TWI896911B - Surface treatment agent - Google Patents

Abstract

The present invention provides a compound represented by the following formula (1) (wherein each symbol has the same meaning as described in the specification).

R^b ₂N-R^d-CO-(R^F2-CO-NR^c-R^a(R^Ac _m)-NR^c-CO)_x-R^F2-CO-R^d-NR^b ₂ (1)

Description

Surface treatment agent

This disclosure relates to novel fluoropolyether-containing acrylic compounds and surface treatment agents containing the same.

Certain fluorinated polyether-containing silane compounds are known to provide excellent water-repellency, oil-repellency, and antifouling properties when used in substrate surface treatment. Layers obtained from surface treatment agents containing fluorinated polyether-containing silane compounds (hereinafter referred to as "surface treatment layers") are applied as so-called functional films to a variety of substrates, such as glass, plastics, fibers, sanitary products, and building materials (Patent Document 1).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2003-238577

While the fluorinated polyether-containing silane compound described in Patent Document 1 can provide a surface treatment layer with excellent functionality, a surface treatment layer with even higher durability is still desired.

The purpose of this disclosure is to provide a fluorinated polyether-based compound that can provide a surface treatment layer with excellent durability.

This disclosure includes the following aspects.

[1] A compound represented by the following formula (1):

R ^b ₂ NR ^d -CO-(R ^F2 -CO-NR ^c -R ^a (R ^Ac _m )-NR ^c -CO) _x -R ^F2 -CO-R ^d -NR ^b ₂ (1)

In the formula,

^RF2 is independently ^-Rf2p - _RF - _Oq- ^,

^Rf2 is a _C1-6 alkylene group which may be substituted by one or more fluorine atoms,

^RF is a divalent fluoropolyether group,

p is 0 or 1,

q is 0 or 1,

R ^a are each independently an (m+2)-valent organic group,

m is an integer from 1 to 4,

R ^b is independently R ^Si , R ^Ac or R ^c ,

R ^Si are independently -X ^C -SiR ¹ _n' R ² _3-n' ,

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

R ¹ is independently a hydroxyl group or a hydrolyzable group,

^R2 are each independently a hydrogen atom or a monovalent organic group,

n’ is an integer from 1 to 3,

R ^Ac are each 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 (m'+1) valence base,

X and ^F are each independently a divalent organic group having 1 to 10 carbon atoms,

^R5 is a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms,

m’ is an integer from 1 to 10,

R ^c are each independently a hydrogen atom or a C _1-6 alkyl group,

R ^d are each independently a single bond or a divalent organic group,

x is an integer greater than 1.

[2] The compound as described in [1] above, wherein R and ^F are each independently a group represented by the following 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, R ^Fa are independently a hydrogen atom, a fluorine atom or a chlorine atom,

a, b, c, d, e, and f are each independently an integer from 0 to 200, the sum of a, b, c, d, e, and f is 1 or greater, and the order of the repeating units labeled a, b, c, d, e, or f and enclosed in parentheses in the formula is arbitrary, except that when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e, and f is 1 or greater.

[3] The compound as described in [1] or [2] above, wherein R ^Fa is a fluorine atom.

[4] The compound as described in any one of [1] to [3] above, wherein ^RF is independently a group represented by the following formula (f1), (f2), (f3), (f4), (f5) or (f6),

-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)

In the formula, d is an integer from 1 to 200, e is an integer from 0 to 2, and the order of the repetitive units marked with the subscript d or e and enclosed in parentheses is arbitrary;

-(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2)

In the formula, c and d are independently integers ranging from 0 to 30.

e and f are independently integers between 1 and 200.

The sum of c, d, e, and f is an integer between 10 and 200.

The order of the repeated units marked with subscripts c, d, e or f and enclosed in brackets 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 a combination of 2 or 3 groups selected from these groups,

R ⁹ is a single bond, or is a group selected from OCF ₂ , OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ ,

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 a combination of 2 or 3 groups independently selected from these 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 a combination of two or three groups independently selected from these groups,

g is an integer from 2 to 100.

g' is an integer from 2 to 100, and R ^r is as shown in the following chemical formula,

Where * represents the bonding position; -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f5)

In the formula, e is an integer from 1 to 200, a, b, c, d, and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e, and f is at least 1. Furthermore, the order of the repeating units labeled a, b, c, d, e, or f and enclosed in parentheses in the formula is arbitrary. -(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)

In the formula, f is an integer from 1 to 200, a, b, c, d, and e are each independently an integer from 0 to 200, and the sum of a, b, c, d, e, and f is at least 1. Furthermore, the order of the repetitive units enclosed in parentheses and labeled a, b, c, d, e, or f in the formula is arbitrary.

[5] The compound as described in any one of [1] to [4] above, wherein ^Rf2 is independently a _C1-6 perfluoroalkylene group.

[6] The compound according to any one of [1] to [5] above, wherein each of ^Ra is independently a group represented by the following formula:

-R ⁹ -(R ^a '-R ⁹ ) _k -

In the formula,

R ⁹ are each independently C _1-6 alkylene,

R ^a' is independently a trivalent organic group,

k is an integer from 1 to 4.

[7] The compound described in [6] above, wherein Ra ^' is independently a trivalent organic group containing a N atom or an O atom.

[8] The compound as described in [6] above, wherein Ra ^' is independently a trivalent organic group which may contain an amine bond, an amide bond, a carbamate bond, a urea bond, an ether bond or an ester bond between carbon atoms.

[9] The compound according to any one of [6] to [8], wherein each of Ra ^' is independently the following:

In the formula, R ⁸ is a hydrogen atom or a C _1-6 alkyl group.

[10] The compound according to any one of [6] to [9] above, wherein Ra ^' is N.

[11] The compound as described in any one of [6] to [10] above, wherein k is 1.

[12] The compound as described in any one of [6] to [10] above, wherein k is 2.

[13] The compound as described in any one of [1] to [12] above, wherein at least one R ^b is R ^Si .

[14] The compound as described in any one of [1] to [13] above, wherein one of the R ^{b groups} bonded to the N atom at each terminal is R ^Si and the others are R ^c .

[15] The compound as described in any one of [1] to [13] above, wherein one of the R ^{b groups} bonded to the N atom at each terminal is R ^Si and the others are R ^Ac .

[16] The compound as described in any one of [1] to [15] above, wherein X ^C is:

C _1-6 alkylene,

-(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 ) _z 3 -phenylene-(CH ₂ ) _{z 4} - (wherein z 3 is an integer from 0 to 6, and z 4 is an integer from 0 to 6).

[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 as described in any one of [1] to [17] above, wherein n' is 2 or 3.

[19] The compound as described in any one of [1] to [18] above, wherein n' is 3.

[20] The compound according to any one of [1] to [19] above, wherein X ^D is -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -OCONH-, -NHCOO-, -NH-CO-NH-, -CH ₂ CH(OH)CH ₂ -, or -CH(CH ₂ OH)CH ₂ -.

[21] The compound according to 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 -.

[22] The compound according to any one of [1] to [21] above, wherein X ^D is -CONH-.

[23] The compound as described in any one of [1] to [22] above, wherein X ^E is a single bond.

[24] The compound as described in any one of [1] to [23] above, wherein X ^E is -X ^G -X ^H ,

X ^G is:

Single key,

C _1-6 alkylene,

-(CH ₂ ) _z9 -O-(CH ₂ ) _z10 -(wherein z9 is an integer from 0 to 6, and z10 is an integer from 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),

^XH is represented by the following chemical formula,

^R8 is a hydrogen atom or a _C1-6 alkyl group.

[25] The compound as described in any one of [1] to [24] above, wherein X ^F is:

C _1-6 alkylene,

-(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).

[26] The compound as described in any one of [1] to [25] above, wherein R ^c is independently a hydrogen atom or a C _1-6 alkyl group.

[27] The compound as described in any one of [1] to [26] above, wherein 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).

[28] The compound as described in any one of [1] to [27] above, wherein x is an integer of 1 to 5.

[29] A surface treatment agent containing the compound described in any one of [1] to [28] above.

[30] The surface treatment agent as described in [29] above further contains one or more other components selected from fluorinated oil, silicone oil and catalyst.

[31] The surface treatment agent as described in [29] or [30] above, which is used as an antifouling coating agent or a water-repellent coating agent.

[32] An article comprising a substrate and a layer formed on the surface of the substrate by the compound described in any one of [1] to [28] or the surface treatment agent described in any one of [29] to [31].

According to the present disclosure, a fluoropolyether-based acrylic compound capable of providing a surface treatment layer with excellent durability can be provided.

As used in this specification, a "monovalent organic group" refers to a univalent group containing carbon. Monovalent organic groups are not particularly limited and may be alkyl groups or their derivatives. Alkyl group derivatives include groups having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, or carbonyloxy groups at the end of the alkyl group or within the molecular chain. Furthermore, when simply referring to an "organic group," it refers to a monovalent organic group. Furthermore, a "divalent organic group" refers to a divalent group containing carbon. These divalent organic groups are not particularly limited and may include divalent groups formed by removing a hydrogen atom from an organic group.

As used herein, the term "alkyl" refers to a group containing carbon and hydrogen, formed by removing one hydrogen atom from a hydrocarbon. The alkyl group is not particularly limited and includes C _1-20 alkyl groups that may be substituted with one or more substituents, such as aliphatic alkyl groups and aromatic alkyl groups. The aforementioned "aliphatic alkyl groups" may be linear, branched, or cyclic, and may be saturated or unsaturated. Furthermore, the alkyl group may contain one or more ring structures.

As used herein, the substituents of "alkyl" are not particularly limited and include, for example, halogen atoms; one or more groups selected from the group consisting of _C1-6 alkyl groups, _C2-6 alkenyl groups, _C2-6 alkynyl groups, _C3-10 cycloalkyl groups, C3-10 unsaturated cycloalkyl groups, _5-10 membered heterocyclic groups, 5-10 membered unsaturated heterocyclic groups, _C6-10 aryl groups, and 5-10 membered heteroaryl groups which may be substituted with one or more halogen atoms.

As used herein, a "hydrolyzable group" refers to a group that is susceptible to hydrolysis, that is, a group that can be detached from the main structure of a compound by hydrolysis. Examples of hydrolyzable groups include -OR ^h , -OCOR ^h , -ON=CR ^h ₂ , -NR ^h ₂ , -NHR ^h , and halogens. In these formulas, R ^h represents a substituted or unsubstituted C _1-4 alkyl group.

The fluorinated polyether group-containing acrylic compound disclosed herein is a fluorinated polyether group-containing acrylic compound represented by the following formula (1):

R ^b ₂ NR ^d -CO-(R ^F2 -CO-NR ^c -R ^a (R ^Ac _m )-NR ^c -CO) _x -R ^F2 -CO-R ^d -NR ^b ₂ (1)

In the formula,

^RF2 is independently ^-Rf2p - _RF - _Oq- ^,

^Rf2 is a _C1-6 alkylene group which may be substituted by one or more fluorine atoms,

^RF is a divalent fluoropolyether group,

p is 0 or 1,

q is 0 or 1,

R ^a are each independently an (m+2)-valent organic group,

m is an integer from 1 to 4,

R ^b is independently R ^Si , R ^Ac or R ^c ,

R ^Si are independently -X ^C -SiR ¹ _n' R ² _3-n' ,

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

R ¹ is independently a hydroxyl group or a hydrolyzable group,

^R2 are each independently a hydrogen atom or a monovalent organic group,

n’ is an integer from 1 to 3,

R ^Ac are each 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 (m'+1) valence base,

X and ^F are each independently a divalent organic group having 1 to 10 carbon atoms,

^R5 is a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms,

m’ is an integer from 1 to 10,

R ^c are each independently a hydrogen atom or a C _1-6 alkyl group,

R ^d are each independently a single bond or a divalent organic group,

x is an integer greater than 1.

In the above formula (1), ^RF2 is ^-Rf2p _- ^RF - _Oq- .

In the above formula, ^Rf2 is a _C1-6 alkylene group which may be substituted with one or more fluorine atoms.

The "C _1-6 alkylene" in the aforementioned C _1-6 alkylene group which may be substituted with one or more fluorine atoms may be a linear or branched chain, preferably a linear or branched chain C _1-3 alkylene group, and more preferably a linear chain C _1-3 alkylene group.

The above-mentioned ^Rf2 is preferably a _C1-6 alkylene group substituted with one or more fluorine atoms, more preferably a _C1-6 perfluoroalkylene group, and even more preferably a _C1-3 perfluoroalkylene group.

The C _1-6 perfluoroalkylene group may be a linear or branched chain, preferably a linear or branched C _1-3 perfluoroalkylene group, more preferably a linear C _1-3 perfluoroalkylene group, specifically -CF ₂ -, -CF ₂ CF ₂ -, or -CF ₂ CF ₂ CF ₂ -.

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

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

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

^RF may preferably contain a group represented by the following formula:

-(OCH ₁ R ^Fa _2h1 ) _h3 -(OCH ₂ 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 greater than 0.

h4 is an integer greater than 0.

However, the sum of h3 and h4 is 1 or greater, preferably 2 or greater, and more preferably 5 or greater. The order of the repetitive units marked with h3 and h4 and enclosed in parentheses in the formula is arbitrary.

In one embodiment, ^RF can be a linear chain or a branched chain. ^RF is preferably a group represented by the following 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, R ^Fa are independently a hydrogen atom, a fluorine atom or a chlorine atom,

a, b, c, d, e, and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e, and f is 1 or greater. The order of the repeating units enclosed in parentheses and labeled a, b, c, d, e, or f in the formula is arbitrary. However, when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e, and f is 1 or greater.

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

Preferably, a, b, c, d, e, and f can each independently be an integer between 0 and 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, and even more preferably 60 or less, for example, 50 or less or 30 or less.

These repeating units can be in the form of linear chains or _branched chains. For _example , - _{( OC6F12} )- can be -( _{OCF2CF2CF2CF2CF2CF2CF2CF2} )-, -(OCF( _{CF3 ) CF2CF2CF2CF2CF2CF2 )} -, -( _{OCF2CF ( CF3} )CF2CF2CF2CF2 ₎ - _, -( _OCF2CF2CF ( _CF3 ) _CF2CF2CF2 )-, -( _OCF2CF2CF ( _{CF3 ) CF2CF2CF2} )-, -(OCF2CF2CF2CF2CF( _CF3 ) _CF2CF2 )-, -( _{OCF2CF2CF2CF2CF ( CF3 ) CF2} )- _, - ₍ OCF2CF2CF2CF2CF( _CF3 ) _{CF2 )} -, etc. -(OC ₅ F ₁₀ )- can be -(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ CF ₂ )-, -(OCF ₂ CF(CF ₃ )CF ₂ CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ )CF ₂ )-, -(OCF ₂ CF ₂ CF ₂ CF(CF ₃ ))-etc. -(OC ₄ F ₈ )-can be -(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 ))-. -(OC ₃ F ₆ )- (that is, in the above formula, R ^Fa is a fluorine atom) can be any of -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )-, and -(OCF ₂ CF(CF ₃ ))-. -(OC ₂ F ₄ )- can be any of -(OCF ₂ CF ₂ )- and -(OCF(CF ₃ ))-.

In one embodiment, the repeating units are arranged in a linear chain. This arrangement improves the surface smoothness and wear resistance of the surface treatment layer.

In one embodiment, the repeating units are in a branched chain shape. By configuring the repeating units in a branched chain shape, the dynamic friction coefficient of the surface treatment layer can be increased.

In one aspect, ^RF may contain a ring structure.

The above-mentioned ring structure can be a three-membered ring, a four-membered ring, a five-membered ring, or a six-membered ring.

In the formula, * represents the bond position.

The above-mentioned ring structure is preferably a four-membered ring, a five-membered ring, or a six-membered ring, and more preferably a four-membered ring or a six-membered ring.

The repeating unit having a ring structure may preferably be the following unit.

In the formula, * represents the bond position.

In one embodiment, R ^{and F} are each independently a group represented by any one of the following formulae (f1) to (f6).

-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)

In the formula, d is an integer from 1 to 200, e is an integer from 0 to 2, and the order of the repetitive units marked with the subscript d or e and enclosed in parentheses is arbitrary;

-(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2)

In the formula, c and d are independently integers from 0 to 30, e and f are independently integers from 1 to 200,

The sum of c, d, e, and f is greater than 2.

The order of the repeated units marked with subscripts c, d, e or f and enclosed in brackets 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 a combination of 2 or 3 groups independently selected from these groups,

R ⁹ is a single bond, or is a group selected from OCF ₂ , OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ ,

g is an integer between 2 and 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 a combination of 2 or 3 groups independently selected from these 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 a combination of two or three groups independently selected from these groups,

g is an integer from 2 to 100.

g’ is an integer from 2 to 100.

R ^r is represented by the following chemical formula:

In the formula, * represents the bond position;

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f5)

In the formula, e is an integer from 1 to 200, and a, b, c, d, and f are each independently an integer from 0 to 200. Furthermore, the order of the repetitive units enclosed in parentheses and labeled 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)

In the formula, f is an integer from 1 to 200, and a, b, c, d, and e are each independently an integer from 0 to 200. Furthermore, the order of the repetitive units enclosed in parentheses and labeled a, b, c, d, e, or f is arbitrary.

In the above formula (f1), d is preferably 5 to 200, more preferably 10 to 100, and even more preferably 15 to 50, for example, an integer of 25 to 35. In one embodiment, e is 1. In another embodiment, e is 0. In another embodiment, e is 2. In one embodiment, the above formula ( _f1 ) is a group represented by - _{( OCF2CF2CF2} ) _d- ( _OCF2CF2 ) _e- or -(OCF( _CF3 ) _{CF2 ) d-} (OCF( _CF3 )) _e- . In another embodiment, the above formula (f1) is a group represented by -(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 from 1 to 200, the total of d1 and d2 is not more than 200, and e1 and e2 are each independently 0 or 1).

In one embodiment, formula (f1) is -(OCF ₂ CF ₂ CF ₂ ) _d -(OCF ₂ CF ₂ ) _e -, preferably -(OCF ₂ CF ₂ CF ₂ ) _d -(OCF ₂ CF ₂ )-.

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 other aspects, 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 ), and 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 preferably each independently an integer of 5 to 200, more preferably an integer of 10 to 200. Furthermore, the sum of c, d, e, and f is preferably 5 or greater, more preferably 10 or greater, for _example , 15 or _greater or 20 or greater. _In one embodiment, the above formula (f2) is preferably a group represented by -( _{OCF2CF2CF2CF2} ) _c- ( _OCF2CF2CF2 ) _d- ( _OCF2CF2 ) _e- ( _{OCF2 ) f-} . In another embodiment, the formula (f2) _may be a group represented by - _{( OC2F4 ) e-} ( _OCF2 ) _f- .

In the above formula (f3), ^R6 is preferably _OC2F4 . In the above formula (f3 ₎ , ^R7 is preferably _a group selected from _OC2F4 , _OC3F6 and _OC4F8 , or a combination of two or _three groups independently selected from _these groups, more preferably a _group selected from _OC3F6 and _{OC4F8 . The combination of two or three groups independently selected from OC2F4 , OC3F6 , and OC4F8 is not particularly limited . Examples thereof include : -OC2F4OC3F6- , -OC2F4OC4F8- , -OC3F6OC2F4- , -OC3F6OC3F6- , -OC3F6OC4F8- , -OC4F8OC4F8- , -OC4F8OC3F6- , -OC4F8OC2F4- , -OC2F4OC2F4OC3F6- , -OC2F4OC2F4OC4F8- , -OC2F4OC3F6OC2F4 . ​ ​ ​ ​ ​ ​ ​ ​ ​} -, _{-OC2F4OC3F6OC3F6- , -OC2F4OC4F8OC2F4- , -OC3F6OC2F4OC2F4- , -OC3F6OC2F4OC3F6- , -OC3F6OC3F6OC2F4- , and -OC4F8OC2F4OC2F4- . In one embodiment , R9} is a single bond. _In another embodiment, ^{R9 is} _{a group selected from OCF2, OC2F4, OC3F6, OC4F8 , OC5F10 , and OC6F12 . In formula ( f3 ) , g is preferably 3 or} ^greater _{, and more preferably an integer of 5 or greater} . The g is preferably an integer less than 50. In formula (f3), _OC2F4 , _OC3F6 ^{, OC4F8, OC5F10, and OC6F12 may be a straight chain or a branched chain, preferably a straight chain. In this embodiment, (R6-R7} _{) g is preferably - ( OC2F4 -} ^OC3F6 _{) g- or - ( OC2F4 - OC4F8 ) g- .}

In formula (f4), R ⁶ , R ⁷ , and g have the same meanings and the same configurations as those described in formula (f3). R ^{6 ′} , R ^{7′ ,} and g′ have the same meanings and the same configurations as those described in formula (f3). ^{R r} is preferably represented by the following chemical formula:

In the formula, * represents the bond position;

More preferably, it is represented by the following chemical formula:

In the formula, * represents the bond position.

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

In the above formula (f6), f is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e, and f is preferably 5 to 10, more preferably 10 to 100.

In one embodiment, the above-mentioned ^RF is a group represented by the above-mentioned formula (f1) or (f2).

In one embodiment, the above-mentioned ^RF is a group represented by the above-mentioned formula (f1).

In one embodiment, the above-mentioned ^RF is a group represented by the above-mentioned formula (f2).

In one embodiment, the above-mentioned ^RF is a group represented by the above-mentioned formula (f3).

In one embodiment, the above-mentioned ^RF is a group represented by the above-mentioned formula (f4).

In one embodiment, the above-mentioned ^RF is a group represented by the above-mentioned formula (f5).

In one embodiment, the above-mentioned ^RF is a group represented by the above-mentioned formula (f6).

In the above ^RF , the ratio of e to f (hereinafter referred to as the "e/f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, even more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. By setting the e/f ratio to 10 or less, the smoothness, abrasion resistance, and chemical resistance (e.g., durability against artificial sweat) of the surface treatment layer obtained from this compound are further improved. The smaller the e/f ratio, the greater the improvement in the smoothness and abrasion resistance of the surface treatment layer. On the other hand, by setting the e/f ratio to 0.1 or greater, the stability of the compound can be further improved. The larger the e/f ratio, the greater the stability of the compound.

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

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

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

In the above formula (1), ^Ra is independently an organic group with a valence of (m+2).

In one embodiment, ^Ra is a group represented by the following formula:

-R ⁹ -(R ^a' -R ⁹ ) _k -

Where:

R ⁹ are each independently C _1-6 alkylene,

R ^a' is independently a trivalent organic group,

k is an integer from 1 to 4.

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

In a preferred embodiment, k is an integer between 1 and 2.

In one embodiment, k is 1.

In one embodiment, k is 2.

In one embodiment, Ra ^' is independently a trivalent group containing a N atom or an O atom.

In a preferred embodiment, Ra ^' is independently a trivalent organic group that may contain an amine bond, an amide bond, a urethane bond, a urea bond, an ether bond, or an ester bond between carbon atoms.

In one embodiment, Ra ^' is independently the following:

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). The O in the above-CR ⁸ (-O-)- is bonded to R ^Ac .

In one embodiment, Ra ^' is N.

In one embodiment, Ra ^' is ^-CR8 (-O-)-.

In the above formula (1), m is an integer from 1 to 4.

In a preferred embodiment, m is 1 or 2.

In one embodiment, m is 1.

In one embodiment, m is 2.

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

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

In a preferred embodiment, at least one of the R ^b groups bonded to the N atoms at each terminal of formula (1) is R ^Si .

In one embodiment, one of the R ^b groups bonded to the N atom at each terminal of formula (1) is R ^Si , and the others are R ^c .

In another embodiment, one of the R ^{b groups} bonded to the N atom at each terminal of formula (1) is R ^Si , and the others are R ^Ac .

The above R ^Si are each independently -X ^C -SiR ¹ _n' R ² _3-n' .

The above-mentioned X ^C is a divalent organic group having 1 to 10 carbon atoms.

In one embodiment, X ^C is:

_C1-6 alkylene, -( _CH2 ) _z1 -O-( _CH2 ) _z2- (wherein z1 is an integer from 0 to 6, for example, an integer from 1 to 6, and z2 is an integer from 0 to 6, for example, an integer from 1 to 6), or -( _CH2 ) _z3 -phenylene-( _CH2 ) _z4- (wherein z3 is an integer from 0 to 6, for example, an integer from 1 to 6, and z4 is an integer from 0 to 6, for example, an integer from 1 to 6).

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. The right side of these groups is bonded to Si.

The aforementioned C _1-6 alkylene group may be a straight chain or a branched chain, preferably a straight chain.

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

The above R ^1s are each independently a hydroxyl group or a hydrolyzable group.

Preferably, R ¹ is independently a hydrolyzable group.

R ¹ is preferably independently -OR ^h , -OCOR ^h , -ON═CR ^h ₂ , -NR ^h ₂ , -NHR ^h , -NCO, or a halogen (in this formula, R ^h represents a substituted or unsubstituted C _1-4 alkyl group), more preferably -OR ^h (i.e., an alkoxy group). R ^h can be exemplified by unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups are preferred, especially unsubstituted alkyl groups, and methyl or ethyl groups are more preferred. In one embodiment, R ^h is methyl, and in another embodiment, R ^h is ethyl.

The above R ² are each independently a hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

In R ² , 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, n' in each (SiR ¹ _n' R ² _3-n' ) unit is independently an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

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

The above-mentioned ^XD is a divalent organic group.

^XD is preferably -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -OCONH-, -NHCOO-, -NH-CO-NH-, _-CH2CH (OH) _CH2- , or -CH( _CH2OH ) _CH2- , more preferably -CONH-, _-CH2CH (OH) _CH2- , or -CH( _CH2OH ) _CH2- , and even more preferably -CONH-. The right side of these groups is bonded to ^XE .

The above ^XE is a single bond or an (m'+1) valent group.

In one embodiment, X ^E is a single key.

In one embodiment, ^XE is a trivalent or tetravalent group represented by ^-XG - ^XH .

X ^G is:

Single key,

C _1-6 alkylene,

-(CH ₂ ) _z9 -O-(CH ₂ ) _z10 - (wherein z9 is an integer from 0 to 6, for example, an integer from 1 to 6, and z10 is an integer from 0 to 6, for example, an integer from 1 to 6), or

-(CH ₂ ) _z11 -phenylene-(CH ₂ ) _z12 - (wherein z11 is an integer from 0 to 6, for example, an integer from 1 to 6, and z12 is an integer from 0 to 6, for example, an integer from 1 to 6),

^XH is represented by the following chemical formula:

^R8 is a hydrogen atom or a _C1-6 alkyl group.

The aforementioned C _1-6 alkylene group may be a straight chain or a branched chain, preferably a straight chain.

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

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

The above X and ^F are each independently a divalent organic group having 1 to 10 carbon atoms.

In one embodiment, X ^F is:

C _1-6 alkylene,

-(CH ₂ ) _z5 -O-(CH ₂ ) _z6 - (wherein z5 is an integer from 0 to 6, for example, an integer from 1 to 6, and z6 is an integer from 0 to 6, for example, an integer from 1 to 6), or

-(CH ₂ ) _z7 -phenylene-(CH ₂ ) _z8 - (wherein z7 is an integer from 0 to 6, for example, an integer from 1 to 6, and z8 is an integer from 0 to 6, for example, an integer from 1 to 6).

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. The left side of these groups is bonded to X ^E.

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

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

In other preferred embodiments, X ^F is -O-(CH ₂ ) _{z 6} -, more preferably -O-(CH ₂ ) _2-4 -.

The above R ⁵ 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, even more preferably a C _1-3 alkyl group, and particularly preferably a methyl group.

In one embodiment, R ⁵ is a hydrogen atom.

In one embodiment, R ⁵ is methyl.

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

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

In the above formula (1), 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. The _{C 1-6} alkyl group may be a straight chain or a branched chain.

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

In one embodiment, R ^c is methyl.

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

In one aspect, ^Rd is a single bond.

In other aspects, ^Rd is a divalent organic group.

The divalent organic group in R ^d is:

C _1-10 alkylene, preferably C _2-6 alkylene,

-(CH ₂ ) _z13 -O-(CH ₂ ) _z14 - (wherein z13 is an integer from 0 to 6, for example, an integer from 1 to 6, and z14 is an integer from 0 to 6, for example, an integer from 1 to 6),

-(CH ₂ ) _z15 -phenylene-(CH ₂ ) _z16 - (wherein z15 is an integer from 0 to 6, for example, an integer from 1 to 6, and z16 is an integer from 0 to 6, for example, an integer from 1 to 6), or

-(CH ₂ ) _{z 17} -NR ¹⁰ -(CH ₂ ) _{z 18} - (wherein R ¹⁰ is a hydrogen atom or a C _1-6 alkyl group, z 17 is an integer from 0 to 6, and z 18 is an integer from 0 to 6). 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. The left side of these groups is bonded to CO.

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, z17 is an integer from 0 to 6, and z18 is an integer from 0 to 6), and more preferably -NR ¹⁰ -(CH ₂ ) _z18 - (wherein R ¹⁰ is a hydrogen atom or a C _1-6 alkyl group, and z18 is an integer from 1 to 6).

The aforementioned C _1-10 alkylene group may be a straight chain or a branched chain, preferably a straight chain.

In the above formula (1), x is an integer greater than 1.

In one embodiment, X is preferably an integer greater than or equal to 1 and less than or equal to 100, more preferably an integer greater than or equal to 1 and less than or equal to 10, and even more preferably an integer greater than or equal to 1 and less than or equal to 5, for example, an integer greater than or equal to 2 and less than or equal to 10, and even more preferably an integer greater than or equal to 2 and less than or equal to 5.

The fluorinated polyether group-containing acrylic compound represented by formula (1) is not particularly limited and may have a number average molecular weight of 5×10 ² to 2×10 ⁵ . Within this range, from the perspective of wear durability, it is preferably 2×10 ³ to 1×10 ⁵ , and more preferably 3×10 ³ to 2×10 ⁴ . The "number average molecular weight" is a value measured by ¹⁹ F-NMR.

In one embodiment, the fluorinated polyether group-containing acrylic compound represented by formula (1) is a compound represented by the following formula,

R ²¹ OOC-R ^F2 -COOR ²¹

[In the formula, ^R21 is a hydrogen atom or a methyl group, and ^RF2 has the same meaning as described in formula (1)]

React with the compound represented by the following chemical formula,

NH ₂ -R ⁹ -(NH-R ⁹ ) _k -NH ₂

[Wherein, R ⁹ and k have the same meaning as described in formula (1)]

The compound represented by the following formula is obtained

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 described in relation to formula (1)].

Next, the obtained compound is reacted with the compound represented by the following formula:

NR ²³ _m H _2-m -R ²² -SiR ¹ _n' R ² _3-n'

[In the formula, 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' have the same meanings as described in relation to formula (1)]

The compound represented by the following formula is obtained:

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' .

Next, the obtained compound is reacted with the compound represented by the following formula:

R ³⁴ -R ³⁵ -OCOCH=CH ₂

[wherein, R ³⁴ is a reactive group such as -NCO, -COOH, etc.,

R ³⁵ is a divalent group]

In this way, the compound represented by formula (1) can be obtained.

In one embodiment, the fluorinated polyether group-containing acrylic compound represented by formula (1) is a compound represented by the following formula,

R ²¹ OOC-R ^F2 -COOR ²¹

[In the formula, ^R21 is a hydrogen atom or a methyl group, and ^RF2 has the same meaning as described in formula (1)]

React with the compound represented by the following chemical formula,

NH ₂ -R ⁹ -(CH(OH)-R ⁹ ) _k -NH ₂

[Wherein, R ⁹ and k have the same meaning as described in formula (1)]

The compound represented by the following formula is obtained

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 described in relation to formula (1)].

Next, the obtained compound is reacted with the compound represented by the following formula:

NR ²³ _m H _2-m -R ²² -SiR ¹ _n' R ² _3-n'

[In the formula, 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' have the same meanings as described in relation to formula (1)]

The compound represented by the following formula is obtained:

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' .

Next, the obtained compound is reacted with the compound represented by the following formula:

R ³⁴ -R ³⁵ -OCOCH=CH ₂

[wherein, R ³⁴ is a reactive group such as -NCO, -COOH, etc.,

R ³⁵ is a divalent group]

In this way, the compound represented by formula (1) can be obtained.

In one embodiment, the fluorinated polyether group-containing acrylic compound represented by the above formula (1) is a compound represented by the following formula,

R ²¹ OOC-R ^F2 -COOR ²¹

[In the formula, ^R21 is a hydrogen atom or a methyl group, and ^RF2 has the same meaning as described in formula (1)]

React with the compound represented by the following chemical formula,

NH ₂ -R ⁹ -(NH-R ⁹ ) _k -NH ₂

Wherein, R ⁹ and k have the same meaning as described in formula (1);

The compound represented by the following formula is obtained:

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 described in relation to formula (1)].

Next, the obtained compound is reacted with the compound represented by the following formula:

NH ₂ -R ^9' -NH ₂

[Wherein, R ^9′ has the same meaning as described for R ⁹ ]

The compound represented by the following formula is obtained:

R ²¹ OOC-(R ^F2 -CONH-R ⁹ -(NH-R ⁹ ) _k -NHCO) _x -(R ^F2 -CONH-R ^9' -NHCO) _x' -R ^F2 -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 in relation to formula (1), and R ^9′ has the same meanings as described in relation to R ⁹ ].

Next, the obtained compound is reacted with the compound represented by the following formula:

NR ²³ _m H _2-m -R ²² -SiR ¹ _n' R ² _3-n'

[In the formula, 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' have the same meanings as described in relation to formula (1)]

The compound represented by the following formula is obtained:

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' -R ^F2 -CONH-R ²² -SiR ¹ _n' R ² _3-n' .

Next, the obtained compound is reacted with the compound represented by the following formula:

R ³⁴ -R ³⁵ -OCOCH=CH ₂

[wherein, R ³⁴ is a reactive group such as -NCO, -COOH, etc.,

R ³⁵ is a divalent group]

In this way, the compound represented by formula (1) can be obtained.

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 disclosed herein is described.

The surface treatment agent disclosed herein contains an acrylic compound represented by formula (1) containing at least one fluoropolyether group.

In one embodiment, in the surface treatment agent disclosed herein, the fluorinated polyether group-containing acrylic compound is a compound represented by formula (1).

The content of the compound represented by formula (1) is preferably 0.1 to 50.0 mass%, more preferably 1.0 to 30.0 mass%, even more preferably 5.0 to 25.0 mass%, and particularly preferably 10.0 to 20.0 mass% relative to the entire surface treatment agent. By setting the content of the fluorinated polyether group-containing acrylic compound within the above range, higher water and oil repellency and wear durability can be obtained.

The surface treatment agent disclosed herein may contain: a solvent, a (non-reactive) fluoropolyether compound which can be understood as a fluorinated oil, preferably a perfluoro(poly)ether compound (hereinafter collectively referred to as "fluorinated oil"), a (non-reactive) polysilicone compound which can be understood as a polysilicone oil (hereinafter referred to as "polysilicone oil"), an alcohol, a catalyst, a surfactant, a polymerization inhibitor, a sensitizer, etc.

Examples of the above-mentioned 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, solvent acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxy butyrate, ethyl acetylacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, and methyl 2-hydroxyisobutyrate. , 2-hydroxyisobutyrate and other esters; acetone, butanone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylamine ketone, 2-heptanone and other ketones; ethyl solvent, methyl solvent, methyl solvent acetate, ethyl solvent acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, ethylene glycol monoalkane ethers; alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butanol, sec-butanol, 3-pentanol, octanol, 3-methyl-3-methoxybutanol, tert-pentanol; diols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; N,N-dimethylformamide, N, Amides such as N-dimethylacetamide; ether alcohols such as methyl solvent, cellulose solvent, isopropyl solvent, butyl solvent, and diethylene glycol monomethyl ether; diethylene glycol monoethyl ether acetate; fluorinated solvents such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, dimethyl sulfoxide, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), Zeorora H, HFE7100, _HFE7200 , _HFE7300 , _CF3CH2OH , _CF3CF2CH2OH , _and ( _CF3 ) _2CHOH . A mixture of two or more of these solvents may also be mentioned.

The fluorine-containing oil is not particularly limited, and examples thereof include compounds represented by the following general formula (3) (perfluoro(poly)ether compounds).

Rf ⁵ -(OC ₄ F ₈ ) _a' -(OC ₃ F ₆ ) _b' -(OC ₂ F ₄ ) _c' -(OCF ₂ ) _d' -Rf ⁶ ． ． ． (3)

In the formula, ^Rf5 represents a C1-16 alkyl group which may be substituted with one or more fluorine atoms (preferably a _C1-16 perfluoroalkyl group), ^Rf6 represents a C1-16 alkyl group which may be substituted with one or more fluorine atoms (preferably a _C1-16 perfluoroalkyl group), a fluorine atom or a hydrogen atom, and ^Rf5 and ^Rf6 are more preferably each independently a _C1-3 perfluoroalkyl group.

a', b', c', and d' each represent the number of four repeating units of perfluoro(poly)ether constituting the main backbone of the polymer and are independently integers of 0 to 300. The sum of a', b', c', and d' is at least 1, preferably 1 to 300, and more preferably 20 to 300. The order of the repeating units enclosed in parentheses and denoted by the subscripts a', b', c', or d' in the formula is arbitrary. _In these repeating units, -( _OC4F8 )- can be _any of -( _{OCF2CF2CF2CF2CF2} )-, -(OCF(CF3 _{) CF2CF2} )-, -( _OCF2CF ( _CF3 ) _CF2 )-, -( _OCF2CF2CF ( _{CF3 )} )-, - ₍ OC _{(CF3 ) 2CF2} )-, -( _OCF2C ( _{CF3 ) 2 )} -, -(OCF( _CF3 )CF(CF3))-, -(OCF( _{C2F5 ) CF2} )-, and ( _OCF2CF ( _{C2F5 )} )-, and is _preferably - _{( OCF2CF2CF2CF2CF2 )} - _. -(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 ))-, and is preferably -(OCF ₂ CF ₂ CF ₂ )-. -(OC ₂ F ₄ )- may be any of -(OCF ₂ CF ₂ )- and (OCF(CF ₃ ))-, and is preferably -(OCF ₂ CF ₂ )-.

Examples of the perfluoro(poly)ether compound represented by the general formula (3) include compounds represented by any one of the following general formulas (3a) and (3b) (which may be a mixture of one or more).

Rf ⁵ -(OCF ₂ CF ₂ CF ₂ ) _b" -Rf ⁶ ...(3a)

Rf ⁵ -(OCF ₂ CF ₂ CF ₂ CF ₂ ) _a” -(OCF ₂ CF ₂ CF ₂ ) _b” -(OCF ₂ CF ₂ ) _c” -(OCF ₂ ) _d” -Rf ⁶ ． ． ． (3b)

In this equation, ^Rf5 and ^Rf6 are as described above; in formula (3a), b" is an integer from 1 to 100; in formula (3b), a" and b" are each independently an integer from 0 to 30, and c" and d" are each independently an integer from 1 to 300. The order of the repetitive units enclosed in parentheses and denoted by the subscripts a", b", c", and d" is arbitrary in the formula.

Furthermore, from another perspective, the fluorinated oil may be a compound represented by the general formula Rf ³ -F (wherein Rf ³ is a C _5-16 perfluoroalkyl group). Furthermore, it may be a chlorotrifluoroethylene oligomer.

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

The surface treatment agent disclosed herein may contain fluorinated oil in an amount of, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass. In one embodiment, the surface treatment agent disclosed herein is substantially free of fluorinated oil. "Substantially free of fluorinated oil" means that it contains no fluorinated oil at all or may contain only a very small amount of fluorinated oil.

In one embodiment, the average molecular weight of the fluorinated oil can be set to be greater than the average molecular weight of the fluorinated polyether-containing acrylic compound. This average molecular weight allows for superior wear resistance and surface smoothness, particularly when the surface treatment layer is formed by vacuum deposition.

In one embodiment, the average molecular weight of the fluorinated oil can be set to be lower than the average molecular weight of the fluorinated polyether-containing acrylic compound. This average molecular weight can suppress the degradation of the transparency of the surface-treated layer obtained from the compound, and form a cured product with high abrasion durability and high surface smoothness.

Fluorine-containing oil is beneficial for improving the surface smoothness of the layer formed by the surface treatment agent disclosed herein.

The silicone oils mentioned above may be linear or cyclic silicone oils with a siloxane bond count of 2,000 or less. Straight silicone oils include so-called straight silicone oils and modified silicone oils. Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrosilicone oil. Examples of modified silicone oils include pure silicone oils modified with alkyl groups, arylalkyl groups, polyethers, higher fatty acid esters, fluoroalkyl groups, amino groups, epoxy groups, carboxyl groups, alcohols, and the like. Examples of cyclic silicone oils include cyclodimethylsiloxane oil.

In the surface treatment agent disclosed herein, the polysilicone oil may be contained in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, relative to a total of 100 parts by mass of the fluorinated polyether group-containing acrylic compound disclosed herein (the total amount when two or more types are present, and the same applies hereinafter).

Silicone oil is beneficial for improving the surface smoothness of the surface treatment layer.

The alcohols are, for _example , alcohols with 1 to 6 carbon atoms that may be substituted with one or more fluorine atoms, such as methanol, ethanol, isopropyl alcohol, tert- _butyl alcohol, _CF3CH2OH , _CF3CF2CH2OH , and ( _{CF3 ) 2CHOH} . Adding these alcohols to the surface treatment agent enhances the stability of the surface treatment agent and improves the compatibility of the perfluoropolyether-containing acrylic compound with the solvent.

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

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

The catalyst promotes the hydrolysis, dehydration condensation, or polymerization of the fluoropolyether-containing acrylic compound disclosed herein, thereby promoting the formation of the layer formed by the surface treatment agent disclosed herein.

In addition to the above, other ingredients include tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and methyltriacetoxysilane.

The surface treatment agent disclosed herein can be impregnated into a porous material (e.g., a porous ceramic material) or metal fibers (e.g., steel wool) fixed in a cotton-like state to form particles. These particles can be used, for example, in vacuum deposition.

In addition to the above-mentioned components, the surface treatment agent disclosed herein may also contain trace amounts of impurities such as Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, and silane condensates.

The following describes the items disclosed in this article.

The article disclosed herein comprises: a substrate, and a layer (surface treatment layer) formed on the surface of the substrate by the surface treatment agent disclosed herein.

The substrates that can be used in the present disclosure can be made of any suitable material, such as glass, resin (natural or synthetic resin, such as a common plastic material), metal, ceramic, semiconductor (silicon, germanium, etc.), fiber (woven, non-woven, etc.), fur, leather, wood, ceramic, stone, building components, and sanitary products.

For example, when the article to be manufactured is an optical component, the material constituting the surface of the substrate can be a material used for optical components, such as glass or transparent plastic. Furthermore, when the article to be manufactured is an optical component, a layer (or film), such as a hard coat or antireflection layer, can be formed on the surface (outermost layer) of the substrate. The antireflection layer can be either a single-layer antireflection layer or a multi-layer antireflection layer. Examples of inorganic materials that can be used in the antireflection layer include _SiO2 , SiO, ZrO2, _TiO2 , _TiO , _Ti2O3 , _Ti2O5 , Al2O3, _Ta2O5 , _Ta3O5 , _Nb2O5 , _HfO2 , _{Si3N4 , CeO2 , MgO} , _Y2O3 , _SnO2 , _MgF2 , _{and WO3} . These inorganic materials can be used alone or in combination ₍ e.g., _as a mixture). When a multi _{- layer} antireflection layer is formed, _SiO2 and/or _SiO are preferably used in the outermost layer. When the product is an optical glass component for a touch panel, a transparent electrode can be formed on a portion of the surface of the substrate (glass), using, for example, a thin film of indium tin oxide (ITO) or indium zinc oxide. Furthermore, depending on its specific specifications, the substrate can also have an insulating layer, an adhesive layer (pressure-sensitive layer), a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coat film layer, a polarizing film, a retardation film, and a liquid crystal display module.

The shape of the substrate is not particularly limited and may be, for example, a plate, film, or other forms. Furthermore, the surface area of the substrate on which the surface treatment agent layer is to be formed may be at least a portion of the substrate surface and can be appropriately determined based on the intended use and specific specifications of the manufactured article.

In one embodiment, at least a portion of the surface of the substrate may be made of a material that originally has a hydroxyl group. Examples of such materials include glass, and examples include metals (especially base metals), ceramics, semiconductors, etc., with natural oxide films or thermal oxide films formed on the surface. Alternatively, when a resin or the like has a hydroxyl group but not enough, or when it originally does not have a hydroxyl group, hydroxyl groups can be introduced or increased on the surface of the substrate by subjecting the substrate to a certain pretreatment. Examples of such pretreatments include plasma treatment (such as coma discharge) or ion beam irradiation. Plasma treatment can introduce or increase hydroxyl groups on the surface of the substrate, and is also suitable for use in purifying the surface of the substrate (removing impurities, etc.). Other examples of pretreatment include forming an interfacial adsorbent with carbon-carbon unsaturated bonds in the form of a monolayer on the substrate surface using the Langmuir-Blodgett method (LB) or chemical adsorption, and then cleaving the unsaturated bonds in an environment containing oxygen or nitrogen.

In other aspects, at least a surface portion of the substrate may be composed of a polysiloxane having one or more other reactive groups, such as Si-H groups, or a material containing an alkoxysilane.

In a preferred embodiment, the substrate is glass. The glass is preferably sapphire glass, sodium calcium glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystallized glass, or quartz glass. Particularly preferred are chemically strengthened sodium calcium glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass.

The article disclosed herein can be manufactured by forming a layer of the surface treatment agent disclosed herein on the surface of the substrate and, if necessary, performing post-treatment on the layer to form a layer from the surface treatment agent disclosed herein.

The surface treatment agent disclosed herein can be applied to the surface of a substrate by forming a layer of the surface treatment agent. The coating method is not particularly limited. For example, wet coating 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 evaporation (usually vacuum evaporation), sputtering, CVD, and similar methods. Specific examples of evaporation methods (usually vacuum evaporation) include resistance heating, electron beam, high-frequency heating using microwaves, ion beam, and similar methods. Specific examples of CVD methods include plasma CVD, optical CVD, thermal CVD, and similar methods.

Furthermore, coating can also be achieved using the atmospheric pressure plasma method.

When using the wet coating method, the surface treatment agent disclosed herein can be applied to the substrate surface after being diluted with a solvent. From the viewpoint of the stability of the composition of the present disclosure and the volatility of the solvent, the following solvents are suitable: perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (e.g., bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C ₆ F ₁₃ CH ₂ CH ₃ (e.g., Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., Zeorora (registered trademark) H manufactured by Zeon Japan Co., Ltd.); hydrofluoroethers (HFEs) (e.g., perfluoropropyl methyl ether (C ₃ F ₇ OCH ₃ ) (e.g., Sumitomo Alkyl perfluoroalkyl ethers (perfluoroalkyl groups and alkyl groups may be linear or branched) such as Novec (trademark) 7000 manufactured by 3M Co., Ltd.), perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Co., Ltd.), and perfluorohexyl methyl ether (C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ ) (e.g., Novec (trademark) 7300 manufactured by Sumitomo 3M Co., Ltd.), or CF ₃ CH ₂ OCF ₂ CHF ₂ (For example, Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.) etc. These solvents can be used alone or as a mixture of two or more. Among them, hydrofluoroethers are preferred, and perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and/or perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) are particularly preferred.

When using the dry coating method, the surface treatment agent disclosed herein can be used directly in the dry coating method, or diluted with the above-mentioned solvent before use in the dry coating method.

The surface treatment agent layer is preferably formed by coexisting the surface treatment agent disclosed herein with a catalyst for hydrolysis and dehydration condensation. Simply put, when using a wet coating method, the surface treatment agent disclosed herein is diluted with a solvent, and the catalyst can be added to the diluted surface treatment agent before applying it to the substrate surface. When using the dry coating method, the surface treatment agent of the present disclosure with a catalyst added thereto can be directly subjected to evaporation (usually vacuum evaporation), or the surface treatment agent of the present disclosure with a catalyst added thereto can be impregnated into a porous metal such as iron or copper to form a granular material, which is then used for evaporation (usually vacuum evaporation).

Any appropriate acid or base can be used as the catalyst. Examples of acid catalysts include acetic acid, formic acid, and trifluoroacetic acid. Examples of alkaline catalysts include ammonia and organic amines.

The surface treatment layer contained in the article disclosed herein has high wear resistance. Furthermore, depending on the composition of the surface treatment agent used, this surface treatment layer may also exhibit water repellency, oil repellency, anti-fouling properties (for example, preventing the adhesion of fingerprints and other contaminants), water repellency (preventing water from penetrating electronic components, etc.), surface smoothness (or lubricity, such as the ability to wipe away fingerprints and other contaminants or providing a pleasant touch to fingers), and chemical resistance, making it suitable for use as a functional film.

Therefore, the present disclosure further relates to an optical material having the above-mentioned surface treatment layer on the outermost layer.

In addition to optical materials related to displays exemplified below, various optical materials are preferably used, including cathode ray tubes (CRTs; e.g., computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, vacuum fluorescent displays (VFDs), field emission displays (FEDs), and other displays, or protective plates for such displays, or surfaces thereof treated with an anti-reflection film.

The articles disclosed herein are not particularly limited and may be optical components. Examples of optical components include: lenses for glasses, etc.; front screens, anti-reflective sheets, polarizing sheets, and anti-glare sheets for displays such as PDPs and LCDs; touch panels for devices such as mobile phones and portable information terminals; the disc surfaces of optical discs such as Blu-ray discs, DVD discs, CD-R discs, and MO discs; optical fibers; and the display surface of clocks.

Furthermore, the articles disclosed herein may be medical devices or medical materials. Furthermore, articles comprising the layers obtained by the present disclosure may be interior or exterior components of automobiles. Examples of exterior components include: windows, headlight housings, and mirror caps. Examples of interior components include: instrument panel covers, navigation system touch panels, and decorative interior components.

The thickness of the above layer is not particularly limited. In optical components, from the perspectives of optical performance, abrasion resistance, and antifouling properties, the thickness of the above layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, and more preferably 1 to 15 nm.

The above describes the articles disclosed herein in detail. However, the articles disclosed herein and their manufacturing methods are not limited to the examples above.

[Example]

The following examples illustrate the compounds disclosed herein, but the present disclosure is not limited to the following examples. In these examples, the order of the repeating units constituting the fluoropolyether is arbitrary, and the chemical formula shown below represents the average composition.

Synthesis example 1

10.0 g of a perfluoropolyether _- modified ester with _an average composition of _{CH₃OCOCF₂O} ( _{CF₂O ) ₁₂} ( _CF₂CF₂O ) _{₁₂CF₂COOCH₃} , 5.0 g of 1,3-bis(trifluoromethyl)benzene, and 0.20 g of diethylenetriamine were placed in a 100 mL three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer. The mixture was stirred at 25°C for ₁ hour under a nitrogen flow. Subsequently, 0.68 g of 3-aminopropyltrimethoxysilane was added, followed by stirring at 25°C for 1 hour. The volatiles were then distilled off under reduced pressure to obtain the perfluoropolyether-containing silane compound (A) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ NHCH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis example 2

10.0 g of the perfluoropolyether group-containing silane compound (A) obtained in Synthesis Example 1 and 0.27 g of 2-ethyl isocyanate acrylate (Karenz (registered trademark) AOI, manufactured by Showa Denko Co., Ltd.) were placed in a 100 mL three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer. The mixture was stirred at 25°C for 1 hour under a nitrogen flow to obtain the perfluoropolyether group-containing silane compound (B) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

-X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Synthesis example 3

10.0 g of the perfluoropolyether group-containing silane compound (A) obtained in Synthesis Example 1 and 0.46 g of 1,1-(diacryloyloxymethyl)ethyl isocyanate (Karenz (registered trademark) BEI, manufactured by Showa Denko Co., Ltd.) were placed in a 100 mL three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer. The mixture was stirred at 25°C for 1 hour under a nitrogen flow to obtain the perfluoropolyether group-containing silane compound (C) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

-X=-CONHC(CH ₃ )(CH ₂ OCOCH=CH ₂ ) ₂

Synthesis example 4

10.0 g of a perfluoropolyether _- modified ester with _an average composition of _{CH₃OCOCF₂O} ( _{CF₂O ) ₁₂} ( _CF₂CF₂O ) _{₁₂CF₂COOCH₃} , 5.0 g of 1,3-bis(trifluoromethyl)benzene, and 0.28 g of triethylenetetramine were placed in a 100 mL three-neck flask equipped with a reflux cooler, a thermometer, and a stirrer. The mixture was stirred at 25°C for ₁ hour under a nitrogen flow. Subsequently, 0.68 g of 3-aminopropyltrimethoxysilane was added, and the mixture was stirred at 25°C for 1 hour. The volatiles were then distilled off under reduced pressure to obtain the perfluoropolyether-containing silane compound (D) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis example 5

10.0 g of the perfluoropolyether group-containing silane compound (D) obtained in Synthesis Example 4 and 0.54 g of 2-ethyl isocyanate acrylate (Karenz (registered trademark) AOI, manufactured by Showa Denko Co., Ltd.) were placed in a 100 mL three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer. The mixture was stirred at 25°C for 1 hour under a nitrogen flow to obtain the perfluoropolyether group-containing silane compound (E) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ N(X)CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

-X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Synthesis example 6

10.0 g of a perfluoropolyether-modified ester represented by the average composition CH ₃ OCOCF(CF ₃ ){OCF ₂ CF(CF _{3 )} } _m OCF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} _n CF(CF 3 )COOCH ₃ (m+n ≒ 34), 5.0 g hexafluorobenzene, and 0.085 g diethylenetriamine were placed in a 100 mL three-neck flask equipped with a reflux cooler, thermometer, and stirrer. The mixture was stirred at 70°C for 13 hours under a nitrogen stream. Subsequently, 0.29 g of 3-aminopropyltrimethoxysilane was added, and the mixture was stirred at 70°C for 12 hours. The volatile matter is then distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (F) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF(CF ₃ ){OCF ₂ CF(CF ₃ )} _m OCF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} _n CF(CF ₃ )CONHCH ₂ CH ₂ NHCH ₂ CH ₂ NHCOCF(CF ₃ ){OCF ₂ CF(CF ₃ )} _m OCF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} _n CF(CF ₃ )CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis Example 7

10.0 g of the perfluoropolyether group-containing silane compound (F) obtained in Synthesis Example 6 and 0.12 g of 2-ethyl isocyanate acrylate (Karenz (registered trademark) AOI, manufactured by Showa Denko Co., Ltd.) were placed in a 100 mL three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer. The mixture was stirred at 25°C for 1 hour under a nitrogen flow to obtain the perfluoropolyether group-containing silane compound (G) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF(CF ₃ ){OCF ₂ CF(CF ₃ )} _m OCF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} _n CF(CF ₃ )CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ NHCOCF(CF ₃ ){OCF ₂ CF(CF ₃ )} _m OCF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} _n CF(CF ₃ )CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

-X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Synthesis example 8

10.0 g of the perfluoropolyether-containing silane compound (A) obtained in Synthesis Example 1 and 0.38 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE, manufactured by Mitsubishi Chemical Co., Ltd.) were placed in a 100 mL three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer. The mixture was stirred at 50°C for 3 hours under a nitrogen flow to obtain the perfluoropolyether-containing silane compound (H) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

-X is a mixture of ^-X1 and ^-X2 ( ^X1 : ^X2 = 80:20)

-X ¹ =-CH ₂ CH(OH)CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCOCH=CH ₂

-X ² =-CH(CH ₂ OH)CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCOCH=CH ₂

Synthesis example 9

10.0 g of a perfluoropolyether _- modified ester with an average composition of _{CH₃OCOCF₂O} ( _{CF₂O ) ₁₂} ( _CF₂CF₂O ) _{₁₂CF₂COOCH₃} , 5.0 g of 1,3-bis(trifluoromethyl)benzene, and 0.20 g of 1,3-diamino-2-propanol were placed in _a 100 mL three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer. The mixture was stirred at ₂₅ °C for 1 hour under a nitrogen flow. Subsequently, 0.68 g of 3-aminopropyltrimethoxysilane was added, and the mixture was stirred at 25°C for 1 hour. The volatiles were then distilled off under reduced pressure to obtain the perfluoropolyether-containing silane compound (I) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH(OH)CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis example 10

10.0 g of the perfluoropolyether group-containing silane compound (I) obtained in Synthesis Example 9, 0.27 g of 2-ethyl isocyanate acrylate (Karenz (registered trademark) AOI, manufactured by Showa Denko Co., Ltd.), and 0.012 g of dibutyltin dilaurate were placed in a 100 mL three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer. The mixture was stirred at 50°C for 2 hours under a nitrogen flow to obtain the perfluoropolyether group-containing silane compound (J) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH(OX)CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

-X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Synthesis example 11

10.0 g of a perfluoropolyether _- modified ester with _an average composition of _{CH₃OCOCF₂O} ( _{CF₂O ) ₁₂} ( _CF₂CF₂O ) _{₁₂CF₂COOCH₃} , 5.0 g of 1,3-bis(trifluoromethyl)benzene, and 0.20 g of diethylenetriamine were placed in a 100 mL three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer. The mixture was stirred at 25°C for ₁ hour under a nitrogen flow. Subsequently, 0.85 g of 3-(2-aminoethylamino)propyltrimethoxysilane was added, and the mixture was stirred at 25°C for 1 hour. The volatiles were then distilled off under reduced pressure to obtain the perfluoropolyether-containing silane compound (K) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ NHCH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis example 12

10.0 g of the perfluoropolyether group-containing silane compound (K) obtained in Synthesis Example 11 and 0.81 g of 2-ethyl isocyanate acrylate (Karenz (registered trademark) AOI, manufactured by Showa Denko Co., Ltd.) were placed in a 100 mL three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer. The mixture was stirred at 25°C for 2 hours under a nitrogen flow to obtain the perfluoropolyether group-containing silane compound (L) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ N(X)CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

-X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Synthesis example 13

10.0 g _of a perfluoropolyether-modified ester with _an average composition _{of CH₃OCOCF₂CF₂O} ( _CF₂CF₂O ) _{₁₆CF₂COOCH₃} , 5.0 g of 1,3-bis(trifluoromethyl)benzene, and 0.17 g of diethylenetriamine were placed in _a 100 mL _three -necked flask equipped with _a reflux cooler, a thermometer, and a stirrer. The mixture was stirred at 25°C for ₁ hour under a nitrogen flow. Subsequently, 0.60 g of 3-aminopropyltrimethoxysilane was added, and the mixture was stirred at 25°C for 1 hour. The volatiles were then distilled off under reduced pressure to obtain the perfluoropolyether-containing silane compound (M) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) ₁₆ CF ₂ CF ₂ CONHCH ₂ CH ₂ NHCH ₂ CH ₂ NHCOCF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) ₁₆ CF ₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis Example 14

10.0 g of the perfluoropolyether group-containing silane compound (M) obtained in Synthesis Example 13 and 0.24 g of 2-ethyl isocyanate acrylate (Karenz (registered trademark) AOI, manufactured by Showa Denko Co., Ltd.) were placed in a 100 mL three-necked flask equipped with a reflux cooler, a thermometer, and a stirrer. The mixture was stirred at 25°C for 1 hour under a nitrogen flow to obtain the perfluoropolyether group-containing silane compound (N) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) ₁₆ CF ₂ CF ₂ CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ NHCOCF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) ₁₆ CF ₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

-X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Example 1

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.

The prepared surface treatment agents were vacuum-evaporated onto chemically strengthened glass (Corning "Gorilla Glass," 0.7 mm thick). Vacuum evaporation conditions were: a 1,900 mm diameter chamber in a resistive heating evaporator, a vacuum level of 5.0E-05, a current of 240 A, a voltage of 10 V, and a substrate temperature of 40°C. The evaporated chemically strengthened glass was then allowed to stand at 150°C for 30 minutes and then allowed to cool to room temperature. The evaporated chemically strengthened glass was then irradiated with 365 nm UV light at an intensity of 1000 mJ/ ^cm² in an air atmosphere to form a surface treatment layer on the glass substrate.

Example 2

The surface treatment agent was prepared and the 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

The surface treatment agent was prepared and the 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

The surface treatment agent was prepared and the 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

The surface treatment agent was prepared and the 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

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

Example 7

The surface treatment agent was prepared and the 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

The surface treatment agent was prepared and the 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

The following compound (O) was dissolved in Novec 7200 (manufactured by 3M) to a concentration of 20 wt% to prepare a surface treatment agent.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

The prepared surface treatment agents were vacuum-deposited onto chemically strengthened glass (Corning "Gorilla" Glass, 0.7mm thick). Vacuum deposition conditions were: a 1,900mmφ chamber in a resistive heating evaporator, a vacuum level of 5.0E-05, a current of 240A, a voltage of 10V, and a substrate temperature of 40°C. The chemically strengthened glass was then placed at 150°C for 30 minutes and then allowed to cool to room temperature, forming a surface treatment layer on the glass substrate.

Comparative example 2

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

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) ₁₆ CF ₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Comparative example 3

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

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ NHCOCF ₂ O(CF ₂ CF ₂ O) ₁₂ (CF ₂ O) ₁₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Comparative example 4

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

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOCF(CF ₃ ){OCF ₂ CF(CF ₃ )} _m OCF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} _n CF(CF ₃ )CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

<evaluate>

The surface-treated glass substrate obtained above was subjected to water contact angle measurement and alkaline test evaluation using the following methods.

(Alkali leaching test)

A 1cm diameter PTFE O-ring was placed on the surface of the substrates treated in Examples 1 to 8 and Comparative Examples 1 to 4. An 8N NaOH solution (alkaline aqueous solution) was dripped into the O-ring to bring the treated surface into contact with the alkaline aqueous solution. The O-ring was then used in an alkaline immersion test. After 20 to 300 minutes of alkaline immersion, the alkaline aqueous solution was removed and the substrates were rinsed with pure water and ethanol. The contact angle relative to water was then measured. The static contact angle of water was determined by dropping 2 μL of pure water onto the surface of the glass substrate after the alkali immersion test. The contact angle relative to water was measured using a contact angle meter (Kyowa Interface Chemical Co., Ltd.: Automatic Contact Angle Meter DropMaster 701). The static contact angle of water after the alkali immersion test was measured at five locations. If the measured static contact angle of water decreased within 300 minutes, the alkali immersion test was terminated. The relationship between immersion time and the average contact angle at the five locations is shown in the table below.

[Table 1]

(Abrasion durability test)

A sample article with a surface treatment layer was placed horizontally. The following friction material was placed in contact with the surface of the surface treatment layer (the contact surface was a 1 cm diameter circle). A 5 N load was applied to the friction material. The friction material was then reciprocated at a speed of 40 mm/s while the load was applied. The friction material was reciprocated up to 4000 times. The static contact angle (°) with water was measured every 1000 reciprocating times (rubbing times). The test was terminated when the measured static contact angle with water fell below 60°. The static contact angle with water was measured in the same manner as in the alkaline test described above. The results are shown in the table below.

Friction parts

The surface of the silicone rubber product (1 cm in diameter) shown below is covered with cotton cloth soaked in artificial sweat of the composition shown below and used as a friction member.

Composition of artificial sweat:

Anhydrous disodium hydrogen phosphate: 2g

Sodium chloride: 20g

85% lactic acid: 2g

Histidine hydrochloride: 5g

Distilled water: 1 kg.

Silicone rubber processed products:

Process the Tigers Polymer silicone rubber plug SR-51 into a cylindrical shape with a diameter of 1 cm and a thickness of 1 cm.

[Table 2]

[Industrial Applicability]

The fluoropolyether-containing acrylic compound disclosed herein is suitable for forming surface treatment layers on various substrates, especially optical components requiring wear resistance and durability.

Claims (32)

A compound represented by the following formula (1): wherein R ^F2 is independently -Rf ² _p -R ^F -O _q -, Rf ² is a C _1-6 alkylene group which may be substituted with one or more fluorine atoms, R ^F is a divalent fluoropolyether group, p is 0 or 1, q is 0 or 1, ^Ra is independently an (m+2)-valent organic group, m is an integer from 1 to 4, R ^b is independently R ^Si , R ^Ac or R ^c , 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, R ¹ is independently a hydroxyl group or a hydrolyzable group, R ² is independently a hydrogen atom or a monovalent organic group, n' is an integer from 1 to 3, and R ^Ac is independently -X ^D -X ^E (-X ^F -OC(=O)-CR ⁵ =CH ₂ ) _m' , ^XD is a divalent organic group, ^XE is a single bond or a (m'+1)-valent group, ^XF each independently represents a divalent organic group having 1 to 10 carbon atoms, ^R5 is a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, m' is an integer from 1 to 10, ^Rc each independently represents a hydrogen atom or a _C1-6 alkyl group, ^Rd each independently represents a single bond or a divalent organic group, and x is an integer greater than 1. The compound of claim 1, wherein R ^F each independently represents a group represented by the following 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 R ^Fa each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom, a, b, c, d, e, and f each independently represents an integer from 0 to 200, the sum of a, b, c, d, e, and f is 1 or greater, and the order of presence of the repeating units labeled a, b, c, d, e, or f and enclosed in parentheses in the formula is arbitrary, provided that when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e, and f is 1 or greater. The compound as described in claim 2, wherein R ^Fa is a fluorine atom. The compound according to any one of claims 1 to 3, wherein ^RF is independently a group represented by 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 from 1 to 200, and e is an integer from 0 to 2, and the order of occurrence of the repeating units marked with the subscript d or e and enclosed in parentheses in the formula is arbitrary; -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2) wherein c and d are independently an integer from 0 to 30, and e and f are 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 the repeating units denoted by the subscript c, d, e, or f and enclosed in parentheses 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 a combination of two or three groups selected from these groups, R 9 is a single bond or a group selected from OCF 2 , OC 2 F ₄ , OC 3 F 6 , OC ₄ F 8 , OC ₅ F ₁₀ , and OC 6 F 12 , and g is an integer from 2 to 100; -(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 , and g is an integer from 2 to 100; ) _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 a combination of two or three groups independently selected from these 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 a combination of two or three groups independently selected from these groups, g is an integer from 2 to 100, g' is an integer from 2 to 100, R ^r is represented by the following chemical formula, In the formula, * represents the bond position; -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F 8 ) _c -(OC 3 F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f5) In the formula, e is an integer greater than or equal to 1 and less than or equal to 200, a, b, c, d, and f are each independently an integer greater than or equal to 0 and less than or equal to 200, _and the sum of a, b, c, d, _e , and f is at least 1. Furthermore, the order of the repeated units marked with a, b, c, d, e, or f and enclosed in parentheses in the formula is arbitrary; -(OC 6 F 12 ) a -(OC 5 F 10 ) b -(OC 4 F 8 ) c -(OC 3 F 6 ) d -(OC ₂ F ₄ ) _e -(OCF 2 ) _f - (f5 ₎ In the formula, e is an integer greater than or equal to 1 and less than or equal to 200, a, b, c, d, and f are each independently an integer greater than or equal to 0 and less than or equal to 200, _and the sum of _a , b, c, d, e, and _f is at least 1. Furthermore, the order of _the repeated units marked with a, b, c, _d , e, or _f and _enclosed in parentheses _{in the} formula _is arbitrary _{; 2} ) _f - (f6) wherein f is an integer greater than or equal to 1 and less than or equal to 200, a, b, c, d, and e are each independently an integer greater than or equal to 0 and less than or equal to 200, and the sum of a, b, c, d, e, and f is at least 1. Furthermore, the order of the repetitive units enclosed in parentheses and labeled a, b, c, d, e, or f in the formula is arbitrary. The compound as described in any one of claims 1 to 3, wherein ^Rf2 is independently _C1-6 perfluoroalkylene. The compound as described in any one of claims 1 to 3, wherein ^Ra is independently a group represented by the following formula: ^-R9- (Ra' ^{- R9} ) _k- wherein ^R9 is independently a _C1-6 alkylene group, Ra ^' is independently a trivalent organic group, and k is an integer from 1 to 4. The compound as described in claim 6, wherein Ra ^' is independently a trivalent organic group containing a N atom or an O atom. The compound as described in claim 6, wherein Ra ^' is independently a trivalent organic group that may contain an amine bond, an amide bond, a carbamate bond, a urea bond, an ether bond, or an ester bond between carbon atoms. The compound as described in claim 6, wherein Ra ^' is independently the following group, In the formula, R ⁸ is a hydrogen atom or a C _1-6 alkyl group. The compound as described in claim 6, wherein Ra ^' is N. The compound as described in claim 6, wherein k is 1. The compound as described in claim 6, wherein k is 2. The compound as described in any one of claims 1 to 3, wherein at least one R ^b is R ^Si . The compound as described in any one of claims 1 to 3, wherein one of the R ^{b groups} bonded to the N atom at each terminal is R ^Si , and the others are R ^c . The compound as described in any one of claims 1 to 3, wherein one of the R ^{b groups} bonded to the N atom at each terminal is R ^Si , and the others are R ^Ac . The compound as described in any one of claims 1 to 3, wherein X ^C is: C _1-6 alkylene, -(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 claims 1 to 3, wherein X ^C is a C _1-6 alkylene group. The compound as described in any one of claims 1 to 3, wherein n' is 2 or 3. The compound as described in any one of claims 1 to 3, wherein n' is 3. The compound of any one of claims 1 to 3, wherein X ^D is -O-, -CO-, -COO-, -OC(=O)-, -CONH-, -NHCO-, -OCONH-, -NHCOO-, -NH-CO-NH-, -CH ₂ CH(OH)CH ₂ -, or -CH(CH ₂ OH)CH ₂ -. The compound according to any one of claims 1 to 3, wherein X ^D is -CONH-, -CH ₂ CH(OH)CH ₂ -, or -CH(CH ₂ OH)CH ₂ -. The compound as described in any one of claims 1 to 3, wherein X ^D is -CONH-. The compound as described in any one of claims 1 to 3, wherein ^XE is a single bond. The compound of any one of claims 1 to 3, wherein ^XE is ^-XG - ^XH ; ^XG is: a single bond, _C1-6 alkylene, -( _CH2 ) _z9 -O-( _CH2 ) _z10- (wherein z9 is an integer from 0 to 6, and z10 is an integer from 0 to 6), or -( _CH2 ) _z11 -phenylene-( _CH2 ) _z12- (wherein z11 is an integer from 0 to 6, and z12 is an integer from 0 to 6); ^XH is represented by the following chemical formula, ; R ⁸ is a hydrogen atom or a C _1-6 alkyl group. The compound as described in any one of claims 1 to 3, wherein ^XF is: _C1-6 alkylene, -( _CH2 ) _z5 -O-( _CH2 ) _z6- (wherein z5 is an integer from 0 to 6, and z6 is an integer from 0 to 6), or -( _CH2 ) _z7 -phenylene-( _CH2 ) _z8- (wherein z7 is an integer from 0 to 6, and z8 is an integer from 0 to 6). The compound as described in any one of claims 1 to 3, wherein R ^c is independently a hydrogen atom or a C _1-6 alkyl group. The compound of any one of claims 1 to 3, wherein 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). The compound according to any one of claims 1 to 3, wherein x is an integer of 1 to 5. A surface treating agent comprises the compound according to any one of claims 1 to 12 and 14 to 28, wherein at least one of the R ^b groups bonded to the N atom at each terminal is R ^Si . The surface treatment agent as described in claim 29 further contains one or more other ingredients selected from fluorinated oil, silicone oil, and a catalyst. The surface treatment agent as described in claim 29 or 30, which is used as an antifouling coating agent or a waterproof coating agent. An article containing a surface treatment agent layer comprises a substrate and a layer formed on the surface of the substrate by the compound described in any one of claims 1 to 28 or the surface treatment agent described in any one of claims 29 to 31.