JP2018172655A - Surface preparation agent containing perfluoropolyether group-containing compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel surface preparation agent suitable for forming a surface preparation layer with improved friction durability.SOLUTION: Provided is a surface preparation agent containing a perfluoropolyether group-containing compound represented by formula (1A) or formula (1B), in which each of symbols denotes the same as described in the specification.SELECTED DRAWING: None

Description

  The present invention relates to a surface treatment agent containing a perfluoro (poly) ether group-containing compound.

  It is known that certain fluorine-containing compounds can provide excellent water repellency, oil repellency, stain resistance and the like when used for surface treatment of a substrate. A layer obtained from a surface treatment agent containing a fluorine-containing compound (hereinafter, also referred to as “surface treatment layer”) is applied as a so-called functional thin film to various substrates such as glass, plastic, fiber, building material and the like There is.

As such a fluorine-containing compound, a compound having a perfluoropolyether group in the molecular main chain is known. For example, Patent Document 1, the molecular _{end, -P (O) (OH)} 2, -OP (O) (OH) 2, or ^{-NR ₈₇} 2 ^(R ₈₇ is a hydrogen atom or a lower alkyl group) or the like The compounds contained are described.

JP, 2016-052779, A

  The surface treatment layer is required to have high durability in order to provide the desired function to the substrate over a long period of time. A layer obtained from a surface treatment agent containing a compound having a perfluoropolyether group can exhibit the above-described function even with a thin film, and therefore, it can be used for optical members such as glasses and touch panels that are required to have light transparency or transparency. It is suitably used.

  However, a surface treatment agent containing a compound having a perfluoropolyether group as described above is not always sufficient to meet the demand for the improvement of friction durability which is gradually increasing.

  Therefore, an object of the present invention is to provide a novel surface treatment agent suitable for forming a surface treatment layer having better friction durability.

  As a result of intensive investigations, the inventor of the present invention finds that the friction durability of the surface treatment layer is further improved by using a surface treatment agent containing a perfluoropolyether compound having a specific structure, and completes the present invention. It came to

［式中：
Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１〜１６のアルキル基を表し；
ＰＦＰＥは、各出現においてそれぞれ独立して、式：
−（ＯＣ_６Ｆ_１２）_ａ−（ＯＣ_５Ｆ_１０）_ｂ−（ＯＣ_４Ｆ_８）_ｃ−（ＯＣ_３Ｆ_６）_ｄ−（ＯＣ_２Ｆ_４）_ｅ−（ＯＣＦ_２）_ｆ−
（ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
ＰＦＰＥ^１は、ＰＦＰＥと同意義であり；
Ｒｆ^１は、各出現においてそれぞれ独立して、（Ｏ−Ｒｆ^１１）_ｍ２を表し；
Ｒｆ^１１は、１以上の水素原子を含む分岐構造を有しないフルオロアルキレン基であり；
ｍ２は、０〜４の整数であり、ｍ２が２〜４の整数の場合（Ｏ−Ｒｆ^１１）_ｍ２は２種以上のＯ−Ｒｆ^１１からなるものであってもよく；
Ｒｆ^２は、各出現においてそれぞれ独立して、（Ｏ−Ｒｆ^２１）_ｍ３を表し；
Ｒｆ^２１は、１以上の水素原子を含む分岐構造を有しないフルオロアルキレン基であり；
ｍ３は、０〜４の整数であり、ｍ３が２〜４の整数の場合（Ｏ−Ｒｆ^２１）_ｍ３は２種以上のＯ−Ｒｆ^２１からなるものであってもよく；
Ｘは、各出現においてそれぞれ独立して、単結合、酸素原子または２〜１０価の有機基を表し；
α１は、各出現においてそれぞれ独立して、１〜９の整数であり；
α２は、各出現においてそれぞれ独立して、１〜９の整数であり；
Ｒ^ｍは、各出現においてそれぞれ独立して、以下の式で表される基であり；

Ｍは、各出現においてそれぞれ独立して、配位結合可能な金属原子であり；
Ｒ^１は、各出現においてそれぞれ独立して、Ｘとの結合手を有する単座配位子を表し；
Ｒ^２は、各出現においてそれぞれ独立して、Ｘとの結合手を有する多座配位子を表し；
Ｒ^３は、各出現においてそれぞれ独立して、単座配位子を表し；
Ｒ^４は、各出現においてそれぞれ独立して、多座配位子を表し；
ｋは、０〜２の整数であり；
ｌは、０〜２の整数であり；
ｍは、０以上の整数であり；
ｎは、０以上の整数であり；
但し、ｋとｌとの和は１〜４であり、ｌにＲ^２の配座数を乗じた値、ｎにＲ^４の配座数を乗じた値、ｋおよびｍの和は、Ｍの配位数である。］ According to a first aspect of the invention,
There is provided a surface treatment agent comprising a perfluoropolyether group-containing compound represented by formula (1A) or formula (1B).

[In the formula:
R f independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
The PFPEs each independently at each occurrence have the formula:
_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(A, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1; , C, d, e or f, and the order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula.)
A group represented by
PFPE ¹ is equivalent to PFPE;
R f ¹ independently represents (O-R f ¹¹ ) _{m 2} at each occurrence;
R f ¹¹ is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms;
m2 is an integer of 0 to 4, and when m2 is an integer of 2 to 4 (O-R f ¹¹ ) _m 2 may consist of two or more O-R f ¹¹ ;
R f ² independently represent (O-R f ²¹ ) _{m 3} at each occurrence;
R f ²¹ is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms;
m3 is an integer of 0 to 4, and when m3 is an integer of 2 to 4 (O-R f ²¹ ) _{m 3} may consist of two or more O-R f ²¹ ;
X represents independently at each occurrence a single bond, an oxygen atom or a di- to 10-valent organic group;
α 1 is an integer of 1 to 9 independently at each occurrence;
α 2 is an integer of 1 to 9 independently at each occurrence;
R ^m is a group represented by the following formula each independently at each occurrence;

M is independently at each occurrence a coordinate bondable metal atom;
R ¹ represents, independently at each occurrence, a monodentate ligand having a bond with X;
R ² represents, independently at each occurrence, a polydentate ligand having a bond with X;
R ³ represents independently at each occurrence a monodentate ligand;
R ⁴ independently at each occurrence represents a polydentate ligand;
k is an integer of 0 to 2;
l is an integer of 0 to 2;
m is an integer of 0 or more;
n is an integer of 0 or more;
However, the sum of k and l is 1 to 4, and the value of l multiplied by the number of conformations of R ² , the value of n multiplied by the number of constellations of R ⁴ , and the sum of k and m is M It is a coordination number. ]

  According to a second aspect of the present invention, there is provided a pellet containing the surface treatment agent.

  According to a third aspect of the present invention, there is provided an article comprising a substrate, and a layer formed of the above surface treatment agent on the surface of the substrate.

  As used herein, “1 to 10 valent organic group” means a carbon containing 1 to 10 valent group. The monovalent organic group is not particularly limited, and includes a hydrocarbon group. Although it does not specifically limit as this 2-10-valent organic group, The 2-10-valent group which eliminated 1-9 hydrogen atoms further from the hydrocarbon group is mentioned. The divalent organic group is not particularly limited, and examples thereof include a carbonyl group or a divalent group obtained by further removing one hydrogen atom from a hydrocarbon group.

  As used herein, "hydrocarbon group" refers to a group containing carbon and hydrogen wherein one hydrogen atom has been eliminated from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by one or more substituents, for example, an aliphatic hydrocarbon group, Aromatic hydrocarbon groups and the like can be mentioned. The “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. Such a hydrocarbon group may have one or more of N, O, S, Si, an amide, a sulfonyl, a siloxane, a carbonyl, a carbonyloxy and the like in the terminal or molecular chain thereof.

As used herein, the substituent of the “hydrocarbon group” is not particularly limited, and for example, a halogen atom; C _1-6 alkyl which may be substituted by one or more halogen atoms Group, _C2-6 alkenyl group, _C2-6 alkynyl group, _C3-10 cycloalkyl group, _C3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl And one or more groups selected from C _6-10 aryl group and 5- to 10-membered heteroaryl group.

In the present specification, an alkyl group and a phenyl group may be unsubstituted or substituted, unless otherwise specified. The substituent of such groups include, but are not limited to, for example, a halogen atom, C _1-6 alkyl group in which one or more groups selected from C _2-6 alkenyl and C _2-6 alkynyl group It can be mentioned.

  As used herein, "complex" refers to a chemical species in which a central metal atom or ion is surrounded by several ligands. As used herein, "ligand" refers to a chemical species that may be present alone or as an ion or molecule. The coordinating atom contained in the ligand is preferably at least one selected from the group consisting of oxygen and nitrogen.

[Surface treatment agent]
Hereinafter, the surface treatment agent containing the perfluoro polyether group (Hereafter, it may be called "PFPE") containing compound of this invention is demonstrated.

The PFPE-containing compound is represented by Formula (1A) or Formula (1B).

  In the above (1A) and (1B), each occurrence of Rf independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms.

  The "C1-C16 alkyl group" in the C1-C16 alkyl group which may be substituted by one or more fluorine atoms is a branched chain even if it is linear or It is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.

The above Rf is preferably an alkyl group having 1 to 16 carbon atoms which is substituted by one or more fluorine atoms, and more preferably a CF ₂ H—C _1-15 perfluoroalkylene group or C _{1 — It is a 16} perfluoroalkyl group, more preferably a C _1-16 perfluoroalkyl group. In addition, an alkylene group is a group which has _a- (C ( _beta ) H2 ( _beta ))-structure.

The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and preferably has 1 to 6 carbon atoms, particularly 1 to 6 carbon atoms, in a linear or branched chain. a 3 perfluoroalkyl group, more preferably a perfluoroalkyl group having 1 to 3 carbon atoms, straight-chain, specifically is _-CF 3, _-CF 2 CF ₃ or _-CF 2 _CF 2 CF _3, .

In the above (1A), the PFPEs are each independently at each occurrence:
_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
Is a group represented by

  In the formula, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1. Preferably, a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less. Preferably, the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more. Preferably, the sum of a, b, c, d, e and f is 200 or less, more preferably 100 or less, for example 10 or more and 200 or less, more specifically 10 or more and 100 or less. In addition, the order in which each repeating unit enclosed in parentheses with a, b, c, d, e or f is present is arbitrary in the formula.

These repeating units may be linear or branched, but are preferably linear. For _{example, - (OC 6 F 12)} - _{is, - (OCF 2 CF 2 CF} 2 CF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2 CF 2 CF 2) -, - (OCF ₂ CF (CF ₃ ) CF ₂ CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF (CF ₃ ) CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ CF (CF ₃ ) CF ₂ )- _{, - (OCF 2 CF 2 CF} 2 CF 2 CF (CF 3)) - may be, etc., but preferably _{- (OCF 2 CF 2 CF 2} CF 2 CF 2 CF 2) - a. - _{(OC 5 F} 10) - _{is, - (OCF 2 CF 2 CF} 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2 CF 2) -, - (OCF 2 CF (CF 3) It may be CF ₂ CF ₂ )-,-(OCF ₂ CF ₂ CF (CF ₃ ) CF ₂ )-,-(OCF ₂ CF ₂ CF ₂ CF (CF ₃ ))-or the like, but is preferably-( _{OCF 2 CF 2 CF 2 CF 2} CF 2) - a. - _{(OC 4} F 8) - _{is, - (OCF 2 CF 2 CF} 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2) -, - (OCF 2 CF (CF 3) CF 2) - _{, - (OCF 2 CF 2 CF} (CF 3)) -, - (OC (CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF 3) CF ( It may be any of CF ₃ )),-(OCF (C ₂ F ₅ ) CF ₂ )-and-(OCF ₂ CF (C ₂ F ₅ ))-, but is preferably-(OCF ₂ CF _2). CF ₂ CF ₂₎ - a. - _{(OC 3} F 6) - _{is, - (OCF 2 CF 2 CF} 2) -, - (OCF (CF 3) CF 2) - and _{- (OCF 2 CF (CF 3} )) - be any of good, preferably _{- (OCF 2 CF 2 CF 2} ) - a. _{Also, - (OC 2 F 4)} - is, - _{(OCF 2} CF 2) - and _{- (OCF (CF 3))} - but it may be any of, preferably - _{(OCF 2} CF 2) - in is there.

In one embodiment, the PFPE may - is (wherein, d is 1 to 200, preferably 5 to 200, more preferably 10 to 200 _{integer) - (OC 3 F 6)} d . Preferably, PFPE is — (OCF ₂ CF ₂ CF ₂ ) _d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) or OCF (CF ₃ ) CF ₂ ) _d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less). More preferably, PFPE is — (OCF ₂ CF ₂ CF ₂ ) _d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) .

In another embodiment, the PFPE is — (OC ₄ F ₈ ) _c — (OC ₃ F ₆ ) _d — (OC ₂ F ₄ ) _e — (OCF ₂ ) _f —, wherein c and d are each independently And e and f are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and c, d, e and The sum of f is at least 5 or more, preferably 10 or more, and the order in which each repeating unit enclosed in parentheses with the subscript c, d, e or f is given is arbitrary in the formula). Preferably, PFPE _{is, - (OCF 2 CF 2 CF} 2 CF 2) c - (OCF 2 CF 2 CF 2) d - (OCF 2 CF 2) e - (OCF 2) f - a. In one aspect, PFPE is — (OC ₂ F ₄ ) _e — (OCF ₂ ) _f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order in which each repeating unit enclosed in parentheses with the subscript e or f is attached may be arbitrary in the formula).

In one aspect, PFPE is — (OC ₂ F ₄ ) _e — (OCF ₂ ) _f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order in which each repeating unit enclosed in parentheses with the subscript e or f is attached may be arbitrary in the formula).

  In PFPE, the ratio of e to f (hereinafter referred to as “e / f ratio”) is 0.1 or more and 10 or less, preferably 0.2 or more and 5.0 or less, more preferably 0.2 or more It is 2.0 or less, more preferably 0.2 or more and 1.5 or less. By setting the e / f ratio in the above range, the water repellency, oil repellency and chemical resistance of the cured product obtained from this compound (for example, durability against aqueous solution of salt, acid or basic solution, acetone, oleic acid or hexane) ) Can be further improved. The smaller the e / f ratio, the better the water repellency, oil repellency and chemical resistance of the cured product. On the other hand, by setting the e / f ratio to 0.1 or more, the stability of the compound can be further enhanced. The higher the e / f ratio, the better the stability of the compound.

In still another aspect, PFPE is a group represented by-(R ⁶¹ -R ⁶² ) _j- . In the formula, R ⁶¹ is OCF ₂ or OC ₂ F ₄ , preferably OC ₂ F ₄ . Wherein R ⁶² 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 selected independently from these groups A combination of two or three groups. Preferably, R ⁶² is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ or from OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ It is a selected group, or a combination of 2 or 3 groups independently selected from these groups. The combination of 2 or 3 groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited. For example, -OC ₂ F ₄ OC ₃ F _6- , -OC ₂ F ₄ OC ₄ F ₈ −, −OC ₃ F ₆ OC ₂ F ₄ −, −OC ₃ F ₆ OC ₃ F ₆ −, −OC ₃ F ₆ OC ₄ F ₈ −, −OC ₄ F ₈ OC ₄ F _{8 -, - OC 4 F 8} OC 3 F 6 -, - OC 4 F 8 OC 2 F 4 -, - OC 2 F 4 OC 2 F 4 OC 3 F 6 -, - OC 2 F 4 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 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 - , and the like. The j is an integer of 2 or more, preferably 3 or more, more preferably 5 or more, and 100 or less, preferably 50 or less. In the above formula, OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ may be linear or branched, preferably linear . In this embodiment, PFPE is _{preferably, - (OC 2 F 4 -OC} 3 F 6) j - or _{- (OC 2 F 4 -OC 4} F 8) j - is.

  The average molecular weight of the Rf-PFPE- moiety is not particularly limited, but is 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000.

  In another embodiment, the number average molecular weight of the Rf-PFPE moiety is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000.

  In another aspect, the number average molecular weight of the Rf-PFPE-moiety or -PFPE-moiety may be from 4,000 to 30,000, preferably 5,000 to 10,000.

In the above formula (1B), PFPE ¹ is the same as PFPE. The PFPE ¹ preferably does not have a branched structure.

In the above formula (1B), Rf ¹ independently represents (O-Rf ¹¹ ) _m2 at each occurrence.

Rf ¹¹ is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms, preferably a fluoroalkylene group having 2 to 6 carbon atoms, and particularly preferably a fluoroalkylene group having 2 carbon atoms preferable. The number of hydrogen atoms contained in Rf ¹¹ is preferably 1 to 4, and particularly preferably 1 or 2. As (O-Rf ¹¹ ), (O-CHFCF ₂ ) and (O-CH ₂ CF ₂ ) are preferable. In the present specification, a fluoroalkylene group means a group in which at least one hydrogen atom of an alkylene group is substituted by a fluorine atom.

It said m2 is an integer of 0 to 4, when m2 is an integer of 2 to 4 _^(O-Rf 11 _{^O) m2} may be one of two or more ^{O-Rf 11.}

In the above formula (1B), Rf ² independently represents (O-Rf ²¹ ) _m3 at each occurrence.

Rf ²¹ is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms, and is preferably a fluoroalkylene group having 2 to 6 carbon atoms. The number of hydrogen atoms contained in Rf ²¹ is preferably 1 to 4, particularly preferably 1 or 2.

It said m3 is an integer of 0 to 4, when m3 is an integer of 2 to 4 ^(O-Rf _{21) m3} may be made of two or more ^{O-Rf 21.} It is preferable that m3 is an integer of 0-2.

In one embodiment, it is represented by ^(O-Rf ₂₁₎ (when X is a single bond, ^{R m)} X in _m3 binds ^(O-Rf 21) ^{is, (O-Rf 21 'CH} 2) Can be R f ^{21 ′} is a group having a carbon number smaller than that of R f ²¹ by one and is a perfluoroalkylene group or a fluoroalkylene group having a hydrogen atom. R f ^{21 ′} is preferably a perfluoroalkylene group. Specific examples of (O-Rf ^{21 '} CH ₂ ) include (O-CF ₂ CH ₂ ), (O-CF ₂ CF ₂ CH ₂ ), (O-CF ₂ CF ₂ CF ₂ CH ₂ ), (O _{-CF 2 CF 2 CF 2 CF 2} CH 2) or the like are preferable. In this case, m3 is preferably 1.

In the PFPE ¹ , preferably, the sum of a, b, c, d, e, f, m2 and m3 is 5 or more, more preferably 10 or more. Preferably, the sum of a, b, c, d, e, f, m2 and m3 is 200 or less, more preferably 100 or less, for example 10 or more and 200 or less, more specifically 10 or more and 100 or less It is below.

  In another embodiment, the sum of a, b, c, d, e, f, m2 and m3 is in the range of 2-210.

In the above formulas (1A) and (1B), X represents a single bond, an oxygen atom or a di- to 10-valent organic group. In the compound represented by the formula (1A) or (1B), the X is a perfluoropolyether moiety (ie, Rf-PFPE moiety) or Rf-Rf ¹ -which mainly provides water repellency and surface slipperiness and the like. It is understood as a linker linking PFPE ¹ -Rf ² part) and R ^m . Accordingly, X may be any organic group as long as the compound represented by the formula (1A) or (1B) can be stably present.

  The divalent to decavalent organic group in X is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.

  In said formula, (alpha) 1 is an integer of 1-9, (alpha) 2 is an integer of 1-9. These α1 and α2 can change according to the valence of X. In formulas (1A) and (1B), the sum of α1 and α2 is the same as the valence of X. For example, when X is a 10-valent organic group, the sum of α1 and α2 is 10, for example, α1 is 9 and α2 is 1, α1 is 5 and α2 is 5, or α1 is 1 and α2 is 9. . When X is a divalent organic group, α1 and α2 are 1.

  In one embodiment, X is a single bond or a divalent to tetravalent organic group, α 1 is an integer of 1 to 3 and α 2 is 1.

  In another embodiment, X is a single bond or a divalent organic group, α 1 is 1 and α 2 is 1. In this case, the formula (1A) is represented by the following formula (1A ′), and the formula (1B) is represented by the following formula (1B ′).

In one embodiment, X represents a single bond or a 2-10 monovalent organic group, preferably a single bond, an alkylene group or _-C 6 _{H 4} - (i.e. - phenylene -. Hereinafter, a phenylene group.) , -CO- (carbonyl group), - represents a 2-10 monovalent organic group having at least one selected from the group consisting of - NR ⁸ -, and -SO _2. Each R ⁸ independently represents a hydrogen atom, a phenyl group, or a C _1-6 alkyl group (preferably a methyl group), preferably a hydrogen atom or a methyl group. Additional _{-C 6 H 4 -, - CO} -, - NR 8 - or -SO ₂ - is preferably contained in the molecular backbone of the PFPE-containing compound. Here, the molecular main chain represents a relatively long PFPE-containing binding chain among the molecules of the PFPE-containing compound.

In this embodiment, X is more preferably a single bond, an alkylene group or ^{_{-C 6 H 4 -, - CONR}} 8 -, - CONR 8 -C 6 H 4 -, - CO -, - CO-C 6 H 4 _{^{-, - SO 2 NR 8 -}} , - SO 2 NR 8 -C 6 H 4 -, - SO 2 -, and _-SO 2 _-C 6 _{H 4} - _2~10 having at least one of from the selected group consisting of Represents a valent organic group. Additional _{^{-C 6 H 4 -, - CONR}} 8 -, - CONR 8 -C 6 H 4 -, - CO -, - CO-C 6 H 4 -, - SO 2 NR 8 -, - SO 2 NR 8 - _{C 6 H 4 -, - SO} 2 -, or _-SO 2 _-C 6 _{H 4} - is preferably contained in the molecular backbone of the PFPE-containing compound.

In this embodiment, in X, the PFPE moiety (ie, the group linked by α2 in formula (1A) or (1B)) and the R ^m group (ie the group linked by α1 in formula (1A) or (1B) The number of atoms connecting) may be preferably 20 or less, more preferably 10 or less, and still more preferably 6 or less. When there are a plurality of routes connecting one PFPE part and one R ^m group, the above “number of atoms connecting the PFPE part and R ^m group” means the shortest distance between the PFPE part and the R ^m group. It means the number of linking atoms.

In another embodiment, examples of X are not particularly limited, and for example, the following formula:
-(R ⁸¹ ) _{p '} -(X ^a ) _q'-
[In the formula:
R ⁸¹ represents a single bond,-(CH ₂ ) _{s '} -or o-, m- or p-phenylene group, preferably-(CH ₂ ) _s'-
s' is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, still more preferably 1 or 2.
X ^a represents-(X ^b ) _{l '} -
X ^b is each independently -O-, -S-, o-, m- or p-phenylene group, -C (O) O-, -Si (R ⁸³ ) ₂ -,-(-) Si (R ⁸³ ) ₂ O) _{m ′} —Si (R ⁸³ ) ₂ —, —CONR ⁸⁴ −, —O—CONR ⁸⁴ −, —NR ⁸⁴ − and — (CH ₂ ) _{n ′} − Represents a group
R ⁸³ each independently represents a phenyl group, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a phenyl group or a C _1-6 alkyl group, and more preferably a methyl group And
R ⁸⁴ each independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group) at each occurrence;
m 'is independently at each occurrence an integer of 1 to 100, preferably an integer of 1 to 20,
n 'in each occurrence is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3,
l 'is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3,
p 'is 0 or 1 and
q 'is 0 or 1 and
Here, at least one of p 'and q' is 1, and the existence order of each repeating unit enclosed in parentheses with p 'or q' is arbitrary.]
The bivalent group represented by these is mentioned. Here, R ⁸¹ and X ^a (typically ^a hydrogen atom of R ⁸¹ and X ^a ) are one or more selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group It may be substituted by the substituent of

Preferably, said X ^is- (R ^<81> ) _{p '} -(X ^<a> ) _q'- R < ⁸² >-. R ⁸² represents a single bond,-(CH ₂ ) _{t '} -or o-, m- or p-phenylene group, preferably-(CH ₂ ) _t'- . t 'is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. Here, R ⁸² (typically a hydrogen atom of R ⁸² ) is substituted with one or more substituents selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group It may be

Preferably, the above X is
Single bond,
C _1-20 alkylene group,
-R ⁸¹ -X ^c -R ⁸² - or ^-X d ^{-R 82,} -
[Wherein, R ⁸¹ and R ⁸² are as defined above. ]
It can be.

More preferably, the above X is
Single bond,
C _1-20 alkylene group,
_{- (CH 2) s' -X} c -,
-(CH ₂ ) _{s '} -X ^c- (CH ₂ ) _t'- ,
-X ^d- or-X ^d- (CH ₂ ) _{t '} -
[Wherein, s ′ and t ′ are as defined above. ]
It is.

In the above formula, X ^c is
-O-,
-S-,
-C (O) O-,
-CONR ⁸⁴ -,
-O-CONR ⁸⁴ -,
-Si (R ⁸³ ) _2- ,
-(Si (R ⁸³ ) ₂ O) _{m '} -Si (R ⁸³ ) _2- ,
_{-O- (CH 2) u '-} (Si (R 83) 2 O) m' -Si (R 83) 2 -,
^{_{-O- (CH 2) u '-Si}} (R 83) 2 -O-Si (R 83) 2 -CH 2 CH 2 -Si (R 83) 2 -O-Si (R 83) 2 -,
_{-O- (CH 2) u '-Si} (OCH 3) 2 OSi (OCH 3) 2 -,
_{^{-CONR 84 - (CH 2) u}} '- (Si (R 83) 2 O) m' -Si (R 83) 2 -,
_{^{-CONR 84 - (CH 2) u}} '-N (R 84) -, or ^-CONR 84 - (o-, m- or p- _phenylene) -Si ^(R 83) ₂ -
[Wherein, R ⁸³ , R ⁸⁴ and m ′ are as defined above,
u 'is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. Represents]. X ^c is preferably -O-.

In the above formula, X ^d is
-S-,
-C (O) O-,
-CONR ⁸⁴ -,
_{^{-CONR 84 - (CH 2) u}} '- (Si (R 83) 2 O) m' -Si (R 83) 2 -,
_{^{-CONR 84 - (CH 2) u}} '-N (R 84) -, or ^-CONR 84 - (o-, m- or p- _phenylene) -Si ^(R 83) ₂ -
[Wherein each symbol is as defined above. ]
Represents

More preferably, the above X is
Single bond,
C _1-20 alkylene group,
_{- (CH 2) s' -X} c - (CH 2) t '-, or ^{_{-X d - (CH 2) t}} ' -
[Wherein each symbol is as defined above. ]
It can be.

Even more preferably, said X is
Single bond,
C _1-20 alkylene group, particularly preferably C _1-10 alkylene group,
_{- (CH 2) s '-O-} (CH 2) t' -,
-(CH ₂ ) _s' -(Si (R ⁸³ ) ₂ O) _{m '} -Si (R ⁸³ ) _2- (CH ₂ ) _t'- ,
_{- (CH 2) s '-O-} (CH 2) u' - (Si (R 83) 2 O) m '-Si (R 83) 2 - (CH 2) t' -, or - _(CH 2) _{s' -O- (CH 2) t} '-Si (R 83) 2 - (CH 2) u' -Si (R 83) 2 - (C v H 2v) -
[Wherein, R ⁸³ , m ′, s ′, t ′ and u ′ are as defined above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably 2 to 3] It is an integer. ]
It is.

In the above formulae,-(C _v H _2v ) _{-may be} linear or branched, and for example, -CH _2- , -CH ₂ CH _2- , -CH ₂ CH ₂ CH _{2 -, - CH (CH 3} ) -, - CH (CH 3) CH 2 - may be.

In one embodiment, X _{^{is, - (O) t1 - (}} R f1 O) t2 -R f2 - may be a group represented by ^{- (C (= O) N} (R f3)) t3 -R f4.

  The above t1 is 0 or 1.

The above R ^f1 is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms. R ^f1 is preferably a C _2-6 fluoroalkylene group. The number of hydrogen atoms contained in R ^f1 is preferably in the range of 1 to 4, and more preferably 1 or 2.

When two or more types of R ^f1 O are present in the above (R ^f1 O) _t2 , the order in which each (R ^f1 O) is present is arbitrary in the formula.

  Said t2 is an integer of 0-4, and it is more preferable that it is an integer of 0-2.

The R ^f2 is a single bond, a perfluoroalkylene group having no branched structure, or a fluoroalkylene group having no branched structure containing one or more hydrogen atoms. It is preferable that the said perfluoro alkylene group or fluoro alkylene group contains 1-10 carbon atoms.

R ^f3 is a hydrogen atom or an alkyl group (preferably a C _1-4 alkyl group).

  The above t3 is 0 or 1.

When t3 is 0, R ^f2 is preferably a single bond. In this case ^(i.e., (if R f1 _{O) t2} and ^{R f4} are directly ^bonded), (R f1 _O) binds to ^{R f4} in _t2 ^{(R f1} O) is ^(R f5 _CH 2 O) It is preferable that it is a group represented by R ^f5 is a group having one less carbon atom than R ^{f1 and} is a perfluoroalkylene group or a fluoroalkylene group having one or more hydrogen atoms. R ^f5 is preferably a perfluoroalkylene group. (R ^f5 CH ₂ O) is (CF ₂ CH ₂ O), (CF ₂ CF ₂ CH ₂ O), (CF ₂ CF ₂ CF ₂ CH ₂ O), (CF ₂ CF ₂ CF ₂ CF ₂ CH ₂₎ O) etc. is preferable. In this case, t2 is preferably 1.
When t3 is 1, t2 is 0 to 2 and R ^f2 is preferably a perfluoroalkylene group or a fluoroalkylene group having one or more hydrogen atoms, and a perfluoroalkylene group more preferably, and particularly preferably a C _1-6 perfluoroalkylene group.

R ^f4 represents a single bond, an alkylene group having 1 to 10 carbon atoms, or an end of an alkylene group having 1 to 10 carbon atoms (with the proviso that the side bonded to the group attached with α1 in formula (1A) or (1B) Terminal) a group having an etheric oxygen atom, a group having an etheric oxygen atom between carbon-carbon atoms of an alkylene group having 2 to 10 carbons, or a terminal (where the formula has an alkylene group having 2 to 10 carbons) (1A) or (1B) is the end of the side bonded to the group attached with α1) and a group having an etheric oxygen atom between carbon and carbon atoms. The group having an etheric oxygen atom, for _{example, -CH 2 CH 2 -O -,} - CH 2 CH 2 -O-CH 2 - , and the like.

The R ^f4 is preferably a single bond or a C _1-4 alkylene group, and more preferably a single bond or a C _1-2 alkylene group.

The above X is, for example,
-(O) _t1- (R ^f1 O) _t2- ,
^{_{- (O) t1 - (R}} f1 O) t2 -CH 2 O-,
-(O) _t1- (R ^f1 O) _t2 -CH ₂ OCH _2- ,
^{_{- (O) t1 - (R}} f1 O) t2 -CH 2 O- (CH 2) 2 -O-,
^{_{- (O) t1 - (R}} f1 O) t2 -CH 2 O- (CH 2) 2 -O-CH 2 -,
-(O) _t1- ( ^Rf1O ) _t2- ^Rf2- C (O) NH-,
^{_{- (O) t1 - (R}} f1 O) t2 -R f2 -C (O) NHCH 2 -,
^{_{- (O) t1 - (R}} f1 O) t2 -R f2 -C (O) NH (CH 2) 2 -,
^{_{- (O) t1 - (R}} f6 CH 2 O) -CH 2 -,
^{_{- (O) t1 - (R}} f6 CH 2 O) -CH 2 -O-CH 2 -,
^{-C (O) NH-R f4} -, or ^{_{- (O) t1 -R f6 CH}} 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-R f4 - ( e.g., _{- (O)} t1 -CF ₂ CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF ₂ -C (O) NH-R ^f 4-)
Etc. can be mentioned. R ^f1 , R ^f2 , R ^f4 , t1 and t2 are as defined above. t1 is preferably 1. R ^f6 is a perfluoroalkylene group having no branched structure.

The X group is substituted by one or more substituents selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group (preferably a C _1-3 perfluoroalkyl group) It may be

［式中、Ｒ^４１は、それぞれ独立して、水素原子、フェニル基、炭素数１〜６のアルキル基、またはＣ_１−６アルコキシ基、好ましくはメチル基であり；
Ｄは、
−ＣＨ_２Ｏ（ＣＨ_２）_２−、
−ＣＨ_２Ｏ（ＣＨ_２）_３−、
−ＣＦ_２Ｏ（ＣＨ_２）_３−、
−（ＣＨ_２）_２−、
−（ＣＨ_２）_３−、
−（ＣＨ_２）₄−、
−ＣＯＮＨ−（ＣＨ_２）_３−、
−ＣＯＮ（ＣＨ_３）−（ＣＨ_２）_３−、
−ＣＯＮ（Ｐｈ）−（ＣＨ_２）_３−（式中、Ｐｈはフェニルを意味する）、および

（式中、Ｒ^４２は、それぞれ独立して、水素原子、Ｃ_１−６のアルキル基またはＣ_１−６のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。）
から選択される基であり、
Ｅは、−（ＣＨ_２）_ｎｅ−（ｎｅは２〜６の整数）であり、
Ｄは、分子主鎖のＰＦＰＥに結合し、Ｅは、ＰＦＰＥと反対の基に結合する。］ In another embodiment, the X group includes, for example, the following groups:

[Wherein, each R ⁴¹ independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group;
D is
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CF 2 O (CH 2) 3} -,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _(CH 2) ₄ -,
-CONH- (CH ₂ ) _3- ,
_{-CON (CH 3) - (CH} 2) 3 -,
-CON (Ph)-(CH ₂ ) _3- (wherein Ph means phenyl), and

(Wherein, R ⁴² each independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group).
Is a group selected from
E is _- a (ne is an integer of from 2 to _6), - _{(CH 2)} ne
D is attached to the PFPE of the molecular backbone and E is attached to the opposite group to the PFPE. ]

などが挙げられる。 As a specific example of the above X, for example:
Single bond,
-CH ₂ OCH _2- ,
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CH 2 O (CH 2) 6} -,
_{- (CH 2) 2 -Si (} CH 3) 2 - (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH ₂ OCF ₂ CHFOCF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF _2- ,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF 2 CF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 CF 2 -,
_{-CH 2 OCH 2 CF 2 CF 2} OCF (CF 3) CF 2 OCF 2 CF 2 CF 2 -,
_{-CH 2 OCF 2 CHFOCF 2 CF 2} CF 2 -C (O) NH-CH 2 -,
-CH ₂ OCH ₂ CHFCF ₂ OCF _2- ,
—CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ —,
—CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ CF ₂ —,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 -,
_{-CH 2 OCH 2 CHFCF 2 OCF (} CF 3) CF 2 OCF 2 CF 2 CF 2 -,
-CH ₂ OCH ₂ (CH ₂ ) ₇ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) _2- ,
—CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₃ —,
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₃ -,-
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ -,-
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₂ -,-
-CH ₂ -,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _{(CH 2)} 4 -,
-(CH ₂ ) _5- ,
- _{(CH 2)} 6 -,
-CO-,
-CONH-,
_-CONH-CH 2 -,
-CONH- (CH ₂ ) _2- ,
-CONH- (CH ₂ ) _3- ,
_{-CON (CH 3) - (CH} 2) 3 -,
-CON (Ph)-(CH ₂ ) _3- (wherein Ph means phenyl),
-CONH- (CH ₂ ) _6- ,
_{-CON (CH 3) - (CH} 2) 6 -,
-CON (Ph)-(CH ₂ ) _6- (wherein Ph means phenyl),
-CONH- (CH ₂ ) ₂ NH (CH ₂ ) _3- ,
_{-CONH- (CH 2) 6 NH (} CH 2) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 3 -,
_{-CH 2 O-CONH- (CH 2} ) 6 -,
-S- _{(CH 2)} 3 -,
-(CH ₂ ) ₂ S (CH ₂ ) _3- ,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,
_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
_{-C (O) O- (CH 2} ) 3 -,
_{-C (O) O- (CH 2} ) 6 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 2 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 3 -,
_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -CH 2 -,
-OCH _2- ,
-O _{(CH 2)} 3 -,
-OCFHCF _2- ,

Etc.

In another preferred embodiment, X is a single bond, an alkylene group having 1 to 6 carbon _{^{atoms, -R 85 -C 6 H 4 -R}} 86 -, - R 85 -CONR 8 -R 86 -, - R 85 -CONR ^8- C ₆ H _4- R ⁸⁶ -,-R ^85- CO-R ⁸⁶ -,-R ^85- CO-C ₆ H _4- R ⁸⁶ -,-R ^85- SO ₂ NR ^8- R ⁸⁶ -,- _{^{R 85 -SO 2 NR 8 -C 6}} H 4 -R 86 -, - R 85 -SO 2 -R 86 -, or _{^{-R 85 -SO 2 -C 6 H 4}} -R 86 - is. R ⁸⁵ and R ⁸⁶ each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 3 carbon atoms. R ⁸ is as defined above. The alkylene group is substituted or unsubstituted, preferably unsubstituted. As a substituent of the said alkylene group, a halogen atom, Preferably a fluorine atom can be mentioned, for example. The alkylene group is linear or branched, and is preferably linear.

In this embodiment, X is more preferably
Single bond,
An alkylene group of 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,
^{_{-C 6 H 4 -R 86 '-}} ,
-CONR ^{8 '-R 86'} -,
_{^{-CONR 8 '-C 6 H 4 -R}} 86' -,
-CO-R ^{86 '} -,
-CO-C ₆ H ₄ -R ^{86 '} -,
-SO ₂ NR ^{8 '} -R ^86'- ,
_{^{-SO 2 NR 8 '-C 6 H}} 4 -R 86' -,
-SO ₂ -R ^{86 '} -,
-SO ₂ -C ₆ H ₄ -R ^{86 '} -,
_{^{-R 85 '-C 6 H 4 -}} ,
-R ^{85 '-CONR 8'} -,
_{^{-R 85 '-CONR 8' -C 6}} H 4 -,
-R ^{85 '} -CO-,
_{^{-R 85 '-CO-C 6 H}} 4 -,
_{^{-R 85 '-SO 2 NR 8'}} -,
_{^{-R 85 '-SO 2 NR 8'}} -C 6 H 4 -,
-R ^{85 '} -SO _2- ,
_{^{-R 85 '-SO 2 -C 6 H}} 4 -,
-C ₆ H ₄ -,
-CONR ^{8 '} -,
_{^{-CONR 8 '-C 6 H 4 -}} ,
-CO-,
_{-CO-C 6 H} 4 -,
-SO ₂ NR ^{8 '} -,
_{^{-SO 2 NR 8 '-C 6 H}} 4 -,
-SO ₂ -, or _-SO 2 _-C 6 _{H 4} -
(Wherein, R ^{85 ′} and R ^{85 ′} each independently represent a linear alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,
R ^{8 ′} is a hydrogen atom or methyl. )
It can be.

In this aspect, as a specific example of X, for example,
Single bond,
An alkylene group having 1 to 6 carbon atoms,
-CONH-,
_-CONH-CH 2 -,
-CONH- (CH ₂ ) _2- ,
-CONH- (CH ₂ ) _3- ,
-CON _(CH 3) -,
_{-CON (CH 3) -CH 2 -} ,
_{-CON (CH 3) - (CH} 2) 2 -,
_{-CON (CH 3) - (CH} 2) 3 -,
-CH ₂ -CONH-,
-CH _{2 -CONH-CH 2} -,
_{-CH 2 -CONH- (CH 2) 2} -,
_{-CH 2 -CONH- (CH 2) 3} -,
_{-CONH-C 6 H} 4 -,
_{-CON (CH 3) -C 6 H} 4 -,
_{-CH 2 -CON (CH 3) -CH} 2 -,
-CH ₂ -CON (CH ₃ )-(CH ₂ ) _2- ,
_{-CH 2 -CON (CH 3) -} (CH 2) 3 -,
_{-CON (CH 3) -C 6 H} 4 -,
-CO-,
_{-CO-C 6 H} 4 -,
-C ₆ H ₄ -,
-SO ₂ NH-,
-SO _{2 NH-CH 2} -,
_{-SO 2 NH- (CH 2) 2} -,
_{-SO 2 NH- (CH 2) 3} -,
_{-SO 2 NH-C 6 H 4} -,
_{-SO 2 N (CH 3) -} ,
_{-SO 2 N (CH 3) -CH} 2 -,
_{-SO 2 N (CH 3) -} (CH 2) 2 -,
_{-SO 2 N (CH 3) -} (CH 2) 3 -,
_{-SO 2 N (CH 3) -C} 6 H 4 -,
-SO _2- ,
-SO ₂ -CH _2- ,
-SO _2- (CH ₂ ) _2- ,
-SO _2- (CH ₂ ) _3- ,
-SO ₂ -C ₆ H ₄ -
Etc.

  In one embodiment, X is a single bond.

［式中、
Ｒ^４１は、それぞれ独立して、水素原子、フェニル基、炭素数１〜６のアルキル基、またはＣ_１−６アルコキシ基、好ましくはメチル基であり；
各Ｘ基において、Ｔのうち任意のいくつかは、分子主鎖のＰＦＰＥに結合する以下の基：
−ＣＨ_２Ｏ（ＣＨ_２）_２−、
−ＣＨ_２Ｏ（ＣＨ_２）_３−、
−ＣＦ_２Ｏ（ＣＨ_２）_３−、
−ＣＨ_２−、
−（ＣＨ_２）_２−、
−（ＣＨ_２）_３−、
−（ＣＨ_２）₄−、
−ＣＯＮＨ−（ＣＨ_２）_３−、
−ＣＯＮ（ＣＨ_３）−（ＣＨ_２）_３−、
−ＣＯＮ（Ｐｈ）−（ＣＨ_２）_３−（式中、Ｐｈはフェニルを意味する）、または

［式中、Ｒ^４２は、それぞれ独立して、水素原子、Ｃ_１−６のアルキル基またはＣ_１−６のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。］
であり、別のＴのいくつかは、分子主鎖のＰＦＰＥと反対の基に結合する−（ＣＨ_２）_ｎ”−（ｎ”は２〜６の整数）であり、存在する場合、残りのＴは、それぞれ独立して、メチル基、フェニル基、Ｃ_１−６アルコキシ基またはラジカル捕捉基もしくは紫外線吸収基であり得る。 In yet another embodiment, examples of X groups include:

[In the formula,
Each R ⁴¹ independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group;
In each X group, some of T are attached to PFPE of the main chain of the molecule:
_{-CH 2 O (CH 2) 2} -,
_{-CH 2 O (CH 2) 3} -,
_{-CF 2 O (CH 2) 3} -,
-CH ₂ -,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _(CH 2) ₄ -,
-CONH- (CH ₂ ) _3- ,
_{-CON (CH 3) - (CH} 2) 3 -,
-CON (Ph)-(CH ₂ ) _3- (wherein Ph means phenyl), or

[Wherein, R ⁴² each independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. ]
And some of the other T's are — (CH ₂ ) _{n ′ ′} (where n ′ ′ is an integer from 2 to 6) attached to the group opposite to the PFPE of the molecular backbone T may be each independently a methyl group, a phenyl group, a C _1-6 alkoxy group, or a radical scavenging group or an ultraviolet absorbing group.

  The radical scavenging group is not particularly limited as long as it can scavenge a radical generated upon irradiation with light, for example, benzophenones, benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonic esters, organoacrylates And residues of hindered amines, hindered phenols, or triazines.

  The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet light, and examples thereof include benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, The residue includes oxanilides, benzoxazinones and benzoxazoles.

が挙げられる。 In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups are

Can be mentioned.

  In this embodiment, X may be a trivalent to ten-valent organic group.

In one embodiment, X ^is represented by ^{_{-X 11 (OH) j1 (X}} 12) 3-j1 or _{^{-X 11 (OX 12) j1 (}} X 12) 3-j1. X ¹¹ is a carbon atom. X ¹² each independently at each occurrence is a single bond or a divalent to hexavalent hydrocarbon group, and may have a silicon atom and / or a siloxane bond. OX ¹² or X ¹² links between X ¹¹ and -R ^m . j1 is each independently an integer of 1 to 3, and preferably 1 at each occurrence.

In the above formulas (1A) and (1B), R ^m is a group represented by the following formula each independently at each occurrence.

  In the above formulae, M is a metal atom capable of coordinate bonding independently at each occurrence. The above M is preferably a transition metal atom such as an aluminum atom, a zinc atom, a titanium atom, a zirconium atom, a chromium atom, an iron atom, a cobalt atom, a nickel atom or a copper atom, more preferably an aluminum atom, a titanium atom, Or a zirconium atom, more preferably an aluminum atom or a titanium atom, particularly preferably an aluminum atom.

In the above formulae, R ¹ each independently represents a monodentate ligand having a bond with X at each occurrence. That is, X (wherein X is a single bond, PFPE in formula (1A) and Rf ² in formula (1B)) and M are linked via R ¹ .

R ¹ is preferably —R ¹¹ —O— or —R ¹¹ N (R ¹² ) —. In the above R ¹ , an oxygen atom or a nitrogen atom coordinates with M. In R ¹ above, R ¹¹ is bonded to X (where X is a single bond, PFPE in formula (1A) and Rf ² in formula (1B)).

In the formula, R ¹² is a hydrogen atom or a monovalent organic group. R ¹² is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

In the formula, each R ¹¹ independently at each occurrence is a single bond or a divalent organic group.

The above R ¹¹ is, for example,
Single bond,
Carbonyl group,
C _1-10 alkylene group, more preferably C _1-6 alkylene group,
-(CH ₂ ) _k1 -C (= O)-,
_{-C (= O) -O- (CH} 2) k1 '-,
_{- (CH 2) k1 C (} = O) -O- (CH 2) k1 '-, or _{- (CH 2) k1 -O- (} CH 2) k1' -
Can be mentioned. k1 is independently an integer of 1 to 10 at each occurrence, and k1 'is an integer of 1 to 10 independently at each occurrence. Preferably, k1 is an integer of 1 to 6, and k1 'is an integer of 1 to 6.

Examples of R ¹ include
-O-,
-NR ¹² -,
-C (= O) -O-,
^{-C (= O) -NR 12 -} ,
- _{(CH 2)} k1 -O-,
^{_{- (CH 2) k1 -NR 12}} -,
_{- (CH 2) k1 -C (} = O) -O-,
_{- (CH 2) k1 -C (} = O) -NR 12 -,
_{-C (= O) -O- (CH} 2) k1 '-O-,
_{-C (= O) -O- (CH} 2) k1 '-NR 12 -,
_{- (CH 2) k1 C (} = O) -O- (CH 2) k1 '-O-,
_{- (CH 2) k1 C (} = O) -O- (CH 2) k1 '-NR 12 -,
_{- (CH 2) k1 -O- (} CH 2) k1 '-O-, or _{- (CH 2) k1 -O- (} CH 2) k1' -NR 12 -
Can be mentioned. In the above, the oxygen atom or the nitrogen atom present at the terminal part is a coordinating atom. R ¹² , k1 and k1 ′ are as defined above.

The above R ¹ is more preferably -R ¹¹ -O-.

More specifically, R ¹ is
-O-,
-CH ₂ -O-,
- _{(CH 2) 2} -O-,
-C (= O) -O-,
_{-CH 2 -C (= O) -O-} , or _{- (CH 2) 2 -C (} = O) -O-
It is. In addition, the oxygen atom which exists in the terminal part of said Formula is a coordination atom.

In the above formulae, R ² each independently represents a polydentate ligand having a bond with X at each occurrence. That is, X (wherein X is a single bond, PFPE in formula (1A) and Rf ² in formula (1B)) and M are linked via R ² .

Preferably, R ² is a bidentate ligand.

More preferably, R ² is one in which any one of the following compounds (1-1) to (1-6) is coordinated. A group other than R ^{21 in} the following formula (for example, in formula (1-1), C (CO) (CH ₂ ) ₁₁ -C (= O) -R ²² ) may be referred to as R ²³ . That is, R ² is one in which a compound that can be represented by R ²¹ -R ²³ is coordinated.

  In the formula, l 1 is an integer of 0 to 6 independently at each occurrence. 11 is independently at each occurrence preferably an integer of 0 to 4, more preferably 1 to 2.

In formula, * shows a coordination atom. For example, the compounds represented by the above formulas (1-1) to (1-6) coordinate with M as in the following (1-1 ′) to (1-6 ′).

More specifically, when l1 is 1, the compound represented by Formula (1-1) coordinates with M as follows.

In the formula, each R ²¹ independently at each occurrence is an oxygen atom or a divalent organic group. In R ² above, R ²¹ is bonded to X (where X is a single bond, PFPE in formula (1A) and Rf ² in formula (1B)).

Preferably, R ²¹ is
-O-,
-C (= O) -O-,
C _1-6 alkylene group, _or- (CH ₂ ) 12 -O-
It is. Incidentally, if there is an oxygen atom at the terminal portion of the above formula, the oxygen atom binds to R ^23. l2 is an integer of 1 to 6;

In the formula, R ²² is independently at each occurrence a hydrogen atom or a monovalent organic group. R ²² is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group, and more preferably an alkyl group having 1 to 6 carbon atoms, More preferably, it is a C1-C3 alkyl group (for example, methyl group).

In a preferred embodiment, R ² preferably contains a structure capable of keto-enol transfer. More preferably, R ² is a group represented by the formula (1-1), in which l 1 is 1, R ²¹ is an oxygen atom, and R ²² is 1 to 3 carbon atoms (For example, a methyl group). In formula, * shows a coordination atom.

In another embodiment, R ² can form a 4- to 12-membered chelate ring with M, preferably form a 4- to 6-membered chelate ring.

In (1A) and (1B) above, R ³ independently represents a monodentate ligand at each occurrence. R ³ represents a monodentate ligand which binds only to M and not directly to X.

R ³ is preferably at least one selected from the group consisting of a halogen atom, a hydrogen atom, a hydroxyl group, and a monovalent organic group. As said halogen atom, a chlorine atom and a fluorine atom can be mentioned. The monovalent organic group described ^above, R 31 -O-, or ^R 31 N ^{(R 32)} - can be exemplified. In the monovalent organic group, an oxygen atom or a nitrogen atom coordinates with M.

R ³¹ is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. R ³² is a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

The above R ³ is preferably R ³¹ -O-. R ³¹ is as defined above, and R ³¹ -O- is, for example, a methoxy group, an ethoxy group or an isopropoxy group.

In the above (1A) and (1B), R ⁴ independently represents a polydentate ligand at each occurrence. R ⁴ represents a polydentate ligand that binds only to M and not directly to X.

Preferably, R ⁴ is a bidentate ligand.

More preferably, R ⁴ is one to which at least one selected from the group consisting of the following compounds (2-1) to (2-6) is bonded.

  In the formula, n1 is an integer of 0 to 6 independently at each occurrence. n1 is independently at each occurrence preferably an integer of 0 to 4, and more preferably 1.

In formula, * shows a coordination atom. For example, the compounds represented by the above formulas (2-1) to (2-6) coordinate with M as in the following (2-1 ') to (2-6').

More specifically, when n1 is 1, the compound represented by Formula (2-1) coordinates with M as follows.

In the formula, R ⁴³ each independently at each occurrence is a hydrogen atom or a monovalent organic group.

Preferably, R ⁴³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. More preferably, R ⁴³ is an alkyl group of 1 to 3 carbon atoms or an alkoxy group of 1 to 3 carbon atoms.

In the formula, R ⁴⁴ is independently at each occurrence a hydrogen atom or a monovalent organic group.

Preferably, R ⁴⁴ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. More preferably, R ⁴⁴ is an alkyl group of 1 to 3 carbon atoms or an alkoxy group of 1 to 3 carbon atoms.

In one aspect, R ⁴³ is an alkyl group having 1 to 3 carbon atoms (for example, a methyl group), and R ⁴⁴ is an alkyl group having 1 to 3 carbon atoms (for example, an ethyl group).

In one aspect, R ⁴³ is an alkyl group having 1 to 3 carbon atoms (for example, a methyl group), and R ⁴⁴ is an alkoxy group having 1 to 3 carbon atoms (for example, an ethoxy group).

In another embodiment, R ⁴ can form a 4- to 12-membered chelate ring with M, and preferably form a 4- to 6-membered chelate ring.

In formula (1A) and formula (1B), k is an integer of 0 to 2; l is an integer of 0 to 2; m is an integer of 0 or more; n is an integer of 0 or more It is. However, the sum of k and l is 1 to 4, and the value of l multiplied by the number of conformations of R ² , the value of n multiplied by the number of constellations of R ⁴ , and the sum of k and m is M It is a coordination number. For example, when M is an aluminum atom, a titanium atom, or a zirconium atom, the coordination number of M is 4 or 6.

In one aspect, k is 0 or 1; l is 0 or 1; m is an integer of 0 or more; n is an integer of 0 or more. However, the sum of k and l is 1, the value of l multiplied by the number of conformations of R ² , the value of n multiplied by the number of conformations of R ⁴ , the sum of k and m is the configuration of M It is a number.

  In one embodiment, k is 1; l is 0.

  In one embodiment, k is 0; l is 1.

In one embodiment, k is 1; l is 0; m is 1; n is 1. In this embodiment, preferably, R ² is a bidentate ligand, and more preferably, M is an aluminum atom or a titanium atom (more preferably, an aluminum atom).

In one embodiment, k is 0; l is 1; m is 0; n is 2. In this embodiment, preferably, R ² is a bidentate ligand, and more preferably, M is an aluminum atom or a titanium atom (more preferably, an aluminum atom).

ｋが、１であり；
ｌが、０であり；
ｍが、１であり；
ｎが、１である。 In preferred embodiments, R ^m is
M is an aluminum atom or a titanium atom (more preferably an aluminum atom);
R ¹ is represented by -R ¹¹ -O-, wherein R ¹¹ is a divalent organic group, preferably a carbonyl group;
R ³ is a monovalent organic group, preferably represented by R ³¹ —O— (wherein R ³¹ is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms , Eg isopropyl group);
R ⁴ is a bidentate ligand, preferably represented by the formula (2-1) (wherein * represents a coordinating atom, n 1 is 1 and R ⁴³ is a carbon number of 1 to 4) And R ⁴⁴ is an alkyl group of 1 to 3 carbon atoms or an alkoxy group of 1 to 3 carbon atoms.

k is 1;
l is 0;
m is 1;
n is 1.

In this aspect, an example of R ^m may be represented by the following formula. In the following formulae, R ¹¹ is as defined above, specifically a C (OO) group; R ³¹ is as defined above, specifically an isopropyl group R ⁴³ is as defined above, specifically a methyl group; and R ⁴⁴ is as defined above, specifically an ethyl group. ** represents a site binding to X.

Ｒ^４が、二座配位子であり、好ましくは式（２−１）で表され（式中、＊は配位原子を表し、ｎ１が、１であり、Ｒ^４３が、各出現においてそれぞれ独立して炭素数１〜３のアルキル基または炭素数１〜３のアルコキシ基であり、Ｒ^４４は、各出現においてそれぞれ独立して、炭素数１〜３のアルキル基または炭素数１〜３のアルコキシ基である。）

ｋが、０であり；
ｌが、１であり；
ｍが、０であり；
ｎが、２である。 In another preferred embodiment, R ^m is
M is an aluminum atom or a titanium atom (more preferably an aluminum atom);
R ² is a bidentate ligand, preferably represented by the formula (1-1) (wherein * represents a coordinating atom, 11 is 1 and R ²¹ is an oxygen atom) , R ²² is an alkyl group having 1 to 3 carbon atoms (eg, a methyl group);

R ⁴ is a bidentate ligand, preferably represented by the formula (2-1) (wherein * represents a coordinating atom, n 1 is 1 and R ⁴³ is each at each occurrence And R ⁴⁴ independently represents an alkyl group having 1 to 3 carbon atoms or 1 to 3 carbon atoms. It is an alkoxy group.)

k is 0;
l is 1;
m is 0;
n is 2.

In this aspect, an example of R ^m may be represented by the following formula. In the following formulae, R ²² is as defined above, specifically a methyl group; R ⁴³ and R ⁴⁴ each independently at each occurrence are a methyl group, an ethyl group or an ethoxy group It is. For example, in the following formulae, R ⁴³ may be a methyl group, one of R ⁴⁴ may be an ethyl group, and the other may be an ethoxy group. ** represents a site binding to X.

  Since the PFPE-containing compounds represented by the formulas (1A) and (1B) contain a metal atom at the end, they have the effect of easily adhering to metal surfaces or metal oxide surfaces.

The PFPE-containing compounds represented by the formulas (1A) and (1B) have water repellency and oil repellency since they have a group represented by Rf-PFPE or a group represented by Rf-Rf ¹ -PFPE-Rf ² It contributes to the formation of a particularly good surface treatment layer. This is because the CF ₃ group contained in the terminal part of Rf exhibits extremely low surface free energy, and this group is oriented to the outermost surface.

  From the viewpoint of providing a surface treatment agent having better water repellency and oil repellency, it is preferable to use the PFPE-containing compound represented by the formula (1A).

The formula (1A) or PFPE-containing compound represented by (1B), for example, a complex represented by the following formula (2A) or PFPE compound and formula (3) represented by (2B), ^{Y 1} and step of forming R ¹ is reacted with Y ² or, can be prepared by a method comprising the step of forming a R ² by reacting Y ¹ and Y ^{2 '.}

In the formulas (2A), (2B) and (3), Rf, PFPE, PFPE ¹ , Rf ¹ , Rf ² , α 1, α 2, X, M, R ³ , R ⁴ and k to n are as defined above It is significant.

Y ¹ contains a reactive group.

As the reactable groups can include, for example, the ^{OR 10} or ^NR 10 ^{R 12 'or} the like, Of these, ^{OR 10} are preferred. R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom. R ^{12 ′} is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

The Y ¹ is, for example,
-R ¹⁹ -OR ¹⁰ or ^-R 19 ^{-NR 10,}
Is represented by R ¹⁰ is as defined above. R ¹⁹ is a single bond or a divalent organic group.

Examples of R ¹⁹ include
Single bond,
Carbonyl group,
C _1-10 alkylene group (more preferably, C _1-6 alkylene group),
_{- (CH 2) l3 -C (} = O) -,
_{-C (= O) -O- (CH} 2) l3 '-,
-(CH ₂ ) ₁₃ C (= O)-O-(CH ₂ ) _{13 '} -or-(CH ₂ ) ₁₃ -O-(CH ₂ ) _13'-
Can be mentioned. l3 is each independently an integer of 1 to 12 at each occurrence, and l3 ^' is an integer of 1 to 12 at each occurrence independently. Preferably, l3 is an integer of 1 to 6, and l3 'is an integer of 1 to 6.

Examples of Y ¹ include
-OH,
-C (= O) OH,
- _{(CH 2)} l3 -OH,
-(CH ₂ ) ₁₃ -C (= O) -OH,
_{-C (= O) -O- (CH} 2) l3 '-OH,
_{-C (= O) -O- (CH} 2) l3 '-C (= O) OH,
— (CH ₂ ) ₁₃ C (= O) —O— (CH ₂ ) _{13 ′} —OH,
— (CH ₂ ) ₁₃ C (= O) —O— (CH ₂ ) _{13 ′} —C (= O) OH,
-(CH ₂ ) ₁₃ -O- (CH ₂ ) _{13 '} -OH _or- (CH ₂ ) ₁₃ -O- (CH ₂ ) _13' -C (= O) -OH
Can be mentioned. l3 is each independently an integer of 1 to 12 at each occurrence, and l3 ^' is an integer of 1 to 12 at each occurrence independently. Preferably, l3 is an integer of 1 to 6, and l3 'is an integer of 1 to 6.

Preferably, said Y ¹ is -R ¹⁹ -OR ¹⁰ . R ¹⁹ and R ¹⁰ are as defined above. Particularly preferably, Y ¹ is
-OH,
-C (= O) OH,
_{- (CH 2) l3 "-OH} , or _{- (CH 2) l3" -C} (= O) -OH
It is. l3 ′ ′ is an integer of 1 to 3, preferably 1.

The above Y ² contains a reactive group Y ²¹ .

As said group Y ^{21 which} can be reacted, a chlorine atom, a bromine atom, an iodine atom, C (= O) OR10 ^' , or OR10 ^' etc. can be mentioned, for example, Among these, OR10 ^' is preferable. R ^{10 ′} is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms (that is, a methyl group, an ethyl group, an n-propyl group or an isopropyl group).

The above Y ^{2 ′} includes a reactive group Y ^{21 ′} . Y ^{21 ′} is the same as Y ²¹ .

Preferably, the reactive group Y ²¹ is a group coordinated to M instead of R ¹ . Preferably, the above-mentioned reactable group Y ^{21 ′} is a group introduced to R ²³ in place of R ²¹ .

More specifically, said Y ² is one in which Y ²¹ is coordinated.

More specifically, said Y ^{2 '} is one in which the following compound is coordinated.

In the formulae, * represents a coordinating atom, and Y ^{21 ′} , R ²² and l 1 are as defined above.

In a preferred embodiment, Y ¹ and Y ² are each a group in which Y ¹ is —C (OHO) —OH, Y ² is —OR ^{10 ′} (wherein R ^{10 ′} is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) Preferably it is a C1-C3 alkyl group).

In another preferred embodiment, Y ¹ and Y ^{2 ′} are each Y ¹ is — (CH ₂ ) _{13 ′ ′ ′} -OH (wherein 13 ′ ′ ′ is an integer of 1 to 3, preferably 1) And Y ^{2 ′} are groups represented by the following formulae. In the formula, * represents a coordinating atom; Y ^{21 ′} is OR ^{10 ′} , 11 is 1, and R ²² is an alkyl group having 1 to 3 carbon atoms (eg, a methyl group). R ^{10 ′} is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms (that is, a methyl group, an ethyl group, an n-propyl group or an isopropyl group).

  The surface treatment agent of the present invention contains the above-mentioned PFPE-containing compound preferably in an amount of 0.01 to 100 parts by mass, more preferably 0.1 to 30 parts by mass, with respect to 100 parts by mass of the surface treatment agent.

  The surface treatment agent of the present invention can impart water repellency, oil repellency, stain resistance, surface slip, and friction durability to a substrate, and the stain resistance coating is not particularly limited. It can be suitably used as an agent or a waterproof coating.

The surface treatment agent of the present invention may be diluted with a solvent. Such solvent is not particularly limited, but, for example:
Perfluorohexane, CF ₃ CF ₂ CHCl ₂ , CF ₃ CH ₂ CF ₂ CH ₃ , CF ₃ CHF CHFC ₂ F ₅ , 1,1,1,2,2,3,3,4,4,5,5,6 , 6-tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane (such as Zeorora H (trade name)), C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , CF ₃ CH ₂ OCF ₂ CHF ₂ , C ₆ F ₁₃ CH = CH ₂ , xylene hexafluoride, perfluorobenzene, methyl pentadecafluoroheptyl ketone, trifluoroethanol, pentafluoropropanol, hexafluoroisopropanol, HCF ₂ CF ₂ CH ₂ OH, methyl trifluoromethanesulfonate, trifluoroacetate and _CF 3 O (C During _{2 CF 2 O) m1 (CF} 2 O) n1 CF 2 CF 3 [ wherein m1 and n1, are each independently zero or greater than 1,000 integer bracketed bear the m1 or n1 The order of existence of each repeating unit is arbitrary in the formula, provided that the sum of m1 and n1 is 1 or more.], 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene, 1 , 2-dichloro-1,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-3,3,3-trifluoro-1-propene, 1,1-dichloro-3,3,3,3 Trifluoro-1-propene, 1,1,2-trichloro-3,3,3-trifluoro-1-propene, 1,1,1,4,4,4-hexafluoro-2-butene Solvents containing fluorine atoms selected from Be

As the solvent, C ₆ F ₁₃ OCH ₃ may be used.

  In one aspect, the water content contained in the solvent is 20 ppm or less in mass conversion. The water content can be measured using the Karl Fischer method. By such a water content, the storage stability of the surface treatment agent can be improved.

  The surface treatment agent of the present invention may further contain other components. Such other components include, but are not limited to, for example, other surface treatment compounds, fluoropolyether compounds (non-reactive) that can be understood as fluorine-containing oils, preferably perfluoro (poly) ethers. Compounds (hereinafter referred to as "fluorine-containing oils"), silicone compounds (hereinafter referred to as "silicone oils") that can be understood as silicone oils (hereinafter referred to as "silicone oils"), alcohols, catalysts, transition of platinum, ruthenium, rhodium, etc. Examples thereof include metals, halide ions, and compounds containing an atom having an unshared electron pair in the molecular structure.

Although it does not specifically limit as said fluorine-containing oil, For example, the compound (perfluoro (poly) ether compound) represented by following General formula (4) is mentioned.
^{_{Rf 5 - (OC 4 F 8}} ) a '- (OC 3 F 6) b' - (OC 2 F 4) c '- (OCF 2) d' -Rf 6 ··· (4)
In the formula, R f ⁵ represents a C _1-16 alkyl group (preferably a C _1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, and R f ⁶ represents Rf ⁵ and Rf ^{6 each} represents a C _1-16 alkyl group (preferably a C _1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom; And more preferably each independently a C _1-3 perfluoroalkyl group.
a ′, b ′, c ′ and d ′ each represent the number of repeating units of four types of perfluoro (poly) ethers constituting the main skeleton of the polymer, and are each independently an integer of 0 or more and 300 or less; The sum of a ′, b ′, c ′ and d ′ is at least 1, preferably 1 to 300, more preferably 20 to 300. The order in which each repeating unit enclosed in parentheses with a subscript a ', b', c 'or d' is given is arbitrary in the formula. Among these repeating _{units, - (OC 4 F 8)} - _{is, - (OCF 2 CF 2 CF} 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2) -, - (OCF 2 CF (CF _{3) CF 2) -, -} (OCF 2 CF 2 CF (CF 3)) -, - (OC (CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF ₃ ) CF (CF ₃ ) —, — (OCF (C ₂ F ₅ ) CF ₂ ) — and — (OCF ₂ CF (C ₂ F ₅ )) —, which may be any of _{- (OCF 2 CF 2 CF 2} CF 2) - a. - _{(OC 3} F 6) - _{is, - (OCF 2 CF 2 CF} 2) -, - (OCF (CF 3) CF 2) - and _{- (OCF 2 CF (CF 3} )) - be any of well, preferably _{- (OCF 2 CF 2 CF 2} ) - a. - _(OC 2 _{F 4)} - is, - _{(OCF 2} CF 2) - and _{- (OCF (CF 3))} - but may be any of, preferably - _{(OCF 2} CF 2) - a.

Examples of the perfluoro (poly) ether compound represented by the above general formula (4) include a compound represented by any one of the following general formulas (4a) and (4b) (one or a mixture of two or more) May be mentioned.
Rf ^5- (OCF ₂ CF ₂ CF ₂ ) _{b ′ ′} −Rf ⁶ (4a)
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. (4b)
In these formulas, Rf ⁵ and Rf ⁶ are as described above; in formula (4a), b ′ ′ is an integer of 1 or more and 100 or less; in formula (4b), a ′ ′ and b ′ ′ are Each is independently an integer of 1 or more and 30 or less, and c ′ ′ and d ′ ′ are each independently an integer of 1 or more and 300 or less. The order in which each repeating unit enclosed in parentheses with the subscripts a ′ ′, b ′ ′, c ′ ′ and d ′ ′ is given is arbitrary in the formula.

  The fluorine-containing oil may have an average molecular weight of 1,000 to 30,000. Thereby, high surface slipperiness can be obtained.

  In the surface treatment agent of the present invention, the fluorine-containing oil is a total of 100 parts by mass of the above-mentioned perfluoro (poly) ether group-containing compound and the above-mentioned carboxylic acid ester compound (in the case of two or more, their total, Similarly, it may be contained, for example, in an amount of 0 to 500 parts by mass, preferably 0 to 400 parts by mass, and more preferably 5 to 300 parts by mass.

  The compound represented by the general formula (4a) and the compound represented by the general formula (4b) may be used alone or in combination. It is preferable to use the compound represented by the general formula (4b) rather than the compound represented by the general formula (4a) because higher surface slipperiness can be obtained. When using these in combination, the mass ratio of the compound represented by the general formula (4a) to the compound represented by the general formula (4b) is preferably 1: 1 to 1:30, and 1: 1 to 1:30. 10 is more preferable. According to this mass ratio, it is possible to obtain a surface treatment layer excellent in the balance between surface slipperiness and friction durability.

  In one aspect, the fluorine-containing oil comprises one or more compounds represented by the general formula (4b). In this aspect, the mass ratio of the PFPE-containing compound in the surface treatment agent to the compound represented by the formula (4b) is preferably 10: 1 to 1:10, and 4: 1 to 1: 4. It is more preferable that

  In one aspect, the average molecular weight of the compound represented by Formula (4a) is preferably 2,000 to 8,000.

  In one aspect, the average molecular weight of the compound represented by Formula (4b) is preferably 8,000 to 30,000.

  In another aspect, the average molecular weight of the compound represented by formula (4b) is preferably 3,000 to 8,000.

  In a preferred embodiment, when the surface treatment layer is formed by a vacuum deposition method, the number average molecular weight of the fluorinated oil may be larger than the number average molecular weight of the PFPE-containing compound. For example, the number average molecular weight of the fluorine-containing oil may be increased by 2,000 or more, preferably 3,000 or more, more preferably 5,000 or more, than the number average molecular weight of the PFPE-containing compound. By setting it as such a number average molecular weight, more superior friction durability and surface slipperiness can be obtained.

From another point of view, the fluorine-containing oil may be a compound represented by the general formula Rf′-F (wherein Rf ′ is a C _5-16 perfluoroalkyl group). Moreover, a chloro trifluoro ethylene oligomer may be sufficient. The compound represented by Rf′-F and the chlorotrifluoroethylene oligomer are preferable in that high affinity is obtained with the above-mentioned PFPE-containing compound in which Rf is a C _1-16 perfluoroalkyl group.

  The fluorine-containing oil contributes to the improvement of the surface slipperiness of the surface treatment layer.

  As the silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used. Linear silicone oils may be so-called straight silicone oils and modified silicone oils. Straight silicone oils include dimethyl silicone oil, methyl phenyl silicone oil and methyl hydrogen silicone oil. Examples of the modified silicone oil include those obtained by modifying a straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like. The cyclic silicone oil may, for example, be a cyclic dimethylsiloxane oil.

  In the surface treatment agent of the present invention, such silicone oil is, for example, 0 to 300 parts by mass, preferably 0 based on 100 parts by mass of the above-mentioned PFPE containing compound (in the case of two or more, the total of them, the same applies hereinafter). It may be contained in 200 parts by mass.

  The silicone oil contributes to the improvement of the surface slipperiness of the surface treatment layer.

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

  The catalyst promotes the hydrolysis and dehydration condensation of the PFPE-containing compound and promotes the formation of the surface treatment layer.

  As other components, other than the above, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane and the like can also be mentioned.

  Chloride ion etc. are mentioned as said halide ion.

  The compound containing an atom having a noncovalent electron pair in the above molecular structure preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom and a sulfur atom, and a sulfur atom or a nitrogen atom More preferably,

  The compound containing an atom having a noncovalent electron pair in the above molecular structure is at least selected from the group consisting of an amino group, an amido group, a sulfinyl group, a P = O group, an S = O group and a sulfonyl group in the molecular structure. It is preferable to include one functional group, and more preferably to include at least one functional group selected from the group consisting of P = O group and S お よ び O group.

  The compound containing an atom having a noncovalent electron pair in the above molecular structure is at least one compound selected from the group consisting of aliphatic amine compounds, aromatic amine compounds, phosphoric acid amide compounds, amide compounds, urea compounds and sulfoxide compounds. At least one compound selected from the group consisting of aliphatic amine compounds, aromatic amines, phosphoric acid amides, urea compounds and sulfoxide compounds, more preferably sulfoxide compounds, aliphatic amine compounds and Particularly preferred is at least one compound selected from the group consisting of aromatic amine compounds, and more preferred is a sulfoxide compound.

  Examples of the aliphatic amine compound include diethylamine and triethylamine. Examples of the aromatic amine compound include aniline and pyridine. As said phosphoric acid amide compound, hexamethyl phosphoramide etc. can be mentioned, for example. Examples of the amide compound include N, N-diethylacetamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylformamide, N, N-dimethylformamide, N-methylpyrrolidone and the like. it can. Tetramethyl urea etc. can be mentioned as said urea compound. Examples of the sulfoxide compound include dimethyl sulfoxide (DMSO), tetramethylene sulfoxide, methylphenyl sulfoxide, diphenyl sulfoxide and the like. Of these compounds, dimethyl sulfoxide or tetramethylene sulfoxide is preferably used.

  As another component, a C1-C6 alcohol compound is mentioned other than the above, for example.

[pellet]
The surface treatment agent of the present invention can be made into pellets by impregnating a porous material such as a porous ceramic material, metal fiber such as steel wool into a cotton-like form. The said pellet can be used for vacuum evaporation, for example.

  The surface treatment agent of the present invention is suitably used as a surface treatment agent because it can impart water repellency, oil repellency, stain resistance, waterproofness, high friction durability and UV resistance to a substrate. Ru. Specifically, the surface treatment agent of the present invention is not particularly limited, but can be suitably used as an antifouling coating agent or a waterproof coating agent.

[Article]
Next, the article of the present invention will be described.

  The article of the present invention comprises a substrate and a layer (surface treated layer) formed on the surface of the substrate from the surface treatment agent of the present invention. This article can be manufactured, for example, as follows.

  First, a base material is prepared. Substrates that can be used in the present invention are, for example, glass, resin (natural or synthetic resin such as general plastic material, may be plate-like, film, other form), metal (aluminum, copper) May be a simple substance of metal such as iron or a complex such as alloy), ceramics, semiconductor (silicon, germanium, etc.), fiber (textile, non-woven fabric, etc.), fur, leather, wood, ceramic, stone etc., construction members, etc. , May be composed of any suitable material.

The glass is preferably sapphire glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, non-alkali glass, crystal glass, quartz glass, chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, And chemically bonded borosilicate glass are particularly preferred.
As the resin, acrylic resin and polycarbonate are preferable.

For example, when the article to be manufactured is an optical member, the material constituting the surface of the substrate may be an optical member material such as glass or transparent plastic. When the article to be manufactured is an optical member, some layer (or film) such as a hard coat layer or an antireflective layer may be formed on the surface (the outermost layer) of the substrate. For the antireflective layer, either a single layer antireflective layer or a multilayer antireflective layer may be used. Examples of inorganic substances that can be used for the antireflective layer include SiO ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ , Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ and MgO. , Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO _{3 and the} like. These inorganic substances may be used alone or in combination of two or more of them (for example, as a mixture). If the multilayer antireflection layer, it is preferable to use SiO ₂ and / or SiO in its outermost layer. When the article to be manufactured is an optical glass part for a touch panel, it has a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide on a part of the surface of a substrate (glass) It may be In addition, the base material may be 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, according to the specific specifications and the like. And a liquid crystal display module.

  The shape of the substrate is not particularly limited. The surface area of the substrate on which the surface treatment layer is to be formed may be at least a part of the surface of the substrate, and may be appropriately determined according to the application and specific specifications of the article to be manufactured.

  As such a substrate, at least the surface portion may be made of a material originally having a hydroxyl group. Examples of such a material include glass, and further, metals (in particular, base metals), ceramics, semiconductors, etc. on which a natural oxide film or a thermal oxide film is formed on the surface. Alternatively, as in the case of resin or the like, when having hydroxyl groups is not sufficient or when the hydroxyl groups are not originally contained, the substrate is subjected to some pretreatment to introduce hydroxyl groups on the surface of the substrate. Can be increased or decreased. Examples of such pretreatment include plasma treatment (eg, corona discharge) and ion beam irradiation. The plasma treatment can introduce or increase hydroxyl groups on the substrate surface, and can also be suitably used to clean the substrate surface (remove foreign substances and the like). In addition, as another example of such pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bond group is previously coated on the surface of the substrate by the LB method (Langmuir-Blodgett method), chemical adsorption method or the like. It may be formed in a form and then the unsaturated bond may be cleaved under an atmosphere containing oxygen, nitrogen and the like.

  Alternatively, as such a substrate, at least the surface portion thereof may be made of a material containing a silicone compound having one or more other reactive groups such as Si-H group, or an alkoxysilane.

  In particular, as a substrate, it is preferable to use a substrate in which metal atoms exist on the surface of the substrate, such as alumite, sapphire glass, or zirconia. Since the affinity between the metal contained in the substrate and the metal atom contained in the PFPE-containing compound represented by formula (1A) or (1B) can be particularly high, the formed surface treatment layer and the substrate Binding can be more robust. Accordingly, the water repellency of the formed surface treatment layer is particularly good, and the abrasion resistance is also improved.

  Next, a film of the above-mentioned surface treatment agent of the present invention is formed on the surface of such a substrate, and this film is post-treated if necessary, thereby forming a surface treatment layer from the surface treatment agent of the present invention Do.

  Film formation of the surface treatment agent of the present invention can be carried out by applying the surface treatment agent of the present invention to the surface of a substrate so as to cover the surface. The coating method is not particularly limited. For example, wet coating and dry coating can be used.

  Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.

  Examples of dry coating methods include vapor deposition (usually vacuum evaporation), sputtering, CVD and similar methods. Specific examples of the deposition method (usually, vacuum deposition method) include resistance heating, high frequency heating using an electron beam, microwave and the like, an ion beam, and similar methods. Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD and similar methods.

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

When using a wet coating method, the surface treatment agent of the present invention can be diluted with a solvent and then applied to the substrate surface. From the viewpoint of the stability of the surface treatment agent of the present invention and the volatility of the solvent, the following solvents are preferably used: C _5-12 perfluoroaliphatic hydrocarbons (eg, perfluorohexane, perfluoromethylcyclohexane and the like) Perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg, bis (trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbons (eg, C ₆ F ₁₃ CH ₂ CH ₃ (eg, Asahi Glass) ASAHIKLIN (registered trademark) AC-6000), 1, 1, 2, 2, 3, 3,4-heptafluorocyclopentane (eg, Zeoror (registered trademark) H, manufactured by Nippon Zeon Co., Ltd.); Hydrofluorocarbons (HFCs) (for example, 1,1,1,3,3-pentafluorobutane (HFC-365) fc)); hydrochlorofluorocarbon (e.g., HCFC-225 (ASAHIKLIN (TM) AK225)); hydrofluoroether (HFE) (e.g., perfluoropropyl methyl ether _{(C 3 F 7 OCH 3)} ( e.g., Sumitomo Novec (trade name) 7000 manufactured by 3M Co., Ltd., perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) (eg, Novec (trade name) 7100 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl ethyl ether (C) ₄ F ₉ OC ₂ H ₅ ) (for example, Novec (trade name) 7200 manufactured by Sumitomo 3M Ltd.), perfluorohexyl methyl ether (C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ ) (for example, Sumitomo ₃ M Novec (brand name) 73 manufactured by Corporation 0) alkyl perfluoroalkyl ethers (such as perfluoroalkyl groups and the alkyl group may be straight or branched), or _{CF 3 CH 2 OCF 2 CHF 2} ( e.g., Asahi Glass ASAHIKLIN Co., Ltd. ( (Registered trademark) AE-3000)), 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene (for example, Bertrel (registered trademark) Scion manufactured by DuPont Fluorochemicals, Inc.) and the like. These solvents may be used alone or as a mixture of two or more, and may be mixed with another solvent, for example, to adjust the solubility of the PFPE-containing compound.

  When the dry coating method is used, the surface treatment agent of the present invention may be directly subjected to the dry coating method, or may be subjected to the dry coating method after being diluted with the above-mentioned solvent.

  Film formation is preferably carried out such that the surface treatment agent of the present invention is present in the film together with a catalyst for hydrolysis and dehydration condensation. Conveniently, in the case of wet coating, after diluting the surface treatment agent of the present invention with a solvent, the catalyst may be added to the diluted solution of the surface treatment agent of the present invention just before application to the substrate surface. In the case of the dry coating method, the catalyst-added surface treatment agent of the present invention is directly subjected to vapor deposition (usually, vacuum deposition), or the catalyst-added surface treatment agent of the present invention is applied to metal porous bodies such as iron and copper. The material may be subjected to vapor deposition (usually vacuum evaporation) using a pellet-like substance impregnated with

  Any suitable acid or base can be used for the catalyst. As an acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used. Moreover, as a base catalyst, ammonia, organic amines etc. can be used, for example.

  The membrane is then post-treated if necessary. This post-treatment is not particularly limited, but may be, for example, sequentially performing water supply and dry heating, and more specifically, may be performed as follows.

  After the surface treatment agent of the present invention is formed into a film on the substrate surface as described above, water is supplied to this film (hereinafter also referred to as "precursor film"). The method of supplying water is not particularly limited, and, for example, a method such as condensation due to a temperature difference between the precursor film (and the substrate) and the ambient atmosphere, spraying of steam (steam), or the like may be used.

  The supply of water may be carried out, for example, in an atmosphere of 0 to 250 ° C., preferably 60 ° C. or more, more preferably 100 ° C. or more, preferably 180 ° C. or less, more preferably 150 ° C. or less. By supplying water in such a temperature range, it is possible to allow the hydrolysis to proceed. The pressure at this time is not particularly limited, but may be simply normal pressure.

  Next, the precursor film is heated on the surface of the substrate under a dry atmosphere over 60 ° C. The method of drying and heating is not particularly limited, and the precursor film and the base material are temperatures higher than 60 ° C., preferably higher than 100 ° C., for example, 250 ° C. or lower, preferably 180 ° C. or lower, and not It may be disposed under an atmosphere of saturated water vapor pressure. The pressure at this time is not particularly limited, but may be simply normal pressure.

  The water supply and the drying and heating described above may be carried out continuously by using superheated steam.

  Post-processing can be performed as described above. It should be noted that such post-treatments may be carried out to further improve the friction durability, but are not essential for producing the articles of the present invention. For example, after applying the surface treatment agent of the present invention to the substrate surface, it may be left standing as it is.

  As described above, the surface treatment layer derived from the film of the surface treatment agent of the present invention is formed on the surface of the substrate to produce the article of the present invention. The surface treatment layer obtained thereby has good UV resistance. In addition to good UV resistance, this surface treatment layer is water-repellent, oil-repellent, antifouling (for example, prevents adhesion of stains such as fingerprints), although it depends on the composition of the composition used. It may have surface slipperiness (or lubricity, for example, the ability to wipe off dirt such as fingerprints, excellent touch to a finger), high friction durability, and the like, and may be suitably used as a functional thin film.

  That is, the present invention further relates to an optical material having the cured product in the outermost layer.

  As the optical material, in addition to optical materials related to displays as exemplified later, a wide variety of optical materials are preferably mentioned: For example, a cathode ray tube (CRT; eg, TV, personal computer monitor), liquid crystal display, plasma display, Displays such as organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFDs), field emission displays (FEDs) or protective plates of those displays, or reflections on those surfaces Those with a protective film treatment.

  An article having a surface treatment layer obtained by the present invention is not particularly limited, but may be an optical member. Examples of optical members include: lenses such as glasses; front protective plates for displays such as PDPs and LCDs; anti-reflection plates; polarizing plates; anti-glare plates; devices such as mobile phones and personal digital assistants Touch panel sheet; disc surface of optical disc such as Blu-ray (registered trademark) disc, DVD disc, CD-R, MO, etc .; optical fiber etc.

  In addition, the article having a surface treatment layer obtained by the present invention may be a medical device or a medical material.

  The thickness of the surface treatment layer is not particularly limited. In the case of an optical member, the thickness of the surface treatment layer is in the range of 1 to 50 nm, more preferably 1 to 30 nm, particularly preferably 1 to 15 nm. Optical performance, surface slipperiness, friction durability and antifouling It is preferable from the point of sex.

  As another form, after forming a layer separately on the surface of a substrate, you may form the film of the surface treatment layer obtained by this invention on the surface of the layer.

  Hereinabove, the article obtained using the surface treatment agent of the present invention has been described in detail. In addition, the use of the surface treatment agent of this invention, the usage method, and the manufacturing method of articles | goods etc. are not limited to what was illustrated above.

The surface treatment agent of the present invention will be more specifically described through the following examples, but the present invention is not limited to these examples. In the present example, the order of existence of the repeating units (OCF ₂ CF ₂ ) and (OCF ₂ CF ₂ CF ₂ ) constituting the perfluoropolyether is arbitrary.

・パーフルオロポリエーテル基含有アルミニウム化合物（Ｂ）：

・ Composition example 1
Perfluoropolyether modified carboxylic acid represented by average composition CF ₃ CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) ₂₀ OCF ₂ CF ₂ CO ₂ H in a 30 mL three-necked flask fitted with a thermometer and a stirrer 2.4 g of an acid form, 3 g of 1,3-bis (trifluoromethyl) benzene, and 0.4 g of an aluminum chelate compound represented by the following compound (A) were charged, and stirred at room temperature for 16 hours under a nitrogen stream. Then, the volatile component was distilled off under reduced pressure to obtain 2.7 g of a perfluoropolyether group-containing aluminum compound (B) of the following formula having an aluminum chelate at the end.
Aluminum chelate compound (A):

Perfluoropolyether group-containing aluminum compound (B):

・パーフルオロポリエーテル基含有アルミニウム化合物（Ｄ）：

・ Composition example 2
Perfluoropolyether modified alcohol represented by average composition CF ₃ CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) ₂₀ OCF ₂ CF ₂ CH ₂ OH in a 30 mL three-necked flask fitted with a thermometer and a stirrer 2.8 g of the compound, 2 g of 1,3-bis (trifluoromethyl) benzene, and 0.3 g of an aluminum chelate compound represented by the following compound (C) were charged, and stirred at room temperature for 16 hours under a nitrogen stream. Then, the volatile component was distilled off under reduced pressure to obtain 3.0 g of a perfluoropolyether group-containing aluminum compound (D) of the following formula having an aluminum chelate at the end.
· Aluminum chelate compound (C):

Perfluoropolyether group-containing aluminum compound (D):

Example 1
The surface treatment agent 1 was prepared by dissolving the compound (B) obtained in the above Synthesis Example 1 in a hydrofluoroether (Novec HFE 7200 manufactured by 3M) so as to have a concentration of 0.2 wt%.

  Using the surface treatment agent 1 prepared above, dip treatment was performed at a pulling speed of 30 mm / sec on the surface of alumite (100 mm × 100 mm × 0.8 mm, manufactured by Toyo Chemical Co., Ltd.). Thereafter, the alumite after dip treatment was allowed to stand at a temperature of 150 ° C. for 1 hour. After that, the surface treatment layer was formed by cooling to room temperature.

Example 2
Using the surface treatment agent 1 prepared in Example 1, dip processing was performed on a surface of SUS304 (manufactured by Nippon Test Panel, BA finish, 90 mm × 60 mm × 1 mm) at a pulling speed of 30 mm / sec. Thereafter, the dip-treated SUS 304 was allowed to stand at a temperature of 150 ° C. for 1 hour. After that, the surface treatment layer was formed by cooling to room temperature.

Examples 3 and 4
A surface treatment layer was formed in the same manner as in Example 1 or 2 except that the compound (D) obtained in the above Synthesis Example 2 was used instead of the compound (B).

Comparative Examples 1 and 2
A surface treatment layer was formed in the same manner as in Example 1 or 2 except that the following control compound 1 was used instead of the compound (B).
・ Control compound 1
_{CF 3 CF 2 CF 2 (OCF} 2 CF 2 CF 2) 20 OCF 2 CF 2 CH 2 OP (O) (OH) 2

(Evaluation)
-Measurement of static contact angle The static contact angle of the water of the surface treatment layer obtained by the above-mentioned Examples 1-4 and comparative examples 1-2 was measured. The static contact angle of water was measured using a contact angle measurement device (manufactured by Kyowa Interface Science Co., Ltd.) under an environment of 21 ° C. and 65% humidity with 1 μL of water.

Evaluation of Friction Durability First, with respect to the surface treated layer formed on the surface of the substrate in Examples 1 to 4 and Comparative Examples 1 and 2 above, as an initial evaluation, the surface is wiped with cotton containing ethanol. After that, the static contact angle of water of the surface treatment layer was measured.

  About the surface treatment layer formed in the base-material surface in said Examples 1-4 and Comparative Examples 1-2, the friction durability was evaluated by the eraser friction durability test. Specifically, the sample article on which the surface treatment layer has been formed is placed horizontally, and an eraser (Kokuyo KESHI-70, planar dimension 1 cm × 1.6 cm) is brought into contact with the surface of the surface treatment layer, A load of 500 gf was applied, and then the eraser was reciprocated at a speed of 20 mm / sec with the load applied. After 100 reciprocations, the static contact angle (degree) of water was measured. The results are shown in Table 1.

  As understood from the results in Table 1, it was confirmed that the surface treatment layers of Examples 1 to 4 exhibit excellent water repellency and excellent abrasion resistance. The aluminum chelate group derived from the PFPE-containing compound contained in the surface treatment layer of Examples 1 to 4 and the substrate surface both contain a metal, so it is considered that the affinity is particularly good. As a result, the bond between the surface treatment layer and the substrate is strengthened, and it is considered that not only the initial water repellency but also the abrasion resistance is improved.

  The present invention can be suitably used to form a surface treatment layer on the surface of a wide variety of substrates, in particular of optical members that require transparency.

Claims (22)

The surface treatment agent containing the perfluoropolyether group containing compound represented by Formula (1A) or Formula (1B).

[In the formula:
R f independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
The PFPEs each independently at each occurrence have the formula:
_{- (OC 6 F 12) a} - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(A, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1; , C, d, e or f, and the order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula.)
A group represented by
PFPE ¹ is equivalent to PFPE;
R f ¹ independently represents (O-R f ¹¹ ) _{m 2} at each occurrence;
R f ¹¹ is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms;
m2 is an integer of 0 to 4, and when m2 is an integer of 2 to 4 (O-R f ¹¹ ) _m 2 may consist of two or more O-R f ¹¹ ;
R f ² independently represent (O-R f ²¹ ) _{m 3} at each occurrence;
R f ²¹ is a fluoroalkylene group having no branched structure containing one or more hydrogen atoms;
m3 is an integer of 0 to 4, and when m3 is an integer of 2 to 4 (O-R f ²¹ ) _{m 3} may consist of two or more O-R f ²¹ ;
X represents independently at each occurrence a single bond, an oxygen atom or a di- to 10-valent organic group;
α 1 is an integer of 1 to 9 independently at each occurrence;
α 2 is an integer of 1 to 9 independently at each occurrence;
R ^m is a group represented by the following formula each independently at each occurrence;

M is independently at each occurrence a coordinate bondable metal atom;
R ¹ represents, independently at each occurrence, a monodentate ligand having a bond with X;
R ² represents, independently at each occurrence, a polydentate ligand having a bond with X;
R ³ represents independently at each occurrence a monodentate ligand;
R ⁴ independently at each occurrence represents a polydentate ligand;
k is an integer of 0 to 2;
l is an integer of 0 to 2;
m is an integer of 0 or more;
n is an integer of 0 or more;
However, the sum of k and l is 1 to 4, and the value of l multiplied by the number of conformations of R ² , the value of n multiplied by the number of constellations of R ⁴ , and the sum of k and m is M It is a coordination number. ] The surface treatment agent according to claim 1, wherein the coordinating atom contained in R ^{1 to} R ⁴ is at least one selected from the group consisting of oxygen and nitrogen. R ^{1 is,} -R 11 -O-, or ^-R 11 N ^{(R 12)} - a is a surface treatment agent according to claim 1 or 2.
[Wherein, each occurrence of R ¹¹ is independently a single bond or a divalent organic group, and R ¹² is a hydrogen atom or a monovalent organic group. ] The surface treatment agent according to any one of claims 1 to 3, wherein R ² is a bidentate ligand. The surface treatment agent according to any one of claims 1 to 4, wherein R ² is one in which any one of the following compounds (1-1) to (1-6) is coordinated.

[In the formula:
* Indicates a coordination atom;
R ²¹ each independently at each occurrence is an oxygen atom or a divalent organic group;
R ²² each independently at each occurrence is a hydrogen atom, or a monovalent organic group;
l1 is an integer of 0 to 6 independently at each occurrence. ] The surface treatment agent according to any one of claims 1 to 5, wherein R ³ is at least one selected from the group consisting of a halogen atom, a hydrogen atom, a hydroxyl group, and a monovalent organic group. The surface treatment agent according to any one of claims 1 to 6, wherein R ⁴ is a bidentate ligand. The surface treatment agent according to any one of claims 1 to 7, wherein R ⁴ is one in which at least one selected from the group consisting of the following compounds (2-1) to (2-6) is bonded.

[In the formula:
* Indicates a coordination atom;
R ⁴³ each independently at each occurrence is a hydrogen atom, or a monovalent organic group;
R ⁴⁴ each independently at each occurrence is a hydrogen atom, or a monovalent organic group;
n1 is an integer of 0 to 6 independently at each occurrence. ]   The surface treatment agent according to any one of claims 1 to 8, wherein k is 1 and l is 0.   The surface treatment agent according to any one of claims 1 to 8, wherein k is 0 and l is 1.   The surface treatment agent according to any one of claims 1 to 10, wherein n is 1 or 2.   The surface treatment agent according to any one of claims 1 to 11, wherein M is an aluminum atom, a zinc atom or a transition metal atom.   The surface treatment agent according to any one of claims 1 to 12, wherein M is an aluminum atom, a titanium atom, or a zirconium atom.   The surface treatment agent according to any one of claims 1 to 13, wherein M is an aluminum atom.   The surface treatment agent according to any one of claims 1 to 14, wherein X is a divalent organic group, α1 is 1 and α2 is 1.   The surface treatment agent according to any one of claims 1 to 15, wherein the perfluoropolyether group-containing compound is represented by the formula (1A). PFPE independently at each occurrence is either of the following formulas (a), (b) or (c):
− (OC ₃ F ₆ ) _d − (a)
[Wherein, d is an integer of 1 to 200. ]
_{- (OC 4 F 8) c} - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (b)
[Wherein, c and d each independently represent an integer of 0 or more and 30 or less;
e and f are each independently an integer of 1 or more and 200 or less;
The sum of c, d, e and f is an integer of 10 or more and 200 or less;
The order in which each repeating unit enclosed in parentheses with a subscript c, d, e or f is given is arbitrary in the formula. ]
-(R ^6- R ⁷ ) _j- (c)
[Wherein, R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or two or three selected from these groups A combination of groups;
j is an integer of 2 to 100. ]
The surface treating agent according to any one of claims 1 to 16, which is   It further contains one or more other components selected from fluorine-containing oils, silicone oils, alcohols, catalysts, transition metals, halide ions, and compounds containing atoms having unshared electron pairs in the molecular structure, The surface treating agent according to any one of claims 1 to 17.   The pellet containing the surface treating agent of any one of Claims 1-18.   An article comprising a substrate, and a layer formed of the surface treatment agent according to any one of claims 1 to 18 on the surface of the substrate.   21. The article of claim 20, wherein the article is an optical member.   An article according to claim 20 or 21, wherein the article is a display.