TWI882260B - Surface treatment agent - Google Patents

Abstract

The present invention provides a compound represented by the following formula (1) or (2) (In the formulae, each symbol has the same meaning as described in the specification).

R^F1-X^A-X^B R^Si _nR^Ac _m (1)

R^Ac _mR^Si _nX^B-X^A-R^F2-X^A-X^B R^Si _nR^Ac _m (2)

Description

Surface treatment agent

This disclosure is about novel acrylic compounds containing fluoropolyether groups, and surface treatment agents containing the compounds.

It is known that a certain silane compound containing a fluoropolyether group can provide excellent water repellency, oil repellency, antifouling properties, etc. when used for substrate surface treatment. The layer obtained by the surface treatment agent containing a silane compound containing a fluoropolyether group (hereinafter also referred to as the "surface treatment layer") is applied as a functional film to various substrates such as glass, plastic, fiber, sanitary products, and building materials (Patent Document 1).

[Prior Art Literature]

[Patent Literature]

Patent document 1: Japanese Patent Publication No. 2003-238577.

The silane compound containing a fluoropolyether group described in Patent Document 1 can provide a surface treatment layer with excellent functions, but the surface treatment layer is required to have higher durability.

The purpose of the present disclosure is to provide a compound containing a fluoropolyether group, which can provide a surface treatment layer with excellent durability.

This disclosure includes the following aspects.

[1] A compound represented by the following formula (1) or (2),

R ^F1 -X ^A -X ^B R ^Si _n R ^Ac _m (1)

R ^Ac _m R ^Si _n X ^B -X ^A -R ^F2 -X ^A -X ^B R ^Si _n R ^Ac _m (2)

[Where,

^RF1 is ^Rf1 - ^RF - _Oq- ,

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

^Rf1 is a _C1-16 alkyl group which may be substituted with one or more fluorine atoms,

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

R and ^F are independently divalent fluoropolyether groups,

p is 0 or 1,

q is independently 0 or 1,

X and ^A are each independently a single bond or a divalent organic group,

X and ^B are independently a group having a valence of (m+n+1) and a carbon number of 1 to 10 and not containing Si atoms,

R ^Si is independently -X ^C -SiR ¹ _n' R ² _3-n' at each occurrence,

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

^R1, at each occurrence, is independently a hydroxyl group or a hydrolyzable group,

^R2 is independently a hydrogen atom or a monovalent organic group at each occurrence,

n’ is an integer from 1 to 3,

R ^Ac is independently -X ^D -X ^E (-X ^F -OCO-CR ⁵ =CH ₂ ) _m' at each occurrence,

X ^D is a single bond or a divalent organic group,

^XE is a single bond or a (m'+1)-valent group,

X ^F, at each occurrence, is independently a single bond, or a divalent organic group having 1 to 10 carbon atoms,

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

m’ is an integer from 1 to 10,

n is an integer from 1 to 10 independently,

m is independently an integer from 1 to 10].

[2] The compound as described in [1] above, wherein ^RF, at each occurrence, is 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 is independently a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence,

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 greater than 1, and the order 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 greater than 1].

[3] The compound according to [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 , at each occurrence, 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 formula (f1), d is an integer from 1 to 200, and e is 0 or 1];

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

[In formula (f2), c and d are independently integers between 0 and 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 c, d, e or f and enclosed in brackets in the formula is arbitrary];

-(R ⁶ -R ⁷ ) _g -R ⁹ - (f3)

[In formula (f3), R ⁶ is OCF ₂ or OC ₂ F ₄ ;

^R7 is a group selected from _OC2F4 , _{OC3F6 , OC4F8} , _{OC5F10 and OC6F12 ,} or a combination of 2 or ₃ 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 ;

g is an integer from 2 to 100];

-(R ⁶ -R ⁷ ) _g -R ^r -(R ^7' -R ^6' ) _g' - (f4)

[In formula (f4), R ⁶ is OCF ₂ or OC ₂ F ₄ ,

^R7 is _a group selected from _OC2F4 , _{OC3F6 , OC4F8 , OC5F10 and OC6F12} , 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 2 or 3 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:

(where * 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 formula (f5), e is an integer greater than 1 and less than 200, a, b, c, d and f are each independently an integer greater than 0 and less than 200, the sum of a, b, c, d, e and f is at least 1, and 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 - (f6)

[In formula (f6), f is an integer between 1 and 200, a, b, c, d and e are each independently an integer between 0 and 200, the sum of a, b, c, d, e and f is at least 1, and the order of the repeated units marked with a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary].

[5] The compound as described in any one of [1] to [4] above, wherein ^Rf1 is independently _C1-16 perfluoroalkyl at each occurrence,

^Rf2 at each occurrence is independently _C1-6 perfluoroalkylene.

[6] The compound according to any one of [1] to [5] above, wherein X ^A is independently a single bond or a divalent organic group that does not contain an amine or ester bond.

[7] The compound as described in any one of [1] to [6] above, wherein X and ^A are each independently a single bond or a group represented by the following formula:

-(C _α R ¹¹ _2α ) _s1 -R ¹² _t1 -

[Where,

R ¹¹ is independently a hydrogen atom or a fluorine atom at each occurrence,

α is an integer from 1 to 10 independently at each occurrence.

R ¹² at each occurrence is independently -O-, -CO-, -NR ¹⁰ -, -CONR ¹⁰ -, -NR ¹⁰ CO-, -COO-, or -OCO-,

^R10 is a hydrogen atom or a _C1-6 alkyl group,

s1 is an integer from 0 to 3,

t1 is an integer between 0 and 3,

The sum of s1 and t1 is greater than 1,

The order of the repeated units in parentheses marked with s1 or t1 in the formula is arbitrary].

[8] The compound according to [7] above, wherein X ^A is -CONR ¹⁰ -C _α1 H _2α1 -, -(C _α2 H _2α2 )-O-(C _α3 H _2α3 )-, or -C _α4 H _2α4 -,

^R10 is a hydrogen atom or a _C1-6 alkyl group,

α1 is an integer from 1 to 10,

α2 is an integer between 0 and 6,

α3 is an integer between 0 and 6,

α4 is an integer between 0 and 6.

[9] The compound according to the above [8], wherein X ^A is -CONR ¹⁰ -C _α1 H _2α1 -.

[10] The compound according to any one of [1] to [9] above, wherein X ^B is a trivalent group, n is 1, and m is 1.

[11] The compound according to any one of [1] to [10] above, wherein ^XB is a compound represented by the following formula, wherein n is 1 and m is 1.

[wherein, R ⁸ is a hydrogen atom or a C _1-6 alkyl group].

[12] The compound as described in any one of [1] to [11] above, wherein X ^C is:

C _1-6 alkylene;

-(CH ₂ ) _z1 -O-(CH ₂ ) _z2 -

(In the formula, z1 is an integer from 0 to 6, and z2 is an integer from 0 to 6);

-(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 -

(where z3 is an integer between 0 and 6, and z4 is an integer between 0 and 6); or

-(CH ₂ ) _z13 -OCONH-(CH ₂ ) _z14 -

(In the formula, z13 is an integer from 0 to 6, and z14 is an integer from 0 to 6).

[13] The compound according to any one of [1] to [12] above, wherein X ^C is a C _1-6 alkylene group.

[14] A compound as described in any one of [1] to [13] above, wherein n' is 2 or 3.

[15] A compound as described in any one of [1] to [14] above, wherein n' is 3.

[16] The compound according to any one of [1] to [15] above, wherein X ^E is a single bond.

[17] The compound as described in any one of [1] to [15] above, wherein ^XE is ^-XG - ^XH ,

^XG is:

Single key;

C _1-6 alkylene;

-(CH ₂ ) _z9 -O-(CH ₂ ) _z10 -

(where z9 is an integer between 0 and 6, and z10 is an integer between 0 and 6); or

-(CH ₂ ) _z11 -phenylene-(CH ₂ ) _z12 -

(In the formula, z11 is an integer from 0 to 6, and z12 is an integer from 0 to 6),

^XH is as follows,

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

[18] The compound according to any one of [1] to [17] above, wherein X ^D is -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -OCONH-, -NHCOO-, -NH-CO-NH-, -CH ₂ CH(OH)CH ₂ -, -CH(CH ₂ OH)CH ₂ -,

[Wherein, * and ** represent bonding positions, * is bonded to X ^B , ** is bonded to X ^E ].

[19] The compound as described in any one of [1] to [18] above, wherein X ^F is: a single bond,

C _1-6 alkylene,

-(CH ₂ ) _z5 -O-(CH ₂ ) _z6 -

(where z5 is an integer between 0 and 6, and z6 is an integer between 0 and 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).

[20] The compound as described in any one of [1] to [19] above, wherein R ⁵ is a hydrogen atom or a methyl group.

[21] A surface treatment agent comprising a compound described in any one of [1] to [20] above.

[22] The surface treatment agent as described in [21] above further contains one or more other components selected from fluorinated oil, silicone oil, and catalyst.

[23] The surface treatment agent as described in [21] or [22] above, which is used as an antifouling coating agent or a water-repellent coating agent.

[24]An article comprising:

Base material, and

A layer formed on the surface of the substrate by using the compound described in any one of [1] to [19] above or the surface treatment agent described in any one of [21] to [23] above.

According to the present disclosure, an acrylic compound containing a fluoropolyether group can be provided, which can provide a surface treatment layer with excellent durability.

The term "monovalent organic group" used in this specification refers to a monovalent group containing carbon. The monovalent organic group is not particularly limited and may be a alkyl group or its derivative. A derivative of a alkyl group refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the alkyl group or in the molecular chain. Furthermore, when it is expressed as "organic group", it refers to a monovalent organic group. In addition, "divalent organic group" refers to a divalent group containing carbon. The divalent organic group is not particularly limited and may be a divalent group in which one hydrogen atom is further removed from the organic group.

The term "alkyl" used in this specification refers to a group containing carbon and hydrogen, which is a group formed by removing one hydrogen atom from a alkyl. The alkyl group is not particularly limited, and examples thereof include C _1-20 alkyl groups that may be substituted with one or more substituents, such as aliphatic alkyl groups and aromatic alkyl groups. The above-mentioned "aliphatic alkyl group" may be any of a straight chain, a branched chain, or a ring, and may be any of saturated or unsaturated. In addition, the alkyl group may contain one or more ring structures.

As used herein, the substituent of the "alkyl group" is not particularly limited, and examples thereof include one or more groups selected from a halogen atom, a _C1-6 alkyl group which may be substituted with one or more halogen atoms, a _C2-6 alkenyl group, a _C2-6 alkynyl group, a _C3-10 cycloalkyl group, a _C3-10 unsaturated cycloalkyl group, a 5- to 10-membered heterocyclic group, a 5- to 10-membered unsaturated heterocyclic group, a _C6-10 aryl group, and a 5- to 10-membered heteroaryl group.

In the present specification, "hydrolyzable group" refers to a group that can undergo hydrolysis, that is, a group that can be separated from the main skeleton of the compound by hydrolysis. Examples of hydrolyzable groups include ^-ORh , ^-OCORh , _-ON = ^CRh2 , _-NRh2 , ^-NHRh , ^-NCO , halogen (in the formula, ^Rh represents a substituted or unsubstituted _C1-4 alkyl group), etc.

The acrylic compound containing a fluoropolyether group disclosed herein is an acrylic compound containing a fluoropolyether group represented by the following formula (1) or (2).

R ^F1 -X ^A -X ^B R ^Si _n R ^Ac _m (1)

R ^Ac _m R ^Si _n X ^B -X ^A -R ^F2 -X ^A -X ^B R ^Si _n R ^Ac _m (2)

[Where,

^RF1 is ^Rf1 - ^RF - _Oq- ,

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

^Rf1 is a _C1-16 alkyl group which may be substituted with one or more fluorine atoms,

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

R and ^F are independently divalent fluoropolyether groups,

p is 0 or 1,

q is independently 0 or 1,

X and ^A are each independently a single bond or a divalent organic group,

X and ^B are independently a group having a valence of (m+n+1) and a carbon number of 1 to 10 and not containing Si atoms,

R ^Si is independently -X ^C -SiR ¹ _n' R ² _3-n ' at each occurrence,

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

^R1, at each occurrence, is independently a hydroxyl group or a hydrolyzable group,

^R2 is independently a hydrogen atom or a monovalent organic group at each occurrence,

n’ is an integer from 1 to 3,

R ^Ac is independently -X ^D -X ^E (-X ^F -OCO-CR ⁵ =CH ₂ ) _m' at each occurrence,

X ^D is a single bond or a divalent organic group,

^XE is a single bond or a (m'+1)-valent group,

X ^F is independently a single bond or an organic group at each occurrence.

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

m’ is an integer from 1 to 10,

n is an integer from 1 to 10 independently,

m is independently an integer from 1 to 10].

In the above formula (1), ^RF1 is ^Rf1 - ^RF - _Oq- .

In the above formula (2), ^RF2 is ^-Rf2p _- ^RF - _Oq- .

In the above formula, ^Rf1 is a _C1-16 alkyl group which may be substituted with one or more fluorine atoms.

The "C _1-16 alkyl" in the above C _1-16 alkyl group which may be substituted with one or more fluorine atoms may be a straight chain or a branched chain, preferably a straight chain or a branched chain C _1-6 alkyl group, especially a C _1-3 alkyl group; more preferably a straight chain C _1-6 alkyl group, especially a C _1-3 alkyl group.

The above ^Rf1 is preferably a _C1-16 alkyl group substituted with one or more fluorine atoms, more preferably _{a CF2HC1-15perfluoroalkylene} group, and even more preferably a _{C1-16perfluoroalkyl} group.

The C _1-16 perfluoroalkyl group may be a linear or branched chain, preferably a linear or branched C _1-6 perfluoroalkyl group, especially a C _1-3 perfluoroalkyl group, more preferably a linear C _1-6 perfluoroalkyl group, especially a C _1-3 perfluoroalkyl group, specifically -CF ₃ , -CF ₂ CF ₃ or -CF ₂ CF ₂ CF ₃ .

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

The above ^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 chain 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 other embodiments, p is 1.

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

In the above formulae (1) and (2), ^RF is independently a divalent fluoropolyether group at each occurrence.

^RF may preferably contain the groups shown below.

-(OC _h1 R ^Fa _2h1 ) _h3 -(OC _h2 R ^Fa _2h2-2 ) _h4 -

[Where,

R ^Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence,

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 more, preferably 2 or more, and more preferably 5 or more, and the order of existence of the repeated units marked with h3 and h4 and enclosed in parentheses in the formula is arbitrary].

In one embodiment, ^RF may be a straight 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 -

[Where,

R ^Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence,

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 more. The order of the repeating units marked with a, b, c, d, e or f and enclosed in parentheses 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 more].

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.

a, b, c, d, e and f are preferably integers between 0 and 100 independently.

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.

The repeating units may be in the form of a linear chain _or a branched chain, and may also include a ring structure. _For example, - _{( OC6F12} )- _may be -( _{OCF2CF2CF2CF2CF2CF2CF2CF2} )-, -(OCF _{( CF3 ) CF2CF2CF2CF2CF2} )-, -( _OCF2CF ( _{CF3 )} CF2CF2CF2CF2)-, - _{( OCF2CF2CF} ( _CF3 ) _{CF2CF2CF2 )} -, -( _OCF2CF2CF ( _CF3 )CF2CF2CF2)-, -(OCF2CF2CF2CF( _CF3 ) _CF2CF2 )-, -( _{OCF2CF2CF2CF2CF} (CF3) _CF2 )-, - _{( OCF2CF2CF2CF2CF} ( _CF3 ) _CF2 )-, -( _{OCF2CF2CF2CF2CF ( CF3} ) _CF2 )-, _and the like. -(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 ))-. _- ( _OC3F6 )- (that _is , ^RFa in the above formula is a fluorine atom) may be any of -( _OCF2CF2CF2 )-, -(OCF( _CF3 ) _CF2 )-, and -( _OCF2CF ( _{CF3 )} )-. - _{( OC2F4} )- may be any of - _{( OCF2CF2} )- and -(OCF( _CF3 ))-.

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

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

[Where * represents the bond position].

The above 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 is preferably the following unit.

[Where * represents the bond position]

In one embodiment, the above-mentioned repeating units are in a straight chain shape. By making the above-mentioned repeating units in a straight chain shape, the surface smoothness and wear resistance of the surface treatment layer can be improved.

In one embodiment, the above-mentioned repeating unit is in a chain-like shape. By making the above-mentioned repeating unit in a chain-like shape, the dynamic friction coefficient of the surface treatment layer can be increased.

In one embodiment, ^RF is independently represented at each occurrence by any one of the following formulae (f1) to (f6).

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

[In formula (f1), d is an integer from 1 to 200, e is 0 or 1, preferably 1];

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

[In formula (f2), c and d are independently integers greater than 0 and less than 30, and e and f are independently integers greater than 1 and less than 200,

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

The order of the repeated units marked with c, d, e or f and enclosed in brackets in the formula is arbitrary];

-(R ⁶ -R ⁷ ) _g -R ⁹ - (f3)

[In formula (f3), R ⁶ is OCF ₂ or OC ₂ F ₄ ,

^R7 is _a group selected from _OC2F4 , _{OC3F6 , OC4F8 , OC5F10 and OC6F12} , or a combination of 2 or ₃ groups independently 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 ,

g is an integer from 2 to 100];

-(R ⁶ -R ⁷ ) _g -R ^r -(R ^7' -R ^6' ) _g' - (f4)

[In formula (f4), R ⁶ is OCF ₂ or OC ₂ F ₄ ,

^R7 is _a group selected from _OC2F4 , _{OC3F6 , OC4F8 , OC5F10 and OC6F12} , 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 2 or 3 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

(where * 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 formula (f5), e is an integer greater than 1 and less than 200, a, b, c, d and f are each independently an integer greater than 0 and less than 200, and 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 - (f6)

[In formula (f6), f is an integer greater than 1 and less than 200, a, b, c, d, and e are each independently an integer greater than 0 and less than 200, and the order of the repeated units marked with a, b, c, d, e, or f and enclosed in parentheses in the formula 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 other embodiments, e is 0. (OC ₃ F ₆ ) in the above formula (f1) is preferably a group represented by (OCF ₂ CF ₂ CF ₂ ), (OCF ₂ CF(CF ₃ )) or (OCF(CF ₃ )CF ₂ ), and more preferably a group represented by -(OCF ₂ CF ₂ CF ₂ ) _d -. (OC ₂ F ₄ ) in the above formula (f1) is preferably a group represented by (OCF ₂ CF ₂ ) or (OCF(CF ₃ )), and more preferably a group represented by (OCF ₂ CF ₂ ).

In the above formula (f2), e and f are independently and preferably an integer of 5 to 200, more preferably 10 to 200. Furthermore, the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably a group represented by -(OCF ₂ CF ₂ CF ₂ CF ₂ ) _c -(OCF ₂ CF ₂ CF ₂ ) _d -(OCF ₂ CF ₂ ) _e -(OCF ₂ ) _f -. In other embodiments, the formula (f2) is a group represented by -(OC ₂ F ₄ ) _e -(OCF ₂ ) _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, and _more preferably a group selected _{from OC3F6} and _{OC4F8 . The combination of two or three radicals independently selected from OC2F4 , OC3F6 and OC4F8 is not particularly limited , and examples thereof include -OC2F4OC3F6- , -OC2F4OC4F8- , -OC3F6OC2F4- , -OC3F6OC3F6- , -OC3F6OC4F8- , -OC4F8OC4F8- , -OC4F8OC3F6- , -OC4F8OC2F4- , -OC2F4OC2F4OC3F6- , -OC2F4OC2F4OC4F8- , -OC2F4OC3F6OC2F4- . ​ ​ ​ ​ ​ ​ ​ ​ ​ ​} In one embodiment, R 9 is a single bond. _{In another} embodiment, R 9 _is a group selected _from OCF ₂ , OC _{2 F 4} , OC _{3 F 6} OC ₃ F _{6 -} , -OC ₂ F ₄ OC ₄ F 8 OC 2 F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₂ F ₄ -, -OC ₃ F 6 OC _{2 F 4} OC ₃ F ₆ -, -OC ₃ F ₆ OC 3 F ₆ OC ₂ F 4 -, and -OC 4 F ₈ OC ₂ F 4 OC 2 F ₄ -. In one embodiment, R ⁹ is a single bond. In another embodiment, R ⁹ 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. In the above formula (f3), g is preferably an integer of 3 or more, and more preferably an integer of 5 or more. The g is preferably an integer of 50 or less. In the formula (f3), _OC2F4 , _{OC3F6 , OC4F8 , OC5F10 and OC6F12} are either 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 the above formula (f4), R ⁶ , R ⁷ and g are synonymous with those described in the above formula ( ^f3 ) and have the same aspects. R ^6' , R ^{7 '} and g' are synonymous with those described in the above formula (f3) and have the same aspects. ^{R r} is preferably:

[Where * represents the bonding position],

Better:

[Where * represents the bond position].

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

In the above formula (f6), f is preferably an integer greater than 1 and less than 100, and more preferably an integer greater than 5 and less than 100. The sum of a, b, c, d, e and f is preferably greater than 5, and more preferably greater than 10, for example, greater than 10 and less than 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 "e/f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, still more preferably 0.2 to 1.5, and still more preferably 0.2 to 0.85. By making the e/f ratio less than 10, the smoothness, wear resistance and chemical resistance (for example, durability to artificial sweat) of the surface treatment layer obtained from the compound will be further improved. The smaller the e/f ratio, the further the smoothness and wear resistance of the surface treatment layer will be improved. On the other hand, by making the e/f ratio greater than 0.1, the stability of the compound can be further improved. The larger the e/f ratio, the more the stability of the compound is improved.

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

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

The number average molecular weight of ^RF1 and ^RF2 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 ^RF1 and ^RF2 is a value measured by ¹⁹ F-NMR.

In the above formulae (1) and (2), X and ^A are each independently a single bond or a divalent organic group.

In one embodiment, X and ^A are independently a single bond or a divalent organic group that does not contain an amine or ester bond.

In a preferred embodiment, X ^{and A} are independently a single bond or a group represented by the following formula:

-(C _α R ¹¹ _2α ) _s1 -R ¹² _t1 -

[Where,

R ¹¹ is independently a hydrogen atom or a fluorine atom at each occurrence,

α is an integer from 1 to 10 independently at each occurrence.

^R12 at each occurrence is independently -O-, -CO-, -CONH-, -NHCO-, -COO-, or -OCO-,

s1 is an integer from 0 to 3,

t1 is an integer between 0 and 3,

The sum of s1 and t1 is greater than 1,

The order of the repeated units marked with s1 or t1 and enclosed in parentheses in the formula is arbitrary]

In the formula, the left side is bonded to R ^F1 or R ^F2 .

In one embodiment, ^XA is a single key.

In one embodiment, ^XA is independently -(C _α R ¹¹ _2α ) _s1 -R ¹² _t1 - as described above.

The above R ¹¹ is preferably a hydrogen atom.

The above α is independent each time it appears, and is preferably an integer from 1 to 6, more preferably an integer from 1 to 4, and even more preferably an integer from 2 to 4.

The above R ¹² is independently each time present and is preferably -O-, -CO-, -NR ¹⁰ -, -CONH-, or -COO-, more preferably -CONH-.

The above R ¹⁰ is a hydrogen atom or a C _1-6 alkyl group, preferably a hydrogen atom.

The above s1 is preferably 1 or 2, and more preferably 1.

The above t1 is preferably an integer between 0 and 2, more preferably 1 or 2, and even more preferably 1.

Among the better samples,

R ¹¹ is a hydrogen atom,

α is an integer between 2 and 4,

R ¹² is -O-, -CO-, -NR ¹⁰ -, -CONH-, or -COO-,

^R10 is a hydrogen atom or a _C1-6 alkyl group,

s1 is 1 or 2,

t1 is 0 or 1.

In a more preferred embodiment, X ^A is -CONR ¹⁰ -C _α1 H _2α1 -, -(C _α2 H _2α2 )-O-(C _α3 H _2α3 )-, or -C _α4 H _2α4 -, and is more preferably -CONR ¹⁰ -C _α1 H _2α1 -. In this group, the left side is bonded to ^RF1 or ^RF2 .

α1 is an integer from 1 to 10. α2 is an integer from 0 to 6, for example, an integer from 1 to 6. α3 is an integer from 0 to 6, for example, an integer from 1 to 6. α4 is an integer from 0 to 6, for example, an integer from 1 to 6.

^XA is preferably -CONH-C _α1 H _2α1 -. In this group, the left side is bonded to ^RF1 or ^RF2 .

The above-mentioned C _α1 H _2α1 is preferably (CH ₂ ) _α1 .

The above-mentioned C _α2 H _2α2 is preferably (CH ₂ ) _α2 .

The above-mentioned C _α3 H _2α3 is preferably (CH ₂ ) _α3 .

The above-mentioned C _α4 H _2α4 is preferably (CH ₂ ) _α4 .

In the above formulae (1) and (2), X and ^B are each independently a group having 1 to 10 carbon atoms and having a valence of (n+n+1) and not containing Si atoms.

In one embodiment, the above ^XB is a 4-valent group, preferably a group represented by the following formula:

In one embodiment, the above-mentioned -C(-O-)= is O-bonded to R ^Si . In another embodiment, the above-mentioned -C(-O-)= is O-bonded to R ^Ac .

In one embodiment, the above ^XB is a trivalent group, preferably a group represented by the following formula:

[In the formula, R ⁸ may be a hydrogen atom or a C _1-6 alkyl group (preferably a methyl group or an ethyl group, more preferably a methyl group)]. In one embodiment, the above-mentioned -CR ⁸ (-O-)- is O-bonded to R ^Si . In another embodiment, -CR ⁸ (-O-)- is O-bonded to R ^Ac .

In a preferred embodiment, X ^B is N. In this case, m is 1 and n is 1.

In the above formulas (1) and (2), m is an integer from 1 to 10 independently, and n is an integer from 1 to 10 independently.

m is preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and particularly preferably 1.

n is preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and particularly preferably 1.

In the optimal case, m is 1 and n is 1.

In the above formulae (1) and (2), R ^Si is independently -X ^C -SiR ¹ _n' R ² _3-n' at each occurrence.

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

In one embodiment, X ^C is:

C _1-6 alkylene,

-(CH ₂ ) _z1 -O-(CH ₂ ) _z2 -

(where 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),

-(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 -

(where z3 is an integer from 0 to 6, such as an integer from 1 to 6, and z4 is an integer from 0 to 6, such as an integer from 1 to 6), or

-(CH ₂ ) _z13 -OCONH-(CH ₂ ) _z14 -

(In the formula, z13 is an integer from 0 to 6, and z14 is an integer from 0 to 6).

These groups may be substituted by one or more substituents selected from fluorine atoms, C _1-6 alkyl groups, C _2-6 alkenyl groups and C _2-6 alkynyl groups, but are preferably unsubstituted. In these groups, the left side is bonded to X ^B .

The 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 ^R1, at each occurrence, is independently a hydroxyl group or a hydrolyzable group.

Preferably, ^R1 is independently a hydrolyzable group at each occurrence.

R ¹ is preferably independently -OR ^h , -OCOR ^h , -ON=CR ^h ₂ , -NR ^h ₂ , -NHR ^h , -NCO, or halogen (in the formula, R ^h represents a substituted or unsubstituted C _1-4 alkyl group), more preferably -OR ^h (i.e., alkoxy). ^{R h} can be exemplified by: unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; substituted alkyl groups such as chloromethyl, etc. Among them, alkyl groups are preferred, unsubstituted alkyl groups are particularly preferred, and methyl or ethyl groups are more preferred. In one embodiment, R ^h is methyl, and in other embodiments, R ^h is ethyl.

The above ^R2 is independently a hydrogen atom or a monovalent organic group at each occurrence. The monovalent organic group is a monovalent organic group other than the above hydrolyzable group.

In ^R2 , the monovalent organic group is preferably a _C1-20 alkyl group, more preferably a _C1-6 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 of 1 to 3, preferably 2 or 3, and more preferably 3.

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

The above X ^D is a single bond or 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- , and more preferably -CONH-, _-CH2CH (OH) _CH2- , -CH( _CH2OH ) _CH2- ,

[Wherein, * and ** represent bonding positions, * is bonded to X ^B , ** is bonded to X ^E ].

In these bases, the left side is bonded to X ^B .

^XD is more preferably -CONH-.

The above-mentioned ^XE is a single bond or a (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 the following formula:

-X ^G -X ^H

[Where,

^XG is:

Single key,

C _1-6 alkylene,

-(CH ₂ ) _z9 -O-(CH ₂ ) _z10 -

(where z9 is an integer from 0 to 6, such as an integer from 1 to 6, and z10 is an integer from 0 to 6, such as 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 as follows,

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

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

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

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

Each occurrence of X ^F is independently a single bond or a divalent organic group (preferably a divalent organic group having 1 to 10 carbon atoms).

In one embodiment, X ^F is:

Single key,

C _1-6 alkylene,

-(CH ₂ ) _z5 -O-(CH ₂ ) _z6 -

(where z5 is an integer from 0 to 6, such as an integer from 1 to 6, and z6 is an integer from 0 to 6, such as an integer from 1 to 6), or

-(CH ₂ ) _z7 -phenylene-(CH ₂ ) _z8 -

(In the formula, 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 by one or more substituents selected from fluorine atoms, C _1-6 alkyl groups, C _2-6 alkenyl groups and C _2-6 alkynyl groups, but are preferably unsubstituted. In these groups, the left side is bonded to X ^B .

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

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

In one embodiment, ^XD , ^XE and ^XF are single keys.

The above R ⁵ is a hydrogen atom, a halogen 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, still 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.

The fluoropolyether group-containing acrylic compound represented by the above formula (1) or formula (2) is not particularly limited, but may have a number average molecular weight of 5×10 ² to 1×10 ^5. From the viewpoint of wear resistance, it is preferably 2,000 to 32,000, and more preferably 2,500 to 12,000. The "number average molecular weight" is a value measured by ¹⁹ F-NMR.

In one embodiment, the fluoropolyether group-containing acrylic compound disclosed herein is a fluoropolyether group-containing acrylic compound represented by formula (1).

In one embodiment, the fluoropolyether group-containing acrylic compound disclosed herein is a fluoropolyether group-containing acrylic compound represented by formula (2).

The acrylic compound containing a fluoropolyether group represented by the above formula (1) and (2) can be obtained by first preparing a silane compound containing a fluoropolyether group having a reactive site such as -NH-, -C(OH)-, and then reacting a compound having an acryl group at the reactive site.

In one embodiment, the acrylic compound containing a fluoropolyether group represented by the above formula (1) and (2) can be obtained by the following method:

A compound represented by R ^F1 -COOR ²¹ , R ²¹ OOC-R ^F2 -COOR ²¹

[wherein, ^R21 is a hydrogen atom or a methyl group, and R ^F1 and R ^F2 have the same meanings as those described in formulas (1) and (2)]

The compound represented by R ²⁴ -R ²³ -NH-R ²² -SiR ¹ _n' R ² _3-n'

[In the formula, R ²² is a divalent group, R ²³ is a divalent group, R ²⁴ is a reactive group such as NH ₂ , and R ¹ , R ² and n' have the same meanings as those described in formulas (1) and (2)]

Reaction to obtain compounds represented by ^RF1 - ^R25 - ^R23 -NH- ^R22 -SiR1n'R23- ⁿ _' , ^R23 _{- n'R1n'Si} - ^R22 -HN- ^R23 - ^R25 - ^{RF2 -R25 - R23} -NH _- ^{R22 - SiR1n'R23 -} _{n' ;}

Next, the above compound is mixed with

The compound represented by R ³⁴ -R ³⁵ -OCOCH=CH ₂

(wherein R ³⁴ is a reactive group such as -NCO, -COOH, -COOCl, etc., and R ³⁵ is a divalent group), or

The compound represented by R ⁵⁶ -OCOCR ⁵⁷ =CH ₂

(wherein, R ⁵⁶ is a halogen, H, or a monovalent alkyl group, and R ⁵⁷ is a hydrogen atom or a C _1-3 alkyl group)

Reaction, obtained thereby.

In one embodiment, the acrylic compound containing a fluoropolyether group represented by the above formula (1) and (2) can be obtained by the following method:

Compounds represented by R ^F1 -COF and FOC-R ^F2 -COF

(In the formula, R ^F1 and R ^F2 have the same meaning as in formula (1) and (2))

Reaction with Br-Mg-CH ₂ CH=CH ₂ to obtain the compound represented by ^RF1 -C(OH)(CH ₂ CH=CH ₂ ) ₂ , (CH ₂ =CHCH ₂ ) ₂ (HO)CR ^F2 -C(OH)(CH ₂ CH=CH ₂ ) ₂ ;

Next, the above compound is reacted with HSiR ¹ _n' R ² _3-n' to obtain a compound represented by ^RF1 -C(OH)(CH ₂ CH=CH ₂ ) ₂ , (R ² _3-n' R ¹ _n' Si-CH ₂ CH ₂ CH ₂ ) ₂ (HO)CR ^F2 -C(OH)(CH ₂ CH ₂ CH ₂ -SiR ¹ _n' R ² _3-n' ) ₂ ;

Next, the above compound is reacted with R ³⁴ -R ³⁵ -OCOCH=CH ₂

(wherein, R ³⁴ is a reactive group such as -NCO, -COOH, etc., and R ³⁵ is a divalent group)

The compound shown is obtained by the reaction.

In one embodiment, the acrylic compound containing a fluoropolyether group represented by the above formula (A1) and (A2) can be obtained by the following method:

反應，而獲得下式化合物， A compound represented by HOCH ₂ ^-RF2 -CH ₂ OH (wherein ^RF1 and ^RF2 have the same meanings as those in formulas (A1) and (A2)) and

Reaction to obtain the following compound:

Next, the above compound is reacted with OCN-(CH ₂ ) ₃ -SiR ¹ _n' R ² _3-n' (wherein each symbol has the same meaning as above) to obtain a compound represented by the following formula:

(In the formula, each symbol has the same meaning as above).

In one embodiment, the acrylic compound containing a fluoropolyether group represented by the above formula (A1) and (A2) can be obtained by the following method:

(式中，各記號與上述同義)所示之化合物與HOOC=CH₂反應，而獲得下式所示之化合物， make

The compound represented by (wherein, each symbol has the same meaning as above) reacts with HOOC=CH ₂ to obtain the compound represented by the following formula,

(In the formula, each symbol has the same meaning as above);

Next, the above compound is reacted with OCN-(CH ₂ ) ₃ -SiR ¹ _n' R ² _3-n' (wherein each symbol has the same meaning as above) to obtain a compound represented by the following formula:

(In the formula, each symbol has the same meaning as above).

The reaction conditions of each step of the above reaction can be appropriately set by a person with ordinary knowledge in the relevant technical field.

Next, the surface treatment agent disclosed in this disclosure is described.

The surface treatment agent disclosed herein contains at least one acrylic compound containing a fluoropolyether group represented by formula (1) or (2).

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

In other aspects, in the surface treatment agent disclosed herein, the acrylic compound containing a fluoropolyether group is a compound represented by formula (2).

In other aspects, in the surface treatment agent disclosed herein, the acrylic compound containing a fluoropolyether group is a compound represented by formula (1) and a compound represented by formula (2).

In the surface treatment agent disclosed herein, the compound represented by formula (2) is preferably 0.1 mol% to 35 mol% relative to the total of the compound represented by formula (1) and the compound represented by formula (2). The lower limit of the content of the compound represented by formula (2) is preferably 0.1 mol%, more preferably 0.2 mol%, more preferably 0.5 mol%, more preferably 1 mol%, particularly preferably 2 mol%, and particularly preferably 5 mol%. The upper limit of the content of the compound represented by formula (2) is preferably 35 mol%, more preferably 30 mol%, more preferably 20 mol%, and even more preferably 15 mol% or 10 mol% relative to the total of the compound represented by formula (1) and the compound represented by formula (2). Relative to the total of the compound represented by formula (1) and the compound represented by formula (2), the compound represented by formula (2) is preferably 0.1 mol% to 30 mol%, more preferably 0.1 mol% to 20 mol%, still more preferably 0.2 mol% to 10 mol%, particularly preferably 0.5 mol% to 10 mol%, particularly preferably 1 mol% to 10 mol%, for example 2 mol% to 10 mol% or 5 mol% to 10 mol%.

The content of the compound represented by the above formula (1) or (2) is preferably 0.1 to 50.0 mass%, more preferably 1.0 to 30.0 mass%, still more preferably 5.0 to 25.0 mass%, and particularly preferably 10.0 to 20.0 mass% relative to the surface treatment agent as a whole. By setting the content of the above fluoropolyether-containing acrylic compound to the above range, higher water-repellency, oil-repellency and friction durability can be obtained.

The surface treatment agent disclosed herein may include: solvent, (non-reactive) fluoropolyether compound which can be understood as fluorine-containing oil, preferably perfluoro(poly)ether compound (hereinafter collectively referred to as "fluorine-containing oil"); (non-reactive) polysilicone compound which can be understood as polysilicone oil (hereinafter referred to as "polysilicone oil"); alcohols, catalysts, surfactants, polymerization inhibitors, sensitizers, etc.

烷等環狀醚類；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺類；甲基賽璐蘇、賽璐蘇、異丙基賽璐蘇、丁基賽璐蘇、二乙二醇單甲基醚等醚醇類；二乙二醇單乙基醚乙酸酯；1,1,2-三氯-1,2,2-三氟乙烷、1,2-二氯-1,1,2,2-四氟乙烷、二甲基亞碸、1,1-二氯-1,2,2,3,3-五氟丙烷(HCFC225)、ZEORORA(

)H、HFE7100、HFE7200、HFE7300、CF₃CH₂OH、CF₃CF₂CH₂OH、 (CF₃)₂CHOH等含氟溶劑等。或者，可舉出此等溶劑的2種以上之混合溶劑等。 The above-mentioned solvent may include, for example, aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirits, benzene, toluene, xylene, naphthalene, solvent oil, etc. naphtha) and other aromatic hydrocarbons; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellulosic acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetylacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylamino ketone, 2-heptanone and other ketones; ethyl Cellulose, methyl cellulose, methyl cellulose acetate, ethyl cellulose 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 monoalkyl ether and other glycol ethers; methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octanol, 3-methyl-3-methoxybutanol, tert-pentanol and other alcohols; ethylene glycol, propylene glycol and other glycols; tetrahydrofuran, tetrahydropyran, dihydrofuran, di ...

Cyclic ethers such as alkanes; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ether alcohols such as methyl cellulosic acid, cellulosic acid, isopropyl cellulosic acid, butyl cellulosic acid, diethylene glycol monomethyl ether; diethylene glycol monoethyl ether acetate; 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, dimethyl sulfoxide, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), ZEORORA (

)H, HFE7100, HFE7200, HFE7300, CF ₃ CH ₂ OH, CF ₃ CF ₂ CH ₂ OH, (CF ₃ ) ₂ CHOH and the like. Alternatively, a mixed solvent of two or more of these solvents may 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 an alkyl group having 1 to 16 carbon atoms (preferably a _C1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, and ^Rf6 represents an alkyl group having 1 to 16 carbon atoms (preferably a _C1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom, and ^Rf5 and ^Rf6 are more preferably independently a _C1-3 perfluoroalkyl group.

a', b', c' and d' respectively represent the number of four repeating units of perfluoro(poly)ether constituting the main skeleton of the polymer, and are independently integers of 0 to 300, and 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 existence of each repeating unit marked with a', b', c' or d' and enclosed in brackets in the formula is arbitrary. The repeating units may be linear or branched, and may also contain a ring structure. For example, -(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 Any one of C(CF ₃ ) ₂ )-, -(OCF(CF ₃ )CF(CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- and (OCF ₂ CF(C ₂ F ₅ ))-, preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₃ F ₆ )- may be any one 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 one of -(OCF ₂ CF ₂ )- and (OCF(CF ₃ ))-, and is preferably -(OCF ₂ CF ₂ )-.

The above ring structure may be a three-membered ring or a four-membered ring as described below.

[Where * represents the bond position]

For example, (OC ₄ F ₈ ) may be represented by the following formula:

[Where * represents the bond position].

Examples of the perfluoro(poly)ether compound represented by the above 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 marked with a", b", c", d" and enclosed in parentheses in the formula is arbitrary.

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

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

The fluorine-containing oil may contain 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass, relative to the surface treatment agent disclosed herein. In one embodiment, the surface treatment agent disclosed herein substantially does not contain fluorine-containing oil. The so-called substantially does not contain fluorine-containing oil means that it does not contain fluorine-containing oil at all, or may contain a very small amount of fluorine-containing oil.

In one embodiment, the average molecular weight of the fluorinated oil can be greater than the average molecular weight of the acrylic compound containing a fluoropolyether group. By setting such an average molecular weight, better wear resistance and surface smoothness can be obtained, especially when the surface treatment layer is formed by vacuum evaporation.

In one embodiment, the average molecular weight of the fluorinated oil can be smaller than the average molecular weight of the acrylic compound containing a fluoropolyether group. By setting such an average molecular weight, the reduction in transparency of the surface treatment layer obtained from the compound can be suppressed, and a hardened material with high wear resistance and high surface smoothness can be formed.

Fluorinated oil helps to improve the surface smoothness of the layer formed by the surface treatment agent disclosed herein.

The above silicone oil can be, for example, a straight chain or cyclic silicone oil with a siloxane bond of less than 2,000. The straight chain silicone oil can be so-called straight silicone oil and modified silicone oil. Straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydro silicone oil. Modified silicone oils include: straight chain silicone oils modified by alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc. Cyclic silicone oils include, for example, cyclic dimethyl siloxane oil, etc.

In the surface treatment agent disclosed in the present invention, the polysilicone oil may contain, 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 acrylic compound containing a fluoropolyether group disclosed in the present invention (the total of these when there are more than two types, and the same applies below).

Silicone oil helps improve the surface smoothness of the surface treatment layer.

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

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

The above catalysts include: acids (such as acetic acid, trifluoroacetic acid, etc.), bases (such as ammonia, triethylamine, diethylamine, etc.), transition metals (such as Ti, Ni, Sn, etc.), etc.

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

As for other ingredients, in addition to the above, examples include: tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, etc.

The surface treatment agent disclosed herein can be impregnated into porous materials (e.g. porous ceramic materials) or metal fibers (e.g. steel wool rolled into a cotton-like shape) to form tablets. The tablets can be used, for example, for 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, condensates of silane, etc.

The following is a description of the items disclosed.

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

The substrate that can be used in the present disclosure can be made of, for example, glass, resin (natural or synthetic resin, such as general plastic materials), metal, ceramic, semiconductor (silicon, germanium, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone and other building components and other sanitary products, and any appropriate material.

For example, when the object to be manufactured is an optical component, the material constituting the surface of the substrate may be a material for optical components, such as glass or transparent plastic. In addition, when the object to be manufactured is an optical component, some layers (or films) may be formed on the surface (outermost layer) of the substrate, such as a hard coating layer or an anti-reflection layer. The anti-reflection layer may be a single-layer anti-reflection layer or a multi-layer anti-reflection layer. Examples of inorganic materials that can be used for the antireflection layer include _SiO2 , SiO, ZrO2, _TiO2 , _TiO , _Ti2O3 , _Ti2O5 , Al2O3, _Ta2O5 , _Ta3O5 , _Nb2O5 , _{HfO2, Si3N4 , CeO2 , MgO, Y2O3 , SnO2} , _MgF2 , _WO3 , _etc. These inorganic materials can be used alone or _in combination of two or more _{thereof (} e.g. _, as a mixture). In the case of a multi _- layer antireflection layer, the _outermost layer is preferably _SiO2 and/or SiO. When the object to be manufactured is an optical glass part for a touch panel, a transparent electrode may be provided on a portion of the surface of the substrate (glass) (the transparent electrode is, for example, a thin film using indium tin oxide (ITO) or indium zinc oxide). In addition, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, and a liquid crystal display module, etc., depending on its specific specifications.

The shape of the substrate is not particularly limited, and may be, for example, a plate, a film, or other forms. In addition, as for the substrate surface area where the surface treatment layer is to be formed, it only needs to be at least a portion of the substrate surface, and can be appropriately determined according to the purpose and specific specifications of the article to be manufactured.

In one embodiment, the substrate may be a material at least part of which has a hydroxyl group. Examples of the material 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, in the case where the substrate has a hydroxyl group but not enough, or does not originally have a hydroxyl group, such as a resin, some pretreatment may be performed on the substrate to introduce hydroxyl groups or increase the number of hydroxyl groups on the substrate surface. Examples of the pretreatment include plasma treatment (such as corona discharge) or ion beam irradiation. Plasma treatment can also be suitably used to introduce hydroxyl groups or increase the number of hydroxyl groups on the substrate surface, and to clean the substrate surface (remove foreign matter, etc.). In addition, other examples of the pretreatment include: forming an interfacial adsorbent having a carbon-carbon unsaturated bond group in the form of a monomolecular film on the surface of the substrate by LB method (Langmuir-Blodget method) or chemical adsorption method, and then breaking the unsaturated bond in a gas environment containing oxygen or nitrogen.

In other embodiments, the substrate may be composed of a polysilicon compound having one or more other reactive groups (such as Si-H groups) or a material containing alkoxysilane at least on its surface.

In a preferred embodiment, the substrate is glass. The glass is preferably sapphire glass, soda-lime glass, alkali-aluminum silicate glass, borosilicate glass, alkali-free glass, crystal glass, quartz glass, and particularly preferably chemically strengthened soda-lime glass, chemically strengthened alkali-aluminum silicate 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 post-treating the layer as needed, thereby forming a layer of the surface treatment agent disclosed herein.

The layer formation of the surface treatment agent disclosed herein can be implemented by applying the above-mentioned surface treatment agent to the surface of the substrate in a manner of coating the surface. The coating method is not particularly limited. For example, a wet coating method and a dry coating method can be used.

Wet coating methods include, for example, dip coating, spin coating, shower coating, spray coating, roller 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; high-frequency heating using electron beams, microwaves, etc.; ion beams and similar methods. Specific examples of CVD (Chemical Vapor Deposition) methods include: plasma-CVD, optical CVD, thermal CVD and similar methods.

In addition, it can also be coated by atmospheric pressure plasma method.

When using the wet coating method, the surface treatment agent disclosed herein can be diluted with a solvent and then applied to the surface of the substrate. From the viewpoint of the stability of the composition of the present disclosure and the volatility of the solvent, it is preferred to use the following solvents: 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 Co., Ltd. of Japan); hydrofluoroethers (HFE) (e.g., perfluoropropyl methyl ether (C ₃ F ₇ OCH ₃ ) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 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.), 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.), and the like alkyl perfluoroalkyl ethers (the perfluoroalkyl group and the alkyl group may be linear or branched), or CF ₃ CH ₂ OCF ₂ CHF ₂ (For example, Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.) etc. These solvents may be used alone or as a mixture of two or more. Among them, hydrofluoroether is preferred, and perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and/or perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ) is particularly preferred.

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

The formation of the surface treatment agent layer is preferably carried out in a manner that the surface treatment agent disclosed herein and the catalyst for hydrolysis and dehydration condensation are simultaneously present in the layer. For simplicity, when the wet coating method is used, the surface treatment agent disclosed herein can be diluted with a solvent and the catalyst can be added to the diluted surface treatment agent disclosed herein before being applied to the substrate surface. When the dry coating method is used, the surface treatment agent disclosed herein to which the catalyst has been added can be directly subjected to evaporation (usually vacuum evaporation) treatment, or a granular material formed by impregnating the surface treatment agent disclosed herein to which the catalyst has been added in a porous metal body such as iron or copper can be subjected to evaporation (usually vacuum evaporation) treatment.

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

The surface treatment layer included in the article disclosed herein has high wear resistance. In addition, the surface treatment layer can also have water repellency, oil repellency, anti-fouling (for example, preventing the adhesion of dirt such as fingerprints), waterproofness (preventing water from invading electronic parts, etc.), surface smoothness (or lubricity, such as the ability to wipe away dirt such as fingerprints, or excellent touch to fingers), drug resistance, etc. due to the composition of the surface treatment agent used, and can be suitable for use as a functional film.

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

In addition to the optical materials related to displays described below, various optical materials can be preferably cited, such as cathode ray tubes (CRT, such as computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFD), field emission displays (FED, Field Emission Display) and other displays or protective plates of such displays, or those with anti-reflection film treatment on their surfaces.

The articles disclosed herein are not particularly limited and can be optical components. Examples of optical components include: lenses of glasses, etc.; front protective plates, anti-reflective plates, polarizing plates, anti-glare plates of displays such as PDP and LCD; touch panel sheets of devices such as mobile phones and portable information terminals; disc surfaces of Blu-ray (registered trademark) optical discs, DVD optical discs, CD-R, MO, etc.; optical fibers; display surfaces of watches, etc.

Furthermore, the article disclosed herein may be a medical device or medical material. Furthermore, the article having the layer obtained by the disclosure herein may be an interior or exterior component of a car. Examples of exterior materials include: windows, lampshades, and aftermarket camera covers. Examples of interior materials include: instrument panel covers, navigation system touch panels, and decorative interior materials.

The thickness of the above layer is not particularly limited. In the case of an optical component, in terms of optical performance, wear resistance and antifouling properties, the thickness of the above layer is 1 to 50 nm, 1 to 30 nm, preferably 1 to 15 nm.

The above is a detailed description of the article disclosed herein. In addition, the article disclosed herein and the method for manufacturing the article are not limited to the examples shown above.

(Implementation example)

The following examples are used to illustrate the compounds disclosed in this disclosure, but the disclosure is not limited to the following examples. In addition, in this example, the order of existence of the repeating units constituting the fluoropolyether is arbitrary, and the chemical formula shown below represents the average composition.

Synthesis example 1

In a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10.0 g of a perfluoropolyether modified acid fluoride with an average composition represented by CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ COF, 10.0 g of 1,3-bis(trifluoromethyl)benzene and 5.0 g of tetrahydrofuran were stirred at 25°C for 30 minutes under a nitrogen flow. Then, 9.6 mL of 0.7 M allylmagnesium bromide was slowly added dropwise, and the mixture was heated at 60°C for 4 hours. Thereafter, the mixture was cooled to 5°C, and 10.0 g of a 3.0 M aqueous hydrochloric acid solution was added dropwise to stop the reaction. The fluorine phase of the lower layer was recovered by liquid separation and then washed with methanol. Thereafter, the volatile components are distilled off under reduced pressure to obtain the perfluoropolyether group-containing allyl compound (A) represented by the following formula.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ C(OH)(CH ₂ CH=CH ₂ ) ₂

Synthesis example 2

In a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10.0 g of the allyl compound (A) containing a perfluoropolyether group obtained in Synthesis Example 1, 10.0 g of 1,3-bis(trifluoromethyl)benzene, 0.020 g of triacetoxymethylsilane and 1.21 g of trichlorosilane were added, and stirred at 5°C for 30 minutes under a nitrogen flow. Then, 0.20 g of a xylene solution of a Pt complex containing 2% of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and stirred at 60°C for 5 hours. Thereafter, the volatile components were distilled off under reduced pressure to obtain a trichlorosilane compound (B) containing a perfluoropolyether group shown in the following formula.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ C(OH)(CH ₂ CH ₂ CH ₂ SiCl ₃ ) ₂

Synthesis example 3

In a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10.0 g of the trichlorosilane compound (B) containing a perfluoropolyether group obtained in Synthesis Example 2 and 10.0 g of 1,3-bis(trifluoromethyl)benzene were added, and stirred at 50°C for 30 minutes under a nitrogen flow. Then, a mixed solution of 0.13 g of methanol and 1.42 g of methyl o-formate was added, and stirred at 65°C for 2 hours. Thereafter, the volatile components were distilled off under reduced pressure to obtain a silane compound (C) containing a perfluoropolyether group shown in the following formula.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ C(OH){CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ } ₂

Synthesis example 4

In a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10.0 g of the silane compound (C) containing a perfluoropolyether group obtained in Synthesis Example 3, 0.32 g of 2-isocyanatoethyl acrylate (Karenz (registered trademark) AOI manufactured by Showa Denko Co., Ltd.), and 0.0014 g of dibutyltin dilaurate were added, and stirred at 50°C for 2 hours under a nitrogen flow to obtain a silane compound (D) containing a perfluoropolyether group shown in the following formula.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ C(OX){CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ } ₂

X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Synthesis example 5

In a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10.0 g of a perfluoropolyether modified ester with an average composition represented by CF ₃ CF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) ₂₄ CF ₂ CF ₂ COOCH ₃ , 5.0 g of 1,3-bis(trifluoromethyl)benzene and 0.51 g of 3-(2-aminoethylamino)propyltrimethoxysilane were added, and stirred at 25° C. for 1 hour under a nitrogen flow. Thereafter, the volatile components were distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (E) represented by the following formula.

CF ₃ CF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) ₂₄ CF ₂ CF ₂ CONHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis example 6

10.0 g of the silane compound (E) containing a perfluoropolyether group obtained in Synthesis Example 5 and 0.32 g of 2-isocyanatoethyl acrylate (Karenz (registered trademark) AOI manufactured by Showa Denko Co., Ltd.) were added to a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred at 25°C for 1 hour under a nitrogen flow to obtain a silane compound (F) containing a perfluoropolyether group represented by the following formula.

CF ₃ CF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) ₂₄ CF ₂ 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 7

In a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10.0 g of a perfluoropolyether modified ester with an average composition represented by CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ COOCH ₃ , 5.0 g of 1,3-bis(trifluoromethyl)benzene and 0.50 g of 3-(2-aminoethylamino)propyltrimethoxysilane were added and stirred at 25° C. for 1 hour under a nitrogen flow. Thereafter, the volatile components were distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (G) represented by the following formula.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ CONHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis example 8

10.0 g of the silane compound (G) containing a perfluoropolyether group obtained in Synthesis Example 7 and 0.31 g of 2-isocyanatoethyl acrylate (Karenz (registered trademark) AOI manufactured by Showa Denko Co., Ltd.) were added to a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred at 25°C for 1 hour under a nitrogen flow to obtain a silane compound (H) containing a perfluoropolyether group represented by the following formula.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ 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 9

In a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10.0 g of a perfluoropolyether modified ester having an average composition represented by CF ₃ CF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} ₁₁ CF(CF ₃ )COOCH ₃ , 5.0 g of 1,3-bis(trifluoromethyl)benzene and 1.02 g of 3-(2-aminoethylamino)propyltrimethoxysilane were added, and stirred at 70° C. for 10 hours under a nitrogen flow. Thereafter, the volatile components were distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (I) represented by the following formula.

CF ₃ CF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} ₁₁ CF(CF ₃ )CONHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis example 10

10.0 g of the silane compound (I) containing a perfluoropolyether group obtained in Synthesis Example 9 and 0.65 g of 2-isocyanatoethyl acrylate (Karenz (registered trademark) AOI manufactured by Showa Denko Co., Ltd.) were added to a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred at 25°C for 1 hour under a nitrogen flow to obtain a silane compound (J) containing a perfluoropolyether group represented by the following formula.

CF ₃ CF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} ₁₁ CF(CF ₃ )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 11

In a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10.0 g of a perfluoropolyether modified ester with an average composition represented by CF ₃ O(CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) ₁₃ CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ COOCH ₃ , 5.0 g of 1,3-bis(trifluoromethyl)benzene and 0.47 g of 3-(2-aminoethylamino)propyltrimethoxysilane were added, and stirred at 25° C. for 1 hour under a nitrogen flow. Thereafter, the volatile components were distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (K) represented by the following formula.

CF ₃ O(CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) ₁₃ CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CONHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis example 12

10.0 g of the silane compound (K) containing a perfluoropolyether group obtained in Synthesis Example 11 and 0.30 g of 2-isocyanatoethyl acrylate (Karenz (registered trademark) AOI manufactured by Showa Denko Co., Ltd.) were added to a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred at 25°C for 1 hour under a nitrogen flow to obtain a silane compound (L) containing a perfluoropolyether group represented by the following formula.

CF ₃ O(CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ O) ₁₃ CF ₂ CF ₂ OCF ₂ CF ₂ 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 the silane compound (G) containing a perfluoropolyether group obtained in Synthesis Example 7 and 0.53 g of 1,1-(diacryloyloxymethyl)ethyl isocyanate (Karenz (registered trademark) BEI manufactured by Showa Denko Co., Ltd.) were added to a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred at 25°C for 1 hour under a nitrogen flow to obtain a silane compound (M) containing a perfluoropolyether group represented by the following formula.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

X=-CONHC(CH ₃ )(CH ₂ OCOCH=CH ₂ ) ₂

Synthesis Example 14

10.0 g of the silane compound (G) containing a perfluoropolyether group obtained in Synthesis Example 7 and 0.45 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE manufactured by Mitsubishi Chemical Co., Ltd.) were added to a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred at 50°C for 2 hours under a nitrogen flow to obtain a silane compound (N) containing a perfluoropolyether group shown in the following formula.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ CONHCH ₂ CH ₂ N(X)CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

X is the following ^X1 or ^X2 ( ^X1 : ^X2 =73:27)

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 15

In a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10.0 g of a perfluoropolyether modified ester with an average composition represented by CH ₃ OCOCF ₂ O(CF ₂ O) ₁₂ (CF ₂ CF ₂ O) ₁₂ CF ₂ COOCH ₃ , 5.0 g of 1,3-bis(trifluoromethyl)benzene and 1.69 g of 3-(2-aminoethylamino)propyltrimethoxysilane were added, and stirred at 25° C. for 1 hour under a nitrogen flow. Thereafter, the volatile components were distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (O) 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 CH ₂ Si(OCH ₃ ) ₃

Synthesis Example 16

10.0 g of the silane compound (O) containing a perfluoropolyether group obtained in Synthesis Example 15 and 1.08 g of 2-isocyanatoethyl acrylate (Karenz (registered trademark) AOI manufactured by Showa Denko Co., Ltd.) were added to a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred at 25°C for 1 hour under a nitrogen flow to obtain a silane compound (P) containing a perfluoropolyether group 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 CH ₂ Si(OCH ₃ ) ₃

X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Synthesis Example 17

In a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 10.0 g of a perfluoropolyether modified ester having an average composition represented by 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 of hexafluorobenzene and 0.73 g of 3-(2-aminoethylamino)propyltrimethoxysilane were added, and stirred at 70° C. for 12 hours under a nitrogen flow. Thereafter, the volatile components were distilled off under reduced pressure to obtain a perfluoropolyether group-containing silane compound (Q) represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH 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 NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Synthesis example 18

10.0 g of the silane compound (Q) containing a perfluoropolyether group obtained in Synthesis Example 17 and 0.46 g of 2-isocyanatoethyl acrylate (Karenz (registered trademark) AOI manufactured by Showa Denko Co., Ltd.) were added to a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred at 25°C for 1 hour under a nitrogen flow to obtain a silane compound (R) containing a perfluoropolyether group represented by the following formula.

(CH ₃ O) ₃ SiCH ₂ CH 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 N(X)CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

X=-CONHCH ₂ CH ₂ OCOCH=CH ₂

Synthesis example 19

10.0 g of the silane compound (O) containing a perfluoropolyether group obtained in Synthesis Example 15 and 1.52 g of 2-(2-methacryloyloxyethyloxy)ethyl isocyanate (Karenz (registered trademark) MOI-EG manufactured by Showa Denko Co., Ltd.) were added to a 100 mL three-necked flask equipped with a reflux condenser, a thermometer and a stirrer, and stirred at 25°C for 1 hour under a nitrogen flow to obtain a silane compound (S) containing a perfluoropolyether group represented by the following formula.

(CH ₃ O) ₂ (CH 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 CH ₂ Si(CH ₃ )(OCH ₃ ) ₂

X=-CONHCH ₂ CH ₂ OCH ₂ CH ₂ OCOC(CH ₃ )=CH ₂

Example 1

The compound (D) obtained in the above-mentioned Synthesis Example 4 was dissolved in Novec 7200 (manufactured by 3M Company) at a concentration of 20 mass % to prepare the surface treatment agent 1.

、真空度5.0E-05、電流值240A、電壓10V、基材溫度40℃。接著，將經蒸鍍的化學強化玻璃於溫度150℃之氣體環境下靜置30分鐘，其後放冷至室溫。接著，對經蒸鍍的化學強化玻璃在空氣環境下以1000mJ/cm²之強度照射含有365nm之紫外光的光線，而於玻璃基材上形成表面處理層。 The surface treatment agent 1 prepared above was vacuum-deposited on chemically strengthened glass (Corning "Gorilla" glass, thickness 0.7 mm). The conditions of the vacuum deposition method were: the chamber size of the resistance heating evaporator was 1,900 mm

, vacuum degree 5.0E-05, current value 240A, voltage 10V, substrate temperature 40℃. Then, the evaporated chemically strengthened glass was placed in a gas environment at a temperature of 150℃ for 30 minutes, and then cooled to room temperature. Then, the evaporated chemically strengthened glass was irradiated with light containing 365nm ultraviolet light at an intensity of 1000mJ/ ^cm2 in an air environment to form a surface treatment layer on the glass substrate.

Example 2

Except for using the compound (F) obtained in the above-mentioned synthesis example 6 to replace the compound (D), the surface treatment agent is prepared in the same manner as in Example 1 and the surface treatment layer is formed.

Implementation Example 3

In addition to using the compound (H) obtained in the above-mentioned synthesis example 8 to replace the compound (D), the surface treatment agent is prepared in the same manner as in Example 1 to form a surface treatment layer.

Example 4

Except for using the compound (J) obtained in the above-mentioned synthesis example 10 to replace the compound (D), the surface treatment agent is prepared in the same manner as in Example 1 and the surface treatment layer is formed.

Example 5

Except for using the compound (L) obtained in the above-mentioned Synthesis Example 12 to replace the compound (D), the surface treatment agent is prepared in the same manner as in Example 1 and the surface treatment layer is formed.

Example 6

Except for using the compound (M) obtained in the above-mentioned Synthesis Example 13 to replace the compound (D), the surface treatment agent is prepared in the same manner as in Example 1 and the surface treatment layer is formed.

Example 7

In addition to using the compound (N) obtained in the above-mentioned synthesis example 14 to replace the compound (D), the surface treatment agent is prepared in the same manner as in Example 1 to form a surface treatment layer.

Example 8

Except for using the compound (P) obtained in the above-mentioned Synthesis Example 16 to replace the compound (D), the surface treatment agent is prepared in the same manner as in Example 1 and the surface treatment layer is formed.

Example 9

Except for using the compound (R) obtained in the above-mentioned Synthesis Example 18 to replace the compound (D), the surface treatment agent is prepared in the same manner as in Example 1 and the surface treatment layer is formed.

Example 10

Except for using the compound (S) obtained in the above-mentioned Synthesis Example 19 to replace the compound (D), the surface treatment agent is prepared in the same manner as in Example 1 and the surface treatment layer is formed.

Comparative example 1

The following compound (T) was dissolved in Novec 7200 (manufactured by 3M Company) at a concentration of 20 mass % to prepare surface treatment agent 2.

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ CF ₂ CON{CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ } ₂

、真空度5.0E-05、電流值240A、電壓10V、基材溫度40℃。接著，將經蒸鍍的化學強化玻璃於溫度150℃之氣 體環境下靜置30分鐘，其後放冷至室溫，而於玻璃基材上形成表面處理層。 The surface treatment agent 2 prepared above was vacuum-deposited on chemically strengthened glass (Corning "Gorilla" glass, thickness 0.7 mm). The conditions of the vacuum deposition method are: the chamber size of the resistance heating evaporator is 1,900 mm

, vacuum degree 5.0E-05, current value 240A, voltage 10V, substrate temperature 40°C. Then, the evaporated chemically strengthened glass was placed in a gas environment at a temperature of 150°C for 30 minutes, and then cooled to room temperature to form 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 (U) was used to replace the compound (T).

CF ₃ O(CF ₂ CF ₂ O) ₂₂ (CF ₂ O) ₂₆ 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 (V) was used to replace the substituted compound (T).

CF ₃ CF ₂ CF ₂ O{CF(CF ₃ )CF ₂ O} ₁₁ CF(CF ₃ )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 (W) was used instead of compound (T).

CF ₃ CF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ CF ₂ O) ₂₅ CF ₂ CF ₂ CONHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃

Comparative example 5

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 (X) was used instead of compound (T).

(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

Comparative example 6

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 (Y) was used to replace the compound (T).

(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

<Evaluation>

For the glass substrate with surface treatment layer obtained above, the water contact angle was measured by the following methods and the alkaline test was evaluated.

(Alkali leaching test)

A 1 cm diameter PTFE O-ring was placed on the surface of the surface treated substrates of Examples 1 to 10 and Comparative Examples 1 to 6, and 8N NaOH solution (alkaline aqueous solution) was dripped into the O-ring to make the surface of the surface treated layer contact the alkaline aqueous solution, and then subjected to an alkaline immersion test. After 20 to 300 minutes of the alkaline immersion test, the alkaline aqueous solution was wiped off, and the substrate was washed with pure water and ethanol, and then the contact angle relative to water was measured. In addition, the static contact angle of water is measured by dropping 2 μL of pure water on the surface of the glass substrate after the above-mentioned alkali immersion test, and using a contact angle meter (automatic contact angle meter DropMaster701 manufactured by Kyowa Interface Chemical Co., Ltd.) to measure the contact angle relative to water. The static contact angle of water after the alkali immersion test was measured at 5 locations. When the measured value of the static contact angle of water decreases within 300 minutes, the alkali immersion test is stopped midway. The relationship between the immersion time and the average value of the contact angle at 5 locations is shown in the table below.

[Table 1]

(Abrasion resistance test)

The sample article with the surface treatment layer is arranged horizontally, and the following friction piece is in contact with the surface of the surface treatment layer (the contact surface is a circle with a diameter of 1 cm), and a load of 5N is applied thereon. Afterwards, the friction piece is moved back and forth at a speed of 40mm/second under the applied load. The friction piece is moved back and forth a maximum of 4000 times, and the static contact angle (°) of water is measured every 1000 times of the number of back and forth (number of frictions). The test is terminated at the time point when the measured value of the static contact angle of water does not reach 60°. Furthermore, the determination of the static contact angle of water is carried out in the same manner as the above-mentioned alkaline test. The results are shown in the table below.

‧Friction parts

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

Composition of artificial sweat:

Disodium hydrogen phosphate anhydrous 2g,

Sodium chloride 20g,

85% lactic acid 2g,

Histidine hydrochloride 5g,

1Kg of distilled water.

Silicone rubber processed products: Process the silicone rubber plug SR-51 made by Tigers Polymer into a cylindrical shape with a diameter of 1cm and a thickness of 1cm.

[Table 2]

(Industrial availability)

The acrylic compound containing fluoropolyether groups disclosed herein can be applied to a variety of substrates, and is particularly suitable for forming a surface treatment layer on the surface of optical components that require friction durability.

Claims (18)

^A compound is a compound represented by the following formula (1) or (2): ^RF1 - ^{XA - XBRSinRAcm} (1) ^RAcmRSinXB - ^XA - ^{RF2 - XA - XBRSinRAcm} (2) wherein _RF1 is ^Rf1 _- ^RF - ^Oq- _{, RF2 is} ^-Rf2p - ^RF - _Oq- ^, _Rf1 is a _C1-16 alkyl group ^which may be substituted by one ^or more fluorine atoms, ^Rf2 is a _C1-6 alkylene group which may be substituted by one or more fluorine atoms, ^RF is independently a divalent fluoropolyether group, _p is ⁰ or ₁ , q is independently 0 or 1, ^XA is independently a single bond or a group represented by the following formula: - _{( CαR112α} ) _{s1 -} ^R12t1- wherein ^{R 11} is independently a hydrogen atom or a fluorine atom at each occurrence, α is independently an integer from 1 to 10 at each occurrence, R ¹² is independently -O-, -CO-, -NR ¹⁰ -, -CONR ¹⁰ -, -NR ¹⁰ CO-, -COO-, or -OCO-, R ¹⁰ is a hydrogen atom or a C _1-6 alkyl group, s1 is an integer from 0 to 3, t1 is an integer from 0 to 3, the total of s1 and t1 is 1 or more, the order of occurrence of the repeating units marked with s1 or t1 and enclosed in brackets in the formula is arbitrary, X ^B is independently a group represented by the following formula,

wherein R ⁸ is a hydrogen atom or a C _1-6 alkyl group, R ^Si is independently -X ^C -SiR ¹ _n' R ² _3-n' at each occurrence, X ^C is: a C _1-6 alkylene group, -(CH ₂ ) _z1 -O-(CH ₂ ) _z2 - (wherein z1 is an integer from 0 to 6, and z2 is an integer from 0 to 6), -(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), or -(CH ₂ ) _z13 -OCONH-(CH ₂ ) _z14 - (wherein z13 is an integer from 0 to 6, and z14 is an integer from 0 to 6), R ¹ is independently a hydroxyl group or a hydrolyzable group at each occurrence, and R ² is independently a hydrogen atom or a C _1-20 alkyl group at each occurrence, n' is an integer from 1 to 3, R ^Ac is independently -X ^D -X ^E (-X ^F -OCO-CR ⁵ =CH ₂ ) _m' at each occurrence, X ^D is a single bond, or -O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-, -OCONH-, -NHCOO-, -NH-CO-NH-, -CH ₂ CH(OH)CH ₂ -, -CH(CH ₂ OH)CH ₂ -,

In the formula, * and ** represent bonding positions, * is bonded to ^XB , ** is bonded to ^XE , ^XE is a single bond, or ^-XG - ^XH , wherein ^XG is: a single bond, _C1-6 alkylene, -( _CH2 ) _z9 -O-( _CH2 ) _z10- (wherein z9 is an integer from 0 to 6, z10 is an integer from 0 to 6), or -( _CH2 ) _z11 -phenylene-( _CH2 ) _z12- (wherein z11 is an integer from 0 to 6, z12 is an integer from 0 to 6), and ^XH is a trivalent or tetravalent group represented by the following formula,

^R8 is a hydrogen atom or a _C1-6 alkyl group, ^XF is independently a single bond, a _C1-6 alkylene group, -( _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), ^R5 is a hydrogen atom, a halogen atom, or a _C1-8 alkyl group, a _C3-8 cycloalkyl group, or a _C5-8 aryl group, m' is an integer from 1 to 10, n is independently an integer from 1 to 10, and m is independently an integer from 1 to 10. The compound as described in claim 1, wherein ^RF is independently represented by the following formula at each occurrence: -(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 ^RF is independently represented by a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence, a, b, c, d, e and f are independently represented by an integer from 0 to 200, the sum of a, b, c, d, e and f is 1 or more, and the order of occurrence of the repeating units marked with a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary, provided that when all ^RF are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more. The compound as described in claim 2, wherein R ^Fa is a fluorine atom. The compound as described in any one of claims 1 to 3, wherein ^RF is independently represented by the following formula (f1), (f2), (f3), (f4), (f5) or (f6) at each occurrence: -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1) In formula (f1), d is an integer from 1 to 200, and e is 0 or 1; -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2) In formula (f2), 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 an integer from 10 to 200; the order of the repetitive units labeled c, d, e or f and enclosed in brackets in the formula is arbitrary; -(R ⁶ -R ⁷ ) _g -R ⁹ - (f3) In formula (f3), 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 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 9 - (f3) In formula (f3), 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 ; _g - ^Rr- ( ^R7' - ^R6' ) _g'- (f4) In the formula (f4), ^R6 is _OCF2 or _OC2F4 , ^R7 is _{a group selected from OC2F4, OC3F6, OC4F8, OC5F10 and OC6F12 , or a combination of} 2 or ₃ groups independently selected from these groups, R6 ^' is _OCF2 or _OC2F4 , R7 ^' is a group selected from _OC2F4 , _{OC3F6 , OC4F8 , OC5F10 and OC6F12} , or a combination of 2 or 3 groups independently selected from these groups, g is an integer from 2 to ₁₀₀ , _g ' is an integer from ₂ to 100, _and ^Rr is:

(wherein * represents a 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 formula (f5), e is an integer from 1 to 200, a, b, c, d and f are each independently an integer from 0 to 200, the sum of a, b, c, d, e and f is at least 1, and the order of presence of each repeating unit 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 formula (f6), f is an integer greater than 1 and less than 200, a, b, c, d and e are each independently an integer greater than 0 and less than 200, the sum of a, b, c, d, e and f is at least 1, and the order of presence of each repeating unit labeled a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary. The compound as described in any one of claims 1 to 3, wherein ^Rf1 is independently _C1-16 perfluoroalkyl at each occurrence, and ^Rf2 is independently _C1-6 perfluoroalkylene at each occurrence. _The compound as described in any one of claims 1 to 3, wherein ^XA is ^-CONR10 - _Cα1H2α1- , -( _Cα2H2α2 )-O- _{(Cα3H2α3 )} -, or _-Cα4H2α4- , ^R10 is _a hydrogen atom or a _C1-6 alkyl group, α1 is an integer from 1 to ₁₀ , α2 is an integer from 0 to 6, α3 is an integer from 0 to 6, and α4 is an integer from 0 to 6. The compound as described in claim 6, wherein X ^A is -CONR ¹⁰ -C _α1 H _2α1 -. The compound as described in any one of claims 1 to 3, wherein X ^B is represented by the following formula, n is 1, m is 1,

In the formula, ^R8 is a hydrogen atom or a _C1-6 alkyl group. The compound as described in any one of claims 1 to 3, wherein X ^C is a C _1-6 alkylene group. A compound as described in any one of claims 1 to 3, wherein n' is 2 or 3. A compound as described in any one of claims 1 to 3, wherein n' is 3. The compound as described in any one of claims 1 to 3, wherein ^XE is a single bond. The compound as described in 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, z10 is an integer from 0 to 6), or -( _CH2 ) _z11 -phenylene-( _CH2 ) _z12- (wherein z11 is an integer from 0 to 6, z12 is an integer from 0 to 6), and ^XH is represented by the following formula,

^R8 is a hydrogen atom or a _C1-6 alkyl group. The compound as described in any one of claims 1 to 3, wherein R ⁵ is a hydrogen atom or a methyl group. A surface treatment agent containing a compound described in any one of claims 1 to 14. The surface treatment agent as described in claim 15 further contains one or more other ingredients selected from fluorinated oil, silicone oil, and catalyst. The surface treatment agent as described in claim 15 is used as an antifouling coating agent or a waterproof coating agent. An article containing a surface treatment layer comprises: a substrate, and a surface treatment layer formed on the surface of the substrate by using a compound described in any one of claims 1 to 14 or a surface treatment agent described in any one of claims 15 to 17.