a preferred embodiment, R ^g1 and R ^h1 are -Z ⁴ -SiR ¹¹ _n1 R ¹² _3-n1 , Z ⁴ is a C _1-6 alkylene group, -(CH ₂ ) _z5" -O-(CH ₂ ) _z6" - (wherein z5" is an integer of 0 to 6, for example an integer of 1 to 6, and z6" is an integer of 0 to 6, for example an integer of 1 to 6) or -(CH ₂ ) _z7" -phenylene-(CH ₂ ) _z8" - (wherein z7" is an integer of 0 to 6, for example an integer of 1 to 6, and z8" is an integer of 0 to 6, for example an integer of 1 to 6), preferably a C _1-6 alkylene group, and n1 is 1 to 3, preferably 2 to 3, and more preferably 3.

m is an integer from 1 to 100, preferably from 5 to 80, more preferably from 10 to 50, for example, from 20 to 50 or from 20 to 40.

n is an integer from 1 to 50, preferably from 1 to 20, more preferably from 1 to 10, for example, from 2 to 10.

o is an integer from 0 to 200, preferably from 5 to 100, more preferably from 10 to 80, and even more preferably from 15 to 50, for example, from 20 to 50, 20 to 40, or 30 to 50.

The fluorosilicone compound represented by the above formula (I) may have a number average molecular weight of, but is not particularly limited to, 1 x 10 ² to 1 x 10 ^6. The fluorosilicone compound represented by the above formula (I) may have a number average molecular weight of preferably 1000 to 100,000, more preferably 2000 to 50,000. The "number average molecular weight" may be measured using GPC.

Fluorosilicone of formula (I) is, for example, the following formula (II):

［式中、各記号は、式（Ｉ）における記載と同意義である。］
で表されるＳｉ－Ｈ含有化合物を、式：
　　Ｒ^Ａ－Ｘ”－ＣＨ＝ＣＨ_２またはＲ^Ｓｉ－Ｙ’－ＣＨ＝ＣＨ_２
［式中、Ｘ”およびＹ’は、それぞれ、２価の基であり、好ましくは１～１８の炭素原子を有する２価の基、または直接結合であり、Ｒ^ＡおよびＲ^Ｓｉは上記式（Ｉ）の記載と同じ意義である。］
で表される化合物とヒドロシリル化反応用触媒の存在下に付加反応させて製造される。

[In the formula, each symbol has the same meaning as defined in formula (I)]
The Si—H-containing compound represented by the formula:
R ^A -X″-CH═CH ₂ or R ^Si -Y′-CH═CH ₂
[In the formula, X″ and Y′ are each a divalent group, preferably a divalent group having 1 to 18 carbon atoms, or a direct bond, and R ^A and R ^Si are as defined above in formula (I)]
and a compound represented by the formula (I) in the presence of a hydrosilylation catalyst.

The present disclosure provides a release composition containing a fluorosilicone compound represented by formula (I) of the present disclosure, wherein the release composition may be only one product or may be a mixture of at least two products.

The fluorosilicone release composition of the present disclosure may contain a curing-accelerating catalyst. This catalyst is for accelerating the dehydration condensation reaction of silanol groups. Examples of curing-accelerating catalysts are organic metal salts (preferably having 1 to 30 carbon atoms), such as dibutyltin dilaurate, dibutyltin diacetate, tetrabutyl titanate (butoxytitanium), tetraisopropyl titanate (isopropoxytitanium), bis-(acetylacetonyl)-diisopropyl titanate, bis(ethylacetoacetate)diisopropyl titanate {bis(ethylacetoacetate)diisopropoxytitanium} and other chelates of titanium and zirconium disclosed in WO2001-49774 (the disclosure of which is incorporated herein by reference), acids (particularly organic acids having 1 to 10 carbon atoms), such as acetic acid or propionic acid, and carboxylates.

The amount of the curing-accelerating catalyst added is usually at most 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the fluorosilicone compound.

The fluorosilicone release composition of the present disclosure is preferably used in the form of a solution in a solvent such as an organic solvent. The solvent dissolves the fluorosilicone release composition and evaporates to deposit the fluorosilicone release agent. Examples of solvents include aliphatic solvents such as hexane, cyclohexane, heptane, octane, isooctane, industrial gasoline, aromatic solvents such as benzene, toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, alcohol solvents such as isopropyl alcohol and ethanol, chlorine solvents such as trichloroethylene, chloroform and m-xylene hexachloride, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as diethyl ether, diisopropyl ether and tetrahydrofuran, fluorine solvents such as HCFC-225, HFC-365, methyl perfluorobutyl ether and ethyl perfluorobutyl ether, and silicone solvents with low boiling points (at most 150°C) such as hexamethyldisiloxane and heptamethyltrisiloxane.

The fluorosilicone release composition of the present disclosure may be in the form of an aerosol in which a solution of the fluorosilicone compound is filled together with a propellant such as LPG.

The fluorosilicone release composition of the present disclosure may be a solution containing a fluorosilicone compound and an organic solvent, or an aqueous emulsion containing water.

When the release composition is an aqueous emulsion, it preferably contains at least one emulsifier selected from the group consisting of nonionic emulsifiers, anionic emulsifiers, and cationic emulsifiers.

The nonionic emulsifier may be any that can emulsify the fluoropolymer of the present disclosure and disperse it in an aqueous emulsion, and examples of such an emulsifier include polyoxyethylene alkyl ethers, sorbitan alkylates, and sorbitan alkyl esters. Examples of polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether.

Anionic emulsifiers include alkyl sulfates, alkyl sulfonates, and alkyl phosphates. Alkyl sulfates include sodium alkyl sulfate.

Cationic emulsifiers include quaternary ammonium salts and alkylamine salts. Quaternary ammonium salts include lauryltrimethylammonium chloride.

The amount of emulsifier is usually 0.5 to 25 parts by weight, preferably 1.0 to 20 parts by weight, and more preferably 2.0 to 15 parts by weight, per 100 parts by weight of the fluoropolymer.

The fluorosilicone release composition of the present disclosure can be applied by well-known methods. For example, the mold can be immersed in a diluted solution of the release composition, sprayed with the diluted solution, or brushed with the diluted solution, followed by evaporation of the solvent. The mold can then be heated to hydrolyze and condense with the silyl moieties to form a cured film, thereby improving durability. Heating is preferably performed at 50-200°C for about 10-60 minutes.

The fluorosilicone release composition of the present disclosure can be used in a form mixed with other release components. Examples of other release components include natural waxes such as carnauba wax and beeswax; synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, and hydrogenated castor oil; various silicone oils and silicone resins; fluoro oils such as CTFE oil and PFPE oil; and fluoro resins such as PTFE and PCTFE. The amount of the other release components may be 1 part by weight to 1000 parts by weight based on 100 parts by weight of the fluorosilicone compound (I).

When the release composition is an aerosol, it can be filled into an aerosol can using a propellant. Examples of propellants include LPG, dimethyl ether, and carbon dioxide. The amount of propellant is usually 10 to 95% by weight, preferably 20 to 90% by weight, and more preferably 30 to 90% by weight, based on the total amount of the release composition and the propellant. If the amount of propellant is 10% by weight or more, the spraying can be performed better and a more uniform coating tends to be obtained. Also, if the amount of propellant is 95% by weight or less, the coating does not tend to become too thin and the release properties do not tend to decrease too much.

The release composition can be used as an internal or external release agent. It is preferred to use it as an external release agent.

　The release composition is usually used as follows: the release composition is applied to the inner surface of a mold, the solvent and dispersant are dried and removed, and then a release agent coating (a fluoropolymer coating) is formed on the mold. The mold is filled with the molding composition to form a molding material, and the molding material is then removed from the mold.

That is, the present disclosure further provides a method for forming the coating. For example, the method for forming the coating of the present disclosure includes the steps of:
(i) applying the release composition of the present disclosure to the inner surface of a mold to form a coating of the release composition.

The present disclosure further provides a method for producing a molded article using the release composition of the present disclosure. For example, the method for producing a molded article of the present disclosure includes the steps of:
(i) applying the release composition of the present disclosure to the inner surface of a mold to form a coating of the release composition;
(ii) filling the mold having the coating of the mold release composition with the molding composition to obtain a molded article; and (iii) removing the molded article from the mold.

Examples of molds for which the release composition can be used include metal molds such as aluminum, SUS, and iron, epoxy resin and wooden molds, and nickel electroformed or chrome plated molds.

Examples of molding materials that can be released using the release composition include rubbers such as urethane rubber, H-NBR, NBR, silicone rubber, EPDM, CR, NR, fluororubber, SBR, BR, IIR and IR, urethane foam, thermosetting resins such as epoxy resin, phenolic resin and FRP (e.g., CFRP and GFRP), and thermoplastic resins such as ABS, polycarbonate and PBT.

The present disclosure provides a coating obtained from a release composition containing a fluorosilicone compound represented by formula (I) of the present disclosure.

In this disclosure, examples of raw materials for molded articles to be demolded include polyurethane, butyl rubber, styrene butadiene rubber, chloroprene rubber, EPDM, NBR, ACM, urethane rubber, silicone rubber, fluororubber, polycarbonate, epoxy resin, phenolic resin, unsaturated polyester, melamine, FRP, PVC, ABS, EVA and PP.

Applications of this disclosure include keypads, o-rings, packing, belts, panels and hoses.

The compounds and release compositions disclosed herein have been described in detail above. Note that the compounds and release compositions disclosed herein are not limited to the above examples.

The fluorosilicone compound and release composition of the present disclosure will be described below in the following examples, but the present disclosure is not limited to the following examples. Note that in the present examples, the order of the repeating units that make up the siloxane portion is arbitrary, and the chemical formula shown below shows the average composition.

Synthesis Example 1
A 100 ml three-neck round bottom flask was equipped with a stirrer, a thermometer/temperature controller, and a dropping funnel. THF (45 g), 4-trifluoromethoxyphenol (5.1 g), and potassium carbonate (8.3 g) were added. Allyl bromide (10.8 g) was then added dropwise, and the mixture was stirred at room temperature for 4 hours to react. Finally, purification was performed to obtain CF ₃ O(C ₆ H ₄ )OCH ₂ CHCH ₂ (Compound 1).

Synthesis Example 2
A 250 mL, 4-neck round bottom flask was equipped with a mechanical stirrer, thermometer/controller, heating mantle, and a water-cooled reflux condenser with a drying tube packed with _CaSO4 , and an addition funnel.
Siloxane (2.0 g) having the structure Me ₃ SiO-(Me ₂ SiO) _n -(MeHSiO) _m -SiMe ₃ (Me is a methyl group, n is 38, and m is 36) was added to a flask and heated to 60° C., followed by CF ₃ O(C ₆ H ₄ )OCH ₂ CHCH ₂ (compound 1, 2.24 g) containing Pt (17 mg) as a complex with 1,2-divinyltetramethyldisiloxane. Vinyltrimethoxysilane (0.4 g) was then added dropwise. Excess olefin was then removed by heating under vacuum. Finally, filtration was performed to obtain compound 2.

Synthesis Example 3
Compound 3 was produced by the same procedure as in Synthesis Example 2, except that the amount of CF ₃ O(C ₆ H ₄ )OCH ₂ CHCH ₂ (Compound 1) used was 2.51 g.

Synthesis Example 4
Compound 4 was produced by the same procedure as in Synthesis Example 2, except that the amount of CF ₃ O(C ₆ H ₄ )OCH ₂ CHCH ₂ (Compound 1) was changed to 2.67 g and the amount of vinyltrimethoxysilane was changed to 0.2 g.

化合物２：ｘ＝２９、ｙ＝７、ｚ＝３８
化合物３：ｘ＝３２、ｙ＝４、ｚ＝３８
化合物４：ｘ＝３４、ｙ＝２、ｚ＝３８

Compound 2: x=29, y=7, z=38
Compound 3: x=32, y=4, z=38
Compound 4: x=34, y=2, z=38

As control compounds, the following target compounds 1 and 2 were prepared.
Control compound 1: x=36, y=0, z=38
Control compound 2: x=0, y=36, z=38

Examples A release test was carried out using the above compounds 2 to 4, control compounds 1 and 2, a compound synthesized according to the method described in Synthesis Example 1 of Japanese Patent No. 5,184,382 (control compound 3), and a commercially available release agent (DAIFREE GF-700, manufactured by Daikin Industries, Ltd.) (control compound 4).

(evaluation)
"Mold release test"
The release composition was diluted with isohexane to a solid content of 0.5% by mass, and the solution was spray-coated on an aluminum plate of 9.5 cm x 9.5 x 0.15 cm. The coated plate was then dried at 150°C for 15 minutes so that 0.2 to 0.3 mg/ ^cm2 of non-volatile matter remained on the metal surface. Next, a gummed tape with holes was attached to the aluminum plate. Next, a CFRP prepreg (3K plain weave carbon, manufactured by Nippon Composites Co., Ltd.) of 3.0 cm x 3.0 cm was attached to the coated plate, and an aluminum plate was placed on top to prepare a molding test sample. The prepared test sample was sandwiched between a press machine, and the CFRP prepreg was cured and molded at a pressure of 10 MPa while being heated at 150°C for 10 minutes. After the test sample was cooled, the aluminum plate that had been covered was removed, and the test sample was set in a push-pull gauge. A push-pull gauge was attached to the hole in the packing tape in the test sample, and the packing tape was pulled up at a constant rhythm to release the CFRP prepreg molded from the coated plate. The force required to pull up the tape was measured as the release force. In addition, the same mold was used to continuously release the article, and the number of continuous releases (i.e., the number of releases) until release was no longer possible was measured.

"Non-transferability evaluation"
The release surface of the CFRP prepreg after the release test was observed with a SEM (JCM-7000, manufactured by JEOL). The components derived from the release agent on the surface were identified by SEM-EDX and their amounts were compared. The less the components derived from the release agent, the better the non-transferability. The comparison results were classified as follows:
○: Almost no residual components derived from the release agent (very good non-transferability)
△: Residual components from release agent remain, but only slightly (good non-transferability)
×: Release agent-derived components remain, and the amount is large (poor non-transferability)

"Paint film adhesion evaluation"
An acrylic urethane paint (NY Polyn K, manufactured by Shinto Paint Co., Ltd.) was applied to the release surface of the CFRP prepreg after the demolding test using a spray gun and dried at room temperature for 12 hours. The adhesion of the coating film to the prepreg was evaluated by a cross-cut test in accordance with JIS K5600. Specifically, a 5 x 5 grid was formed on the coating film using a cutter knife so that each grid was 2 mm long and 2 mm wide. Cellophane tape (registered trademark) was applied to the coating film after the grid was formed, pressed with a finger, and then the cellophane tape was peeled off. The remaining rate of the coating film was calculated from the grids remaining on the prepreg, and the results were classified as follows:

◎: Residual rate of coating film is 80% or more (very good adhesion)
○: Residual rate of coating film is 60-80% or more (good non-transferability)
△: Residual rate of coating film is 20-60% or more (non-transferability is poor)
×: Residual rate of coating film is less than 20% (non-transferability is very poor)

The above results show that the fluorosilicone compound of the present invention exhibited good releasability and non-transferability. On the other hand, the compound of the comparative example did not exhibit either releasability or non-transferability.

The fluorosilicone compounds disclosed herein can be usefully used as release agents.

Claims (16)

Formula (I):

[Wherein:
R ^A is CF ₃ -, CF ₃ O-, CF ₃ NH-, CF ₃ CH ₂ NH-, (CF ₃ ) ₂ N-, (CF ₃ CH ₂ ) ₂ N-, CF ₃ S-, CF ₃ C(=O)-, CF ₃ CH ₂ C(=O)-, CF ₃ C(=O)O-, CF ₃ CH ₂ OC(=O)-, CF ₃ CONH-, CF ₃ CH ₂ CONH-, CF ₃ NHCO-, CF ₃ CH ₂ NHCO-, CF ₃ CON(CF ₃ )-, CF ₃ CH ₂ CON(CF ₃ )-, CF ₃ CON(CH ₂ CF ₃ )-, CF _3CH2CON ( _{CH2CF3 )} -, _{( CF3} ) _{2NCO- or} ( _CF3CH2 ) _2NCO- ;
R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group;
R ³ and R ¹⁰ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, R ^A -X-, or R ^Si -Y-;
X and Y are each independently a divalent organic group;
R ^Si is a monovalent group containing a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto;
m is an integer from 1 to 100;
n is an integer from 1 to 50;
o is an integer from 0 to 200;
The repeating units enclosed in parentheses with m, n, and o may be present in any order.
A fluorosilicone compound represented by the formula: 2. The fluorosilicone compound of claim 1, wherein R ^A is CF ₃ O-, CF ₃ NH-, or (CF ₃ ) ₂ N-. 3. The fluorosilicone compound of claim 1 or 2, wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a C _1-4 alkyl group. The fluorosilicone compound according to any one of claims 1 to 3, wherein R ³ and R ¹⁰ are each independently a C _1-4 alkyl group. X is,
-(Ar) _a1 -(CFH) _b1 -(CH ₂ ) _c1 -(O) _d1 -
[Wherein:
Ar is a divalent aromatic group optionally substituted by a fluorine atom or R ^A ;
a1 is an integer from 0 to 10,
b1 is an integer from 0 to 200,
c1 is an integer from 0 to 200,
d1 is an integer from 0 to 10,
The repeating units denoted by symbols a1, b1, c1, and d1 and enclosed in parentheses may be present in any order.]
The fluorosilicone compound according to any one of claims 1 to 4, wherein the fluorosilicone compound is a group represented by the formula: X is,
-(Ar) _a1 -(O) _d1 -(CH ₂ ) _c1 -
[Wherein:
Ar is a divalent aromatic group which may be substituted by a fluorine atom or R ^A , preferably an unsubstituted divalent aromatic group;
a1 is 0 or 1;
c1 is an integer from 1 to 36,
d1 is 0 or 1.
The fluorosilicone compound according to any one of claims 1 to 5, wherein the fluorosilicone compound is a group represented by the formula: The fluorosilicone compound according to any one of claims 1 to 6, wherein Y is an alkylene group or an alkyleneoxyalkylene group. R ^Si is represented by the following formula (S1), (S2), (S3), (S4) or (S5):

[Wherein:
Each R ¹¹ is independently a hydroxyl group or a hydrolyzable group;
Each R ¹² is independently a monovalent organic group;
n1 is independently an integer of 0 to 3 for each (SiR ¹¹ _n1 R ¹² _3-n1 ) unit,
Each ^X11 independently represents a single bond or a divalent organic group;
Each R ¹³ is independently a hydrogen atom or a monovalent organic group.
Each t is independently an integer of 2 or more;
R ¹⁴ is each independently a hydrogen atom, a halogen atom or -X ¹¹ -SiR ¹¹ _n1 R ¹² _3-n1 ;
R ¹⁵ is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms;
Each R ^a1 is independently -Z ¹ -SiR ²¹ _p1 R ²² _q1 R ²³ _r1 ;
^Each Z1 is independently a divalent organic group;
Each R ²¹ is independently -Z ^1' -SiR ^21' _p1' R ^22' _q1' R ^23' _r1' ;
Each R ²² is independently a hydroxyl group or a hydrolyzable group;
Each R ²³ is independently a monovalent organic group;
Each p1 is independently an integer from 0 to 3;
Each q1 is independently an integer from 0 to 3,
Each r1 is independently an integer from 0 to 3;
Each Z ^1′ is independently a divalent organic group;
Each R ^21' is independently -Z ^1'' -SiR ^22'' _q1'' R ^23'' _r1'' ;
Each R ^22′ is independently a hydroxyl group or a hydrolyzable group;
Each R ^23′ is independently a monovalent organic group,
Each p1' is independently an integer of 0 to 3,
Each q1' is independently an integer of 0 to 3,
Each r1' is independently an integer of 0 to 3;
Each Z ^1″ is independently a divalent organic group;
Each R ^22″ is independently a hydroxyl group or a hydrolyzable group;
Each R ^{23 ″} is independently a monovalent organic group,
Each q1″ is independently an integer from 0 to 3,
Each r1″ is independently an integer from 0 to 3;
Each R ^b1 is independently a hydroxyl group or a hydrolyzable group;
Each R ^c1 is independently a monovalent organic group,
Each k1 is independently an integer from 0 to 3;
Each l1 is independently an integer from 0 to 3;
Each m1 is independently an integer of 0 to 3;
Each R ^d1 is independently -Z ² -CR ³¹ _p2 R ³² _q2 R ³³ _r2 ;
Each ^Z2 is independently a single bond, an oxygen atom, or a divalent organic group;
Each R ³¹ is independently -Z ^2' -CR ^32' _q2' R ^33' _r2' ;
Each R ³² is independently —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 ;
R ³³ is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group,
p2 is independently an integer of 0 to 3,
Each q2 is independently an integer from 0 to 3,
Each r2 is independently an integer from 0 to 3;
Each Z ^2′ is independently a single bond, an oxygen atom, or a divalent organic group;
Each R ^32' is independently -Z ³ -SiR ³⁴ _n2 R ³⁵ _3-n2 ;
Each R ^33′ is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group,
Each q2' is independently an integer of 0 to 3,
Each r2' is independently an integer of 0 to 3,
Each ^Z3 is independently a single bond, an oxygen atom, or a divalent organic group;
Each R ³⁴ is independently a hydroxyl group or a hydrolyzable group;
Each R ³⁵ is independently a monovalent organic group.
Each n2 is independently an integer from 0 to 3;
Each R ^e1 is independently —Z ³ —SiR ³⁴ _n2 R ³⁵ _3-n2 ;
Each R ^f1 is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group,
Each k2 is independently an integer from 0 to 3;
Each l2 is independently an integer from 0 to 3;
Each m2 independently represents an integer of 0 to 3.
R ^g1 and R ^h1 are each independently -Z ⁴ -SiR ¹¹ _n1 R ¹² _3-n1 , -Z ⁴ -SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 , or -Z ⁴ -CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ;
Each ^Z4 is independently a single bond, an oxygen atom, or a divalent organic group,
k3 is 1 or 2;
l3 is 0 or 1;
However, in formula (S1), (S2), (S3), (S4), or (S5), there are at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded.]
The fluorosilicone compound according to any one of claims 1 to 7, wherein the fluorosilicone compound is a group represented by the formula: A release composition comprising the fluorosilicone compound according to any one of claims 1 to 8. The release composition according to claim 9, further comprising at least one liquid medium selected from water and an organic solvent. The release composition according to claim 9 or 10, which is a solution or aerosol containing an organic solvent, or an aqueous emulsion containing water. The release composition according to any one of claims 9 to 11, further comprising a curing-accelerating catalyst in an amount of 0.05 parts by weight to 10 parts by weight based on 100 parts by weight of the fluorosilicone compound (I). The release composition according to any one of claims 9 to 12, further comprising at least one selected from the group consisting of silicone oil, silicone resin, synthetic wax, natural wax, fluorine oil and fluorine resin in an amount of 0.1 to 99 parts by weight based on 100 parts of the fluorosilicone compound (I). A coating obtained from the release composition according to any one of claims 9 to 13. (i) A method for forming a release agent coating, comprising the step of applying the release composition according to any one of claims 9 to 13 to an inner surface of a molding die to form a coating of the release composition. (i) a step of applying the mold release composition according to any one of claims 9 to 13 to the inner surface of a molding die to form a coating of the mold release composition;
(ii) filling a molding composition into a mold having a coating of the mold release composition to obtain a molded body; and (iii) removing the molded body from the mold.