CN110461985A - Surface treating agent containing perfluoro-polyether based compound - Google Patents

Abstract

The present invention provides the surface treating agent [in formula, each mark is identical as the record meaning in specification] containing perfluoro-polyether based compound shown in formula (1A) or formula (1B).(Rf-PFPE)_α2‑X‑R^m _α1(1A), (Rf-Rf¹‑PFPE¹‑Rf²)_α2‑X‑R^m _α1(1B)。

Description

Surface treating agent containing perfluoro-polyether based compound

Technical field

The present invention relates to contain the surface treating agent containing perfluor (poly-) based compound.

Background technique

Certain known fluorochemical in the surface treatment for substrate, be capable of providing excellent water-repellancy, dial oiliness, Soil resistance etc..The layer (hereinafter also referred to " surface-treated layer ") obtained by the surface treating agent containing fluorochemical is as so-called Functional film, such as the diversified substrate such as be applied to glass, plastics, fiber, construction material.

As such fluorochemical, it is known that there is the compound of holo-fluorine polyester in molecular backbone.For example, in patent It is described in document 1 and contains-P (O) (OH) in molecular end₂,-OP (O) (OH)₂Or-NR⁸⁷ ₂(R⁸⁷For hydrogen atom or rudimentary Alkyl) etc. compound.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2016-052779 bulletin

Summary of the invention

Technical problems to be solved by the inivention

In order to assign desired function, durability demanding for surface-treated layer for a long time to substrate.By containing tool Even the layer film for having the surface treating agent of the compound of holo-fluorine polyester to obtain can also play function as described above, because This is suitable for requiring the glasses of translucency or the transparency or the optical component of touch panel etc..

But the surface treating agent as described above containing the compound with holo-fluorine polyester, reply is gradually risen Raising friction durability requirement for, can not say it is certain sufficiently.

Therefore, the purpose of the present invention is to provide suitably form the novel of the friction more good surface-treated layer of durability Surface treating agent.

For solving the technological means of technical problem

The present inventor further investigation as a result, discovery by using containing with specific structure perfluoropolyether The surface treating agent of object is closed, the friction durability of surface-treated layer further increases, so as to complete the present invention.

First purport according to the present invention is provided containing perfluoro-polyether based compound shown in formula (1A) or formula (1B) Surface treating agent.

(Rf-PFPE)_α2-X-R^m _α1 (1A)

(Rf-Rf¹-PFPE¹-Rf²)_α2X-R^m _α1 (1B)

[in formula:

The Rf carbon atom number 1 that separately expression can be replaced by 1 or 1 or more fluorine atom at each occurrence~ 16 alkyl；

PFPE is separately group shown in following formula at each occurrence:

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

Wherein, a, b, c, d, e and f are separately 0 or more 200 integer below, and the sum of a, b, c, d, e and f are at least It is 1, marks a, b, c, d, e or f and be arbitrary in formula by the presence sequence for each repetitive unit that bracket is included；

PFPE¹It is identical as the meaning of PFPE；

Rf¹(O-Rf is separately indicated at each occurrence¹¹)_m2；

Rf¹¹For the fluorine alkylidene without branched structure comprising 1 or more hydrogen atom；

M2 be 0~4 integer, m2 be 2~4 integer when, (O-Rf¹¹)_m2It may include O-Rf of more than two kinds¹¹；

Rf²(O-Rf is separately indicated at each occurrence²¹)_m3；

Rf²¹For the fluorine alkylidene without branched structure comprising 1 or more hydrogen atom；

M3 be 0~4 integer, m3 be 2~4 integer when, (O-Rf²¹)_m3It may include O-Rf of more than two kinds²¹；

X separately indicates singly-bound, oxygen atom or 2~10 valence organic groups at each occurrence；

α 1 is separately 1~9 integer at each occurrence；

α 2 is separately 1~9 integer at each occurrence；

R^mIt is separately at each occurrence group shown in formula below；

M is separately at each occurrence being capable of complex bound metallic atom；

R¹The monodentate ligand for having with the associative key of X is separately indicated at each occurrence；

R²The multidentate ligand for having with the associative key of X is separately indicated at each occurrence；

R³Monodentate ligand is separately indicated at each occurrence；

R⁴Multidentate ligand is separately indicated at each occurrence；

The integer that k is 0~2；

The integer that l is 0~2；

The integer that m is 0 or more；

The integer that n is 0 or more；

Wherein, the sum of k and l are 1~4, l multiplied by R²The value obtained with the number of teeth, n is multiplied by R⁴The value obtained with the number of teeth, k The ligancy for being M with the sum of m.]

Second purport according to the present invention, provides the pellet containing above-mentioned surface treating agent.

Third purport according to the present invention is provided including substrate and on the surface of the substrate by above-mentioned surface treatment dosage form At layer article.

Specific embodiment

In the case of using in this manual, " 1~10 valence organic group " refers to 1~10 valence group containing carbon.Make It for such 1 valence organic group, is not particularly limited, alkyl can be enumerated.As such 2~10 valence organic group, do not have It is particularly limited to, 2~10 valence groups after being detached from 1~9 hydrogen atom again from alkyl can be enumerated.As divalent organic group, do not have Be particularly limited to, can enumerate from carbonyl or alkyl be detached from 1 hydrogen atom again after divalent group.

In the case of using in this manual, " alkyl " refers to the group comprising carbon and hydrogen, and from hydrocarbon departing from 1 hydrogen Group after atom.It as such alkyl, is not particularly limited, can enumerate and be replaced by 1 or 1 or more substituent group , the alkyl of carbon atom number 1~20, such as aliphatic alkyl, aromatic hydrocarbyl.Above-mentioned " aliphatic alkyl " can be straight chain Shape, branched or it is cricoid any one, can for it is saturated or unsaturated any one.In addition, alkyl may include 1 or 1 or more ring structure.In addition, such alkyl can have at its end or in strand 1 or 1 or more N, O, S, Si, amide, sulfonyl, siloxanes, carbonyl, carbonyloxy group etc..

In the case of using in this manual, the substituent group as " alkyl ", is not particularly limited, such as can arrange It lifts: halogen atom；Selected from can be replaced by 1 or 1 or more halogen atom, C_1-6Alkyl, C_2-6Alkenyl, C_2-6Alkynyl, C_3-10Cycloalkanes Base, C_3-10Unsaturated ring alkyl, 5~10 yuan of heterocycle, 5~10 yuan of unsaturated heterocycle base, C_6-10Aryl and 5~10 yuan 1 or 1 or more group in heteroaryl.

In the present specification, alkyl and phenyl unless otherwise specified, can also be substituted to be non-substituted.Make It for the substituent group of above-mentioned group, is not particularly limited, can enumerate for example selected from halogen atom, C_1-6Alkyl, C_2-6Alkenyl and C_2-6Alkynes 1 or 1 or more group in base.

In the present specification, " complex " indicates that several ligands surround central metal atom or ion suchization Learn kind.In the present specification, " ligand " is even if indicate individually to can be used as chemical seed existing for lewis' acid.As matching The coordination atom that position body is included, is preferably selected from least one kind of in oxygen and nitrogen.

[surface treating agent]

Hereinafter, containing perfluoro-polyether base (hereinafter, sometimes referred to as " PFPE " to of the invention.) compound surface treatment Agent is illustrated.

Above-mentioned formula (1A) or formula (1B) containing PFPE indicates.

(Rf-PFPE)_α2-X-R^m _α1 (1A)

(Rf-Rf¹-PFPE¹-Rf2)_α2-X-R^m _α1 (1B)

In above-mentioned (1A) and (1B), Rf is separately indicated at each occurrence can be by 1 or 1 or more fluorine atom The alkyl of substituted carbon atom number 1~16.

In the alkyl of the above-mentioned carbon atom number 1~16 that can be replaced by 1 or 1 or more fluorine atom " carbon atom number 1~ 16 alkyl " can be straight chain, be also possible to branch, preferably the carbon atom number 1~6 of linear chain or branched chain, specifically for carbon atom The alkyl of number 1~3, the more preferably alkyl of the carbon atom number 1~3 of straight chain.

Above-mentioned Rf is preferably the alkyl of the carbon atom number 1~16 replaced by 1 or 1 or more fluorine atom, more preferably CF₂H-C_1-15Perfluorinated alkylidene or C_1-16Perfluoroalkyl, more preferably C_1-16Perfluoroalkyl.In addition, alkylidene refers to tool There is-(C_βH_2βThe group of)-structure.

The perfluoroalkyl of the carbon atom number 1~16 can be straight chain, or branch, the preferably carbon of linear chain or branched chain Atomicity 1~6, specifically for the perfluoroalkyl of carbon atom number 1~3, the more preferably perfluoroalkyl of the carbon atom number 1~3 of straight chain, Specially-CF₃,-CF₂CF₃Or-CF₂CF₂CF₃。

In above-mentioned (1A), PFPE is separately group shown in following formula :-(OC at each occurrence₆F₁₂)_a (OC₅F₁₀)_b(OC₄F₈)_c(OC₃F₆)_d(OC₂F₄)_e(OCF₂)_f.

In formula, a, b, c, d, e and f are separately 0 or more 200 integer below, and the sum of a, b, c, d, e and f are at least It is 1.It is preferred that a, b, c, d, e and f are separately 0 or more 100 integer below.It is preferred that the sum of a, b, c, d, e and f be 5 with On, more preferably 10 or more.It is preferred that the sum of a, b, c, d, e and f are for 200 hereinafter, more preferably 100 hereinafter, for example, 10 or more 200 hereinafter, more specifically 10 or more 100 or less.In addition, mark a, b, c, d, e or f and each repetitive unit for being included by bracket There are sequences to be arbitrary in formula.

These repetitive units can be straight-chain, or branched, preferably straight-chain.For example,-(OC₆F₁₂)- It can be-(OCF₂CF₂CF₂CF₂CF₂CF₂)-,-(OCF (CF₃)CF₂CF₂CF₂CF₂)-,-(OCF₂CF(CF₃) CF₂CF₂CF₂)-,-(OCF₂CF₂CF(CF₃)CF₂CF₂)-,-(OCF₂CF₂CF₂CF(CF₃)CF₂)-,- (OCF₂CF₂CF₂CF₂CF(CF₃))-etc., preferably-(OCF₂CF₂CF₂CF₂CF₂CF₂)-.(OC₅F₁₀)-can be- (OCF₂CF₂CF₂CF₂CF₂)-,-(OCF (CF₃)CF₂CF₂CF₂)-,-(OCF₂CF(CF₃)CF₂CF₂)-,-(OCF₂CF₂CF (CF₃)CF₂)-,-(OCF₂CF₂CF₂CF(CF₃))-etc., preferably-(OCF₂CF₂CF₂CF₂CF₂)-.(OC₄F₈)-can Think-(OCF₂CF₂CF₂CF₂)-,-(OCF (CF₃)CF₂CF₂)-,-(OCF₂CF(CF₃)CF₂)-,-(OCF₂CF₂CF (CF₃))-,-(OC (CF₃)₂CF₂)-,-(OCF₂C(CF₃)₂)-,-(OCF (CF₃)CF(CF₃))-,-(OCF (C₂F₅) CF₂)-and-(OCF₂CF(C₂F₅))-any number of, preferably-(OCF₂CF₂CF₂CF₂)-.(OC₃F₆)-can be- (OCF₂CF₂CF₂)-,-(OCF (CF₃)CF₂)-and-(OCF₂CF(CF₃))-it is any number of, preferably- (OCF₂CF₂CF₂)-.In addition ,-(OC₂F₄)-can be-(OCF₂CF₂)-and-(OCF (CF₃))-it is any number of, preferably For-(OCF₂CF₂)-.

In a mode, above-mentioned PFPE is-(OC₃F₆)_d(in formula, d be 1 or more 200 integer below, preferably 5 Above 200 integer below, more preferably 10 or more 200 integers below).It is preferred that PFPE is-(OCF₂CF₂CF₂)_d(formula In, d is 1 or more 200 integer below, and preferably 5 or more 200 integers below, more preferably 10 or more 200 is below whole Number) or-(OCF (CF₃)CF₂)_d(in formula, d be 1 or more 200 integer below, preferably 5 or more 200 integers below, more Preferably 10 or more 200 integers below).More preferable PFPE is-(OCF₂CF₂CF₂)_d(in formula, d is 1 or more 200 or less Integer, preferably 5 or more 200 integers below, more preferably 10 or more 200 integers below).

In another way, PFPE is-(OC₄F₈)_c(OC₃F₆)_d(OC₂F₄)_e(OCF₂)_f(in formula, c and d difference Independently be 0 or more 30 integer below, e and f are separately 1 or more 200 integer below, preferably 5 or more 200 with Under integer, more preferably 10 or more 200 integers below, the sum of c, d, e and f be at least 5 or more, preferably 10 or more, mark It pours down mark c, d, e or f and is arbitrary in formula by the presence sequence for each repetitive unit that bracket is included).It is preferred that PFPE be- (OCF₂CF₂CF₂CF₂)_c(OCF₂CF₂CF₂)_d(OCF₂CF₂)_e(OCF₂)_f.In a mode, PFPE can for- (OC₂F₄)_e(OCF₂)_f(in formula, e and f are separately 1 or more 200 integer below, preferably 5 or more 200 or less Integer, more preferably 10 or more 200 integers below, the presence of each repetitive unit for marking subscript e or f and being included by bracket Sequence is arbitrary in formula).

In a mode, PFPE can be-(OC₂F₄)_e(OCF₂)_f(in formula, e and f are separately 1 or more 200 integers below, preferably 5 or more 200 integers below, more preferably 10 or more 200 integers below mark subscript e Or f and be arbitrary in formula by the presence of each repetitive unit that bracket is included sequence).

In PFPE, e is 0.1 or more 10 hereinafter, preferably 0.2 or more relative to the ratio (hereinafter referred to as " e/f ratio ") of f 5.0 hereinafter, more preferably 0.2 or more 2.0 hereinafter, more preferably 0.2 or more 1.5 or less.By making e/f ratio in above-mentioned model It encloses, the water-repellancy of the solidfied material obtained by the compound, to dial oiliness and chemical resistance (such as water-soluble for salt water, acid or alkalinity Liquid, acetone, oleic acid or hexane durability) can further increase.E/f than smaller, then the water-repellancy of above-mentioned solidfied material, dial oil Property, chemical resistance are higher.On the other hand, by making e/f ratio 0.1 or more, the stability of compound can be made to further increase. E/f ratio is bigger, and the stability of compound is higher.

In another way, PFPE is-(R⁶¹- R⁶²)_jShown in group.In formula, R⁶¹For OCF₂Or OC₂F₄, preferably For OC₂F₄.In formula, R⁶²For selected from OC₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀And OC₆F₁₂In group, or for from these groups The combination of 2 or 3 groups of independent choice.It is preferred that R⁶²For selected from OC₂F₄、OC₃F₆And OC₄F₈In group, or for selected from OC₃F₆、OC₄F₈、OC₅F₁₀And OC₆F₁₂In group, or the combination for 2 or 3 groups of independent choice from these groups. As from OC₂F₄、OC₃F₆And OC₄F₈The combination of 2 or 3 groups of middle independent choice, is not particularly limited, such as can arrange Act-OC₂F₄OC₃F₆,-OC₂F₄OC₄F₈,-OC₃F₆OC₂F₄,-OC₃F₆OC₃F₆,-OC₃F₆OC₄F₈,- OC₄F₈OC₄F₈,-OC₄F₈OC₃F₆,-OC₄F₈OC₂F₄,-OC₂F₄OC₂F₄OC₃F₆,-OC₂F₄OC₂F₄OC₄F₈,- OC₂F₄OC₃F₆OC₂F₄,-OC₂F₄OC₃F₆OC₃F₆,-OC₂F₄OC₄F₈OC₂F₄,-OC₃F₆OC₂F₄OC₂F₄,- OC₃F₆OC₂F₄OC₃F₆,-OC₃F₆OC₃F₆OC₂F₄And-OC₄F₈OC₂F₄OC₂F₄Etc..Above-mentioned j be 2 or more, preferably 3 with On, more preferably 5 or more, it is 100 hereinafter, preferably 50 integers below.In above-mentioned formula, OC₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ And OC₆F₁₂It can be any one of linear chain or branched chain, preferably straight chain.In this approach, PFPE is preferably-(OC₂F₄ OC₃F₆)_jOr-(OC₂F₄- OC₄F₈)_j.

The average molecular weight of the part Rf-PFPE- is not particularly limited, and is 500~30,000, preferably 1,500~30, 000, more preferably 2,000~10,000.

In another way, the number-average molecular weight of the part Rf-PFPE is 500~30,000, preferably 1,000~20, 000, more preferably 2,000~15,000.

In another mode, the number-average molecular weight of the part Rf-PFPE- or the part-PFPE- can for 4,000~ 30,000, preferably 5,000~10,000.

In above-mentioned formula (1B), PFPE¹It is identical as the meaning of PFPE.PFPE¹It is preferred that not having branched structure.

In above-mentioned formula (1B), Rf¹(O-Rf is separately indicated at each occurrence¹¹)_m2。

Above-mentioned Rf¹¹For the fluorine alkylidene without branched structure comprising 1 or more hydrogen atom, preferably carbon atom number 2 ~6 fluorine alkylidene, particularly preferably the fluorine alkylidene of carbon atom number 2.Rf¹¹The quantity of contained hydrogen atom is preferably 1~4, Particularly preferably 1 or 2.As (O-Rf¹¹), preferably (O-CHFCF₂) and (O-CH₂CF₂).In addition, in the present specification, Fluorine alkylidene refer to 1 of the hydrogen atom of alkylidene or more be replaced by fluorine atoms after group.

Above-mentioned m2 be 0~4 integer, m2 be 2~4 integer when, (O-Rf¹¹O)_m2It may include O- of more than two kinds Rf¹¹。

In above-mentioned formula (1B), Rf²(O-Rf is separately indicated at each occurrence²¹)_m3。

Above-mentioned Rf²¹For the fluorine alkylidene without branched structure comprising 1 or more hydrogen atom, preferably carbon atom number 2 ~6 fluorine alkylidene.Rf²¹The quantity of contained hydrogen atom is preferably 1~4, particularly preferably 1 or 2.

In the case where the integer that integer that above-mentioned m3 is 0~4, m3 are 2~4, (O-Rf²¹)_m3It may include of more than two kinds O-Rf²¹.M3 is preferably 0~2 integer.

In a mode, (O-Rf²¹)_m3In (it is R that X, which is in the case where singly-bound, with X^m) combine (O-Rf²¹) can be with For (O-Rf^21’CH₂) shown in group.Rf^21’For than Rf²¹The group of few 1 carbon atom number, and be perfluorinated alkylidene or have The fluorine alkylidene of hydrogen atom.It is preferred that Rf^21’For perfluorinated alkylidene.As specific (O-Rf^21’CH₂), preferably (O-CF₂CH₂)、 (O-CF₂CF₂CH₂), (O-CF₂CF₂CF₂CH₂), (O-CF₂CF₂CF₂CF₂CH₂) etc..In this case, m3 is preferably 1.

In above-mentioned PFPE¹In, preferably the sum of a, b, c, d, e, f, m2 and m3 are 5 or more, more preferably 10 or more.It is preferred that a, B, the sum of c, d, e, f, m2 and m3 are 200 hereinafter, more preferably 100 hereinafter, for example, 10 or more 200 hereinafter, more specifically 10 Above 100 or less.

In other modes, the range of the sum of a, b, c, d, e, f, m2 and m3 2~210.

In above-mentioned formula (1A) and (1B), X indicates singly-bound, oxygen atom or 2~10 valence organic groups.The X in formula (1A) or In (1B) compound represented, it is understood to mainly provide perfluoropolyether portion (the i.e. Rf- of water-repellancy and surface slipperiness etc. The portion PFPE or Rf-Rf¹- PFPE¹- Rf²Portion) and R^mThe connector of connection.Therefore, as long as shown in the X formula (1A) or (1B) Compound can steadily exist, and can be any organic group.

2~10 valence organic groups in above-mentioned X are preferably 2~7 valence organic groups, more preferably 2~4 valence organic groups, More preferably divalent organic group.

In above-mentioned formula, the integer that α 1 is 1~9, the integer that α 2 is 1~9.These α 1 and α 2 can become with the valence mumber of X Change.In formula (1A) and (1B), the sum of α 1 and α 2 and the valence mumber of X are identical.Such as in the case where X is 10 valence organic group, α 1 With α's 2 and it is 10, such as can be 9 and α 2 with α 1 be 1, α 1 is that 5 and α 2 is 5 or α 1 be 1 and α 2 is 9.In addition, being divalent in X In the case where organic group, α 1 and α 2 are 1.

In a mode, X is singly-bound or 2~4 valence organic groups, and the integer that α 1 is 1~3, α 2 is 1.

In other modes, X is singly-bound or divalent organic group, and α 1 is that 1, α 2 is 1.In this case, formula (1A) is by following Formula (1A ') indicates that formula (1B) following formula (1B ') indicates.

Rf-PFPE-X-R^m (1A′)

Rf-Rf¹-PFPE¹-Rf²-X-R^m (1B′)

In a mode, X indicates singly-bound or 2~10 valence organic groups, preferably indicates singly-bound, alkylidene or has choosing From-C₆H₄(i.e.-phenylene-.Following presentation phenylene.) ,-CO- (carbonyl) ,-NR⁸And-SO₂In at least one kind of 2~10 Valence organic group.Above-mentioned R⁸Separately indicate hydrogen atom, phenyl or C_1~6Alkyl (preferably methyl), preferably hydrogen atom Or methyl.It is preferred that containing above-mentioned-C in the molecular backbone of the compound containing PFPE₆H₄-、-CO-、-NR⁸Or-SO₂-.Wherein, Molecular backbone indicates the relatively longest marriage chain containing PFPE in the molecule of the compound containing PFPE.

In this mode, X more preferably indicates singly-bound, alkylidene or has selected from-C₆H₄-、-CONR⁸-、-CONR⁸- C₆H₄-、-CO-、-CO-C₆H₄-、-SO₂NR⁸-、-SO₂NR⁸-C₆H₄-、-SO₂And-SO₂-C₆H₄In 2~10 at least one kind of valences Organic group.Above-mentioned-C₆H₄-、-CONR⁸-、-CONR⁸-C₆H₄-、-CO-、-CO-C₆H₄-、-SO₂NR⁸-、-SO₂NR⁸-C₆H₄-、- SO₂Or-SO₂-C₆H₄It preferably is contained in the molecular backbone of the compound containing PFPE.

In this mode, in X, by the portion PFPE (group bracketed in formula (1A) or (1B) by α 2) and R^mBase is (i.e. By group that α 1 is bracketed in formula (1A) or (1B)) quantity of the atom of connection be preferably 20 hereinafter, more preferably 10 hereinafter, More preferably 6 or less.In addition, there are multiple by a portion PFPE and a R^mIt is above-mentioned in the case where the path of base connection " by the portion PFPE and R^mThe quantity of the atom of base connection " means to link the portion PFPE and R most shortly^mThe quantity of atom between base.

It in other modes, as the example of above-mentioned X, is not particularly limited, divalent shown in such as following formula can be enumerated Group:

-(R⁸¹)_p’-(X^a)_q’-

[in formula:

R⁸¹Indicate singly-bound ,-(CH₂)_s’Or adjacent phenylene, metaphenylene or to phenylene, preferably-(CH₂)_s’,

The integer that s ' is 1~20, preferably 1~6 integer, more preferably 1~3 integer, more preferably 1 or 2,

X^aExpression-(X^b)_l’,

X^bIt separately indicates selected from-O- ,-S-, adjacent phenylene, metaphenylene or to sub- benzene at each occurrence Base ,-C (O) O- ,-Si (R⁸³)₂,-(Si (R⁸³)₂O)_m’- Si (R⁸³)₂,-CONR⁸⁴,-O-CONR⁸⁴,- NR⁸⁴And-(CH₂)_n’In group,

R⁸³Phenyl, C are separately indicated at each occurrence_1-6Alkyl or C_1-6Alkoxy, preferably phenyl or C_1-6 Alkyl, more preferably methyl,

R⁸⁴Hydrogen atom, phenyl or C are separately indicated at each occurrence_1-6Alkyl (preferably methyl),

M ' at each occurrence separately be 1~100 integer, preferably 1~20 integer,

N ' is separately 1~20 integer at each occurrence, preferably 1~6 integer, more preferably 1~3 Integer,

The integer that l ' is 1~10, preferably 1~5 integer, more preferably 1~3 integer,

P ' is 0 or 1,

Q ' is 0 or 1,

Wherein, at least one of p ' and q ' are 1, the presence sequence of mark p ' or q ' and each repetitive unit included by bracket It is arbitrary].

Wherein, R⁸¹And X^a(R for typical⁸¹And X^aHydrogen atom) can by be selected from fluorine atom, C_1-3Alkyl and C_1-3Fluothane 1 or 1 or more substituent group in base replaces.

It is preferred that above-mentioned X is-(R⁸¹)_p’(X^a)_q’- R⁸².R⁸²Indicate singly-bound ,-(CH₂)_t’Or adjacent phenylene, Phenylene or to phenylene, preferably-(CH₂)_t’.The integer that t ' is 1~20, preferably 2~6 integer, more preferably 2 ~3 integer.Wherein, R⁸²(typically R⁸²Hydrogen atom) can by be selected from fluorine atom, C_1-3Alkyl and C_1-3In fluoroalkyl 1 or 1 or more substituent group replaces.

It is preferred that above-mentioned X can be

Singly-bound,

C_1-20Alkylidene,

- R⁸¹- X^c- R⁸²Or

- X^d- R⁸²

[in formula, R⁸¹And R⁸²It is identical as above-mentioned meaning.].

More preferable above-mentioned X is

Singly-bound,

C_1-20Alkylidene,

(CH₂)_s’- X^c,

(CH₂)_s’- X^c(CH₂)_t’,

- X^dOr

- X^d(CH₂)_t’

[in formula, s ' and t ' are identical as above-mentioned meaning.].

In above-mentioned formula, X^cIt indicates

- 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(adjacent phenylene, metaphenylene or to phenylene)-Si (R⁸³)₂

[in formula, R⁸³、R⁸⁴It is identical with the above-mentioned meaning of m ',

The integer that u ' is 1~20, preferably 2~6 integer, more preferably 2~3 integer.].X^cPreferably-O-.

In above-mentioned formula, X^dIt indicates:

- S-,

- C (O) O-,

- CONR⁸⁴,

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

- CONR⁸⁴(CH₂)_u’- N (R⁸⁴)-or

- CONR⁸⁴(adjacent phenylene, metaphenylene or to phenylene)-Si (R⁸³)₂

[in formula, each mark is identical as above-mentioned meaning.].

More preferable above-mentioned X can be

Singly-bound,

C_1-20Alkylidene,

(CH₂)_s’- X^c(CH₂)_t’Or

- X^d(CH₂)_t’

[in formula, each mark is identical as above-mentioned meaning.].

More preferred above-mentioned X is

Singly-bound,

C_1-20Alkylidene, particularly preferred C_1-10Alkylidene,

(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 formula, R⁸³, m ', s ', t ' and u ' it is identical as above-mentioned meaning, v be 1~20 integer, preferably 2~6 it is whole Number, more preferably 2~3 integer.].

In above-mentioned formula ,-(C_vH_2v)-can be straight chain, or branch, such as can be-CH₂,- CH₂CH₂,-CH₂CH₂CH₂,-CH (CH₃)-,-CH (CH₃)CH₂.

In a mode, X can be-(O)_t1(R^f1O)_t2- R^f2(C (=O) N (R^f3))_t3- R^f4Shown in Group.

Above-mentioned t1 is 0 or 1.

Above-mentioned R^f1For the fluorine alkylidene without branched structure comprising 1 or more hydrogen atom.R^f1Preferably C_2-6Fluorine is sub- Alkyl.R^f1The quantity of contained hydrogen atom preferably 1~4 range, more preferably 1 or 2.

In above-mentioned (R^f1O)_t2In, there are R of more than two kinds^f1In the case where O, each (R^f1O presence sequence) in formula is Arbitrarily.

The integer that above-mentioned t2 is 0~4, more preferably 0~2 integer.

Above-mentioned R^f2For singly-bound, the perfluorinated alkylidene without branched structure or not having comprising 1 or more hydrogen atom The fluorine alkylidene of branched structure.Above-mentioned perfluorinated alkylidene or fluorine alkylidene preferably comprise 1~10 carbon atom.

Above-mentioned R^f3For hydrogen atom or alkyl (preferably C_1-4Alkyl).

Above-mentioned t3 is 0 or 1.

In the case where t3 is 0, R^f2Preferably singly-bound.In this case, (i.e. (R^f1O)_t2And R^f4In the case where bonding), (R^f1O)_t2In and R^f4In conjunction with (R^f1It O) is preferably (R^f5CH₂O group shown in).R^f5For than R^f1The base of few 1 carbon atom number Group is perfluorinated alkylidene or the fluorine alkylidene with 1 or more hydrogen atom.R^f5Preferably perfluorinated alkylidene.(R^f5CH₂O) preferably For (CF₂CH₂O)、(CF₂CF₂CH₂O)、(CF₂CF₂CF₂CH₂O)、(CF₂CF₂CF₂CF₂CH₂O) etc..In this case, t2 is preferably 1。

When t3 is 1, t2 is 0~2, and R^f2Preferably perfluorinated alkylidene or the fluorine alkylidene with 1 or more hydrogen atom, more Preferably perfluorinated alkylidene, particularly preferred C_1-6Perfluorinated alkylidene.

Above-mentioned R^f4For singly-bound, carbon atom number 1~10 alkylidene, carbon atom number 1~10 alkylidene end (its In, in formula (1A) or (1B), the end of the side in conjunction with the group bracketed by α 1.) with etheric oxygen atom group, There is the group of etheric oxygen atom between the carbon-to-carbon atom of the alkylidene of carbon atom number 2~10 or in carbon atom number 2~10 Alkylidene end (wherein, in formula (1A) or (1B), for the end of side in conjunction with the group bracketed by α 1.) and With the group of etheric oxygen atom between carbon-to-carbon atom.As the group with etheric oxygen atom, can enumerate for example- CH₂CH₂- O- ,-CH₂CH₂- O-CH₂Etc..

Above-mentioned R^f4Preferably singly-bound or C_1-4Alkylidene, more preferably singly-bound or C_1-2Alkylidene.

Above-mentioned X can be enumerated for example:

(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^f4Or

(O)_t1- R^f6CH₂OCF₂CHFOCF₂CF₂CF₂- C (O) NH-R^f4(such as-(O)_t1 CF₂CH₂OCF₂CHFOCF₂CF₂CF₂- C (O) NH-R^f4) etc..

R^f1、R^f2、R^f4, t1 and t2 it is identical as above-mentioned meaning.T1 is preferably 1.R^f6For the perfluor alkylene without branched structure Base.

Above-mentioned X base can be selected from fluorine atom, C_1-3Alkyl and C_1-3Fluoroalkyl (preferably C_1-3Perfluoroalkyl) in 1 Or 1 or more substituent group replaces.

In other modes, as X base, example group described as follows can be enumerated:

[in formula, R⁴¹It is separately hydrogen atom, the alkyl or C of phenyl, carbon atom number 1~6_1-6Alkoxy, preferably Methyl；

D is selected from following groups:

- 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(in formula, Ph refers to phenyl) and

(in formula, R⁴²Separately indicate hydrogen atom, C_1-6Alkyl or C_1-6Alkoxy, preferred expression methyl or first Oxygroup, more preferably expression methyl.),

E is-(CH₂)_ne(integer that ne is 2~6),

D is in conjunction with the PFPE of molecular backbone, E and in conjunction with the group of the opposite side PFPE.]

As the concrete example of above-mentioned X, can enumerate for example:

Singly-bound,

- 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 formula, Ph refers to phenyl),

- CONH- (CH₂)₆,

- CON (CH₃)-(CH₂)₆,

- CON (Ph)-(CH₂)₆(in formula, Ph refers to phenyl),

- 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,

Deng.

In other preferred modes, X is singly-bound, the alkylidene of carbon atom number 1~6 ,-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- R⁸⁶Or-R⁸⁵- SO₂ C₆H₄- R⁸⁶.R⁸⁵And R⁸⁶Separately indicate the alkylidene of singly-bound or carbon atom number 1~6, preferably singly-bound or carbon atom The alkylidene of number 1~3.R⁸It is identical as above-mentioned meaning.Above-mentioned alkylidene be it is substituted or non-substituted, it is preferably non-substituted.As upper The substituent group of alkylidene is stated, such as halogen atom, preferably fluorine atom can be enumerated.Above-mentioned alkylidene be straight-chain or branched, it is excellent It is selected as straight-chain.

In this mode, X can be more preferred are as follows:

Singly-bound,

Carbon atom number 1~6, preferably carbon atom number 1~3 alkylidene,

- 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,

- SO₂Or

- SO₂- C₆H₄

(in formula, R^85’And R^85’It is separately carbon atom number 1~6, the alkylene of the straight chain of preferably carbon atom number 1~3 Base,

R^8’For hydrogen atom or methyl.).

In this mode, it as the concrete example of X, can enumerate for example:

Singly-bound,

The alkylidene of carbon atom number 1~6,

- 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- C₆H₄Etc..

In a mode, X is singly-bound.

In other mode, as the example of X base, following radicals can be enumerated:

[in formula,

R⁴¹It is separately hydrogen atom, the alkyl or C of phenyl, carbon atom number 1~6_1-6Alkoxy, preferably methyl；

In each X group, any several following groups in conjunction with the PFPE of molecular backbone in T:

- 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(in formula, Ph refers to phenyl) or

[in formula, R⁴²Separately indicate hydrogen atom, C_1-6Alkyl or C_1-6Alkoxy, preferred expression methyl or first Oxygroup, more preferably expression methyl.], other several T be and in conjunction with the group of the opposite side PFPE of molecular backbone- (CH₂)_n”(integer that n " is 2~6), in the presence of, remaining T separately can be methyl, phenyl, C_1-6Alkane Oxygroup or radical-scavenging base or ultraviolet radiation absorption base.

Radical-scavenging base is not particularly limited as long as it can capture the free radical generated by light irradiation, can enumerate Such as benzophenone, benzotriazole, benzoates, phenyl salicylate class, crotons acids, malonic acid esters, You Jibing Olefin(e) acid esters, hindered amines, Hinered phenols or triazines residue.

As long as ultraviolet radiation absorption base can absorb ultraviolet light, there is no particular limitation, can enumerate for example: benzotriazole The esters of class, hydroxy benzophenone ketone, substitution and unsubstituting phenenyl formic acid or salicylic acid compound, acrylate or alkoxy cortex cinnamomi Esters of gallic acid, Oxamides, oxanilide class, benzoxazine ketone, benzoxazoles class residue.

In a preferred manner, it as preferred radical-scavenging base or ultraviolet radiation absorption base, can enumerate:

In this approach, X can be 3~10 valence organic groups.

In a mode, X is by-X¹¹(OH)_j1(X¹²)_3-j1Or-X¹¹(OX¹²)_j1(X¹²)_3-j1It indicates.X¹¹For carbon original Son.X¹²It is separately at each occurrence singly-bound or 2~6 valency alkyls, can have silicon atom and/or siloxanes key. OX¹²Or X¹²By X¹¹With-R^mBetween link.J1 is 1~3 integer at each occurrence independently, preferably 1.

In above-mentioned formula (1A) and (1B), R^mIt is separately at each occurrence group shown in formula below.

In above-mentioned formula, M is separately at each occurrence being capable of complex bound metallic atom.Above-mentioned M is preferably The transition metal atoms such as aluminium atom, zinc atom, titanium atom, zirconium atom, chromium atom, iron atom, cobalt atom, nickle atom, copper atom, More preferably aluminium atom, titanium atom or zirconium atom, more preferably aluminium atom or titanium atom, particularly preferably aluminium atom.

In above-mentioned formula, R¹The monodentate ligand for having with the associative key of X is separately indicated at each occurrence.Change speech It, via R¹, X (X be singly-bound when, in formula (1A) be PFPE, in formula (1B) be Rf²) and M connection.

R¹Preferably-R¹¹- O- or-R¹¹N(R¹²)-.In above-mentioned R¹In, oxygen atom or nitrogen-atoms and M are coordinated.Upper State R¹In, R¹¹(it is PFPE in formula (1A) when X is singly-bound, is Rf in formula (1B) with X²) combine.

In formula, R¹²For hydrogen atom or 1 valence organic group.R¹²Preferably hydrogen atom or the alkyl of carbon atom number 1~3, it is more excellent It is selected as hydrogen atom or methyl.

In formula, R¹¹It is at each occurrence separately singly-bound or divalent organic group.

Above-mentioned R¹¹It can enumerate for example:

Singly-bound,

Carbonyl,

C_1~10Alkylidene, more preferably C_1~6Alkylidene,

(CH₂)_k1- C (=O)-,

- C (=O)-O- (CH₂)_k1’,

(CH₂)_k1C (=O)-O- (CH₂)_k1’Or

(CH₂)_k1- O- (CH₂)_k1’.

K1 is separately 1~10 integer at each occurrence, k1 ' at each occurrence separately for 1~ 10 integer.It is preferred that the integer that k1 is 1~6, the integer that k1 ' is 1~6.

As above-mentioned R¹, it can enumerate for example:

- 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 addition, the oxygen atom existing for end section or nitrogen-atoms are coordination atom among the above.R¹², k1 and k1 ' with it is upper It is identical to state meaning.

Above-mentioned R¹More preferably-R¹¹- O-.

R¹More specifically:

- O-,

- CH₂- O-,

(CH₂)₂- O-,

- C (=O)-O-,

- CH₂- C (=O)-O- or

(CH₂)₂- C (=O)-O-.

In addition, the oxygen atom existing for the end section of above-mentioned formula is coordination atom.

In above-mentioned formula, R²The multidentate ligand for having with the associative key of X is separately indicated at each occurrence.Change speech It, via R², X (X be singly-bound when, in formula (1A) be PFPE, in formula (1B) be Rf²) and M connection.

It is preferred that R²For bidentate ligand.

More preferably R²It is to be coordinated following compounds (1-1)~(1-6) ligand of any one.Under in addition, State the R of formula²¹Group in addition is (such as in formula (1-1), sometimes by C (=O) (CH₂)_l1- C (=O)-R²²) it is known as R²³.I.e. R²It is that be coordinated can be by R²¹- R²³The ligand of compound represented.

In formula, l1 is separately 0~6 integer at each occurrence.L1 at each occurrence independently, preferably For 0~4 integer, more preferably 1~2.

In formula, * indicates coordination atom.For example, above-mentioned formula (1-1)~(1-6) compound represented (1- for example below 1 ')~(1-6 ') is coordinated with M respectively like that.

More specifically, formula (1-1) compound represented is coordinated when l1 is 1 with M as follows.

In formula, R²¹It is at each occurrence separately oxygen atom or divalent organic group.In above-mentioned R²In, R²¹With X (X It is PFPE in formula (1A) when for singly-bound, is Rf in formula (1B)²) combine.

It is preferred that R²¹Are as follows:

- O-,

- C (=O)-O-,

C_1~6Alkylidene or

(CH₂)_l2- O-.

In addition, in the end section of above-mentioned formula there are in the case where oxygen atom, oxygen atom and R²³In conjunction with.L2 be 1~6 it is whole Number.

In formula, R²²It at each occurrence independently, is hydrogen atom or 1 valence organic group.R²²Preferably hydrogen atom, carbon The alkoxy or phenyl of the alkyl of atomicity 1~6, carbon atom number 1~6, the more preferably alkyl of carbon atom number 1~6, it is more excellent It is selected as the alkyl (such as methyl) of carbon atom number 1~3.

In a preferred manner, R²Preferably comprise the structure for capableing of ketonenol interconversion.More preferable R²For shown in formula (1-1) Group, in formula, l1 1, R²¹For oxygen atom, R²²For the alkyl (such as methyl) of carbon atom number 1~3.In formula, * indicates coordination Atom.

In other modes, R²It can be formed together the chelate ring of 4~12 member rings with M, be preferably formed as the chela of 4~6 member rings Cyclization.

In above-mentioned (1A) and (1B), R³At each occurrence independently, monodentate ligand is indicated.R³Indicate only in conjunction with M and The monodentate ligand not bound directly with X.

R³It is preferably selected from least one kind of in halogen atom, hydrogen atom, hydroxyl and 1 valence organic group.It is former as above-mentioned halogen Son can enumerate chlorine atom, fluorine atom.As above-mentioned 1 valence organic group, R can be enumerated³¹- O- or R³¹N(R³²)-.Upper It states in 1 valence organic group, oxygen atom or nitrogen-atoms and M are coordinated.

Above-mentioned R³¹For the alkyl of carbon atom number 1~6, the preferably alkyl of carbon atom number 1~3.Above-mentioned R³²For hydrogen atom or 1 valence organic group, preferably hydrogen atom or the alkyl of carbon atom number 1~3, more preferably hydrogen atom or methyl.

Above-mentioned R³Preferably R³¹- O-.R³¹It is identical as above-mentioned meaning, R³¹- O- is, for example, methoxyl group, ethyoxyl, different Propoxyl group.

In above-mentioned (1A) and (1B), R⁴At each occurrence independently, multidentate ligand is indicated.R⁴Indicate only in conjunction with M and The multidentate ligand not bound directly with X.

It is preferred that R⁴For bidentate ligand.

More preferable R⁴To combine at least one kind of ligand in following compounds (2-1)~(2-6).

In formula, n1 is at each occurrence 0~6 integer independently.N1 at each occurrence independently, preferably For 0~4 integer, more preferably 1.

In formula, * indicates coordination atom.For example, above-mentioned formula (2-1)~(2-6) compound represented (2- for example below 1 ')~(2-6 ') is coordinated with M respectively like that.

More specifically, formula (2-1) compound represented is coordinated when n1 is 1 with M as follows.

In formula, R⁴³It at each occurrence independently, is hydrogen atom or 1 valence organic group.

It is preferred that R⁴³For the alkoxy of hydrogen atom, the alkyl of carbon atom number 1~6 or carbon atom number 1~6.More preferable R⁴³For carbon The alkyl of atomicity 1~3 or the alkoxy of carbon atom number 1~3.

In formula, R⁴⁴It at each occurrence independently, is hydrogen atom or 1 valence organic group.

It is preferred that R⁴⁴For the alkoxy of hydrogen atom, the alkyl of carbon atom number 1~6 or carbon atom number 1~6.More preferable R⁴⁴For carbon The alkyl of atomicity 1~3 or the alkoxy of carbon atom number 1~3.

In a mode, R⁴³For the alkyl (such as methyl) of carbon atom number 1~3, and R⁴⁴For the alkane of carbon atom number 1~3 Base (such as ethyl).

In a mode, R⁴³For the alkyl (such as methyl) of carbon atom number 1~3, and R⁴⁴For the alkane of carbon atom number 1~3 Oxygroup (such as ethyoxyl).

In other modes, R⁴It can be formed together the chelate ring of 4~12 member rings with M, be preferably formed as the chela of 4~6 member rings Cyclization.

In formula (1A) and formula (1B), k be 0~2 integer；The integer that l is 0~2；The integer that m is 0 or more；N is 0 or more Integer.Wherein, k and l's and for 1~4, l multiplied by R²The value obtained with the number of teeth, n is multiplied by R⁴The value obtained with the number of teeth, k with And the sum of m is the ligancy of M.Such as in the case where M is aluminium atom, titanium atom or zirconium atom, the ligancy of M is 4 or 6.

In a mode, k is 0 or 1；L is 0 or 1；The integer that m is 0 or more；The integer that n is 0 or more.Wherein, k and l And for 1, l multiplied by R²The value obtained with the number of teeth, n is multiplied by R⁴Value, k and the m obtained with the number of teeth sum for M ligancy.

In a mode, k 1；L is 0.

In a mode, k 0；L is 1.

In a mode, k 1；L is 0；M is 1；N is 1.In this mode, preferably R²For bidentate ligand, more preferable M For aluminium atom or titanium atom (more preferably aluminium atom).

In a mode, k 0；L is 1；M is 0；N is 2.In this mode, preferably R²For bidentate ligand, more preferable M For aluminium atom or titanium atom (more preferably aluminium atom).

In a preferred manner, R^mAre as follows:

M is aluminium atom or titanium atom (more preferably aluminium atom)；

R¹By-R¹¹- O- expression (in formula, R¹¹For divalent organic group, preferably carbonyl)；

R³For 1 valence organic group, preferably by R³¹- O- expression (in formula, R³¹For the alkyl of carbon atom number 1~6, preferably The alkyl of carbon atom number 1~3, for example, isopropyl)；

R⁴For bidentate ligand, preferably indicate that (in formula, * indicates coordination atom, n1 1, R by formula (2-1)⁴³For carbon atom The alkyl of number 1~3 or the alkoxy of carbon atom number 1~3, R⁴⁴For the alkyl of carbon atom number 1~3 or the alcoxyl of carbon atom number 1~3 Base.)；

K is 1；

L is 0；

M is 1；

N is 1.

In this mode, R^mAn example can be indicated by the following formula.In the following formula, R¹¹It is identical as above-mentioned meaning, Specially C (=O) base；R³¹It is identical as above-mentioned meaning, specially isopropyl；R⁴³It is identical as above-mentioned meaning, specially first Base；R⁴⁴It is identical as above-mentioned meaning, specially ethyl.* indicates the position in conjunction with X.

In other preferred modes, R^mAre as follows:

M is aluminium atom or titanium atom (more preferably aluminium atom)；

R²For bidentate ligand, preferably indicate that (in formula, * indicates coordination atom, l1 1, R by formula (1-1)²¹For oxygen atom, R²²For the alkyl (such as methyl) of carbon atom number 1~3)；

R⁴For bidentate ligand, preferably indicate that (in formula, * indicates coordination atom, n1 1, R by formula (2-1)⁴³Going out every time It now independently, is the alkyl of carbon atom number 1~3 or the alkoxy of carbon atom number 1~3, R⁴⁴It is only respectively at each occurrence It is vertical, it is the alkyl of carbon atom number 1~3 or the alkoxy of carbon atom number 1~3.)

K is 0；

L is 1；

M is 0；

N is 2.

In this mode, R^mAn example can be indicated by the following formula.In following formula, R²²With above-mentioned meaning phase Together, specifically methyl；R⁴³And R⁴⁴It at each occurrence independently, is methyl, ethyl or ethyoxyl.Such as following Formula in, R⁴³For methyl, R⁴⁴Can be with one for ethyl, another is ethyoxyl.* indicates the position in conjunction with X.

Compound containing PFPE shown in formula (1A) and (1B) due to containing metallic atom in end, so have be easy it is tight It is affixed on the effect of metal surface or metal oxidized surface.

Compound containing PFPE shown in formula (1A) and (1B) is as with group shown in Rf-PFPE or Rf-Rf¹ PFPE-Rf²Shown in group, so can aid in be formed water-repellancy and dial the particularly good surface-treated layer of oiliness.This is Because of CF contained by the end section of Rf₃Base shows extremely low surface free energy, the reason which is orientated in outmost surface.

, it is preferable to use formula from the viewpoint of providing the surface treating agent be more good water-repellancy and group oiliness Containing the compound of PFPE shown in (1A).

Compound containing PFPE shown in above-mentioned formula (1A) or (1B) can for example manufacture by the following method, this method packet Include: complex shown in the PFPE compound as shown in following formula (2A) or (2B) and formula (3) makes Y¹And Y²Reaction is formed R¹Process or make Y¹And Y^2’Reaction forms R²Process.

(Rf-PFPE)_α2-X-(Y¹)_α1 (2A)

(Rf-Rf¹-PFPE¹-Rf²)_α2-X-(Y¹)_α1 (2B)

In formula (2A), (2B) and (3), Rf, PFPE, PFPE¹、Rf¹、Rf²、α1、α2、X、M、R³、R⁴With k~n and above-mentioned meaning Justice is identical.

Y1 includes the group that can be reacted.

As the above-mentioned group that can be reacted, such as OR can be enumerated¹⁰Or NR¹⁰R^12’Deng, among these, preferably OR¹⁰。R¹⁰ For hydrogen atom or the alkyl of carbon atom number 1~3, preferably hydrogen atom.R^12’Preferably hydrogen atom or the alkane of carbon atom number 1~3 Base, more preferably hydrogen atom.

Above-mentioned Y¹Such as by

-R¹⁹-OR¹⁰Or

-R¹⁹-NR¹⁰It is shown.

R¹⁰It is identical as above-mentioned meaning.R¹⁹For singly-bound or divalent organic group.

As above-mentioned R¹⁹, it can enumerate for example:

Singly-bound,

Carbonyl,

C_1~10Alkylidene (more preferably C_1~6Alkylidene),

-(CH₂)₁₃- C (=O)-,

- C (=O)-O- (CH₂)_13’-、

-(CH₂)₁₃C (=O)-O- (CH₂)_13’Or

-(CH₂)₁₃-O-(CH₂)_13’-。

13 at each occurrence independently, is 1~12 integer, and it is 1~12 that 13 ' at each occurrence independently Integer.It is preferred that 13 be 1~6 integer, 13 ' be 1~6 integer.

As above-mentioned Y¹, it can enumerate for example:

-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 at each occurrence 1~12 integer independently, and l3 ' is at each occurrence 1~12 independently Integer.It is preferred that the integer that l3 is 1~6, the integer that l3 ' is 1~6.

It is preferred that above-mentioned Y¹For-R¹⁹- OR¹⁰。R¹⁹And R¹⁰It is identical as above-mentioned meaning.Particularly preferred Y¹Are as follows:

- OH,

- C (=O) OH,

(CH₂)_l3”- OH or

(CH₂)_l3”- C (=O)-OH.

The integer that l3 " is 1~3, preferably 1.

Above-mentioned Y²Including the group Y that can be reacted²¹。

As the above-mentioned group Y that can be reacted²¹, such as chlorine atom, bromine atom, iodine atom, C (=O) OR can be enumerated^10’ Or OR^10’Deng, among these, preferably OR^10’。R^10’For hydrogen atom or the alkyl of carbon atom number 1~3, preferably carbon atom number 1~3 Alkyl (i.e. methyl, ethyl, n-propyl or isopropyl).

Above-mentioned Y^2’Include the group Y that can be reacted^21’。Y^21’With Y²¹Meaning it is identical.

It is preferred that the above-mentioned group Y that can be reacted²¹It is to replace R¹And the group with M coordination.It is preferred that the above-mentioned base that can be reacted Group Y^21’It is to replace R²¹And it is imported into R²³Group.

More specifically, above-mentioned Y²For Y²¹Group after coordination.

More specifically, above-mentioned Y^2’For the group after the coordination of following compounds.

In formula, * indicates coordination atom, Y^21’、R²²It is identical as above-mentioned meaning with l1.

In a preferred manner, above-mentioned Y¹And Y²In, Y¹For-C (=O)-OH, Y²For-OR^10’(R^10’For hydrogen atom or The alkyl of carbon atom number 1~3, the preferably alkyl of carbon atom number 1~3).

In other preferred modes, above-mentioned Y¹And Y^2’In, Y¹For-(CH₂)_l3”'- OH (integer that l3 " ' is 1~3, it is excellent It is selected as 1), Y^2’For group shown in following formula.In formula, * indicates coordination atom；Y^21’For OR^10’, l1 1, R²²For carbon atom number 1~3 alkyl (such as methyl).R^10’For hydrogen atom or the alkyl of carbon atom number 1~3, the preferably alkyl of carbon atom number 1~3 (i.e. methyl, ethyl, n-propyl or isopropyl).

In surface treating agent of the invention, relative to 100 mass parts of surface treating agent, 0.01~100 mass is preferably comprised Part, the above-mentioned compounds containing PFPE of more preferable 0.1~30 mass parts.

Surface treating agent of the invention can assign water-repellancy to substrate, dial oiliness, soil resistance, surface slipperiness, friction Durability is not particularly limited, and can be suitable as soil resistance coating agent or waterproofness coating agent uses.

Surface treating agent of the invention can be diluted by solvent.It as such solvent, is not particularly limited, can enumerate Such as: it is selected from perflexane, CF₃CF₂CHCl₂、CF₃CH₂CF₂CH₃、CF₃CHFCHFC₂F₅、1,1,1,2,2,3,3,4,4,5,5, 13 fluoro-octane of 6,6-, seven fluorine pentamethylene of 1,1,2,2,3,3,4- ((ZEORORA H (trade name) etc.), C₄F₉OCH₃、 C₄F₉OC₂H₅、CF₃CH₂OCF₂CHF₂、C₆F₁₃CH=CH₂, lithium dimethylbenzene, perfluor benzene, 15 fluorine heptanone of methyl, trifluoro second Alcohol, five fluorine propyl alcohol, hexafluoroisopropanol, HCF₂CF₂CH₂OH, Methyl triflate, trifluoroacetic acid and CF₃O(CF₂CF₂O)_m1 (CF₂O)_n1CF₂CF₃[in formula, m1 and n1 are 0 or more 1000 integer below independently, mark m1 or n1 and are included by bracket Each repetitive unit presence sequence be arbitrary in formula, but m1 and n1's and be 1 or more.], 1,1- bis- chloro- 2,3,3, 3- tetrafluoro-1-propene, the chloro- 1,3,3,3- tetrafluoro-1-propene of 1,2- bis-, the chloro- 3,3,3- tri- of 1,2- bis- are fluoro- 1- propylene, the bis- fluoro- 1- propylene of chloro- 3,3,3- tri- of 1,1-, the tri- fluoro- 1- propylene of chloro- 3,3,3- tri- of 1,1,2-, 1, The solvent etc. containing fluorine atom in 1,1,4,4,4- hexafluoro -2- butylene.

As above-mentioned solvent, C can be used₆F₁₃OCH₃。

In a mode, moisture content contained in above-mentioned solvent is calculated as 20ppm or less with mass conversion.Above-mentioned moisture Content is able to use karl fischer method to measure.By for such moisture content, the storage stability energy of surface treating agent It is enough to improve.

Surface treating agent of the invention can also include other compositions.As such other compositions, it is not particularly limited, Can enumerate for example: other surfaces processing compound, can be understood as fluorine-containing oil (non-reacted) fluoropolyether compound, It is preferred that perfluor (poly-) ether compound (hereinafter referred to as " fluorine-containing oil "), (non-reacted) that can be understood as silicone oil are siliconated Close object (hereinafter referred to as " silicone oil "), alcohol, catalyst, platinum, ruthenium, the transition metal of rhodium etc., halide ion, in molecular structure Compound etc. comprising the atom with localization of the unshared electron pair.

It as above-mentioned fluorine-containing oil, is not particularly limited, it is (complete that general formula (4) compound represented for example below can be enumerated Fluorine (poly-) ether compound).

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

In formula, Rf⁵Indicating can be by 1~16 alkyl of carbon atom number that 1 or 1 or more fluorine atom replaces (preferably C_1―16Perfluoroalkyl), Rf⁶Indicating can be by 1~16 alkyl of carbon atom number that 1 or 1 or more fluorine atom replaces (preferably For C_1-16Perfluoroalkyl), fluorine atom or hydrogen atom, Rf⁵And Rf⁶It more preferably independently, is C_1-3Perfluoroalkyl.

A ', b ', c ' and d ' respectively indicate 4 kinds of number of repeat unit for constituting perfluor (poly-) ether of main framing of polymer, mutually Mutually it independently is 0 or more 300 integer below, a ', b ', c ' and d's ' and at least 1, preferably 1~300, more preferably 20 ~300.It marks subscript a ', b ', c ' or d ' and is arbitrary in formula by the presence sequence for each repetitive unit that bracket is included.This In a little repetitive units ,-(OC₄F₈)-be-(OCF₂CF₂CF₂CF₂)-,-(OCF (CF₃)CF₂CF₂)-,-(OCF₂CF(CF₃) CF₂)-,-(OCF₂CF₂CF(CF₃))-,-(OC (CF₃)₂CF₂)-,-(OCF₂C(CF₃)₂)-,-(OCF (CF₃)CF (CF₃))-,-(OCF (C₂F₅)CF₂)-and-(OCF₂CF(C₂F₅))-it is any number of, preferably- (OCF₂CF₂CF₂CF₂)-.(OC₃F₆)-can be-(OCF₂CF₂CF₂)-,-(OCF (CF₃)CF₂)-and-(OCF₂CF (CF₃))-any number of, preferably-(OCF₂CF₂CF₂)-.(OC₂F₄)-can be-(OCF₂CF₂)-and-(OCF (CF₃))-any number of, preferably-(OCF₂CF₂)-.

As the example of perfluor (poly-) ether compound shown in above-mentioned general formula (4), can enumerate general formula below (4a) and Any formula compound represented (can be one kind or two or more mixture) of (4b).

Rf⁵(OCF₂CF₂CF₂)_b"-Rf⁶···(4a)

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

In these formulas, Rf⁵And Rf⁶As described above；In formula (4a), b " is 1 or more 100 integer below；At formula (4b) In, a " and b " they are 1 or more 30 integer below independently, and c " and d " they are 1 or more 300 integer below independently.Mark It pours down mark a ", b ", c ", d " and is arbitrary in formula by the presence sequence for each repetitive unit that bracket is included.

Above-mentioned fluorine-containing oil can have 1,000~30,000 average molecular weight.Thereby, it is possible to obtain high surface sliding Property.

In surface treating agent of the invention, contain perfluor (poly-) based compound and above-mentioned carboxylate compound relative to above-mentioned Total 100 mass parts (being the total of these in situation respectively of more than two kinds, below similarly), may include such as 0~ The fluorine-containing oil of 500 mass parts, preferably 0~400 mass parts, more preferable 5~300 mass parts.

General formula (4a) compound represented and general formula (4b) compound represented can use individually, and can also combine It uses.Compared to general formula (4a) compound represented is used, can be obtained when using general formula (4b) compound represented higher Surface slipperiness, thus preferably.When they are applied in combination, change shown in general formula (4a) compound represented and general formula (4b) The mass ratio for closing object is preferably 1 ﹕, 1~1 ﹕ 30,1~1 ﹕ 10 of more preferably 1 ﹕.According to such mass ratio, it is sliding that surface can be obtained The surface-treated layer of the balancing good of dynamic property and the durability that rubs.

In a mode, fluorine-containing oil includes a kind or a kind or more shown in general formula (4b) of compound.In such side In formula, the mass ratio of compound shown in the above-mentioned compound containing PFPE and formula (4b) in surface treating agent is preferably 10 ﹕, 1~1 ﹕ 10, more preferable 4 ﹕, 1~1 ﹕ 4.

In a mode, the average molecular weight of formula (4a) compound represented is preferably 2,000~8,000.

In a mode, the average molecular weight of formula (4b) compound represented is preferably 8,000~30,000.

In other modes, the average molecular weight of formula (4b) compound represented is preferably 3,000~8,000.

In a preferred manner, when forming surface-treated layer using vacuum vapour deposition, the equal molecule of the number of fluorine-containing oil can be made Amount is greater than the number-average molecular weight of the compound containing PFPE.Such as the number-average molecular weight of fluorine-containing oil can be made than the compound containing PFPE Number-average molecular weight it is big 2,000 or more, preferably big 3,000 or more, more preferably big by 5,000 or more.It is equal by being set as such number Molecular weight can obtain more excellent friction durability and surface slipperiness.

In addition, fluorine-containing oil can (in formula, Rf ' be C for general formula R f '-F from other viewpoints_5-16Perfluoroalkyl.) institute The compound shown.Furthermore it is possible to be chlorotrifluoroethylene oligomer.Rf '-F compound represented and chlorotrifluoroethylene oligomer exist Available and Rf is C_1-16The aspect of the high compatibility of the above-mentioned compound containing PFPE of perfluoroalkyl is preferred.

Fluorine-containing oil helps to improve the surface slipperiness of surface-treated layer.

As above-mentioned silicone oil, it is 2,000 straight-chain below or cricoid silicone oil that such as siloxanes key, which can be used,.Straight chain The silicone oil of shape can be so-called common silicone oil and modified silicon oil.As common silicone oil, dimethicone, methylbenzene can be enumerated Base silicone oil, Methyl Hydrogen Polysiloxane Fluid.As modified silicon oil, it can enumerate and common silicone oil is utilized into alkyl, aralkyl, polyethers, advanced The modified obtained modified silicon oil such as aliphatic ester, fluoroalkyl, amino, epoxy group, carboxyl, alcohol.Cricoid silicone oil can enumerate example Such as ring shape dimethylsiloxane oil.

In surface treating agent of the invention, relative to the above-mentioned compound 100 mass parts (situation of more than two kinds containing PFPE It is down the total of them, below similarly), such as can the above-mentioned silicon containing 0~300 mass parts, preferably 0~200 mass parts Oil.

Silicone oil helps to improve the surface slipperiness of surface-treated layer.

As above-mentioned catalyst, sour (such as acetic acid, trifluoroacetic acid etc.), alkali (such as ammonia, triethylamine, diethyl can be enumerated Amine etc.), transition metal (such as Ti, Ni, Sn etc.) etc..

Catalyst promotes hydrolysis and the dehydrating condensation of the above-mentioned compound containing PFPE, promotes the formation of surface-treated layer.

As other compositions, other than above-mentioned, can also enumerate for example: tetraethoxysilane, methyltrimethoxysilane, 3- TSL 8330,3- glycidoxypropyltrime,hoxysilane, methyl triacetoxysilane etc..

As above-mentioned halide ion, chloride ion etc. can be enumerated.

In above-mentioned molecular structure comprising with localization of the unshared electron pair atom compound preferably comprise selected from nitrogen-atoms, At least one kind of atom in oxygen atom, phosphorus atoms and sulphur atom more preferably includes sulphur atom or nitrogen-atoms.

Compound comprising the atom with localization of the unshared electron pair in above-mentioned molecular structure preferably wraps in molecular structure Containing at least one functional group in amino, amide groups, sulfinyl, P=O base, S=O base and sulfonyl, more preferably include At least one functional group in P=O base and S=O base.

Compound comprising the atom with localization of the unshared electron pair in above-mentioned molecular structure is preferably selected from aliphatic amine It is at least one kind of in compound, aromatic amines compound, phosphamide compound, amide compound, carbamide compound and sulfoxide compound Compound, more preferably in aliphatic amine compound, aromatic amine, phosphamide, carbamide compound and sulfoxide compound At least one kind of compound, particularly preferably in sulfoxide compound, aliphatic amine compound and aromatic amines compound at least 1 kind of compound, more preferably sulfoxide compound.

As above-mentioned aliphatic amine compound, can enumerate such as diethylamine, triethylamine.As above-mentioned aromatic series amination Object is closed, can be enumerated such as aniline, pyridine.As above-mentioned phosphamide compound, can enumerate such as hexamethyl phosphoramide. As above-mentioned amide compound, such as N, N- diethyl acetamide, N, N- diethylformamide, N, N- diformazan can be enumerated Yl acetamide, N-METHYLFORMAMIDE, N,N-dimethylformamide, N-Methyl pyrrolidone etc..As above-mentioned carbamide compound, Tetramethylurea etc. can be enumerated.As above-mentioned sulfoxide compound, can enumerate dimethyl sulfoxide (DMSO), tetramethylene sulfoxide, Methyl phenyl sulfoxide, diphenyl sulfoxide etc.., it is preferable to use dimethyl sulfoxide or tetramethylene sulfoxide in these compounds.

As other compositions, other than above-mentioned, the alcoholic compound of such as carbon atom number 1~6 can also be enumerated.

[pellet]

Surface treating agent of the invention, which can contain, is dipped into porous mass, such as porous ceramic material, metallic fiber, such as Steel wool is compacted into the substance of cotton like, and pellet is made.The pellet for example can be used in vacuum evaporation.

Surface treating agent of the invention can assign water-repellancy to substrate, dial oiliness, soil resistance, waterproofness, high friction Durability and uv-resistance, therefore it is suitable as surface treating agent use.Specifically, surface treating agent of the invention can be suitble to It uses, but is not particularly limited as soil resistance coating agent or waterproofness coating agent.

[article]

Next, being illustrated to article of the invention.

Article of the invention includes substrate and the layer (table that is formed on the surface of the substrate by surface treating agent of the invention Surface treatment layer).The article for example can be such as manufacture of getting off.

Firstly, preparing substrate.The substrate being able to use in the present invention for example can be by glass, resin (natural or synthetic tree Rouge, for example can be common plastic material, can be plate, film, other forms), metal (can be the gold of aluminium, copper, iron etc. Belong to the complex of simple substance or alloy etc.), ceramics, semiconductor (silicon, germanium etc.), fiber (fabric, non-woven fabrics etc.), fur, leather, wood Any suitable material such as material, pottery chinaware, stone material etc., building component is constituted.

As above-mentioned glass, preferably sapphire glass, soda-lime glass, alkali alumino-silicates glass, pyrex, alkali-free Glass, crystal glass, quartz glass, the alkali alumino-silicates after soda-lime glass, chemical strengthening after particularly preferred chemical strengthening Pyrex after glass and chemical bonding.

As resin, preferred acrylic resins, polycarbonate.

For example, the material for constituting the surface of substrate can be optics in the case where the article to be manufactured is optical component Component material, such as glass or transparent plastic.In addition, in the case where the article to be manufactured is optical component, Ke Yi The surface (outermost layer) of substrate forms certain layer (or film), such as hard conating or anti-reflection layer.List can be used in anti-reflection layer Any one of layer anti-reflection layer and multilayer anti-reflection layer.It, can be with as the example for the inorganic matter being able to use in anti-reflection layer Enumerate SiO₂、SiO、ZrO₂、TiO₂、TiO、Ti₂O₃、Ti₂O₅、Al₂O₃、Ta₂O₅、CeO₂、MgO、Y₂O₃、SnO₂、MgF₂、WO₃Deng.This A little inorganic matters can use individually or by these two or more combination (such as mixture).It is being set as multilayer anti-reflection layer In the case where, preferably SiO is used in its outermost layer₂And/or SiO.The article to be manufactured is the optical glass portion of touch panel In the case where part, can have transparent electrode in a part on the surface of substrate (glass), for example using tin indium oxide (ITO) or The film of indium zinc oxide etc..In addition, substrate can have insulating layer, adhesive layer, protective layer, dress according to its specific specification etc. Escutcheon layer (I-CON), atomization film layer, hard coat film, light polarizing film, phase difference film and LCD assembly etc..

The shape of substrate is not particularly limited.In addition, as long as the surface region that form the substrate of surface-treated layer is base At least part on material surface can be suitably determined according to the purposes for the article to be manufactured and specific specification etc..

As such substrate, at least its surface portion can have the material of hydroxyl to constitute by script.As such Material can enumerate glass, furthermore it is possible to enumerate, surface is formed with natural oxide film or the metal of heat oxide film is (especially low-priced Metal), ceramics, semiconductor etc..Alternatively, as resin etc., although having a case that hydroxyl is insufficient and does not have originally In the case where having hydroxyl, hydroxyl can be imported on the surface of substrate, or increase hydroxyl by implementing certain pre-treatment to substrate. As the example of such pre-treatment, corona treatment (such as corona discharge), ion beam irradiation can be enumerated.Plasma Processing can import hydroxyl in substrate surface or increase hydroxyl, and also fit for cleaning to substrate surface and (removing foreign matter etc.) It closes and utilizes.In addition, the other examples as such pre-treatment, can enumerate will inhale with the interface of carbon-to-carbon unsaturated bond base Attached dose, using LB method (Langmuir-Blodgett method) or chemiadsorption etc., is pre-formed into monomolecular film in substrate surface Form, then, the method for making unsaturated bond crack under the atmosphere comprising oxygen and/or nitrogen etc..

In addition alternatively, as such substrate, there can be 1 or more other reactive bases by least its surface portion Group, the organo-silicon compound of such as Si-H base, and/or the material comprising alkoxy silane are constituted.

Especially as substrate, it is preferable to use alumite, sapphire glass or zirconium oxide etc. are in substrate surface, there are metals The substrate of atom.The parent of metal contained by substrate and metallic atom contained by the compound containing PFPE shown in formula (1A) or (1B) It is especially high with property, therefore the combination for being formed by surface-treated layer and substrate can become stronger.Therefore, it is formed by surface The water-repellancy of process layer becomes especially good, and rub resistance also further increases.

Then, the film that above-mentioned surface treating agent of the invention is formed on the surface of such substrate, to the film according to need It is post-processed, surface-treated layer is formed by surface treating agent of the invention as a result,.

The film formation of surface treating agent of the invention can be answered in a manner of coating the surface by the surface for substrate Implemented with surface treating agent of the invention.Method for coating is not particularly limited.Such as it is able to use wet cladding process and drying Cladding process.

As the example of wet cladding process, dip-coating, spin coating, flow coat, spraying, roller coating, gravure coating and similar can be enumerated Method.

As the example of dry cladding process, vapor deposition (usually vacuum evaporation), sputtering, CVD and similar side can be enumerated Method.As the concrete example of vapour deposition method (usually vacuum vapour deposition), resistance heating, electron beam can be enumerated, using microwave etc. High-frequency heating, ion beam and similar method.As the concrete example of CVD method, plasma-CVD, optics can be enumerated CVD, hot CVD and similar method.

In addition it is also possible to be coated using ordinary pressure atmospheric plasma method.

Using wet cladding process, surface treating agent of the invention is applied to substrate after being diluted with solvent Surface., it is preferable to use following solvent from the viewpoint of the stability of surface treating agent of the invention and the volatility of solvent: C_5-12Perfluorinated polyether hydrocarbon (for example, perflexane, perfluoromethylcyclohexane (PFMCH) and perfluor -1,3- dimethyl cyclohexane)；It is more Fluorine aromatic hydrocarbon (for example, bis- (trifluoromethyl) benzene)；Polyfluoro aliphatic hydrocarbon is (for example, C₆F₁₃CH₂CH₃(such as Asahi Glass strain formula meeting ASAHIKLIN (registered trademark) AC-6000 of society's manufacture), (such as the Japanese auspicious father-in-law strain of seven fluorine pentamethylene of 1,1,2,2,3,3,4- ZEORORA (registered trademark) H of formula commercial firm manufacture)；Hydrofluorocarbon (HFC) (such as 1,1,1,3,3-pentafluorobutane (HFC- 365mfc))；Hydrochlorofluorocarazeotropic (such as HCFC-225 (ASAHIKLIN (registered trademark) AK225))；Hydrofluoroether (HFE) (for example, Perfluoro propyl methyl ether (C₃F₇OCH₃) (for example, Novec (trade (brand) name) 7000 of Sumitomo 3M Co., Ltd. manufacture), perfluoro butyl Methyl ether (C₄F₉OCH₃) (for example, Novec (trade (brand) name) 7100 of Sumitomo 3M Co., Ltd. manufacture), perfluorobutyl ethyl ether (C₄F₉OC₂H₅) (for example, Novec (trade (brand) name) 7200 of Sumitomo 3M Co., Ltd. manufacture), perfluoro hexyl methyl ether (C₂F₅CF (OCH₃)C₃F₇) alkyl perfluoroalkyl ethers (the perfluor alkane such as the Novec (trade (brand) name) 7300 of manufacture (for example, Sumitomo 3M Co., Ltd.) Base and alkyl can be straight or branched) or CF₃CH₂OCF₂CHF₂(for example, manufactured by Asahi Glass Co., Ltd ASAHIKLIN (registered trademark) AE-3000)), 1,2- bis- chloro- 1,3,3,3- tetrafluoro-1-propenes are (for example, three wells-Du Vertrel (registered trademark) SION of fluorine chemistry Co., Ltd, nation manufacture) etc..These solvents can be used alone or combine 2 kinds It is used above as mixture.In addition, such as the dissolubility in order to adjust the compound containing PFPE, it can also be with other solvents Mixing.

Using dry cladding process, surface treating agent of the invention is used directly for dry cladding process, or Person is used to dry cladding process after being diluted with above-mentioned solvent.

Film is formed preferably so as to surface treating agent of the invention and exist together for hydrolyze with the catalyst of dehydrating condensation Mode in film is implemented.For simplicity, using wet cladding process, by surface treating agent solvent of the invention After dilution, before it will be applied to substrate surface, catalyst can be added in the dilution of surface treating agent of the invention. Using dry cladding process, the surface treating agent of the invention for being added to catalyst can be directly deposited (usually vacuum evaporation) processing, or this hair added with catalyst has been impregnated with using in the metal porous body of iron or copper etc. (usually vacuum evaporation) processing is deposited in the partical substance of bright surface treating agent.

Catalyst is able to use any suitable acid or alkali.As acid catalyst, such as it is able to use acetic acid, formic acid, three Fluoroacetic acid etc..In addition, as base catalyst, such as be able to use ammonia, organic amine etc..

Then, as needed, film is post-processed.The post-processing is not particularly limited, such as can gradually implement water Divide supply and dry heat, can more specifically be implemented as follows.

Formed as described above in substrate surface after the film of surface treating agent of the invention, to the film (hereinafter also referred to as " precursor film ") supply moisture.The supply method of moisture is not particularly limited, can be used for example using precursor film (and substrate) with The moisture condensation or vapor (steam) of the temperature difference of surrounding atmosphere it is the methods of spraying.

The supply of moisture for example can be set as 0~250 DEG C, preferably 60 DEG C or more, more preferably 100 DEG C or more and It is preferred that 180 DEG C or less, implement under more preferred 150 DEG C of atmosphere below.Moisture is supplied in such temperature range, thus, it is possible to Enough carry out hydrolysis.Pressure at this time is not particularly limited, and can be set to normal pressure for easy.

Then, which is heated under the surface of the substrate and drying atmosphere more than 60 DEG C.Dry heat method It is not particularly limited, can configure by precursor film together with substrate and be more than 60 DEG C, be preferably greater than 100 DEG C of temperature and such as For at 250 DEG C or less, preferably 180 DEG C temperature below and the atmosphere of unsaturated water vapor pressure.Pressure at this time does not limit especially It is fixed, it can be set to normal pressure for easy.

Above-mentioned moisture supply and dry heat can continuously be implemented by using overheated steam.

By operating as described above, can implement to post-process.The post-processing can be in order to further increase friction durability And implement, but needing to pay attention to not is necessary to manufacture article of the invention.Such as it is answered by surface treating agent of the invention After substrate surface, only directly standing can also be with.

As described above, forming the surface-treated layer of the film from surface treating agent of the invention, manufacture on the surface of substrate Article of the invention.Thus obtained surface-treated layer has good uv-resistance.In addition, the surface-treated layer is in addition to good Good uv-resistance, although also depending on the composition of the composition used, can also have water-repellancy, dial oiliness, soil resistance (such as Prevent the attachment of the spots such as fingerprint), surface slipperiness (or lubricity, the erasing of the spot such as fingerprint, to the excellent of finger Sense of touch), high friction durability etc., functional film utilization can be suitable as.

I.e. the invention further relates to the optical materials in outermost layer with above-mentioned solidfied material.

As optical material, in addition to the relevant optical material such as the display that illustrates as be described hereinafter, further preferably enumerate a variety of The optical material of multiplicity: for example, cathode-ray tube (CRT；Such as TV, computer monitor), liquid crystal display, plasma show Device, organic el display, inorganic thin film EL matrix display, rear projection type display, fluorescent display tube (VFD), field emission display Device (FED；Field Emission Display) etc. displays or these displays protection board or these surface implement The optical material of antireflection film processing.

It is not particularly limited using the article with surface-treated layer that the present invention obtains, can be optical component.Optics The example of component can be listed below example: the eyeglass of glasses etc.；The front surface protection plate of the display of PDP, LCD etc., antireflection Plate, polarizer, anti-dazzle tabula rasa；The touch panel sheet material of the equipment such as portable phone, portable information terminal；Blue light (Blu-ray (note Volume trade mark)) CD, DVD disc, CD-R, MO etc. CD disk；Optical fiber etc..

In addition, can be Medical Devices or medical material using the article with surface-treated layer that the present invention obtains.

The thickness of surface-treated layer is not particularly limited.In the case where optical component, surface-treated layer with a thickness of 1~ 50nm, more preferably 1~30nm, the particularly preferably range of 1~15nm, from optical property, surface slipperiness, friction durability With from the viewpoint of soil resistance preferably.

Alternatively, it can be formed on the surface of this layer after the surface of substrate is additionally formed layer and utilize the present invention The film of obtained surface-treated layer.

More than, the article for using surface treating agent of the invention to obtain is described in detail.In addition, surface of the invention Purposes, application method or manufacturing method of article of inorganic agent etc. are not limited to foregoing illustrative situation.

Embodiment

It about surface treating agent of the invention, is more specifically illustrated by embodiment below, but the present invention is unlimited In these embodiments.In addition, in the present embodiment, constituting the repetitive unit (OCF of perfluoropolyether₂CF₂) and (OCF₂CF₂CF₂) In the presence of being sequentially arbitrary.

Synthesis example 1

Average composition CF is added in 3 mouthfuls of flasks for being equipped with the 30mL of thermometer and blender₃CF₂CF₂ (OCF₂CF₂CF₂)₂₀OCF₂CF₂CO₂It is bis- (trifluoromethyl) the benzene 3g of perfluoropolyether-modified carboxylic acid body 2.4g, 1,3- shown in H, following Aluminium complex 0.4g shown in compound (A), is stirred at room temperature 16 hours under nitrogen flowing.Then, it will wave under reduced pressure Hair ingredient is distilled off, and thus obtains the aluminium compound of the perfluoro-polyether base for the following formula for having aluminium complex in end (B)2.7g。

Aluminium complex (A):

The aluminium compound (B) of perfluoro-polyether base:

Synthesis example 2

Average composition CF is added in 3 mouthfuls of flasks for being equipped with the 30mL of thermometer and blender₃CF₂CF₂ (OCF₂CF₂CF₂)₂₀OCF₂CF₂CH₂It is bis- (trifluoromethyl) the benzene 2g of perfluoropolyether-modified alcohol 2.8g, 1,3- shown in OH, following Aluminium complex 0.3g shown in compound (C) under nitrogen flowing, is stirred at room temperature 16 hours.Then, it will wave under reduced pressure Hair ingredient is distilled off, and thus obtains the aluminium compound of the perfluoro-polyether base for the following formula for having aluminium complex in end (D)3.0g。

Aluminium complex (C):

The aluminium compound (D) of perfluoro-polyether base:

Embodiment 1

By compound (B) obtained in above-mentioned synthesis example 1 in such a way that concentration becomes 0.2wt%, it is dissolved in hydrofluoroether (3M Corporation, Novec HFE7200) in, prepare surface treating agent 1.

Using the surface treating agent 1 of above-mentioned preparation, in alumite (manufacture of Co., Ltd.'s Dongyang Chemical and Chemical Research Institute, 100mm × 100mm × 0.8mm) surface on, with 30mm/ seconds pull rate, carry out impregnation.It then, will be after impregnation Alumite stands 1 hour at 150 DEG C of temperature.It is then cooled to room temperature, surface-treated layer is consequently formed.

Embodiment 2

Using the surface treating agent 1 prepared in embodiment 1, in SUS304 (Japanese testpanel manufacture, BA processing, 90mm × 60mm × 1mm) surface on, impregnation was carried out with 30mm/ seconds pull rate.It then, will be after impregnation SUS304 stands 1 hour at 150 DEG C of temperature.It is then cooled to room temperature, surface-treated layer is consequently formed.

Embodiment 3 and 4

It is same with embodiment 1 or 2 other than replacing compound (B) to use compound (D) obtained in above-mentioned synthesis example 2 Sample operation, forms surface-treated layer.

Comparative example 1 and 2

Other than replacing compound (B) to use following control compounds 1, with embodiment 1 or 2 same operations, table is formed Surface treatment layer.

Control compound 1

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

(evaluation)

The measurement of static contact angle

Measure the static contact angle of the water of surface-treated layer obtained in the above embodiments 1~4 and comparative example 1~2.Water Static contact angle measurement using contact angle determination device (consonance interface science Co., Ltd. manufacture), with 1 μ L of water 21 DEG C, Implement in the environment of 65% humidity.Rub durability evaluation

About the surface-treated layer formed in the above embodiments 1~4 and comparative example 1~2 in substrate surface, firstly, making The static contact angle of the water of surface-treated layer is measured after cotton wiping of its surface comprising ethyl alcohol for preliminary evaluation.

About the surface-treated layer formed in the above embodiments 1~4 and comparative example 1~2 in substrate surface, rubber is utilized Rub endurance test, evaluation friction durability.Specifically, the sample article horizontal arrangement that will be formed with surface-treated layer, is used The surface of rubber (manufacture of KOKUYO Co., Ltd., KESHI-70, planar dimension 1cm × 1.6cm) contact surface process layer, In The load of 500gf is assigned thereon, it is then, in the state of being applied with load that rubber is round-trip with 20mm/ seconds speed.Round-trip After number 100 times, the static contact angle (degree) of water is measured.It the results are shown in table 1.

[table 1]

It is appreciated that the surface-treated layer for confirming Examples 1 to 4 shows excellent water-repellancy and excellent from the result of table 1 Different rub resistance.It is believed that the aluminium coordination of the compound containing PFPE contained by the surface-treated layer from Examples 1 to 4 Group and substrate surface contain metal, therefore compatibility is especially good.As a result, the combination of surface-treated layer and substrate becomes Stronger, so that not only initial stage water-repellancy improves, rub resistance is also improved.

Industrial availability

The present invention can be suitable for the surface shape in various substrates, particularly the optical component for requiring permeability At surface-treated layer.

Claims (22)

1. a kind of surface treating agent, it is characterised in that:

Containing perfluoro-polyether based compound shown in formula (1A) or formula (1B),

(Rf-PFPE)_α2-X-R^m _α1 (1A)

(Rf-Rf¹-PFPE¹-Rf²)_α2-X-R^m _α1 (1B)

In formula,

Rf separately indicates the carbon atom number 1~16 that can be replaced by 1 or 1 or more fluorine atom at each occurrence Alkyl；

PFPE is separately group shown in following formula at each occurrence:

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

Wherein, a, b, c, d, e and f are separately 0 or more 200 integer below, and the sum of a, b, c, d, e and f are at least 1, It marks a, b, c, d, e or f and is arbitrary in formula by the presence sequence for each repetitive unit that bracket is included；

PFPE¹It is identical as the meaning of PFPE；

Rf¹(O-Rf is separately indicated at each occurrence¹¹)_m2；

Rf¹¹For the fluorine alkylidene without branched structure comprising 1 or more hydrogen atom；

M2 be 0~4 integer, m2 be 2~4 integer when, (O-Rf¹¹)_m2It may include O-Rf of more than two kinds¹¹；

Rf²(O-Rf is separately indicated at each occurrence²¹)_m3；

Rf²¹For the fluorine alkylidene without branched structure comprising 1 or more hydrogen atom；

M3 be 0~4 integer, m3 be 2~4 integer when, (O-Rf²¹)_m3It may include O-Rf of more than two kinds²¹；

X separately indicates singly-bound, oxygen atom or 2~10 valence organic groups at each occurrence；

α 1 is separately 1~9 integer at each occurrence；

α 2 is separately 1~9 integer at each occurrence；

R^mIt is separately at each occurrence group shown in formula below:

M is separately at each occurrence being capable of complex bound metallic atom；

R¹The monodentate ligand for having with the associative key of X is separately indicated at each occurrence；

R²The multidentate ligand for having with the associative key of X is separately indicated at each occurrence；

R³Monodentate ligand is separately indicated at each occurrence；

R⁴Multidentate ligand is separately indicated at each occurrence；

The integer that k is 0~2；

The integer that l is 0~2；

The integer that m is 0 or more；

The integer that n is 0 or more；

Wherein, the sum of k and l are 1~4, l multiplied by R²The value obtained with the number of teeth, n is multiplied by R⁴Value, k and the m obtained with the number of teeth it With the ligancy for M.

2. surface treating agent as described in claim 1, it is characterised in that:

R¹~R⁴Contained coordination atom is at least one kind of in oxygen and nitrogen.

3. surface treating agent as claimed in claim 1 or 2, it is characterised in that:

R¹For-R¹¹- O- or-R¹¹N(R¹²)-,

In formula, R¹¹It is at each occurrence separately singly-bound or divalent organic group, R¹²For hydrogen atom or 1 valence organic group.

4. surface treating agent according to any one of claims 1 to 3, it is characterised in that:

R²For bidentate ligand.

5. surface treating agent as described in any one of claims 1 to 4, it is characterised in that:

R²Ligand made of being coordinated for any a kind in following compounds (1-1)~(1-6):

In formula,

* coordination atom is indicated；

R²¹It is at each occurrence separately oxygen atom or divalent organic group；

R²²It is at each occurrence separately hydrogen atom or 1 valence organic group；

L1 is separately 0~6 integer at each occurrence.

6. such as surface treating agent according to any one of claims 1 to 5, it is characterised in that:

R³It is at least one kind of in halogen atom, hydrogen atom, hydroxyl and 1 valence organic group.

7. such as surface treating agent according to any one of claims 1 to 6, it is characterised in that:

R⁴For bidentate ligand.

8. such as surface treating agent according to any one of claims 1 to 7, it is characterised in that:

R⁴For at least one kind of ligand being combined into following compounds (2-1)~(2-6):

In formula,

* coordination atom is indicated；

R⁴³It is at each occurrence separately hydrogen atom or 1 valence organic group；

R⁴⁴It is at each occurrence separately hydrogen atom or 1 valence organic group；

N1 is separately 0~6 integer at each occurrence.

9. such as surface treating agent according to any one of claims 1 to 8, it is characterised in that: k 1, l 0.

10. such as surface treating agent according to any one of claims 1 to 8, it is characterised in that: k 0, l 1.

11. such as surface treating agent according to any one of claims 1 to 10, it is characterised in that: n is 1 or 2.

12. the surface treating agent as described in any one of claim 1~11, it is characterised in that: M be aluminium atom, zinc atom or Transition metal atoms.

13. the surface treating agent as described in any one of claim 1~12, it is characterised in that: M be aluminium atom, titanium atom or Zirconium atom.

14. the surface treating agent as described in any one of claim 1~13, it is characterised in that: M is aluminium atom.

15. the surface treating agent as described in any one of claim 1~14, it is characterised in that: X is divalent organic group, and α 1 is 1 and α 2 is 1.

16. the surface treating agent as described in any one of claim 1~15, it is characterised in that: perfluoro-polyether based compound By shown in formula (1A).

17. the surface treating agent as described in any one of claim 1~16, it is characterised in that: PFPE is only at each occurrence It is vertical, be following formula (a), (b) or (c):

(OC₃F₆)_d(a)

In formula (a), d be 1~200 integer；

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

In formula (b), c and d are separately 0 or more 30 integer below；

E and f is separately 1 or more 200 integer below；

C, the sum of d, e and f are 10 or more 200 integers below；

It marks subscript c, d, e or f and is arbitrary in formula by the presence sequence for each repetitive unit that bracket is included；

(R⁶- R⁷)_j(c)

In formula (c), R⁶For OCF₂Or OC₂F₄；

R⁷For selected from OC₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀And OC₆F₁₂In group, or be 2 or 3 in these groups The combination of group；

The integer that j is 2~100.

18. the surface treating agent as described in any one of claim 1~17, it is characterised in that:

Also contain selected from fluorine-containing oil, silicone oil, alcohol, catalyst, transition metal, halide ion, include to have in molecular structure 1 kind or a kind or more of other compositions in the compound of the atom of localization of the unshared electron pair.

19. a kind of pellet containing surface treating agent described in any one of claim 1~18.

20. a kind of including substrate and in the surface of the substrate institute of the surface treating agent as described in any one of claim 1~18 The article of the layer of formation.

21. article as claimed in claim 20, it is characterised in that:

Article is optical component.

22. the article as described in claim 20 or 21, it is characterised in that:

Article is display.