CN110461985B - Surface treatment agent containing compound containing perfluoropolyether group - Google Patents

Abstract

The present invention provides a surface treatment agent containing a perfluoropolyether group-containing compound represented by the formula (1A) or (1B) [ wherein each symbol is as defined in the description]。(Rf‑PFPE)_α2‑X‑R^m _α1 (1A) (Rf‑Rf¹‑PFPE¹‑Rf²)_α2‑X‑R^m _α1(1B)。

Description

Surface treatment agent containing compound containing perfluoropolyether group

Technical Field

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

Background

It is known that a certain fluorine-containing compound can provide excellent water repellency, oil repellency, stain resistance and the like when used for surface treatment of a base material. 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 film to various substrates such as glass, plastic, fiber, and building material.

As such a fluorine-containing compound, a compound having a perfluoropolyether group in the molecular main chain is known. For example, patent document 1 describes that a terminal of a molecule contains-P (O) (OH)₂、－OP(O)(OH)₂or-NR⁸⁷ ₂(R⁸⁷Hydrogen atom or lower alkyl group).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2016-052779

Disclosure of Invention

Technical problem to be solved by the invention

In order to impart a desired function to a substrate for a long period of time, the surface treatment layer is required to have high durability. Since the layer obtained from the surface treatment agent containing a compound having a perfluoropolyether group can exhibit the above-described functions even in a thin film, it is suitably used for optical members such as glasses and touch panels which require light transmittance and transparency.

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

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

Means for solving the problems

As a result of intensive studies, the inventors of the present invention have found 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 have completed the present invention.

According to a first aspect of the present invention, there is provided a surface treatment agent containing a perfluoropolyether group-containing compound represented by formula (1A) or formula (1B).

(Rf-PFPE)_α2-X-R^m _α1 (1A)

(Rf-Rf¹-PFPE¹-Rf²)_α2X-R^m _α1 (1B)

[ in the formula:

rf independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with 1 or more fluorine atoms at each occurrence;

The PFPE at each occurrence is independently a group of the formula:

-(OC₆F₁₂)_a-(OC₅F₁₀)_b-(OC₄F₈)_c-(OC₃F₆)_d-(OC₂F₄)_e-(OCF₂)_f-

wherein a, b, c, d, e and f are each independently an integer of 0 to 200 inclusive, the sum of a, b, c, d, e and f is at least 1, and the order of the presence of each repeating unit denoted by a, b, c, d, e or f and enclosed by parentheses is arbitrary in the formula;

PFPE¹the same as PFPE;

Rf¹each occurrence of (O-Rf)¹¹)_m2；

Rf¹¹Is a fluoroalkylene group having no branched structure containing 1 or more hydrogen atoms;

m2 is an integer of 0 to 4, and m2 is an integer of 2 to 4, (O-Rf)¹¹)_m2May contain 2 or more kinds of O-Rf¹¹；

Rf²Each occurrence of (O-Rf)²¹)_m3；

Rf²¹Is a fluoroalkylene group having no branched structure containing 1 or more hydrogen atoms;

m3 is an integer of 0 to 4, and m3 is an integer of 2 to 4, (O-Rf)²¹)_m3May contain 2 or more kinds of O-Rf²¹；

X independently represents a single bond, an oxygen atom or a 2-10 valent organic group at each occurrence;

alpha 1 is independently an integer of 1-9 at each occurrence;

alpha 2 is independently an integer of 1-9 at each occurrence;

R^meach occurrence is independently a group represented by the formula;

m is independently at each occurrence a metal atom capable of coordinate bonding;

R¹Each occurrence independently represents a monodentate ligand having a bond to X;

R²each occurrence independently represents a multidentate ligand having a bonding bond to X;

R³each occurrence independently represents a monodentate ligand;

R⁴independently at each occurrence represents a multidentate ligand;

k is an integer of 0-2;

l is an integer of 0 to 2;

m is an integer of 0 or more;

n is an integer of 0 or more;

wherein the sum of k and l is 1-4, and l is multiplied by R²By the number of teeth, n times R⁴The sum of the values obtained for the number of matched teeth in (c), k and M is the coordination number for M.]

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 base material and a layer formed of the surface treatment agent on a surface of the base material.

Detailed Description

As used herein, the term "1 to 10 valent organic group" means a 1 to 10 valent group containing carbon. The 1-valent organic group is not particularly limited, and examples thereof include hydrocarbon groups. The organic group having a valence of 2 to 10 is not particularly limited, and examples thereof include groups having a valence of 2 to 10 wherein 1 to 9 hydrogen atoms are further removed from the hydrocarbon group. The 2-valent organic group is not particularly limited, and includes a 2-valent group in which 1 hydrogen atom is further removed from a carbonyl group or a hydrocarbon group.

As used herein, "hydrocarbyl" refers to a group that contains carbon and hydrogen, and is free of 1 hydrogen atom from the hydrocarbon. Such a hydrocarbon group is not particularly limited, and examples thereof include hydrocarbon groups having 1 to 20 carbon atoms substituted with 1 or more substituents, for example, aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain 1 or more ring structures. Such a hydrocarbon group may have 1 or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, or the like at its terminal or in the molecular chain.

When used in the present specification, the substituent of the "hydrocarbon group" is not particularly limited, and examples thereof include: a halogen atom; selected from C which may be substituted by 1 or more than 1 halogen atom_1-6Alkyl radical, C_2-6Alkenyl radical, C_2-6Alkynyl, C_3-10Cycloalkyl radical, C_3-10Unsaturated cycloalkyl, 5-10 membered heterocyclic group, 5-10 membered unsaturated heterocyclic group, C_6-101 or more than 1 of aryl and 5-10 membered heteroaryl.

In the present specification, an alkyl group and a phenyl group may be unsubstituted or substituted unless otherwise specified. The substituent for the above-mentioned group is not particularly limited, and may be, for example, a halogen atom or C_1-6Alkyl radical, C_2-6Alkenyl and C_2-61 or more groups in the alkynyl group.

In the present specification, the term "complex compound" means a chemical species in which several ligands surround a central metal atom or ion. In the present specification, "ligand" means a chemical species that can exist as an ion or a molecule even alone. The coordinating atom contained in the ligand is preferably at least 1 selected from oxygen and nitrogen.

[ surface treating agent ]

Hereinafter, the surface treatment agent containing a perfluoropolyether group-containing (hereinafter, sometimes referred to as "PFPE") compound of the present invention will be described.

The above PFPE-containing compound is represented by the formula (1A) or the formula (1B).

(Rf-PFPE)_α2-X-R^m _α1 (1A)

(Rf-Rf¹-PFPE¹-Rf2)_α2-X-R^m _α1 (1B)

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

The "C1-16 alkyl group" in the C1-16 alkyl group which may be substituted with 1 or more fluorine atoms may be a straight chain or branched chain, and is preferably a straight chain or branched chain C1-6 alkyl group, particularly a C1-3 alkyl group, more preferably a straight chain C1-3 alkyl group.

The Rf is preferably an alkyl group having 1 to 16 carbon atoms substituted with 1 or more fluorine atoms, and more preferably CF₂H－C_1－15Perfluoroalkylene or C_1－16Perfluoroalkyl group, more preferably C_1－16A perfluoroalkyl group. Furthermore, alkylene means having- (C)_βH_2β) -a group of structures.

The perfluoroalkyl group having 1 to 16 carbon atoms may be a linear or branched one, preferably a linear or branched one having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, more preferably a linear one having 1 to 3 carbon atoms, particularly-CF₃、－CF₂CF₃or-CF₂CF₂CF₃。

In (1A) above, the PFPE is independently at each occurrence a group of the formula: - (OC)₆F₁₂)_a－(OC₅F₁₀)_b－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－。

Wherein a, b, c, d, e and f are each independently an integer of 0 to 200 inclusive, 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 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more. The sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, for example, 10 to 200, more specifically 10 to 100. In addition, the sequence of the repeating units denoted by a, b, c, d, e or f and enclosed by parentheses is arbitrary in the formula.

These repeating units may be linear or branched, and are preferably linear. For example, - (OC)₆F₁₂) May be- (OCF)₂CF₂CF₂CF₂CF₂CF₂)－、－(OCF(CF₃)CF₂CF₂CF₂CF₂)－、－(OCF₂CF(CF₃)CF₂CF₂CF₂)－、－(OCF₂CF₂CF(CF₃)CF₂CF₂)－、－(OCF₂CF₂CF₂CF(CF₃)CF₂)－、－(OCF₂CF₂CF₂CF₂CF(CF₃) -) etc., preferably- (OCF)₂CF₂CF₂CF₂CF₂CF₂)－。－(OC₅F₁₀) May be- (OCF)₂CF₂CF₂CF₂CF₂)－、－(OCF(CF₃)CF₂CF₂CF₂)－、－(OCF₂CF(CF₃)CF₂CF₂)－、－(OCF₂CF₂CF(CF₃)CF₂)－、－(OCF₂CF₂CF₂CF(CF₃) -) etc., preferably- (OCF)₂CF₂CF₂CF₂CF₂)－。－(OC₄F₈) May be- (OCF)₂CF₂CF₂CF₂)－、－(OCF(CF₃)CF₂CF₂)－、－(OCF₂CF(CF₃)CF₂)－、－(OCF₂CF₂CF(CF₃))－、－(OC(CF₃)₂CF₂)－、－(OCF₂C(CF₃)₂)－、－(OCF(CF₃)CF(CF₃))－、－(OCF(C₂F₅)CF₂) -and- (OCF)₂CF(C₂F₅) -, preferably- (OCF)₂CF₂CF₂CF₂)－。－(OC₃F₆) May be- (OCF)₂CF₂CF₂)－、－(OCF(CF₃)CF₂) -and- (OCF)₂CF(CF₃) -, preferably- (OCF)₂CF₂CF₂)-. Additionally, - (OC)₂F₄) May be- (OCF)₂CF₂) -and- (OCF (CF)₃) -, preferably- (OCF)₂CF₂)－。

In one embodiment, the PFPE is- (OC)₃F₆)_d- (wherein d is an integer of 1 to 200 inclusive, preferably an integer of 5 to 200 inclusive, and more preferably an integer of 10 to 200 inclusive). Preferably PFPE is- (OCF)₂CF₂CF₂)_d- (wherein d is an integer of 1 to 200 inclusive, preferably an integer of 5 to 200 inclusive, more preferably an integer of 10 to 200 inclusive) or- (OCF (CF)₃)CF₂)_d- (wherein d is an integer of 1 to 200 inclusive, preferably an integer of 5 to 200 inclusive, and more preferably an integer of 10 to 200 inclusive). More preferably PFPE is- (OCF)₂CF₂CF₂)_d- (wherein d is an integer of 1 to 200 inclusive, preferably an integer of 5 to 200 inclusive, and more preferably an integer of 10 to 200 inclusive).

In another embodiment, the PFPE is- (OC)₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f- (wherein c and d are each independently an integer of 0 to 30 inclusive, e and f are each independently an integer of 1 to 200 inclusive, preferably an integer of 5 to 200 inclusive, more preferably an integer of 10 to 200 inclusive, the sum of c, d, e and f is at least 5 or more, preferably 10 or more, and the order of presence of each repeating unit indicated by a subscript c, d, e or f and enclosed by parentheses is arbitrary). Preferably PFPE is- (OCF)₂CF₂CF₂CF₂)_c－(OCF₂CF₂CF₂)_d－(OCF₂CF₂)_e－(OCF₂)_f-. In one approach, the PFPE may be- (OC)₂F₄)_e－(OCF₂)_fWherein e and f are each independently an integer of 1 to 200 inclusive, preferably an integer of 5 to 200 inclusive, more preferably an integer of 10 to 200 inclusive, each repeating unit being enclosed in parentheses and denoted by a subscript e or fThe order of presence is arbitrary in the formula).

In one approach, the PFPE may be- (OC)₂F₄)_e－(OCF₂)_f- (wherein e and f are each independently an integer of 1 to 200 inclusive, preferably an integer of 5 to 200 inclusive, more preferably an integer of 10 to 200 inclusive), and the sequence of the repeating units indicated by the subscript e or f and enclosed by parentheses is arbitrary in the formula).

In PFPE, the ratio of e to f (hereinafter referred to as "e/f ratio") is 0.1 to 10, preferably 0.2 to 5.0, more preferably 0.2 to 2.0, and still more preferably 0.2 to 1.5. When the e/f ratio is in the above range, the water repellency, oil repellency, and chemical resistance (for example, durability against saline water, an acid or alkaline aqueous solution, acetone, oleic acid, or hexane) of a cured product obtained from the compound can be further improved. The smaller the e/f ratio, the higher 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 improved. The greater the e/f ratio, the greater the stability of the compound.

In another embodiment, PFPE is- (R)⁶¹－R⁶²)_j-a group as shown. In the formula, R⁶¹Is OCF₂Or OC₂F₄Preferably OC₂F₄. In the formula, R⁶²Is selected from OC₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀And OC₆F₁₂Or a combination of 2 or 3 groups independently selected from these groups. Preferably R⁶²Is selected from OC₂F₄、OC₃F₆And OC₄F₈Or is selected from the group consisting of OC₃F₆、OC₄F₈、OC₅F₁₀And OC₆F₁₂Or a combination of 2 or 3 groups independently selected from these groups. As slave OC₂F₄、OC₃F₆And OC₄F₈2 or 3 radicals independently selected fromThe combination of the groups is not particularly limited, and examples thereof include-OC₂F₄OC₃F₆－、－OC₂F₄OC₄F₈－、－OC₃F₆OC₂F₄－、－OC₃F₆OC₃F₆－、－OC₃F₆OC₄F₈－、－OC₄F₈OC₄F₈－、－OC₄F₈OC₃F₆－、－OC₄F₈OC₂F₄－、－OC₂F₄OC₂F₄OC₃F₆－、－OC₂F₄OC₂F₄OC₄F₈－、－OC₂F₄OC₃F₆OC₂F₄－、－OC₂F₄OC₃F₆OC₃F₆－、－OC₂F₄OC₄F₈OC₂F₄－、－OC₃F₆OC₂F₄OC₂F₄－、－OC₃F₆OC₂F₄OC₃F₆－、－OC₃F₆OC₃F₆OC₂F₄-and-OC₄F₈OC₂F₄OC₂F₄-and the like. J is an integer of 2 or more, preferably 3 or more, more preferably 5 or more, 100 or less, preferably 50 or less. In the above formula, OC₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀And OC₆F₁₂The polymer may be either linear or branched, and is preferably linear. In this mode, PFPE is preferably- (OC)₂F₄－OC₃F₆)_j-or- (OC)₂F₄－OC₄F₈)_j－。

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, and more preferably 2,000 to 10,000.

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

In yet another embodiment, the Rf-PFPE-moiety or-PFPE-moiety may have a number average molecular weight of 4,000 to 30,000, preferably 5,000 to 10,000.

In the above formula (1B), PFPE¹The same as PFPE. PFPE¹Preferably without a branched structure.

In the above formula (1B), Rf¹Each occurrence of (O-Rf)¹¹)_m2。

Rf above¹¹The fluorinated alkylene group having no branched structure and containing 1 or more hydrogen atoms is preferably a fluorinated alkylene group having 2 to 6 carbon atoms, and particularly preferably a fluorinated alkylene group having 2 carbon atoms. Rf¹¹The number of hydrogen atoms contained is preferably 1 to 4, and particularly preferably 1 or 2. As (O-Rf)¹¹) Preferably (O-CHFCF)₂) And (O-CH)₂CF₂). In the present specification, a fluoroalkylene group refers to a group in which 1 or more hydrogen atoms of an alkylene group are substituted with fluorine atoms.

When m2 is an integer of 0 to 4 and m2 is an integer of 2 to 4, (O-Rf)¹¹O)_m2More than 2O-Rf groups may be included¹¹。

In the above formula (1B), Rf²Each occurrence of (O-Rf)²¹)_m3。

Rf above²¹The fluorinated alkylene group is a fluorinated alkylene group having no branched structure and containing 1 or more hydrogen atoms, and preferably a fluorinated alkylene group having 2 to 6 carbon atoms. Rf²¹The number of hydrogen atoms contained is preferably 1 to 4, and particularly preferably 1 or 2.

When m3 is an integer of 0 to 4 and m3 is an integer of 2 to 4, (O-Rf)²¹)_m3May contain 2 or more kinds of O-Rf²¹. m3 is preferably an integer of 0 to 2.

In one embodiment, (O-Rf)²¹)_m3With X (R when X is a single bond)^m) Bound (O-Rf)²¹) May be (O-Rf)^21’CH₂) The groups shown. Rf^21’Is a ratio of Rf²¹A group having 1 or less carbon atoms, and is a perfluoroalkylene group or a fluoroalkylene group having a hydrogen atom. Preferably Rf^21’Is a perfluoroalkylene group. As specific (O-Rf)^21’CH₂) Preferably (O-CF)₂CH₂)、(O－CF₂CF₂CH₂)、(O－CF₂CF₂CF₂CH₂)、(O－CF₂CF₂CF₂CF₂CH₂) And the like. In this case, m3 is preferably 1.

In the above PFPE¹Of these, the sum of a, b, c, d, e, f, m2 and m3 is preferably 5 or more, more preferably 10 or more. The sum of a, b, c, d, e, f, m2 and m3 is preferably 200 or less, more preferably 100 or less, for example 10 to 200, more preferably 10 to 100.

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

In the formulae (1A) and (1B), X represents a single bond, an oxygen atom or a 2-to 10-valent organic group. The X in the compound represented by the formula (1A) or (1B) is understood to be a perfluoropolyether moiety (i.e., Rf-PFPE moiety or Rf-Rf) that will mainly provide water repellency, surface slidability, and the like¹－PFPE¹－Rf²Moiety) and R^mA joint for connection. Therefore, X may be any organic group as long as the compound represented by formula (1A) or (1B) can stably exist.

The organic group having a valence of 2 to 10 in the X is preferably an organic group having a valence of 2 to 7, more preferably an organic group having a valence of 2 to 4, and still more preferably an organic group having a valence of 2.

In the formula, alpha 1 is an integer of 1-9, and alpha 2 is an integer of 1-9. These α 1 and α 2 may vary depending on the valence of X. In the formulae (1A) and (1B), the sum of α 1 and α 2 is the same as the valence of X. For example, in the case where X is a 10-valent organic group, the sum of α 1 and α 2 is 10, and for example, α 1 may be 9 and α 2 may be 1, α 1 may be 5 and α 2 may be 5, or α 1 may be 1 and α 2 may be 9. In addition, in the case where X is a 2-valent organic group, α 1 and α 2 are 1.

In one embodiment, X is a single bond or a 2-to 4-valent organic group, α 1 is an integer of 1 to 3, and α 2 is 1.

In other embodiments, X is a single bond or a 2-valent organic group, α 1 is 1, and α 2 is 1. In this case, formula (1A) is represented by formula (1A '), and formula (1B) is represented by formula (1B').

Rf-PFPE-X-R^m (1A′)

Rf-Rf¹-PFPE¹-Rf²-X-R^m (1B′)

In one embodiment, X represents a single bond or a 2-to 10-valent organic group, preferably a single bond, an alkylene group or a group having a valence selected from-C₆H₄- (i.e., -phenylene-hereinafter), -CO- (carbonyl), -NR- (-phenylene-) -⁸-and-SO₂At least 1 of (a) 2 to 10 valent organic groups. R is as defined above⁸Each independently represents a hydrogen atom, a phenyl group or C_1～6An alkyl group (preferably a methyl group), preferably a hydrogen atom or a methyl group. It is preferable that the PFPE-containing compound has the above-mentioned-C in the molecular main chain ₆H₄-、-CO-、-NR⁸-or-SO₂-. Wherein the molecular backbone represents the relatively longest binding chain comprising PFPE in the molecule of the PFPE-containing compound.

In this embodiment, X more preferably represents a single bond, an alkylene group or a group having a structure selected from the group consisting of-C₆H₄-、-CONR⁸-、-CONR⁸-C₆H₄-、-CO-、-CO-C₆H₄-、-SO₂NR⁸-、-SO₂NR⁸-C₆H₄-、-SO₂-and-SO₂-C₆H₄At least 1 of (a) 2 to 10 valent organic groups. above-mentioned-C₆H₄-、-CONR⁸-、-CONR⁸-C₆H₄-、-CO-、-CO-C₆H₄-、-SO₂NR⁸-、-SO₂NR⁸-C₆H₄-、-SO₂-or-SO₂-C₆H₄Preferably in the molecular backbone of the PFPE-containing compound.

In this embodiment, in X, the PFPE part (i.e., the PFPE part)Groups enclosed by. alpha.2 in formula (1A) or (1B) and R^mThe number of atoms linked by the group (i.e., the group enclosed by α 1 in formula (1A) or (1B)) is preferably 20 or less, more preferably 10 or less, and still more preferably 6 or less. In addition, there are more than one PFPE part and one R^mIn the case of a path connected to the base, the above-mentioned "connecting PFPE part to R" means^mThe number of atoms to which the group is bonded "means that the PFPE portion and R are bonded at the shortest distance^mNumber of atoms between radicals.

In another embodiment, X is not particularly limited, and may be, for example, a 2-valent group represented by the following formula:

-(R⁸¹)_p’-(X^a)_q’-

[ in the formula:

R⁸¹represents a single bond, - (CH)₂)_s’-or o-, m-or p-phenylene, 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^aIs represented by (X)^b)_l’－，

X^bEach occurrence independently represents a group selected from-O-, -S-, O-, m-, or p-phenylene, -C (O) O-, -Si (R)⁸³)₂－、－(Si(R⁸³)₂O)_m’－Si(R⁸³)₂－、－CONR⁸⁴－、－O－CONR⁸⁴－、－NR⁸⁴-and- (CH)₂)_n’The group of (a) to (b),

R⁸³each occurrence independently represents phenyl, C_1－6Alkyl or C_1－6Alkoxy, preferably phenyl or C_1－6The alkyl group, more preferably the methyl group,

R⁸⁴each occurrence independently represents a hydrogen atom, phenyl or C_1－6An alkyl group (preferably a methyl group),

m' is independently at each occurrence an integer from 1 to 100, preferably an integer from 1 to 20,

n' is independently at each occurrence 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 p' is,

q 'is 0 or 1 and q' is,

wherein at least one of p 'and q' is 1, and the sequence of the repeating units denoted by p 'or q' and enclosed by parentheses is arbitrary ].

Wherein R is⁸¹And X^a(typically R)⁸¹And X^aHydrogen atom) may be selected from fluorine atom, C_1－3Alkyl and C_1－31 or more than 1 substituent in the fluoroalkyl group.

Preferably, X is- (R)⁸¹)_p’－(X^a)_q’－R⁸²－。R⁸²Represents a single bond, - (CH)₂)_t’Or o-, m-or p-phenylene, 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. Wherein R is⁸²(typically R)⁸²Hydrogen atom) may be selected from fluorine atom, C_1－3Alkyl and C_1－31 or more than 1 substituent in the fluoroalkyl group.

Preferably, X may be

A single bond, a,

C_1－20Alkylene, or a mixture thereof,

－R⁸¹－X^c－R⁸²-, or

－X^d－R⁸²－

[ in the formula, R⁸¹And R⁸²The same as above.]。

More preferably, X is

A single bond, a,

C_1－20Alkylene, or a mixture thereof,

－(CH₂)_s’－X^c－、

－(CH₂)_s’－X^c－(CH₂)_t’－、

－X^d-, or

－X^d－(CH₂)_t’－

[ in the formula, s 'and t' have the same meanings as described above. ].

In the above formula, X^cTo represent

－O－、

－S－、

－C(O)O－、

－CONR⁸⁴－、

－O－CONR⁸⁴－、

－Si(R⁸³)₂－、

－(Si(R⁸³)₂O)_m’－Si(R⁸³)₂－、

－O－(CH₂)_u’－(Si(R⁸³)₂O)_m’－Si(R⁸³)₂－、

－O－(CH₂)_u’－Si(R⁸³)₂－O－Si(R⁸³)₂－CH₂CH₂－Si(R⁸³)₂－O－Si(R⁸³)₂－、

－O－(CH₂)_u’－Si(OCH₃)₂OSi(OCH₃)₂－、

－CONR⁸⁴－(CH₂)_u’－(Si(R⁸³)₂O)_m’－Si(R⁸³)₂－、

－CONR⁸⁴－(CH₂)_u’－N(R⁸⁴) -, or

－CONR⁸⁴- (o-phenylene, m-phenylene or p-phenylene) -Si (R)⁸³)₂－

[ in the formula, R⁸³、R⁸⁴And m' aboveThe meaning is the same as that of the prior art,

u' is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3.]。X^cpreferably-O-.

In the above formula, X^dRepresents:

－S－、

－C(O)O－、

－CONR⁸⁴－、

－CONR⁸⁴－(CH₂)_u’－(Si(R⁸³)₂O)_m’－Si(R⁸³)₂－、

－CONR⁸⁴－(CH₂)_u’－N(R⁸⁴) -, or

－CONR⁸⁴- (o-phenylene, m-phenylene or p-phenylene) -Si (R)⁸³)₂－

[ in the formula, the symbols have the same meanings as described above. ].

More preferably, X may be

A single bond, a,

C_1－20Alkylene, or a mixture thereof,

－(CH₂)_s’－X^c－(CH₂)_t’-, or

－X^d－(CH₂)_t’－

[ in the formula, the symbols have the same meanings as described above. ].

More preferably, X is

A single bond, a,

C_1－20Alkylene, particularly preferably C_1－10Alkylene, or a mixture thereof,

－(CH₂)_s’－O－(CH₂)_t’－、

－(CH₂)_s’－(Si(R⁸³)₂O)_m’－Si(R⁸³)₂－(CH₂)_t’－、

－(CH₂)_s’－O－(CH₂)_u’－(Si(R⁸³)₂O)_m’－Si(R⁸³)₂－(CH₂)_t’-, or

－(CH₂)_s’－O－(CH₂)_t’－Si(R⁸³)₂－(CH₂)_u’－Si(R⁸³)₂－(C_vH_2v)－

[ in the formula, R⁸³M ', s', t 'and u' have the same meanings as described above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. ]。

In the above formula, - (C)_vH_2v) -may be a straight chain or a branched chain, and may be, for example, -CH₂－、－CH₂CH₂－、－CH₂CH₂CH₂－、－CH(CH₃)－、－CH(CH₃)CH₂－。

In one embodiment, X may be- (O)_t1－(R^f1O)_t2－R^f2－(C(＝O)N(R^f3))_t3－R^f4-a group as shown.

T1 is 0 or 1.

R is as defined above^f1Is a fluoroalkylene group having no branched structure and containing 1 or more hydrogen atoms. R^f1Preferably C_2－6A fluoroalkylene group. R^f1The number of hydrogen atoms contained is preferably in the range of 1 to 4, more preferably 1 or 2.

In the above (R)^f1O)_t2In the presence of more than 2 kinds of R^f1In the case of O, each (R)^f1O) is arbitrary in the formula.

T2 is an integer of 0 to 4, preferably 0 to 2.

R is as defined above^f2Is a single bond, a perfluoroalkylene group having no branched structure, or a fluoroalkylene group having no branched structure and containing 1 or more hydrogen atoms. The perfluoroalkylene group or the fluoroalkylene group preferably contains 1 to 10 carbon atoms.

R is as defined above^f3Is a hydrogen atom or an alkyl group (preferably C)_1－4Alkyl groups).

T3 is 0 or 1.

When t3 is 0, R^f2Preferably a single bond. In this case, (i.e., (R)^f1O)_t2And R^f4In the case of bonding), (R)^f1O)_t2And R in^f4Bound (R)^f1O) is preferably (R)^f5CH₂O) is a group represented by the formula. R^f5Is a ratio R^f1The group having 1 or less carbon atoms is a perfluoroalkylene group or a fluoroalkylene group having 1 or more hydrogen atoms. R ^f5Preferably a perfluoroalkylene group. (R)^f5CH₂O) is preferably (CF)₂CH₂O)、(CF₂CF₂CH₂O)、(CF₂CF₂CF₂CH₂O)、(CF₂CF₂CF₂CF₂CH₂O), and the like. In this case, t2 is preferably 1.

When t3 is 1, t2 is 0-2, and R^f2It is preferably a perfluoroalkylene group or a fluoroalkylene group having 1 or more hydrogen atoms, more preferably a perfluoroalkylene group, and particularly preferably C_1－6A perfluoroalkylene group.

R is as defined above^f4The group is a single bond, an alkylene group having 1 to 10 carbon atoms, a group having an etheric oxygen atom at a terminal of the alkylene group having 1 to 10 carbon atoms (wherein, in the formula (1A) or (1B), the terminal of the side bonded to the group enclosed by alpha 1) or a group having an etheric oxygen atom between carbon-carbon atoms of the alkylene group having 2 to 10 carbon atoms or a group having an etheric oxygen atom between carbon-carbon atoms and a terminal of the alkylene group having 2 to 10 carbon atoms (wherein, in the formula (1A) or (1B), the terminal of the side bonded to the group enclosed by alpha 1) or a group having an etheric oxygen atom between carbon-carbon atoms. Examples of the group having an etheric oxygen atom include-CH₂CH₂－O－、－CH₂CH₂－O－CH₂-and the like.

R is as defined above^f4Preferably a single bond or C_1－4Alkylene, more preferably a single bond or C_1－2An alkylene group.

Examples of the above X include:

－(O)_t1－(R^f1O)_t2－、

－(O)_t1－(R^f1O)_t2－CH₂O－、

－(O)_t1－(R^f1O)_t2－CH₂OCH₂－、

－(O)_t1－(R^f1O)_t2－CH₂O－(CH₂)₂－O－、

－(O)_t1－(R^f1O)_t2－CH₂O－(CH₂)₂－O－CH₂－、

－(O)_t1－(R^f1O)_t2－R^f2－C(O)NH－、

－(O)_t1－(R^f1O)_t2－R^f2－C(O)NHCH₂－、

－(O)_t1－(R^f1O)_t2－R^f2－C(O)NH(CH₂)₂－、

－(O)_t1－(R^f6CH₂O)－CH₂－、

－(O)_t1－(R^f6CH₂O)－CH₂－O－CH₂－、

－C(O)NH－R^f4-, or

－(O)_t1－R^f6CH₂OCF₂CHFOCF₂CF₂CF₂－C(O)NH－R^f4- (e.g., - (O)_t1－CF₂CH₂OCF₂CHFOCF₂CF₂CF₂－C(O)NH－R^f4-) and the like.

R^f1、R^f2、R^f4T1 and t2 have the same meanings as described above. t1 is preferably 1. R is^f6Is a perfluoroalkylene group having no branched structure.

The X group may be selected from fluorine atom, C_1－3Alkyl and C_1－3Fluoroalkyl (preferably C)_1－3Perfluoroalkyl) or 1 or more substituent(s).

In another embodiment, the group X includes, for example, the following groups:

[ wherein, R⁴¹Each independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms or C_1－6Alkoxy, preferably methyl;

d is a group selected from:

－CH₂O(CH₂)₂－、

－CH₂O(CH₂)₃－、

－CF₂O(CH₂)₃－、

－(CH₂)₂－、

－(CH₂)₃－、

－(CH₂)₄－、

－CONH－(CH₂)₃－、

－CON(CH₃)－(CH₂)₃－、

－CON(Ph)－(CH₂)₃- (wherein Ph means phenyl), and

(in the formula, R⁴²Each independently represents a hydrogen atom or C_1－6Alkyl or C_1－6The alkoxy group of (b) preferably represents a methyl group or a methoxy group, more preferably a methyl group. ),

e is- (CH)₂)_ne- (ne is an integer of 2 to 6),

d binds to the PFPE on the backbone of the molecule and E binds to the group on the opposite side of the PFPE. ]

Specific examples of X include:

a single bond, a,

－CH₂OCH₂－、

－CH₂O(CH₂)₂－、

－CH₂O(CH₂)₃－、

－CH₂O(CH₂)₆－、

－(CH₂)₂－Si(CH₃)₂－(CH₂)₂－、

－CH₂O(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂－、

－CH₂O(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂－、

－CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂－、

－CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₃Si(CH₃)₂(CH₂)₂－、

－CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₁₀Si(CH₃)₂(CH₂)₂－、

－CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂₀Si(CH₃)₂(CH₂)₂－、

－CH₂OCF₂CHFOCF₂－、

－CH₂OCF₂CHFOCF₂CF₂－、

－CH₂OCF₂CHFOCF₂CF₂CF₂－、

－CH₂OCH₂CF₂CF₂OCF₂－、

－CH₂OCH₂CF₂CF₂OCF₂CF₂－、

－CH₂OCH₂CF₂CF₂OCF₂CF₂CF₂－、

－CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂－、

－CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂－、

－CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂CF₂－、

－CH₂OCF₂CHFOCF₂CF₂CF₂－C(O)NH－CH₂－、

－CH₂OCH₂CHFCF₂OCF₂－、

－CH₂OCH₂CHFCF₂OCF₂CF₂－、

－CH₂OCH₂CHFCF₂OCF₂CF₂CF₂－、

－CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂－、

－CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂－、

－CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂CF₂－、

－CH₂OCH₂(CH₂)₇CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂－、

－CH₂OCH₂CH₂CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₃－、

－CH₂OCH₂CH₂CH₂Si(OCH₂CH₃)₂OSi(OCH₂CH₃)₂(CH₂)₃－、

－CH₂OCH₂CH₂CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂－、

－CH₂OCH₂CH₂CH₂Si(OCH₂CH₃)₂OSi(OCH₂CH₃)₂(CH₂)₂－、

－CH₂－、

－(CH₂)₂－、

－(CH₂)₃－、

－(CH₂)₄－、

－(CH₂)₅－、

－(CH₂)₆－、

－CO－、

－CONH－、

－CONH－CH₂－、

－CONH－(CH₂)₂－、

－CONH－(CH₂)₃－、

－CON(CH₃)－(CH₂)₃－、

－CON(Ph)－(CH₂)₃- (in type)Ph is phenyl,

－CONH－(CH₂)₆－、

－CON(CH₃)－(CH₂)₆－、

－CON(Ph)－(CH₂)₆- (wherein Ph means a phenyl group),

－CONH－(CH₂)₂NH(CH₂)₃－、

－CONH－(CH₂)₆NH(CH₂)₃－、

－CH₂O－CONH－(CH₂)₃－、

－CH₂O－CONH－(CH₂)₆－、

－S－(CH₂)₃－、

－(CH₂)₂S(CH₂)₃－、

－CONH－(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂－、

－CONH－(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂－、

－CONH－(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂－、

－CONH－(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₃Si(CH₃)₂(CH₂)₂－、

－CONH－(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₁₀Si(CH₃)₂(CH₂)₂－、

－CONH－(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂₀Si(CH₃)₂(CH₂)₂－、

－C(O)O－(CH₂)₃－、

－C(O)O－(CH₂)₆－、

－CH₂－O－(CH₂)₃－Si(CH₃)₂－(CH₂)₂－Si(CH₃)₂－(CH₂)₂－、

－CH₂－O－(CH₂)₃－Si(CH₃)₂－(CH₂)₂－Si(CH₃)₂－CH(CH₃)－、

－CH₂－O－(CH₂)₃－Si(CH₃)₂－(CH₂)₂－Si(CH₃)₂－(CH₂)₃－、

－CH₂－O－(CH₂)₃－Si(CH₃)₂－(CH₂)₂－Si(CH₃)₂－CH(CH₃)－CH₂-、

－OCH₂－、

－O(CH₂)₃－、

－OCFHCF₂－、

And the like.

In another preferred embodiment, X is a single bond, an alkylene group having 1 to 6 carbon atoms, -R⁸⁵－C₆H₄－R⁸⁶－、－R⁸⁵－CONR⁸－R⁸⁶－、－R⁸⁵－CONR⁸－C₆H₄－R⁸⁶－、－R⁸⁵－CO－R⁸⁶－、－R⁸⁵－CO－C₆H₄－R⁸⁶－、－R⁸⁵－SO₂NR⁸－R⁸⁶－、－R⁸⁵－SO₂NR⁸－C₆H₄－R⁸⁶－、－R⁸⁵－SO₂－R⁸⁶-or-R⁸⁵－SO₂－C₆H₄－R⁸⁶－。R⁸⁵And R⁸⁶Each independently represents 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. R⁸The same as above. The alkylene group is substituted or unsubstituted, and is preferably unsubstituted. Examples of the substituent of the alkylene group include a halogen atom, preferably a fluorine atom. The alkylene group is linear or branched, and is preferably linear.

In this embodiment, X may be more preferably:

a single bond,

An alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,

－C₆H₄－R^86’－、

－CONR^8’－R^86’－、

－CONR^8’－C₆H₄－R^86’－、

－CO－R^86’－、

－CO－C₆H₄－R^86’－、

－SO₂NR^8’－R^86’－、

－SO₂NR^8’－C₆H₄－R^86’－、

－SO₂－R^86’－、

－SO₂－C₆H₄－R^86’－、

－R^85’－C₆H₄－、

－R^85’－CONR^8’－、

－R^85’－CONR^8’－C₆H₄－、

－R^85’－CO－、

－R^85’－CO－C₆H₄－、

－R^85’－SO₂NR^8’－、

－R^85’－SO₂NR^8’－C₆H₄－、

－R^85’－SO₂－、

－R^85’－SO₂－C₆H₄－、

－C₆H₄－、

－CONR^8’－、

－CONR^8’－C₆H₄－、

－CO－、

－CO－C₆H₄－、

－SO₂NR^8’－、

－SO₂NR^8’－C₆H₄－、

－SO₂-, or

－SO₂－C₆H₄－

(in the formula, R^85’And R^85’Each independently a linear alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,

R^8’is a hydrogen atom or a methyl group. ).

In this embodiment, specific examples of X include:

a single bond, a,

An alkylene group having 1 to 6 carbon atoms,

－CONH－、

－CONH－CH₂－、

－CONH－(CH₂)₂－、

－CONH－(CH₂)₃－、

－CON(CH₃)－、

－CON(CH₃)－CH₂－、

－CON(CH₃)－(CH₂)₂－、

－CON(CH₃)－(CH₂)₃－、

－CH₂－CONH－、

－CH₂－CONH－CH₂－、

－CH₂－CONH－(CH₂)₂－、

－CH₂－CONH－(CH₂)₃－、

－CONH－C₆H₄－、

－CON(CH₃)－C₆H₄－、

－CH₂－CON(CH₃)－CH₂－、

－CH₂－CON(CH₃)－(CH₂)₂－、

－CH₂－CON(CH₃)－(CH₂)₃－、

－CON(CH₃)－C₆H₄－、

－CO－、

－CO－C₆H₄－、

－C₆H₄－、

－SO₂NH－、

－SO₂NH－CH₂－、

－SO₂NH－(CH₂)₂－、

－SO₂NH－(CH₂)₃－、

－SO₂NH－C₆H₄－、

－SO₂N(CH₃)－、

－SO₂N(CH₃)－CH₂－、

－SO₂N(CH₃)－(CH₂)₂－、

－SO₂N(CH₃)－(CH₂)₃－、

－SO₂N(CH₃)－C₆H₄－、

－SO₂－、

－SO₂－CH₂－、

－SO₂－(CH₂)₂－、

－SO₂－(CH₂)₃－、

－SO₂－C₆H₄-and the like.

In one embodiment, X is a single bond.

In another embodiment, examples of groups X include the following groups:

[ in the formula,

R⁴¹each independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms or C_1－6Alkoxy, preferably methyl;

in each X group, any of T is the following group bound to the PFPE of the molecular backbone:

－CH₂O(CH₂)₂－、

－CH₂O(CH₂)₃－、

－CF₂O(CH₂)₃－、

－CH₂－、

－(CH₂)₂－、

－(CH₂)₃－、

－(CH₂)₄－、

－CONH－(CH₂)₃－、

－CON(CH₃)－(CH₂)₃－、

－CON(Ph)－(CH₂)₃- (wherein Ph means phenyl), or

[ in the formula, R⁴²Each independently represents a hydrogen atom, C_1－6Alkyl or C_1－6The alkoxy group of (b) preferably represents a methyl group or a methoxy group, more preferably a methyl group.]Several other T's are- (CH) bound to groups on opposite sides of the molecular backbone from the PFPE₂)_n”- (n' is an integer of 2 to 6), and in the presence of (a), the remaining T may be independently a methyl group, a phenyl group, or C _1－6Alkoxy groups or radical trapping groups or UV-absorbing groups.

The radical trapping group is not particularly limited as long as it can trap a radical generated by light irradiation, and examples thereof include residues of benzophenones, benzotriazoles, benzoates, salicylates, crotonic acids, malonates, organic acrylates, hindered amines, hindered phenols, and triazines.

The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays, and examples thereof include: benzotriazole, hydroxybenzophenone, esters of substituted and unsubstituted benzoic or salicylic acid compounds, acrylate or alkoxycinnamic acid esters, oxamides, oxanilide, benzoxazinone, benzoxazole residues.

In a preferred embodiment, the radical scavenger or ultraviolet absorbing group is preferably selected from the group consisting of:

in this mode, X may be a 3-10 valent organic group.

In one embodiment, X is represented by-X¹¹(OH)_j1(X¹²)_3－j1or-X¹¹(OX¹²)_j1(X¹²)_3－j1And (4) showing. X¹¹Is a carbon atom. X¹²Each independently represents a single bond or a 2-to 6-valent hydrocarbon group, and may have a silicon atom and/or a siloxane bond. OX¹²Or X¹²Mixing X¹¹and-R^mAre connected with each other. j1 is independent at each occurrence and is an integer of 1 to 3, preferably 1.

In the above formulae (1A) and (1B), R^mEach occurrence is independently a group represented by the formula.

In the above formula, M is independently at each occurrence a metal atom capable of coordinate bonding. The 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, still more preferably an aluminum atom or a titanium atom, and particularly preferably an aluminum atom.

In the above formula, R¹Each occurrence is independently a monodentate ligand having a bond to X. In other words, via R¹X (when X is a single bond, it is PFPE in the formula (1A) or Rf in the formula (1B)²) And M are linked.

R¹Preferably is-R¹¹-O-or-R¹¹N(R¹²)-. In the above-mentioned R¹In (1), an oxygen atom or a nitrogen atom is coordinated to M. In the above-mentioned R¹In, R¹¹And X (when X is a single bond, it is PFPE in formula (1A) or Rf in formula (1B)²) And (4) combining.

In the formula, R¹²Is a hydrogen atom or a 1-valent organic group. R¹²Preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.

In the formula, R¹¹Independently at each occurrence is a single bond or a 2-valent organic group.

R is as defined above¹¹Examples thereof include:

a single bond,

A carbonyl group,

C_1～10Alkylene, more preferably C_1～6Alkylene, or a mixture thereof,

－(CH₂)_k1－C(＝O)－、

－C(＝O)－O－(CH₂)_k1’－、

－(CH₂)_k1C(＝O)－O－(CH₂)_k1’-, or

－(CH₂)_k1－O－(CH₂)_k1’－。

k1 is independently an integer from 1 to 10 at each occurrence, and k 1' is independently an integer from 1 to 10 at each occurrence. Preferably, k1 is an integer of 1 to 6, and k 1' is an integer of 1 to 6.

As the above-mentioned R¹Examples thereof include:

－O－、

－NR¹²－、

－C(＝O)－O－、

－C(＝O)－NR¹²－、

－(CH₂)_k1－O－、

－(CH₂)_k1－NR¹²－、

－(CH₂)_k1－C(＝O)－O－、

－(CH₂)_k1－C(＝O)－NR¹²－、

－C(＝O)－O－(CH₂)_k1’－O－、

－C(＝O)－O－(CH₂)_k1’－NR¹²－、

－(CH₂)_k1C(＝O)－O－(CH₂)_k1’－O－、

－(CH₂)_k1C(＝O)－O－(CH₂)_k1’－NR¹²－、

－(CH₂)_k1－O－(CH₂)_k1’-O-, or

－(CH₂)_k1－O－(CH₂)_k1’－NR¹²－。

In the above, the oxygen atom or the nitrogen atom present in the terminal portion is a coordinating atom. R¹²K1 and k 1' have the same meanings as described above.

R is as defined above¹More preferably-R¹¹－O－。

R¹More specifically:

－O－、

－CH₂－O－、

－(CH₂)₂－O－、

－C(＝O)－O－、

－CH₂-C (═ O) -O-, or

－(CH₂)₂－C(＝O)－O－。

Further, the oxygen atom present at the terminal part of the above formula is a coordinating atom.

In the above formula, R²Each occurrence independently represents a multidentate ligand having a bonding bond to X. In other words, via R²X (when X is a single bond, it is PFPE in the formula (1A) or Rf in the formula (1B)²) And M are linked.

Preferably R²Are bidentate ligands.

More preferably R²Is a ligand to which any one of the following compounds (1-1) to (1-6) is coordinated. In addition, R of the following formula²¹Other groups (e.g. in formula (1-1), C (═ O) (CH) may be substituted₂)_l1－C(＝O)－R²²) Is referred to as R²³. Namely R²Is coordinated to ²¹－R²³Ligands to the compounds shown.

Wherein l1 is an integer of 0 to 6 independently at each occurrence. l1 is independent at each occurrence, preferably an integer of 0 to 4, more preferably 1 to 2.

Wherein, represents a coordinating atom. For example, the compounds represented by the above formulae (1-1) to (1-6) coordinate to M as shown in the following (1-1 ') to (1-6'), respectively.

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

In the formula, R²¹Independently at each occurrence is an oxygen atom or a 2-valent organic group. In the above-mentioned R²In, R²¹And X (when X is a single bond, it is PFPE in formula (1A) or Rf in formula (1B)²) And (4) combining.

Preferably R²¹Comprises the following steps:

－O－、

－C(＝O)－O－、

C_1～6alkylene, or

－(CH₂)_l2－O－。

Further, in the case where an oxygen atom is present in the terminal part of the above formula, the oxygen atom is bonded to R²³And (4) combining. l2 is an integer of 1 to 6.

In the formula, R²²Independently at each occurrence, is a hydrogen atom or a 1-valent organic group. R²²Preferably 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, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms (e.g., a methyl group).

In a preferred mode, R ²Preferably comprising a structure capable of ketoenol tautomerization. More preferably R²Is a group represented by the formula (1-1) wherein l1 is 1 and R is²¹Is an oxygen atom, R²²An alkyl group having 1 to 3 carbon atoms (e.g., methyl group). Wherein is represented byA coordinating atom.

In other modes, R²The chelate ring which can form a 4-to 12-membered ring together with M, preferably a chelate ring which forms a 4-to 6-membered ring.

In the above (1A) and (1B), R³Independently at each occurrence, represents a monodentate ligand. R³Denotes a monodentate ligand that binds only to M and not directly to X.

R³Preferably at least 1 selected from the group consisting of a halogen atom, a hydrogen atom, a hydroxyl group and a 1-valent organic group. Examples of the halogen atom include a chlorine atom and a fluorine atom. As the above-mentioned 1-valent organic group, R is exemplified³¹-O-or R³¹N(R³²)-. In the above-mentioned 1-valent organic group, an oxygen atom or a nitrogen atom is coordinated to M.

R is as defined above³¹Is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. R is as defined above³²Is a hydrogen atom or a 1-valent organic group, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.

R is as defined above³Preferably R³¹－O－。R³¹As defined above, R³¹O-is, for example, methoxy, ethoxy, isopropoxy.

In the above (1A) and (1B), R⁴Each occurrence is independently a polydentate ligand. R⁴Denotes a polydentate ligand that binds only to M and not directly to X.

Preferably R⁴Is a bidentate ligand.

More preferably R⁴Is a ligand binding to at least 1 selected from the following compounds (2-1) to (2-6).

Wherein n1 is independent at each occurrence and is an integer of 0 to 6. n1 is independent at each occurrence, preferably an integer of 0 to 4, more preferably 1.

Wherein, represents a coordinating atom. For example, the compounds represented by the above formulas (2-1) to (2-6) coordinate to M as shown in the following formulas (2-1 ') to (2-6').

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

In the formula, R⁴³Independently at each occurrence, is a hydrogen atom or a 1-valent organic group.

Preferably R⁴³Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. More preferably R⁴³Is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.

In the formula, R⁴⁴Independently at each occurrence, is a hydrogen atom or a 1-valent organic group.

Preferably R⁴⁴Is 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 ⁴⁴Is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.

In one embodiment, R⁴³Is an alkyl group having 1 to 3 carbon atoms (e.g., methyl group), and R⁴⁴An alkyl group having 1 to 3 carbon atoms (e.g., ethyl group).

In one embodiment, R⁴³Is an alkyl group having 1 to 3 carbon atoms (e.g., methyl group), and R⁴⁴An alkoxy group having 1 to 3 carbon atoms (e.g., ethoxy group).

In other modes, R⁴The chelate ring which can form a 4-to 12-membered ring together with M, preferably a chelate ring which forms a 4-to 6-membered ring.

Formula (1A) and formula(1B) In the formula, k is an integer of 0-2; l is an integer of 0 to 2; m is an integer of 0 or more; n is an integer of 0 or more. Wherein the sum of k and l is 1-4, and l is multiplied by R²By the number of teeth, n times R⁴The sum of the values obtained for the number of teeth in (c), k and M is the coordination number for M. For example, in the case where M is an aluminum atom, a titanium atom or a zirconium atom, the coordination number of M is 4 or 6.

In one embodiment, 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. Wherein the sum of k and l is 1, l multiplied by R²By the number of teeth, n times R⁴The sum of the values obtained for the number of teeth in (c), k and M is the coordination number for M.

In one embodiment, k is 1; l is 0.

In one mode, k is 0; l is 1.

In one mode, k is 1; l is 0; m is 1; n is 1. In this embodiment, R is preferably²More preferably, M is an aluminum atom or a titanium atom (more preferably, an aluminum atom) as a bidentate ligand.

In one mode, k is 0; l is 1; m is 0; n is 2. In this embodiment, R is preferably²Is a bidentate ligand, more preferably M is an aluminum atom or a titanium atom (more preferably an aluminum atom).

In a preferred mode, R^mComprises the following steps:

m is an aluminum atom or a titanium atom (more preferably an aluminum atom);

R¹from-R¹¹-O-represents (wherein R is¹¹Is a 2-valent organic group, preferably a carbonyl group);

R³is a 1-valent organic radical, preferably formed from R³¹-O-represents (wherein R is³¹An alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, for example, an isopropyl group);

R⁴is a bidentate ligand, preferably represented by the formula (2-1) (wherein, represents a coordinating atom, n1 is 1, R⁴³Is alkyl of 1 to 3 carbon atoms or alkoxy of 1 to 3 carbon atoms, R⁴⁴Is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. ) (ii) a

k is 1;

l is 0;

m is 1;

n is 1.

In this mode, R^mAn example of this can be represented by the following equation. In the following formula, R¹¹The same as above, specifically a C (═ O) group; r³¹The same meaning as above, specifically isopropyl; r ⁴³The same meanings as above, specifically methyl; r⁴⁴The same meaning as above, specifically ethyl. The site binding to X.

In other preferred modes, R^mComprises the following steps:

m is an aluminum atom or a titanium atom (more preferably an aluminum atom);

R²is a bidentate ligand, preferably represented by the formula (1-1) (wherein, X represents a coordinating atom, l1 is 1, R²¹Is an oxygen atom, R²²An alkyl group having 1 to 3 carbon atoms (e.g., methyl group));

R⁴is a bidentate ligand, preferably represented by the formula (2-1) (wherein, represents a coordinating atom, n1 is 1, R⁴³Each occurrence is independently C1-3 alkyl or C1-3 alkoxy, R⁴⁴Each occurrence is independently an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. )

k is 0;

l is 1;

m is 0;

n is 2.

In this mode, R^mAn example of this can be represented by the following equation. In the following formula, R²²The same meanings as above, specifically methyl; r⁴³And R⁴⁴Independently at each occurrence, is methyl, ethyl or ethoxy. For example, in the following formula, R⁴³Is methyl, R⁴⁴One may be ethyl and the other ethoxy. The site binding to X.

The PFPE-containing compounds represented by the formulae (1A) and (1B) have an effect of easily adhering to a metal surface or a metal-oxidized surface because they contain a metal atom at the terminal.

The PFPE-containing compound represented by the formula (1A) or (1B) has a group represented by Rf-PFPE or Rf-Rf¹－PFPE－Rf²The group shown can contribute to the formation of a surface treatment layer having particularly good water repellency and oil repellency. This is because CF contained in the terminal portion of Rf₃The radicals exhibit extremely low surface free energy and are oriented at the outermost surface.

From the viewpoint of providing a surface treatment agent having more excellent water repellency and oil repellency, the PFPE-containing compound represented by formula (1A) is preferably used.

The PFPE-containing compound represented by the above formula (1A) or (1B) can be produced, for example, by a method comprising: a PFPE compound represented by the following formula (2A) or (2B) and a complex compound represented by the formula (3) are reacted with Y¹And Y²Reaction to form R¹Or Y or¹And Y^2’Reaction to form R²The process (2).

(Rf-PFPE)_α2-X-(Y¹)_α1 (2A)

(Rf-Rf¹-PFPE¹-Rf²)_α2-X-(Y¹)_α1 (2B)

In the formulae (2A), (2B) and (3), Rf, PFPE¹、Rf¹、Rf²、α1、α2、X、M、R³、R⁴And k to n have the same meanings as described above.

Y1 includes a group capable of reacting.

Examples of the group capable of reacting as described above include OR ¹⁰Or NR¹⁰R^12’Etc., among these, OR is preferable¹⁰。R¹⁰Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom. R^12’Preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

Y is above¹For example, by

-R¹⁹-OR¹⁰Or is

-R¹⁹-NR¹⁰As shown.

R¹⁰The same as described above. R is¹⁹Is a single bond or a 2-valent organic group.

As the above-mentioned R¹⁹Examples thereof include:

a single bond, a,

A carbonyl group,

C_1～10Alkylene (more preferably C)_1～6Alkylene) s,

-(CH₂)₁₃-C(＝O)-、

-C(＝O)-O-(CH₂)_13’-、

-(CH₂)₁₃C(＝O)-O-(CH₂)_13’-, or

-(CH₂)₁₃-O-(CH₂)_13’-。

13 is independent at each occurrence and is an integer from 1 to 12, and 13' is independent at each occurrence and is an integer from 1 to 12. Preferably, 13 is an integer of 1 to 6, and 13' is an integer of 1 to 6.

As the above Y¹Examples thereof include:

-OH、

－C(＝O)OH、

－(CH₂)_l3－OH、

－(CH₂)_l3－C(＝O)－OH、

－C(＝O)－O－(CH₂)_l3’－OH、

－C(＝O)－O－(CH₂)_l3’－C(＝O)OH、

－(CH₂)_l3C(＝O)－O－(CH₂)_l3’－OH、

－(CH₂)_l3C(＝O)－O－(CH₂)_l3’－C(＝O)OH、

－(CH₂)_l3－O－(CH₂)_l3’-OH, or

－(CH₂)_l3－O－(CH₂)_l3’－C(＝O)－OH。

l3 is independent at each occurrence and is an integer from 1 to 12, and l 3' is independent at each occurrence and is an integer from 1 to 12. Preferably, l3 is an integer of 1 to 6, and l 3' is an integer of 1 to 6.

Preferably Y is as defined above¹is-R¹⁹－OR¹⁰。R¹⁹And R¹⁰The same as above. Y is particularly preferred¹Comprises the following steps:

－OH、

－C(＝O)OH、

－(CH₂)_l3”-OH, or

－(CH₂)_l3”－C(＝O)－OH。

l 3' is an integer of 1 to 3, preferably 1.

Y is above²Comprising a group Y capable of reacting²¹。

As the above-mentioned group Y capable of reacting²¹Can be made ofExamples thereof include a chlorine atom, a bromine atom, an iodine atom, and C (═ O) OR ^10’OR OR^10’Etc., of these, OR is preferred^10’。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 (i.e., methyl, ethyl, n-propyl or isopropyl).

Above Y^2’Containing groups Y capable of reacting^21’。Y^21’And Y²¹The meaning of (A) is the same.

Preference is given to the abovementioned reactive groups Y²¹Is substituted for R¹And a group coordinated to M. Preference is given to the abovementioned reactive groups Y^21’Is substituted for R²¹Is introduced into R²³A group of (1).

More specifically, Y is as defined above²Is Y²¹Groups after coordination.

More specifically, Y is as defined above^2’Is a group coordinated by the following compound.

Wherein, represents a coordinating atom, Y^21’、R²²And l1 are as defined above.

In a preferred embodiment, Y is¹And Y²In, Y¹is-C (═ O) -OH, Y²is-OR^10’(R^10’A hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms).

In another preferred embodiment, Y is¹And Y^2’In, Y¹Is- (CH)₂)_l3”'-OH (l 3' is an integer of 1 to 3, preferably 1), Y^2’Is a group represented by the following formula. Wherein, represents a coordinating atom; y is^21’Is OR^10’L1 is 1, R²²Is an alkyl group having 1 to 3 carbon atoms (e.g., 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 (i.e., methyl, ethyl, n-propyl or isopropyl).

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

The surface treatment agent of the present invention can impart water repellency, oil repellency, stain resistance, surface slipperiness and frictional durability to a base material, and is not particularly limited, and can be suitably used as a stain-resistant coating agent or a water-repellent coating agent.

The surface treatment agent of the present invention may be diluted with a solvent. Such a solvent is not particularly limited, and examples thereof include: selected from perfluorohexane, CF₃CF₂CHCl₂、CF₃CH₂CF₂CH₃、CF₃CHFCHFC₂F₅1,1,1,2,2,3,3,4,4,5,5,6, 6-tridecafluorooctane, 1,1,2,2,3,3, 4-heptafluorocyclopentane ((ZEORORA H (trade name), etc.), C₄F₉OCH₃、C₄F₉OC₂H₅、CF₃CH₂OCF₂CHF₂、C₆F₁₃CH＝CH₂Hexafluoroxylene, perfluorobenzene, methylpentadecafluoroheptanone, trifluoroethanol, pentafluoropropanol, hexafluoroisopropanol, HCF₂CF₂CH₂OH, methyl triflate, trifluoroacetic acid and CF₃O(CF₂CF₂O)_m1(CF₂O)_n1CF₂CF₃[ in the formula, m1 and n1 are each independently an integer of 0 to 1000 inclusive, and the order of the repeating units denoted by m1 or n1 and enclosed by parentheses is arbitrary in the formula, but the sum of m1 and n1 is 1 or more.]The fluorine-containing atom in 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, 2-trichloro-3, 3, 3-trifluoro-1-propene, 1,1,1,4,4, 4-hexafluoro-2-butene Solvents for the molecules, and the like.

As the solvent, C can be used₆F₁₃OCH₃。

In one embodiment, the content of moisture contained in the solvent is 20ppm or less in terms of mass. The above moisture content can be measured using the karl fischer method. By setting the water content to such a level, 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 are not particularly limited, and examples thereof include: other surface-treated compounds include a (non-reactive) fluoropolyether compound which is understood to be a fluorine-containing oil, preferably a perfluoro (poly) ether compound (hereinafter referred to as "fluorine-containing oil"), a (non-reactive) organosilicon compound which is understood to be a silicone oil (hereinafter referred to as "silicone oil"), an alcohol, a catalyst, a transition metal such as platinum, ruthenium, and rhodium, a halide ion, a compound containing an atom having an unshared electron pair in its molecular structure, and the like.

The fluorine-containing oil is not particularly limited, and examples thereof include compounds represented by the following general formula (4) (perfluoro (poly) ether compounds).

Rf⁵－(OC₄F₈)_a’－(OC₃F₆)_b’－(OC₂F₄)_c’－(OCF₂)_d’－Rf⁶···(4)

In the formula, Rf⁵Represents an alkyl group having 1 to 16 carbon atoms (preferably C) which may be substituted with 1 or more fluorine atoms _1―16Perfluoroalkyl group of (ii) Rf⁶Represents an alkyl group having 1 to 16 carbon atoms (preferably C) which may be substituted with 1 or more fluorine atoms_1－16Perfluoroalkyl group), fluorine atom or hydrogen atom, Rf⁵And Rf⁶More preferably independently of each other, is C_1－3A perfluoroalkyl group.

a ', b', c 'and d' each represent the number of 4 kinds of repeating units of the perfluoro (poly) ether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 300, and the sum of a ', b', c 'and d' is at least 1, preferablyThe concentration is preferably 1 to 300, more preferably 20 to 300. The order of occurrence of each repeat unit, designated by subscripts a ', b', c 'or d' and enclosed by parentheses, is arbitrary in the formula. Among these repeating units, - (OC)₄F₈) Is- (OCF)₂CF₂CF₂CF₂)－、－(OCF(CF₃)CF₂CF₂)－、－(OCF₂CF(CF₃)CF₂)－、－(OCF₂CF₂CF(CF₃))－、－(OC(CF₃)₂CF₂)－、－(OCF₂C(CF₃)₂)－、－(OCF(CF₃)CF(CF₃))－、－(OCF(C₂F₅)CF₂) -and- (OCF)₂CF(C₂F₅) -, preferably- (OCF)₂CF₂CF₂CF₂)－。－(OC₃F₆) May be- (OCF)₂CF₂CF₂)－、－(OCF(CF₃)CF₂) -and- (OCF)₂CF(CF₃) -, preferably- (OCF)₂CF₂CF₂)－。－(OC₂F₄) May be- (OCF)₂CF₂) -and- (OCF (CF)₃) -, preferably- (OCF)₂CF₂)－。

Examples of the perfluoro (poly) ether compound represented by the above general formula (4) include compounds represented by any one of the following general formulae (4a) and (4b) (which may be a mixture of 1 or 2 or more).

Rf⁵－(OCF₂CF₂CF₂)_b”－Rf⁶···(4a)

Rf⁵－(OCF₂CF₂CF₂CF₂)_a”－(OCF₂CF₂CF₂)_b”－(OCF₂CF₂)_c”－(OCF₂)_d”－Rf⁶···(4b)

In these formulae, Rf⁵And Rf⁶As described above; in formula (4a), b' is an integer of 1 to 100; in that In the formula (4b), a "and b" are each independently an integer of 1 to 30 inclusive, and c "and d" are each independently an integer of 1 to 300 inclusive. The sequence of the occurrence of each repeating unit indicated by the subscripts a ", b", c ", and d" and enclosed by parentheses is arbitrary in the formula.

The fluorine-containing oil may have an average molecular weight of 1,000 to 30,000. This can provide high surface sliding properties.

The surface treatment agent of the present invention may contain, for example, 0 to 500 parts by mass, preferably 0 to 400 parts by mass, and more preferably 5 to 300 parts by mass of a fluorine-containing oil per 100 parts by mass of the total amount of the perfluoro (poly) ether group-containing compound and the carboxylic acid ester compound (in the case where each of the perfluoro (poly) ether group-containing compound and the carboxylic acid ester compound is 2 or more, the same applies to the total amount, hereinafter).

The compound represented by the general formula (4a) and the compound represented by the general formula (4b) may be used alone or in combination. The use of the compound represented by the general formula (4b) is preferable because higher surface sliding properties can be obtained than the use of the compound represented by the general formula (4 a). When used 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, more preferably 1: 1 to 1: 10. According to such a mass ratio, a surface-treated layer having an excellent balance between surface slipperiness and friction durability can be obtained.

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

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

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

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

In a preferred embodiment, when the surface treatment layer is formed by a vacuum evaporation method, the number average molecular weight of the fluorine-containing 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 2,000 or more, preferably 3,000 or more, more preferably 5,000 or more, larger than the number average molecular weight of the PFPE-containing compound. By setting the number average molecular weight as described above, more excellent friction durability and surface sliding property can be obtained.

From another viewpoint, the fluorine-containing oil may be represented by the general formula Rf '-F (wherein Rf' is C)_5－16A perfluoroalkyl group. ) The compounds shown. In addition, a chlorotrifluoroethylene oligomer may be used. The compound represented by Rf' -F and chlorotrifluoroethylene oligomer can be obtained when Rf is C _1－16The perfluoroalkyl group is preferable in view of high affinity of the above-mentioned PFPE-containing compound.

The fluorine-containing oil contributes to the improvement of the surface slidability 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. The linear silicone oil may be a so-called ordinary silicone oil or a modified silicone oil. Examples of the ordinary silicone oil include dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil. Examples of the modified silicone oil include modified silicone oils obtained by modifying ordinary silicone oils with an alkyl group, an aralkyl group, a polyether, a higher fatty acid ester, a fluoroalkyl group, an amino group, an epoxy group, a carboxyl group, an alcohol, and the like. Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.

The surface treatment agent of the present invention may contain the silicone oil in an amount of, for example, 0 to 300 parts by mass, preferably 0 to 200 parts by mass, based on 100 parts by mass of the PFPE-containing compound (in the case of 2 or more species, the total amount thereof is the same hereinafter).

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

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

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

Other components than the above may include, for example: tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane and the like.

Examples of the halide ion include a chloride ion.

The compound containing an atom having an unshared electron pair in the above molecular structure preferably contains at least 1 atom selected from a nitrogen atom, an oxygen atom, a phosphorus atom and a sulfur atom, and more preferably contains a sulfur atom or a nitrogen atom.

The compound containing an atom having an unshared electron pair in the above molecular structure preferably contains at least 1 functional group selected from the group consisting of an amino group, an amide group, a sulfinyl group, a P ═ O group, an S ═ O group and a sulfonyl group in the molecular structure, and more preferably contains at least 1 functional group selected from the group consisting of a P ═ O group and an S ═ O group.

The compound containing an atom having an unshared electron pair in the molecular structure is preferably at least 1 compound selected from the group consisting of an aliphatic amine compound, an aromatic amine compound, a phosphoramide compound, an amide compound, a urea compound and a sulfoxide compound, more preferably at least 1 compound selected from the group consisting of an aliphatic amine compound, an aromatic amine, a phosphoramide, a urea compound and a sulfoxide compound, particularly preferably at least 1 compound selected from the group consisting of a sulfoxide compound, an aliphatic amine compound and an aromatic amine compound, and even more preferably a sulfoxide compound.

Examples of the aliphatic amine compound include diethylamine and triethylamine. Examples of the aromatic amine compound include aniline and pyridine. Examples of the phosphoramide compound include hexamethylphosphoramide. Examples of the amide compound include N, N-diethylacetamide, N-diethylformamide, N-dimethylacetamide, N-methylformamide, N-dimethylformamide, and N-methylpyrrolidone. Examples of the urea compound include tetramethylurea. Examples of the sulfoxide compound include dimethyl sulfoxide (DMSO), tetramethylene sulfoxide, methylphenyl sulfoxide, and diphenyl sulfoxide. Among these compounds, dimethyl sulfoxide or tetramethylene sulfoxide is preferably used.

Examples of the other components other than the above-mentioned compounds include alcohol compounds having 1 to 6 carbon atoms.

[ pellets ]

The surface treatment agent of the present invention can be impregnated into a porous material, for example, a porous ceramic material, a metal fiber, or a material obtained by compacting, for example, steel wool into a cotton-like form, and made into a pellet. The pellets can be used for vacuum evaporation, for example.

The surface treatment agent of the present invention can impart water repellency, oil repellency, stain resistance, water repellency, high friction durability, and UV resistance to a base material, and therefore is suitably used as a surface treatment agent. Specifically, the surface treatment agent of the present invention can be suitably used as an antifouling coating agent or a water repellent coating agent, but is not particularly limited.

[ article ]

Next, the article of the present invention will be explained.

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

First, a substrate is prepared. The substrate usable in the present invention may be made of any suitable material such as glass, resin (natural or synthetic resin, for example, common plastic material, and may be in the form of plate, film, or other form), metal (composite of simple metal such as aluminum, copper, or iron, or alloy), ceramic, semiconductor (silicon, germanium, or the like), fiber (woven fabric, nonwoven fabric, or the like), fur, leather, wood, ceramics, stone, or the like, or building parts.

The glass is preferably sapphire glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, or quartz glass, and particularly preferably chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, or chemically bonded borosilicate glass.

As the resin, acrylic resin and polycarbonate are preferable.

For example, in the case where the article to be manufactured is an optical member, the material constituting the surface of the base material may be a material for an optical member, such as glass or transparent plastic. When the article to be manufactured is an optical member, a layer (or film) of some kind, for example, a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the base material. The antireflection layer may be either a single-layer antireflection layer or a multilayer antireflection layer. Examples of inorganic substances that can be used for the antireflection layer include SiO ₂、SiO、ZrO₂、TiO₂、TiO、Ti₂O₃、Ti₂O₅、Al₂O₃、Ta₂O₅、CeO₂、MgO、Y₂O₃、SnO₂、MgF₂、WO₃And the like. These inorganic substances may be used alone or in combination of 2 or more of these (for example, as a mixture). When a multilayer antireflection layer is used, it is preferable to use SiO as the outermost layer₂And/or SiO. When the article to be manufactured is an optical glass member for a touch panel, a transparent electrode, for example, a thin film of Indium Tin Oxide (ITO) or indium zinc oxide may be provided on a part of the surface of the substrate (glass). The substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coat film layer, a polarizing film, a retardation film, a liquid crystal display module, and the like according to specific specifications and the like.

The shape of the substrate is not particularly limited. The surface area of the substrate on which the surface-treated layer is to be formed may be at least a part of the surface of the substrate, and may be determined as appropriate depending on the application, specific specifications, and the like of the article to be manufactured.

As such a base material, at least a surface portion thereof may be composed of a material originally having a hydroxyl group. Examples of such a material include glass, and metals (particularly base metals), ceramics, semiconductors, and the like, on the surface of which a natural oxide film or a thermally oxidized film is formed. Alternatively, in the case where the resin or the like has a hydroxyl group but is insufficient, or in the case where the resin or the like does not originally have a hydroxyl group, the hydroxyl group can be introduced into the surface of the base material or increased by subjecting the base material to some kind of pretreatment. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation. Plasma treatment can introduce hydroxyl groups or increase hydroxyl groups on the surface of the substrate, and is also suitable for cleaning the surface of the substrate (removing foreign matter and the like). As another example of such pretreatment, a method may be mentioned in which an interfacial adsorbent having a carbon-carbon unsaturated bond group is preliminarily formed as a monomolecular film on the surface of a substrate by an LB method (Langmuir-Blodgett method) or a chemisorption method, and then the unsaturated bond is cleaved in an atmosphere containing oxygen and/or nitrogen.

Alternatively, such a base material may be composed of an organosilicon compound having 1 or more other reactive groups, for example, Si — H groups, at least in a surface portion thereof, and/or a material containing an alkoxysilane.

In particular, as the substrate, a substrate having metal atoms on the surface thereof, such as alumite, sapphire glass, or zirconia, is preferably used. The metal contained in the substrate has particularly high affinity for the metal atom contained in the PFPE-containing compound represented by formula (1A) or (1B), and therefore the surface treatment layer formed becomes more firmly bonded to the substrate. Therefore, the water repellency of the surface-treated layer formed is particularly improved, and the abrasion resistance is further improved.

Then, a film of the surface treatment agent of the present invention is formed on the surface of such a base material, and the film is post-treated as necessary, thereby forming a surface treatment layer with the surface treatment agent of the present invention.

The 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 the base material so as to coat the surface. The coating method is not particularly limited. For example, a wet coating method and a dry coating method can be used.

As examples of the wet coating method, dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and the like can be cited.

As examples of the dry coating method, vapor deposition (generally, vacuum vapor deposition), sputtering, CVD, and the like can be cited. Specific examples of the vapor deposition method (usually, a vacuum vapor deposition method) include resistance heating, electron beam, high-frequency heating using a microwave or the like, ion beam, and the like. As specific examples of the CVD method, plasma-CVD, optical CVD, thermal CVD and the like can be cited.

Further, the coating may be performed by an atmospheric pressure plasma method.

In the case of using the wet coating method, the surface treatment agent of the present invention may be diluted with a solvent and applied to the surface of the substrate. From the viewpoint of stability of the surface treatment agent of the present invention and volatility of the solvent, the following solvents are preferably used: c_5－12Perfluoroaliphatic hydrocarbons (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1, 3-dimethylcyclohexane); polyfluorinated aromatic hydrocarbons (e.g., bis (trifluoromethyl) benzene); polyfluorinated aliphatic hydrocarbons (e.g. C)₆F₁₃CH₂CH₃(e.g., ASAHIKLIN (registered trademark) AC-6000, manufactured by Asahi glass Co., Ltd.), 1,2,2,3,3, 4-heptafluorocyclopentane (e.g., ZEORORA (registered trademark) H, manufactured by Nippon ruing Co., Ltd.); hydrofluorocarbons (HFCs) (e.g., 1,1,1,3, 3-pentafluorobutane (HFC-365 mfc)); hydrochlorofluorocarbons (e.g., HCFC-225 (ASAHIKLIN (registered trademark) AK 225)); hydrofluoroethers (HFE) (e.g., perfluoropropyl methyl ether (C) ₃F₇OCH₃) (e.g., Novec (trade name) 7000 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl methyl ether (C)₄F₉OCH₃) (e.g., Novec (trade name) 7100 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutylethyl ether (C)₄F₉OC₂H₅) (e.g., Novec (trade name) 7200 manufactured by Sumitomo 3M Co., Ltd.), perfluorohexylmethyl ether (C)₂F₅CF(OCH₃)C₃F₇) (for example, Novec (trade name) 7300 manufactured by Sumitomo 3M Co., Ltd.) or the like, or CF₃CH₂OCF₂CHF₂(e.g., ASAHIKLIN (registered trademark) AE-3000 manufactured by Asahi glass Co., Ltd.)), 1, 2-dichloro-benzene1,3,3, 3-tetrafluoro-1-propene (e.g., Vertrel (registered trademark) SION, manufactured by Mitsui-Dupont fluorine chemical Co., Ltd.) and the like. These solvents may be used alone or in combination of 2 or more as a mixture. In addition, for example, in order to adjust the solubility of the PFPE-containing compound, other solvents may be mixed.

In the case of using the dry coating method, the surface treatment agent of the present invention may be used in the dry coating method as it is, or may be used in the dry coating method after being diluted with the above-mentioned solvent.

The film formation is preferably carried out in such a manner that the surface treatment agent of the present invention and the catalyst for hydrolysis and dehydration condensation are present together in the film. In the case of the wet coating method, a catalyst may be added to a diluted solution of the surface treatment agent of the present invention after the surface treatment agent is diluted with a solvent and immediately before the surface treatment agent is applied to the surface of the substrate. In the case of the dry coating method, the surface treatment agent of the present invention to which a catalyst is added may be directly subjected to a vapor deposition (usually, vacuum vapor deposition) treatment, or a granular material obtained by impregnating a porous metal body such as iron or copper with the surface treatment agent of the present invention to which a catalyst is added may be subjected to a vapor deposition (usually, vacuum vapor deposition) treatment.

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

The film is then post-treated as necessary. The post-treatment is not particularly limited, and for example, the moisture supply and the drying and heating may be performed sequentially, and more specifically, may be performed as follows.

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

The supply of water can be performed, for example, in an atmosphere of 0 to 250 ℃, preferably 60 ℃ or higher, more preferably 100 ℃ or higher, and preferably 180 ℃ or lower, and more preferably 150 ℃ or lower. By supplying water in such a temperature range, hydrolysis can be performed. The pressure at this time is not particularly limited, and may be simply normal pressure.

The precursor film is then heated at the surface of the substrate and in a dry atmosphere above 60 ℃. The drying and heating method is not particularly limited, and the precursor film and the substrate may be placed together in an atmosphere having a temperature exceeding 60 ℃, preferably exceeding 100 ℃, and, for example, a temperature of 250 ℃ or less, preferably 180 ℃ or less, and an unsaturated water vapor pressure. The pressure at this time is not particularly limited, and may be simply normal pressure.

The above-described moisture supply and drying heating may be continuously performed by using superheated steam.

By operating as described above, post-processing can be implemented. This post-treatment may be performed to further improve frictional durability, but care is taken that it is not necessary to manufacture the article of the present invention. For example, after the surface treatment agent of the present invention is applied to the surface of a substrate, it may be left alone.

As described above, the article of the present invention is produced by forming a surface-treated layer derived from a film of the surface-treating agent of the present invention on the surface of a substrate. The surface treatment layer thus obtained has good UV resistance. The surface-treated layer has good UV resistance, and may have water repellency, oil repellency, stain resistance (for example, prevention of adhesion of stains such as fingerprints), surface slidability (or lubricity, for example, wiping-off of stains such as fingerprints, and excellent touch to fingers), high frictional durability, and the like, depending on the composition of the composition used, and can be suitably used as a functional film.

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

As the optical material, in addition to optical materials related to displays and the like as exemplified below, various optical materials are preferably listed: for example, displays such as cathode ray tubes (CRTs; e.g., TVs, computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent Display tubes (VFDs), Field Emission Displays (FEDs), protective plates for these displays, and optical materials having surfaces treated with an antireflection film.

The article having a surface-treated layer obtained by the present invention is not particularly limited, and may be an optical member. Examples of the optical member include the following: lenses for eyeglasses and the like; front protective plates, antireflection plates, polarizing plates, and antiglare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and portable information terminals; the disc surface of an optical disc such as a Blu-ray (registered trademark) optical disc, a DVD optical disc, a CD-R, MO, or the like; optical fibers, and the like.

In addition, the article having a surface-treated 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-treated layer is preferably in the range of 1 to 50nm, more preferably 1 to 30nm, and particularly preferably 1 to 15nm, from the viewpoint of optical performance, surface slipperiness, frictional durability, and stain resistance.

In another embodiment, a layer is separately formed on the surface of the substrate, and then a film of the surface-treated layer obtained by the present invention is formed on the surface of the layer.

The article obtained by using the surface treatment agent of the present invention is described in detail above. The use, the method of using, the method of producing an article, and the like of the surface treatment agent of the present invention are not limited to the above-exemplified cases.

Examples

The surface treating agent of the present invention is more specifically described by the following examples, but the present invention is not limited to these examples. Further, in the present example, the repeating unit (OCF) constituting perfluoropolyether₂CF₂) And (OCF)₂CF₂CF₂) The order of presence of (a) is arbitrary.

Synthesis example 1

In a structure provided with a thermometer and a stirrer 30mL of a 3-necked flask was charged with CF having an average composition₃CF₂CF₂(OCF₂CF₂CF₂)₂₀OCF₂CF₂CO₂2.4g of a perfluoropolyether-modified carboxylic acid compound represented by H, 3g of 1, 3-bis (trifluoromethyl) benzene, and 0.4g of an aluminum complex represented by the following compound (A) were stirred at room temperature for 16 hours under a nitrogen stream. Then, volatile matter was distilled off under reduced pressure, whereby 2.7g of a perfluoropolyether group-containing aluminum compound (B) having an aluminum complex at the terminal thereof and represented by the following formula was obtained.

Aluminum complex (a):

an aluminum compound (B) containing a perfluoropolyether group:

synthesis example 2

A30 mL 3-neck flask equipped with a thermometer and a stirrer was charged with CF as an average composition₃CF₂CF₂(OCF₂CF₂CF₂)₂₀OCF₂CF₂CH₂2.8g of perfluoropolyether-modified alcohol represented by OH, 2g of 1, 3-bis (trifluoromethyl) benzene, and 0.3g of an aluminum complex represented by the following compound (C) were stirred at room temperature for 16 hours under a nitrogen stream. Then, volatile matter was distilled off under reduced pressure, whereby 3.0g of a perfluoropolyether group-containing aluminum compound (D) having an aluminum complex at the terminal thereof and represented by the following formula was obtained.

Aluminum complex (C):

an aluminum compound (D) containing a perfluoropolyether group:

EXAMPLE 1

The compound (B) obtained in synthesis example 1 was dissolved in hydrofluoroether (Novec HFE7200, manufactured by 3M) so that the concentration thereof became 0.2 wt%, to prepare a surface treatment agent 1.

The surface-treating agent 1 prepared above was immersed in alumite (100 mm. times.100 mm. times.0.8 mm, manufactured by Toyoyang chemical research Co., Ltd.) at a pull rate of 30 mm/sec. Then, the dipped alumite was allowed to stand at 150 ℃ for 1 hour. And then cooled to room temperature, thereby forming a surface treatment layer.

EXAMPLE 2

Using the surface treating agent 1 prepared in example 1, a dipping treatment was performed on the surface of SUS304 (manufactured by Japanese testpanel, BA treatment, 90 mm. times.60 mm. times.1 mm) at a pull-up rate of 30 mm/sec. Then, the SUS304 after the dipping treatment was allowed to stand at a temperature of 150 ℃ for 1 hour. And then cooled to room temperature, thereby forming a surface treatment layer.

Examples 3 and 4

A surface-treated layer was formed in the same manner as in example 1 or 2, except that the compound (D) obtained in synthesis example 2 was used instead of the compound (B).

Comparative examples 1 and 2

A surface-treated 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

CF₃CF₂CF₂(OCF₂CF₂CF₂)₂₀OCF₂CF₂CH₂OP(O)(OH)₂

(evaluation)

Measurement of static contact Angle

The static contact angles of water in the surface treatment layers obtained in examples 1 to 4 and comparative examples 1 to 2 were measured. The measurement of the static contact angle of water was carried out using a contact angle measuring apparatus (manufactured by Kyowa interface science Co., Ltd.) using 1. mu.L of water at 21 ℃ under an atmosphere of 65% humidity. Evaluation of Friction durability

In the surface-treated layers formed on the surfaces of the substrates in examples 1 to 4 and comparative examples 1 to 2, first, as an initial evaluation, the surfaces were wiped with cotton cloth containing ethanol, and then the static contact angle of water in the surface-treated layers was measured.

The surface-treated layers formed on the surfaces of the substrates in examples 1 to 4 and comparative examples 1 to 2 were evaluated for friction durability by a rubber friction durability test. Specifically, the sample article having the surface treatment layer formed thereon was horizontally arranged, the surface of the surface treatment layer was touched with a rubber (KESHI-70, manufactured by KOKUYO corporation, plane size 1cm × 1.6cm), a load of 500gf was applied thereto, and then the rubber was reciprocated at a speed of 20 mm/sec in a state where the load was applied. After 100 round trips, the static contact angle (degree) of water was measured. The results are shown in table 1.

[ Table 1]

As can be understood from the results in Table 1, it was confirmed that the surface-treated layers of examples 1 to 4 exhibited excellent water repellency and excellent rubbing resistance. It is considered that the affinity is particularly good because both the aluminum coordinating group of the PFPE-containing compound contained in the surface-treated layers of examples 1 to 4 and the surface of the substrate contain a metal. As a result, the surface-treated layer and the base material are more firmly bonded to each other, and not only the initial water repellency but also the abrasion resistance are improved.

Industrial applicability

The present invention can be suitably used for forming a surface-treated layer on the surface of various substrates, particularly optical members requiring permeability.

Claims (21)

1. A surface treating agent characterized by:

comprising a perfluoropolyether group-containing compound represented by the formula (1A) or the formula (1B),

(Rf-PFPE)_α2-X-R^m _α1 (1A)

(Rf-Rf¹-PFPE¹-Rf²)_α2-X-R^m _α1 (1B)

in the formula (I), the compound is shown in the specification,

rf independently represents a C1-16 perfluoroalkyl group at each occurrence;

PFPE at each occurrence is independently a group of the formula:

-(OC₆F₁₂)_a-(OC_sF₁₀)_b-(OC₄F₈)_c-(OC₃F₆)_d-(OC₂F₄)_e-(OCF₂)_f-

wherein a, b, c, d, e and f are each independently an integer of 0 to 200 inclusive, the sum of a, b, c, d, e and f is at least 1, and the order of the presence of each repeating unit denoted by a, b, c, d, e or f and enclosed by parentheses is arbitrary in the formula;

PFPE¹The same as PFPE;

Rf¹each occurrence of (O-Rf)¹¹)_m2；

Rf¹¹Is a fluoroalkylene group having no branched structure containing 1 or more hydrogen atoms;

m2 is an integer of 0 to 4, and m2 is an integer of 2 to 4, (O-Rf)¹¹)_m2May contain 2 or more kinds of O-Rf¹¹；

Rf²Each occurrence of (O-Rf)²¹)_m3；

Rf²¹Is a fluoroalkylene group having no branched structure containing 1 or more hydrogen atoms;

m3 is an integer of 0 to 4, and m3 is an integer of 2 to 4, (O-Rf)²¹)_m3May contain 2 or more kinds of O-Rf²¹；

X independently represents a single bond, an oxygen atom or a 2-10 valent organic group at each occurrence;

alpha 1 is independently an integer of 1-9 at each occurrence;

alpha 2 is independently an integer of 1-9 at each occurrence;

R^mindependently at each occurrence is a group represented by the formula:

m is independently at each occurrence a metal atom capable of coordinate bonding;

R¹each occurrence independently represents a monodentate ligand having a bond to X;

R²each occurrence independently represents a multidentate ligand having a bonding bond to X;

R³each occurrence independently represents a monodentate ligand;

R⁴independently at each occurrence represents a multidentate 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 1 or 2;

wherein the sum of k and l is 1-4, and l is multiplied by R²N multiplied by R⁴The sum of the values obtained for the number of teeth in (c), k and M is the coordination number for M.

2. The surface treating agent according to claim 1, wherein:

R¹～R⁴the contained coordinating atoms are at least 1 selected from oxygen and nitrogen.

3. The surface treating agent according to claim 1 or 2, characterized in that:

R¹is-R¹¹-O-or-R¹¹N(R¹²)－，

In the formula, R¹¹Independently at each occurrence a single bond or a 2-valent organic group, R¹²Is a hydrogen atom or a 1-valent organic group.

4. The surface treating agent according to claim 1 or 2, characterized in that:

R²are bidentate ligands.

5. The surface treating agent according to claim 1 or 2, characterized in that:

R²a ligand coordinated to any 1 of the following compounds (1-1) to (1-6):

in the formula (I), the compound is shown in the specification,

represents a coordinating atom;

R²¹independently at each occurrence is an oxygen atom or a 2-valent organic group;

R²²each occurrence independently is a hydrogen atom or a 1-valent organic group;

l1 is independently at each occurrence an integer from 0 to 6.

6. The surface treating agent according to claim 1 or 2, characterized in that:

R³Is at least 1 kind selected from a halogen atom, a hydrogen atom, a hydroxyl group and a 1-valent organic group.

7. The surface treating agent according to claim 1 or 2, characterized in that:

R⁴are bidentate ligands.

8. The surface treating agent according to claim 1 or 2, characterized in that:

R⁴a ligand in which at least 1 kind selected from the following compounds (2-1) to (2-6) is bonded:

in the formula (I), the compound is shown in the specification,

represents a coordinating atom;

R⁴³each occurrence independently is a hydrogen atom or a 1-valent organic group;

R⁴⁴each occurrence independently is a hydrogen atom or a 1-valent organic group;

n1 is independently at each occurrence an integer from 0 to 6.

9. The surface treating agent according to claim 1 or 2, characterized in that:

k is 1 and l is 0.

10. The surface treating agent according to claim 1 or 2, characterized in that:

k is 0 and l is 1.

11. The surface treating agent according to claim 1 or 2, characterized in that:

m is an aluminum atom, a zinc atom or a transition metal atom.

12. The surface treating agent according to claim 1 or 2, characterized in that:

m is an aluminum atom, a titanium atom or a zirconium atom.

13. The surface treating agent according to claim 1 or 2, characterized in that:

m is an aluminum atom.

14. The surface treating agent according to claim 1 or 2, characterized in that:

x is a 2-valent organic group, α 1 is 1 and α 2 is 1.

15. The surface treating agent according to claim 1 or 2, characterized in that:

the compound containing the perfluoropolyether group is represented by the formula (1A).

16. The surface treating agent according to claim 1 or 2, characterized in that:

PFPE, independently at each occurrence, is of formula (a), (b) or (c):

－(OC₃F₆)_d－ (a)

in the formula (a), d is an integer of 1-200;

－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－ (b)

in the formula (b), c and d are each independently an integer of 0 to 30;

e and f are each independently an integer of 1 to 200;

c. the sum of d, e and f is an integer of 10 to 200;

the order of occurrence of each repeat unit denoted by subscripts c, d, e, or f and enclosed by parentheses is arbitrary in the formula;

－(R⁶－R⁷)_j－ (c)

in the formula (c), R⁶Is OCF₂Or OC₂F₄；

R⁷Is selected from OC₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀And OC₆F₁₂Or a combination of 2 or 3 groups selected from these groups;

j is an integer of 2 to 100.

17. The surface treating agent according to claim 1 or 2, characterized in that:

further contains 1 or more components selected from fluorine-containing oil, silicone oil, alcohol, catalyst, transition metal, halide ion, and a compound having an atom having an unshared electron pair in a molecular structure.

18. A pellet containing the surface treatment agent according to any one of claims 1 to 17.

19. An article comprising a substrate and a layer formed on the surface of the substrate by the surface treatment agent according to any one of claims 1 to 17.

20. The article of claim 19, wherein:

the article is an optical component.

21. The article of claim 19 or 20, wherein:

the article is a display.