CN109689786A - Composition containing the silane compound containing perfluor (poly-) ether - Google Patents

Composition containing the silane compound containing perfluor (poly-) ether Download PDF

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Publication number
CN109689786A
CN109689786A CN201780054313.7A CN201780054313A CN109689786A CN 109689786 A CN109689786 A CN 109689786A CN 201780054313 A CN201780054313 A CN 201780054313A CN 109689786 A CN109689786 A CN 109689786A
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formula
independently
integer
ocf
och
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三桥尚志
野村孝史
能势雅聪
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Daikin Industries Ltd
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Daikin Industries Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
    • C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films

Abstract

The present invention provides one kind and contains the following general formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2): [in formula, each symbol is identical as the record meaning of specification] at least one kind of silane compound and following formula (E1) containing perfluor (poly-) ether shown in any general formula: the composition of at least one kind of compound shown in [in formula, each symbol is identical as the record meaning of specification]. (Rf1‑PFPE1)β’‑X5‑(SiR1 n1R2 3‑n1)β…(B1)(R2 3‑n1R1 n1Si)β‑X5‑PFPE1‑X5‑(SiR1 n1R2 3‑n1)β…(B2)(Rf1‑PFPE1)γ’‑X7(SiRa k1Rb l1Rc m1)γ…(C1)(Rc m1Rb l1Ra k1Si)γ‑X7‑PFPE1‑X7‑(SiRa k1Rb l1Rc m1)γ…(C2)(Rf1‑PFPE1)δ’‑X9‑(CRd k2Re l2Rf m2)δ…(D1)(Rf m2Re l2Rd k2C)δ‑X9‑PFPE1‑X‑(CRd k2Re l2Rf m2)δ…(D2)(Rf2‑PFPE2‑Z2)x‑A…(E1)。

Description

Composition containing the silane compound containing perfluor (poly-) ether
Technical field
The present invention relates to the compositions containing the silane compound containing perfluor (poly-) ether, in particular to containing The composition of the silane compound of perfluor (poly-) ether and acid or acid derivative containing perfluor (poly-) ether.
Background technique
If known certain fluorine containing silane compounds are used for the surface treatment of substrate, excellent water-repellancy can be provided, dialled Oiliness, soil resistance etc..The layer obtained by the surface treating agent containing fluorine containing silane compound is (hereinafter also referred to as " surface treatment Layer ") it is used as called function film to be for example applied to the diversified substrate such as glass, plastics, fiber, construction material.
As such fluorine containing silane compound, it is known to there is holo-fluorine polyester in molecular backbone, in molecular end or Terminal part has the silane compound with the perfluoro-polyether base of the group that can be hydrolyzed of Si atomistic binding.For example, in patent In document 1 and 2, describe in molecular end or terminal part with poly- containing perfluor with the group that can be hydrolyzed of Si atomistic binding The silane compound of ether.
Existing technical literature
Patent document
Patent document 1: International Publication No. 97/07155
Patent document 2: Japanese Unexamined Patent Application Publication 2008-534696 bulletin
Summary of the invention
Technical problems to be solved by the inivention
The layer obtained by the surface treating agent of the silane compound containing perfluoro-polyether base can as film The function of water-repellancy, group oiliness, soil resistance etc. is played, therefore is suitably used in the glasses for requiring translucency and the transparency, touching Touch the optical component of panel etc..Especially at these with friction durability is required on the way, so that even if being subjected to friction repeatedly It is able to maintain that above-mentioned function.
The purpose of the present invention is to provide a kind of compositions containing the silane compound containing perfluor (poly-) ether, can It formed with water-repellancy, dial oiliness, soil resistance, waterproofness and the layer with high friction durability.
For solving the technological means of technical problem
It is that the present inventor is furtherd investigate as a result, it has been found that, by using containing containing perfluor (poly-) ether silane The composition of compound and acid or acid derivative containing perfluor (poly-) ether is capable of forming the surface with high friction durability Process layer, so that complete the present invention.
That is, the first main idea according to the present invention provides a kind of composition, which is characterized in that contain:
In the following general formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) at least 1 shown in any general formula Kind contains the silane compound of perfluor (poly-) ether；With at least one kind of compound shown in following formula (E1),
(Rf1-PFPE1)β,-X5-(SiR1 n1R2 3-n1)β…(B1)
(R2 3-n1R1 n1Si)β-X5-PFPE1-X5-(SiR1 n1R2 3-n1)β…(B2)
(Rf1-PFPE1)γ’-X7(SiRa k1Rb 11Rc m1)γ…(C1)
(Rc m1Rb 11Ra k1Si)γ-X7-PFPE1-X7-(SiRa k1Rb 11Rc m1)γ…(C2)
(Rf1-PFPE1)δ’-X9-(CRd k2Re 12Rf m2)δ…(D1)
(Rf m2Re 12Rd k2C)δ-X9-PFPE1-X-(CRd k2Re 12Rf m2)δ…(D2)
[in formula:
PFPE1At each occurrence independently, it is group shown in following formula:
(OC6F12)a(OC5F10)b(OC4F8)c(OC3F6)d(OC2F4)e(OCF2)f?
(in formula, a, b, c, d, e and f are 0 or more 200 integer below, the sum of a, b, c, d, e and f are at least independently It is 1, is arbitrary in formula with a, b, c, d, e or f and by the presence sequence for each repetitive unit that bracket brackets.)
Rf1At each occurrence independently, the carbon atom number 1 that can be replaced by 1 or 1 or more fluorine atom is indicated ~16 alkyl；
R1At each occurrence independently, the group that indicates hydroxyl or can hydrolyze；
R2At each occurrence independently, the alkyl of hydrogen atom or carbon atom number 1~22 is indicated；
R11At each occurrence independently, hydrogen atom or halogen atom are indicated；
R12At each occurrence independently, hydrogen atom or low alkyl group are indicated；
N1 is in each (- SiR1 n1R2 3-n1) independent in unit, it is 0~3 integer；
Wherein, in formula (A1), (A2), (B1) and (B2), at least one n1 be 1~3 integer；
X1Independently, the organic group of singly-bound or 2~10 valences is indicated；
X2At each occurrence independently, the organic group of singly-bound or divalent is indicated；
T is at each occurrence 1~10 integer independently；
α is 1~9 integer independently；
α ' is 1~9 integer independently；
X5Independently, the organic group of singly-bound or 2~10 valences is indicated；
β is 1~9 integer independently；
β ' is 1~9 integer independently；
X7Independently, the organic group of singly-bound or 2~10 valences is indicated；
γ is 1~9 integer independently；
γ ' is 1~9 integer independently；
RaAt each occurrence independently, expression-Z1- SiR71 p1R72 q1R73 r1；
Z1At each occurrence independently, the organic group of oxygen atom or divalent is indicated；
R71At each occurrence independently, R is indicateda’；
Ra’With RaMeaning is identical；
RaIn, via Z1Base connection is that the Si of straight-chain is up to 5；
R72At each occurrence independently, the group that indicates hydroxyl or can hydrolyze；
R73At each occurrence independently, hydrogen atom or low alkyl group are indicated；
P1 is at each occurrence 0~3 integer independently；
Q1 is at each occurrence 0~3 integer independently；
R1 is at each occurrence 0~3 integer independently；
Wherein, in formula (C1) and (C2), at least one q1 be 1~3 integer；
RbAt each occurrence independently, the group that indicates hydroxyl or can hydrolyze；
RcAt each occurrence independently, hydrogen atom or low alkyl group are indicated；
K1 is at each occurrence 1~3 integer independently；
L1 is at each occurrence 0~2 integer independently；
M1 is at each occurrence 0~2 integer independently；
X9Independently, the organic group of singly-bound or 2~10 valences is indicated；
δ is 1~9 integer independently；
δ ' is 1~9 integer independently；
RdAt each occurrence independently, expression-Z2- CR81 p2R82 q2R83 r2；
Z2At each occurrence independently, the organic group of oxygen atom or divalent is indicated；
R81At each occurrence independently, R is indicatedd’；
Rd’With RdMeaning is identical；
RdIn, via Z2Base connection is that the C of straight-chain is up to 5；
R82At each occurrence independently, expression-Y-SiR85 n2R86 3-n2；
Y independently, indicates the organic group of divalent at each occurrence；
R85At each occurrence independently, the group that indicates hydroxyl or can hydrolyze；
R86At each occurrence independently, hydrogen atom or low alkyl group are indicated；
N2 is in each (- Y-SiR85 n2R86 3-n2) independent in unit, indicate 1~3 integer；
Wherein, in formula (D1) and (D2), at least one n2 be 1~3 integer；
R83At each occurrence independently, hydrogen atom or low alkyl group are indicated；
P2 is at each occurrence 0~3 integer independently；
Q2 is at each occurrence 0~3 integer independently；
R2 is at each occurrence 0~3 integer independently；
ReAt each occurrence independently, expression-Y-SiR85 n2R86 3-n2；
RfAt each occurrence independently, hydrogen atom or low alkyl group are indicated；
K2 is at each occurrence 0~3 integer independently；
12 at each occurrence independently, is 0~3 integer；
M2 is at each occurrence 0~3 integer independently；
Wherein, in formula (D1) and (D2), at least one q2 is 2 or 3 or at least one 12 is 2 or 3.]
(Rf2-PFPE2-Z2)X-A…(E1)
[in formula:
PFPE2At each occurrence independently, it is group shown in following formula:
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f-
(in formula, a, b, c, d, e and f are 0 or more 200 integer below, the sum of a, b, c, d, e and f are at least independently It is 1, is arbitrary in formula with a, b, c, d, e or f and by the presence sequence for each repetitive unit that bracket brackets.)
Rf2At each occurrence independently, the carbon atom number 1 that expression can be replaced by 1 or 1 or more fluorine atom~ 16 alkyl；
Z2Indicate the organic group of singly-bound or divalent；
X is 1 or 2；
When x is 1, A is-COOR3、-PO(OR3)2、-SO2(OR3) or-SO (OR3)；
When x is 2, A is-PO (OR3)-；
R3For hydrogen atom or alkyl.].
Second main idea according to the present invention, provide it is a kind of comprising substrate and on the surface of the substrate using aforementioned present invention The article for the layer that composition is formed.
Third main idea according to the present invention, the condensation for providing a kind of silane compound containing perfluor (poly-) ether promote Agent contains at least one kind of compound shown in following formula (E1):
(Rf2-PFPE2-Z2)X-A…(E1)
[in formula:
Rf2Independently, the alkyl for the carbon atom number 1~16 that can be replaced by 1 or 1 or more fluorine atom is indicated；
PFPE2Independently, expression-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d(OC2F4)e? (OCF2)f, wherein a, b, c, d, e and f are 0 or more 200 integer below, the sum of a, b, c, d, e and f are at least independently It is 1, is arbitrary in formula with a, b, c, d, e or f and by the presence sequence for each repetitive unit that bracket brackets；
Z2Indicate the organic group of singly-bound or divalent；
X is 1 or 2；
When x is 1, A is-COOR3,-PO (OR3)2,-SO2(OR3) or-SO (OR3)；
When x is 2, A is-PO (OR3)-；
R3For hydrogen atom or alkyl.].
The effect of invention
By using the silane compound containing containing perfluor (poly-) ether of the invention and contain perfluor (poly-) ether acid or The composition of acid derivative is capable of forming the surface-treated layer with high friction durability.
Specific embodiment
Hereinafter, being illustrated to composition of the invention.
When using in the present specification, " alkyl " is the group containing carbon and hydrogen, refers to that being detached from 1 hydrogen atom from hydrocarbon obtains Group.It as such alkyl, is not particularly limited, can be replaced by 1 or 1 or more substituent group, carbon can be enumerated The alkyl of atomicity 1~20, for example, aliphatic alkyl, aromatic hydrocarbyl etc..Above-mentioned " aliphatic alkyl " can for straight-chain, Branched is cricoid any, or any one of saturation or unsaturation.In addition, alkyl can contain 1 or 1 Above ring structure.In addition, such alkyl can at its end or in strand with 1 or 1 or more N, O, S, Si, Amide, sulphonyl, siloxanes, carbonyl, carbonyloxy group etc..
When using in the present specification, the substituent group as " alkyl ", is not particularly limited, such as can enumerate: halogen Atom；Selected from can be replaced by 1 or 1 or more halogen atom, C1-6Alkyl, C2-6Alkenyl, C2-6Alkynyl, C3-10Cycloalkanes Base, C3-10Unsaturated ring alkyl, 5~10 yuan of heterocycle, 5~10 yuan of unsaturated heterocycle base, C6-10Aryl and 5~10 yuan 1 or 1 or more group in heteroaryl.
When using in the present specification, " organic groups of 2~10 valences " refer to the group of 2~10 valences containing carbon.As The organic group of such 2~10 valence, is not particularly limited, and can enumerate further diverging from 1~9 hydrogen atom from alkyl and obtain 2~10 valences group.For example, the organic group as divalent, is not particularly limited, it can enumerate from alkyl and further diverge from 1 The group of the divalent of a hydrogen atom.
The present invention provides a kind of composition (hereinafter also referred to as " composition of the invention "), and the composition contains: Xia Shutong It is at least one kind of shown in any general formula in formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) to contain perfluor (poly-) The silane compound of ether；With at least one kind of acid containing perfluor (poly-) ether shown in following formula (E1) or acid derivative (with Under, also referred to as " perfluor (poly-) ether modified compound ").
(Rf1-PFPE1)β’-X5-(SiR1 n1R2 3-n1)β…(B1)
(R2 3-n1R1 n1Si)β-X5-PFPE1-X5-(SiR1 n1R2 3-n1)β…(B2)
(Rf1-PFPE1)γ’-X7-(SiRa k1Rb 11Rc ml)γ…(C1)
(Rc m1Rb 11Ra k1Si)γ-X7-PFPE1-X7-(SiRa k1Rb 11Rc ml)γ…(C2)
(Rf1-PFPE1)δ,-X9-(CRd k2Re 12Rf m2)δ…(D1)
(Rf m2Re 12Rd k2C)δ-X9-PFPE1-X-(CRd k2Re 12Rf m2)δ…(D2)
(Rf2-PFPE2-Z2)X-A…(E1)
Hereinafter, containing perfluor to shown in above-mentioned formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) The silane compound of (poly-) ether is illustrated.
Formula (A1) and (A2):
In above-mentioned formula, PFPE1Independently, it is group shown in following formula:
(OC6F12)a(OC5F10)b(OC4F8)c(OC3F6)d(OC2F4)e(OCF2)f?
In formula, a, b, c, d, e and f are 0 or more 200 integer below independently, and the sum of a, b, c, d, e and f are at least 1.It is preferred that a, b, c, d, e and f are independently, it is 0 or more 100 integer below.It is preferred that the sum of a, b, c, d, e and f are 5 or more, More preferably 10 or more, for example, 10 or more and 100 or less.In addition, being bracketed with a, b, c, d, e or f and by bracket each The presence sequence of repetitive unit is arbitrary in formula.
These repetitive units can may be branched for straight-chain, 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 kind of mode, above-mentioned PFPE1For-(OC3F6)d(in formula, d is 1 or more 200 or less, preferably 5 or more 200 or less, 10 or more 200 integers below are more preferably).It is preferred that PFPE1For-(OCF2CF2CF2)d(in formula, d is 1 or more 200 or less, it is preferably 5 or more 200 or less, more preferably 10 or more 200 integers below) or-(OCF (CF3)CF2)d? (in formula, d is 1 or more 200 or less, is preferably 5 or more 200 or less, more preferably 10 or more 200 integers below).More preferably PFPE1For-(OCF2CF2CF2)d(in formula, d is 1 or more 200 or less, preferably 5 or more 200 or less, more preferably 10 or more 200 integers below).
In another way, PFPE1For-(OC4F8)c(OC3F6)d(OC2F4)e(OCF2)f(in formula, c and d divide It is not independent, be 0 or more 30 integer below, e and f independently, be 1 or more 200 or less, preferably 5 or more 200 or less, it is more excellent 10 or more 200 integers below are selected, the presence sequence with subscript c, d, e or f and each repetitive unit for being bracketed by bracket exists It is arbitrary in formula).It is preferred that PFPE1For-(OCF2CF2CF2CF2)c(OCF2CF2CF2)d(OCF2CF2)e(OCF2)f?. In a kind of mode, PFPE1It can be-(OC2F4)e(OCF2)f(in formula, e and f independently, be 1 or more 200 or less, It is preferred that 5 or more 200 or less, more preferable 10 or more 200 integer below, with subscript e or f and each repetition for being bracketed by bracket The presence sequence of unit is arbitrary in formula).
In another other way, PFPE1For-(R6- R7)qShown in group.In formula, R6For OCF2Or OC2F4, excellent It is selected as OC2F4.In formula, R7For selected from OC2F4、OC3F6、OC4F8、OC5F10And OC6F12Group, or to be independently selected from these bases The combination of 2 or 3 groups of group.It is preferred that R7For selected from OC2F4、OC3F6And OC4F8Group, or to be independently selected from these bases The combination of 2 or 3 groups of group.As being independently selected from OC2F4、OC3F6And OC4F82 or 3 groups combination, without special It limits, such as-OC can be enumerated2F4OC3F6,-OC2F4OC4F8,-OC3F6OC2F4,-OC3F6OC3F6,- OC3F6OC4F8,-OC4F8OC4F8,-OC4F8OC3F6,-OC4F8OC2F4,-OC2F4OC2F4OC3F6,- OC2F4OC2F4OC4F8,-OC2F4OC3F6OC2F4,-OC2F4OC3F6OC3F6,-OC2F4OC4F8OC2F4,- OC3F6OC2F4OC2F4,-OC3F6OC2F4OC3F6,-OC3F6OC3F6OC2F4And-OC4F8OC2F4OC2F4Etc..It is above-mentioned The integer that q is 2~100, preferably 2~50 integer.In above-mentioned formula, OC2F4、OC3F6、OC4F8、OC5F10And OC6F12Can be Any, preferably straight chain of linear chain or branched chain.In this approach, PFPE1Preferably-(OC2F4- OC3F6)qOr- (OC2F4- OC4F8)q?.
In above-mentioned formula, Rf1Indicate the alkyl for the carbon atom number 1~16 that can be replaced by 1 or 1 or more fluorine atom.
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 may be branch for straight chain, preferably the carbon atom number 1~6, particularly carbon atom number 1 of linear chain or branched chain ~3 alkyl, the more preferably alkyl of the carbon atom number 1~3 of straight chain.
Above-mentioned Rf1The alkyl of the carbon atom number 1~16 preferably replaced by 1 or 1 or more fluorine atom, more preferably CF2H-C1-15Fluorianted alkylene, the further preferably perfluoroalkyl of carbon atom number 1~16.
The perfluoroalkyl of the carbon atom number 1~16 can may be branch for straight chain, and preferably the carbon of linear chain or branched chain is former The perfluoroalkyl of subnumber 1~6, particularly carbon atom number 1~3, the more preferably perfluoroalkyl of the carbon atom number 1~3 of straight chain, tool It is-CF for body3,-CF2CF3Or-CF2CF2CF3。
In above-mentioned formula, R1At each occurrence independently, the group that indicates hydroxyl or can hydrolyze.
When using in the present specification, above-mentioned " group that can be hydrolyzed " refers to can be from compound by hydrolysis The group that main framing is detached from.As the example for the group that can be hydrolyzed ,-OR ,-OCOR ,-O-N=CR can be enumerated2,- NR2,-NHR, halogen (in these formulas, R indicates the alkyl of substituted or non-substituted carbon atom number 1~4) etc., preferably-OR (that is, alkoxy).In the example of R, the non substituted alkyl including methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group etc.； The substitution alkyl of chloromethyl etc..Among these, optimizing alkyl, particularly non substituted alkyl, more preferable methyl or ethyl.Hydroxyl It is not particularly limited, the hydroxyl that the group hydrolysis that can be can hydrolyze generates.
In above-mentioned formula, R2At each occurrence independently, the alkyl of hydrogen atom or carbon atom number 1~22 is indicated, preferably Indicate the alkyl of carbon atom number 1~4.
In above-mentioned formula, R11At each occurrence independently, hydrogen atom or halogen atom are indicated.Halogen atom is preferably iodine Atom, chlorine atom or fluorine atom, more preferably fluorine atom.
In above-mentioned formula, R12At each occurrence independently, hydrogen atom or low alkyl group are indicated.Low alkyl group is preferably carbon The alkyl of atomicity 1~20, the more preferably alkyl of carbon atom number 1~6, such as methyl, ethyl, propyl can be enumerated etc..
In above-mentioned formula, n1 is in each (- SiR1 n1R2 3-n1) independent in unit, it is 0~3 integer, preferably 1~3, more Preferably 3.But in formula, whole n1 are not 0 simultaneously.In other words, in formula, there are at least one R1。
In above-mentioned formula, X1Independently, the organic group of singly-bound or 2~10 valences is indicated.The X1Shown in formula (A1) and (A2) Compound in be perfluoropolyether portion by water-repellancy and surface slip etc. is mainly provided (that is, Rf1- PFPE1Portion or- PFPE1Portion) and provide with the combination of substrate can the company that links, silane portion (that is, with α and group for being bracketed by bracket) Connect base.Therefore, the X1As long as the group that can be stabilized with formula (A1) and (A2) compound represented can be and appoint The organic group of meaning.
In above-mentioned formula, the integer that α is 1~9, the integer that α ' is 1~9.These α and α ' can be according to X1Valence mumber variation. In formula (A1), the sum of α and α ' and X1Valence mumber it is identical.For example, X1For 10 valences organic group when, α and α's ' and be 10, example It is that 1, α is 5 and α ' is that 5 or α is 1 and α ' is 9 that such as to can be α, which be 9 and α ',.In addition, X1For divalent organic group when, α and α ' It is 1.In formula (A2), α is from X1Valence mumber subtract 1 value.
Above-mentioned X1The organic group of preferably 2~7 valences, more preferably 2~4 valences, further preferably divalent.
In a kind of mode, X1For the organic group of 2~4 valences, α is that 1~3, α ' is 1.
In another way, X1For the organic group of divalent, α 1, α ' is 1.At this point, formula (A1) and (A2) are by following formula (A1 ') and (A2 ') is indicated.
As above-mentioned X1Example, be not particularly limited, such as divalent group shown in following formula can be enumerated:
(R31)p’(Xa)q’?
[in formula:
R31Independently, singly-bound ,-(CH are indicated2)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, still more preferably for 1 or 2,
XaExpression-(Xb)1’,
XbAt each occurrence independently, it indicates selected from-O- ,-S-, adjacent phenylene, metaphenylene or to sub- benzene Base ,-C (O) O- ,-Si (R33)2,-(Si (R33)2O)m’- Si (R33)2,-CONR34,-O-CONR34,- NR34And-(CH2)n’In group,
R33At each occurrence independently, phenyl, C are indicated1-6Alkyl or C1-6Alkoxy, preferably phenyl or C1-6Alkane Base, more preferably methyl,
R34At each occurrence independently, hydrogen atom, phenyl or C are indicated1-6Alkyl (preferably methyl),
M ' is 1~100 integer at each occurrence independently, preferably 1~20 integer,
N ' is 1~20 integer at each occurrence independently, 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 0,1 or 2,
Q ' is 0 or 1,
Wherein, at least one of p ' and q ' are 1, with p ' or q ' and each repetitive unit for being bracketed by bracket there are suitable Sequence is arbitrary.]
Wherein, R31And Xa(for typical, R31And XaHydrogen atom) can by be selected from fluorine atom, C1-3Alkyl and C1-3Fluorine 1 or 1 or more substituent group in substituted alkyl replaces.
It is preferred that above-mentioned X1For-(R31)p’(Xa)q’- R32?.R32Indicate 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, R32(for typical, R32Hydrogen atom) can by be selected from fluorine atom, C1-3Alkyl and C1-3Fluoro-alkyl In 1 or 1 or more substituent group replace.
It is preferred that above-mentioned X1Are as follows:
Singly-bound,
C1-20Alkylidene,
- R31- Xc- R32Or
- Xd- R32?
[in formula, R31And R32It is identical as above-mentioned meaning.].
More preferable above-mentioned X1Are as follows:
Singly-bound,
C1-20Alkylidene,
(CH2)s’- Xc,
(CH2)s’- Xc(CH2)t’?
- XdOr
- Xd(CH2)t’?
[in formula, s ' and t ' are identical as above-mentioned meaning.].
In above-mentioned formula, XcIt indicates:
- O-,
- S-,
- C (O) O-,
- CONR34,
- O-CONR34,
- Si (R33)2,
(Si (R33)2O)m’- Si (R33)2,
- O- (CH2)u’(Si (R33)2O)m’- Si (R33)2,
- O- (CH2)u’- Si (R33)2- O-Si (R33)2- CH2CH2- Si (R33)2- O-Si (R33)2,
- O- (CH2)u’- Si (OCH3)2OSi(OCH3)2,
- CONR34(CH2)u’(Si (R33)2O)m’- Si (R33)2,
- CONR34(CH2)u’- N (R34)-or
- CONR34(adjacent phenylene, metaphenylene or to phenylene)-Si (R33)2?
[in formula, R33、R34It is identical as above-mentioned meaning with m ',
The integer that u ' is 1~20, preferably 2~6 integer, more preferably 2~3 integer.].XcPreferably-O-.
In above-mentioned formula, XdIt indicates:
- S-,
- C (O) O-,
- CONR34,
- CONR34(CH2)u’(Si (R33)2O)m’- Si (R33)2,
- CONR34(CH2)u’- N (R34)-or
- CONR34(adjacent phenylene, metaphenylene or to phenylene)-Si (R33)2?
[in formula, each symbol is identical as above-mentioned meaning.].
More preferable above-mentioned X1For
Singly-bound,
C1-20Alkylidene,
(CH2)s’- Xc(CH2)t’Or
- Xd(CH2)t’?
[in formula, each symbol is identical as above-mentioned meaning.].
Still more preferably above-mentioned X1Are as follows:
Singly-bound,
C1-20Alkylidene,
(CH2)s’- O- (CH2)t’,
(CH2)s’(Si (R33)2O)m’- Si (R33)2(CH2)t’,
(CH2)s’- O- (CH2)u’(Si (R33)2O)m’- Si (R33)2(CH2)t’Or
(CH2)s’- O- (CH2)t’- Si (R33)2(CH2)u’- Si (R33)2(CvH2v)-
[in formula, R33, m ', s ', t ' and u ' it is identical as above-mentioned meaning, v be 1~20 integer, preferably 2~6 integer, More preferably 2~3 integer.].
In above-mentioned formula ,-(CvH2v)-can may be branch for straight chain, such as can be-CH2CH2,- CH2CH2CH2,-CH (CH3)-,-CH (CH3)CH2?.
Above-mentioned X1Base can be selected from fluorine atom, C1-3Alkyl and C1-3Fluoro-alkyl (preferably C1-3Perfluoroalkyl) in 1 A or 1 or more substituent group replaces.
In another way, as X1Base, such as following groups can be enumerated:
[in formula, R41It independently, is hydrogen atom, the alkyl or C of phenyl, carbon atom number 1~61-6Alkoxy, preferably Methyl；
D is the group selected from following radicals:
- 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, R42Independently, hydrogen atom, C are indicated1-6Alkyl or C1-6Alkoxy, preferred expression methyl or first Oxygroup, more preferably expression methyl.)
E is-(CH2)n(integer that n is 2~6),
The PFPE of D and molecular backbone1Bonding, E and and PFPE1The group bonding of opposite side.]
As above-mentioned X1Concrete example, such as can enumerate:
Singly-bound,
- CH2O(CH2)2,
- CH2O(CH2)3,
- CH2O(CH2)6,
- 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,
- CH2OCH2CHFCF2OCF2,
- CH2OCH2CHFCF2OCF2CF2,
- CH2OCH2CHFCF2OCF2CF2CF2,
- CH2OCH2CHFCF2OCF(CF3)CF2OCF2,
- CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2,
- CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2?
- CH2OCF2CHFOCF2CF2CF2- C (O) NH-CH2,
- 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,
(CH2)2- Si (CH3)2(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 another way in turn, X1For formula :-(R16)x(CFR17)y(CH2)zShown in group.In formula, x, y Independently with z, be 0~10 integer, the sum of x, y and z be 1 or more, each repetitive unit bracketed by bracket there are suitable Sequence is arbitrary in formula.
In above-mentioned formula, R16It at each occurrence independently, is oxygen atom, phenylene, sub- carbazyl ,-NR26(formula In, R26Indicate hydrogen atom or organic group) or divalent organic group.It is preferred that R16For the polarity group of oxygen atom or divalent.
It as above-mentioned " the polarity group of divalent ", is not particularly limited ,-C (O)-,-C (=NR can be enumerated27)- With-C (O) NR27(in these formulas, R27Indicate hydrogen atom or low alkyl group).Should " low alkyl group " be, for example, carbon atom number 1~ 6 alkyl, for example, methyl, ethyl, n-propyl, these can be replaced by 1 or 1 or more fluorine atom.
In above-mentioned formula, R17It at each occurrence independently, is hydrogen atom, fluorine atom or lower fluoro-alkyl, preferably Fluorine atom.It is somebody's turn to do the fluoro-alkyl that " lower fluoro-alkyl " is, for example, carbon atom number 1~6, preferably carbon atom number 1~3, preferably carbon The perfluoroalkyl of atomicity 1~3, more preferably trifluoromethyl, pentafluoroethyl group, further preferably trifluoromethyl.
In this approach, X1Preferably formula :-(O)x(CF2)y(CH2)z(in formula, x, y and z and above-mentioned meaning phase Together, be arbitrary in formula by the presence sequence of each repetitive unit that bracket brackets) shown in group.
As above-mentioned formula :-(O)x(CF2)y(CH2)zShown in group, such as-(O) can be enumeratedx’? (CH2)z”- O- [(CH2)z”’- O-]z””With-(O)x’(CF2)y”(CH2)z”- O- [(CH2)z”’- O-]z””(formula In, x ' be 0 or 1, y ", z " and z " ' independently, integer, the z " for being 1~10 " be 0 or 1) shown in group.In addition, these bases The left end of group and PFPE1Side switch closes.
In another preferred embodiment, X1For-O-CFR13(CF2)g?.
Above-mentioned R13Independently, fluorine atom or lower fluoro-alkyl are indicated.Lower fluoro-alkyl be, for example, carbon atom number 1~ 3 fluoro-alkyl, the preferably perfluoroalkyl of carbon atom number 1~3, more preferably trifluoromethyl, pentafluoroethyl group, further preferably For trifluoromethyl.
Above-mentioned g is 0 or 1 independently.
In a concrete example, R13For fluorine atom, e 1.
In another way in turn, X1For-Xc- CO-NR14- XdOr-Xc- CO-N (- Xd)2Shown in base Group.- Xc- CO-NR14- XdIt is the group of divalent ,-Xc- CO-N (- Xd)2For the group of trivalent.
R14Indicate hydrogen atom, low alkyl group or phenyl.Low alkyl group is preferably C1-6Alkyl, more preferably C1-3Alkyl, Further preferably methyl.
Above-mentioned XcIndicate the organic group of singly-bound or divalent.
Above-mentioned XcIn the organic group of divalent preferably can be-(CR8 2)k1(O)k2(NR9)k3Shown in group.
[in formula:
R8It independently, is hydrogen atom or fluorine atom；
R9Independently, hydrogen atom, phenyl or C are indicated1-6Alkyl；
The integer that k1 is 1~20；
The integer that k2 is 0~10；
The integer that k3 is 0~10；
Wherein, the presence sequence with k1, k2 or k3 and each repetitive unit for being bracketed by bracket is any in formula 's.]
Above-mentioned XdIndicate the organic group of divalent.
Above-mentioned XdThe organic group of divalent preferably can be-(CR20 2)k4(O)k5(NR21)k6Shown in group.
[in formula:
R20It independently, is hydrogen atom or fluorine atom；
R21Independently, hydrogen atom, phenyl or C are indicated1-6Alkyl；
The integer that k4 is 1~20；
The integer that k5 is 0~10；
The integer that k6 is 0~10；
Wherein, the presence sequence with k4, k5 or k6 and each repetitive unit for being bracketed by bracket is any in formula 's.]
In a kind of mode, XcFor-(CF2)k1’Or-(CF2)k1’(O)k2’,
[in formula:
The integer that k1 ' is 1~6；
The integer that k2 ' is 1~3；
Wherein, it is arbitrary in formula with k1 ' or k2 ' and by the presence sequence for each repetitive unit that bracket brackets.]
XdFor-(CH2)k4’Or-(CH2)k4’- Ok5’?.
[in formula:
The integer that k4 ' is 1~6；
The integer that k5 ' is 1~3；
Wherein, it is arbitrary in formula with k4 ' or k5 ' and by the presence sequence for each repetitive unit that bracket brackets.]
In mode other in turn, as X1The example of base can enumerate following groups:
[in formula,
R41It independently, is hydrogen atom, the alkyl or C of phenyl, carbon atom number 1~61-6Alkoxy, preferably methyl；
In each X1Any several PFPE for molecular backbone in base, in T1The group below of bonding:
- 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) or
[in formula, R42Independently, hydrogen atom, C are indicated1-6Alkyl or C1-6Alkoxy, preferred expression methyl or first Oxygroup, more preferably expression methyl.]
The several of other T are and molecular backbone and PFPE1The group of opposite side is (that is, in formula (A1), (A2), (D1) It is carbon atom in (D2), is in addition Si atom in following formula (B1), (B2), (C1) and (C2)) bonding-(CH2)n”? (integer that n " is 2~6), in the presence of, remaining T is methyl, phenyl, C independently1-6Alkoxy or radical-scavenging group Or ultraviolet-absorbing group.
As long as radical-scavenging group can capture the free radical generated by light irradiation, it is not particularly limited, example Can such as enumerate benzophenone, benzotriazole, benzoates, phenyl salicylate class, crotons acids, malonic acid esters, Organic crylic acid esters, hindered amines, Hinered phenols or triazines residue.
As long as ultraviolet-absorbing group can absorb the group of ultraviolet light, it is not particularly limited, such as can arranges Lift the esters of benzotriazole, hydroxy benzophenone ketone, substitution and unsubstituting phenenyl formic acid or salicylic acid compound, acrylate or Alkoxy cinnamic acid ester class, Oxamides, oxanilide class, benzoxazine ketone, benzoxazoles class residue.
In a preferred manner, it as preferred radical-scavenging group or ultraviolet-absorbing group, can enumerate:
In this approach, X1It independently, is the organic group of 3~10 valences.
In above-mentioned formula, t is 1~10 integer independently.In a preferred manner, the integer that t is 1~6.Another In preferred embodiment, the integer that t is 2~10, preferably 2~6 integer.
In above-mentioned formula, X2At each occurrence independently, the organic group of singly-bound or divalent is indicated.X2Preferably carbon atom The alkylidene of number 1~20, more preferably-(CH2)u(in formula, u be 0~2 integer).
Preferred formula (A1) and (A2) compound represented are following formula (A1 ') and (A2 ') compound represented.
[in formula:
PFPE1It independently, is formula-(OC4F8)a(OC3F6)b(OC2F4)c(OCF2)dShown in group,
(in formula, a, b, c and d independently, be 0~200 integer, the sum of a, b, c and d be at least 1, with subscript a, B, it c or d and is arbitrary in formula by the presence of each repetitive unit that bracket brackets sequence.)；
Rf1At each occurrence independently, the carbon atom number 1 that expression can be replaced by 1 or 1 or more fluorine atom~ 16 alkyl；
R1At each occurrence independently, the group that indicates hydroxyl or can hydrolyze；
R2At each occurrence independently, the alkyl of hydrogen atom or carbon atom number 1~22 is indicated；
R11At each occurrence independently, hydrogen atom or halogen atom are indicated；
R12At each occurrence independently, hydrogen atom or low alkyl group are indicated；
The integer that n1 is 1~3, preferably 3；
X1For-O-CFR13(CF2)e?；
R13For fluorine atom or lower fluoro-alkyl；
E is 0 or 1；
X2For-(CH2)u-；
Integer that u is 0~2 (X when u is 02For singly-bound)；
The integer that t is 1~10.]
Above-mentioned formula (A1) and (A2) compound represented for example can be by that will correspond to Rf1-PFPE1Partial perfluor is poly- Ether derivant is as raw material, after end imports iodine, and corresponds to-CH2CR12(X2-SiR1 n1R2 3-n1)-vinyl monomer Reaction is to obtain.
Formula (B1) and (B2):
(Rf1-PFPE1)β’-X5-(SiR1 n1R2 3-n1)β…(B1)
(R2 3-n1R1 n1Si)β-X5-PFPE1-X5-(SiR1 n1R2 3-n1)β…(B2)
In above-mentioned formula (B1) and (B2), Rf1、PFPE1、R1、R2Meaning is recorded to relevant above-mentioned formula (A1) and (A2) with n1 Justice is identical.
In above-mentioned formula, X5Independently, the organic group of singly-bound or 2~10 valences is indicated.The X5It is in formula (B1) and (B2) institute The perfluoropolyether portion of water-repellancy and surface slip etc. will be mainly provided in the compound shown (that is, Rf1-PFPE1Portion or-PFPE1- Portion) and the silane portion with the combination of substrate energy is provided (specifically,-SiR1 n1R2 3-n1) connection linker.Therefore, the X5Only If the group that formula (B1) and (B2) compound represented can be stabilized, can be arbitrary organic group.
The integer that β in above-mentioned formula is 1~9, the integer that β ' is 1~9.These β and β ' can be according to X3Valence mumber determine, In formula (B1), the sum of β and β ' and X5Valence mumber it is identical.For example, X5For 10 valences organic group when, the sum of β and β ' be 10, example It is that 1, β is 5 and β ' is that 5 or β is 1 and β ' is 9 that such as to can be β, which be 9 and β ',.In addition, X5For divalent organic group when, β and β ' It is 1.β is from X in formula (B2)5Valence mumber value subtract 1 value.
Above-mentioned X5Preferably 2~7 valences, more preferably 2~4 valences, the further preferably organic group of divalent.
In a kind of mode, X5For the organic group of 2~4 valences, β is that 1~3, β ' is 1.
In another way, X5For the organic group of divalent, β 1, β ' is 1.At this point, formula (B1) and (B2) are by following formula (B1 ') and (B2 ') is indicated.
Rf1-PFPE1-X5-SiR1 n1R2 3-n1…(B1’)
R2 3-n1R1 n1Si-X5-PFPE1-X5-SiR1 n1R2 3-n1…(B2’)
As above-mentioned X5Example, be not particularly limited, for example, can enumerate with about X1The identical base of documented group Group.
X as a preferred method,5For-Xc-CO-NR14-XdOr-Xc-CO-N(-Xd-)2Shown group.Xc、XdAnd R14 With about above-mentioned X1Be recorded as same position.
Preferred specific X5It can enumerate:
Singly-bound,
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-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-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-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-、
-(CH2)2-Si(CH3)2-(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.
Preferred formula (B1) and (B2) compound represented are following formula (B1 ') and (B2 ') compound represented.
Rf1-PFPE1-X5-SiR1 n1R2 3-n1…(B1’)
R2 3-n1R1 n1Si-X5-PFPE1-X5-SiR1 n1R2 3-n1…(B2’)
[in formula:
PFPE1It independently, is formula-(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)dShown in group,
(in formula, a, b, c and d independently, be 0~200 integer, the sum of a, b, c and d be at least 1, with subscript a, B, it c or d and is arbitrary in formula by the presence of each repetitive unit that bracket brackets sequence.)；
Rf1At each occurrence independently, the carbon atom number 1 that expression can be replaced by 1 or 1 or more fluorine atom~ 16 alkyl；
R1At each occurrence independently, the group that indicates hydroxyl or can hydrolyze；
R2At each occurrence independently, the alkyl of hydrogen atom or carbon atom number 1~22 is indicated；
The integer that n1 is 1~3, preferably 3；
X5For-CH2O(CH2)2-、-CH2O(CH2)3Or-CH2O(CH2)6-]。
Above-mentioned formula (B1) and (B2) compound represented can pass through side described in well known method, such as patent document 1 Method or the manufacture of its modification method.For example, formula (B1) and (B2) compound represented can be by following formula (B1-4) or (B2-4) institutes The compound and HSiM shown3(in formula, M is halogen atom, R independently1Or R2, R1It at each occurrence independently, is hydroxyl Base or the group that can be hydrolyzed, R2At each occurrence independently, it is hydrogen atom or the alkyl of carbon atom number 1~22) reaction And above-mentioned halogen atom is transformed to R as needed1Or R2And obtained as formula (B1 ") or (B2 ") compound represented,
(Rf1-PFPE1)β’-X5’-(R92- CH=CH2)β…(B1-4)
(CH2=CH-R92)β-X5’-PFPE1-X5’-(R92- CH=CH2)β…(B2-4)
[in formula:
PFPE1It independently, is formula-(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)dShown in group,
(in formula, a, b, c and d independently, be 0~200 integer, the sum of a, b, c and d be at least 1, with subscript a, B, it c or d and is arbitrary in formula by the presence of each repetitive unit that bracket brackets sequence.)；
Rf1At each occurrence independently, the carbon atom number 1 that expression can be replaced by 1 or 1 or more fluorine atom~ 16 alkyl；
X5’Independently, the organic group of singly-bound or 2~10 valences is indicated；
β is 1~9 integer independently；
β ' is 1~9 integer independently；
R92For singly-bound or the organic group of divalent.]
(Rf1-PFPE1)β’-X5’-(R92-CH2CH2-SiR1 n1R2 3-n1)β…(B1”)
(R1 n1R2 3-n1Si-CH2CH2-R92)β-X5’-PFPE1-X5’-*
*(R92-CH2CH2-SiR1 n1R2 3-n1)β…(B2”)
[in formula, PFPE1、Rf1、X5’, β, β ' and R92It is identical as above-mentioned meaning；
The integer that n1 is 0~3.].
In formula (B1 ") or (B2 "), from X5’To R92-CH2CH2Part correspond to formula (B1) or (B2) in X5。
Formula (C1) and (C2) are
(Rf1-PFPE1)γ’-X7-(SiRa k1Rb 11Rc m1)γ…(C1)
(Rc m1Rb 11Ra k1Si)γ-X7-PFPE1-X7-(SiRa k1Rb 11Rc m1)γ…(C2)
In above-mentioned formula (C1) and (C2), Rf1And PFPE1It is identical as the record meaning about above-mentioned formula (A1) and (A2).
In above-mentioned formula, X7Independently, the organic group of singly-bound or 2~10 valences is indicated.The X7It is in formula (C1) and (C2) institute Perfluoropolyether portion (the Rf of water-repellancy and surface slip etc. will be mainly provided in the compound shown1-PFPE1Portion or-PFPE1Portion) and It provides and the silane portion of the combination of substrate energy is (specifically,-SiRa k1Rb 11Rc m1Base) connection linker.Therefore, the X7As long as It is the group that can be stabilized with formula (C1) and (C2) compound represented, organic group can be arbitrary.
The integer that γ in above-mentioned formula is 1~9, the integer that γ ' is 1~9.These γ and γ ' are according to X7Valence mumber determine, In formula (C1), the sum of γ and γ ' and X7Valence mumber it is identical.For example, X7For 10 valences organic group when, the sum of γ and γ ' are 10, such as it be 1, γ be 5 and γ ' is that 5 or γ is 1 and γ ' is 9 that can be γ, which be 9 and γ ',.In addition, X7For divalent organic group When group, γ and γ ' are 1.In formula (C1), γ is from X7The value of valence mumber subtract 1 obtained value.
Above-mentioned X7Preferably 2~7 valences, more preferably 2~4 valences, the further preferably organic group of divalent.
In a kind of mode, X7For the organic group of 2~4 valences, γ is that 1~3, γ ' is 1.
In another way, X7For the organic group of divalent, γ 1, γ ' is 1.At this point, formula (C1) and (C2) such as following formula Shown in (C1 ') and (C2 ').
Rf1-PFPE1-X7-SiRa k1Rb 11Rc m1…(C1’)
Rc m1Rb 11Ra k1Si-X7-PFPE1-X7-SiRa k1Rb 11Rc m1…(C2’)
As above-mentioned X7Example, be not particularly limited, for example, can enumerate with about X1The identical base of documented group Group.
X as a preferred method,5It can be-Xc-CO-NR14-XdOr-Xc-CO-N(-Xd-)2Shown group.XcAnd Xd With about above-mentioned X1Be recorded as same position.
Preferred specific X7It can enumerate:
Singly-bound,
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-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-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
- CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2,
- CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2?
- CH2OCF2CHFOCF2CF2CF2- C (O) NH-CH2,
- 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,
(CH2)2- Si (CH3)2(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 above-mentioned formula, RaAt each occurrence independently, expression-Z1- SiR71 p1R72 q1R73 r1。
In formula, Z1At each occurrence independently, the organic group of oxygen atom or divalent is indicated.
Above-mentioned Z1The preferably organic group of divalent does not include the end Si original of the molecular backbone with formula (C1) or formula (C2) Son (RaIn conjunction with Si atom) formed siloxanes key group.
Above-mentioned Z1Preferably C1-6Alkylidene ,-(CH2)g- O- (CH2)h(in formula, the integer that g is 1~6, h is 1~6 Integer) or-phenylene-(CH2)i(in formula, i be 0~6 integer), more preferably C1-3Alkylidene.These group examples Can such as fluorine atom, C be selected from1-6Alkyl, C2-6Alkenyl and C2-61 or 1 or more substituent group in alkynyl replaces.
In formula, R71At each occurrence independently, R is indicateda’。Ra’With RaMeaning is identical.
RaIn, via Z1Base connection is that the Si of straight-chain is up to 5.In other words, in above-mentioned RaIn, R71At least there is 1 When, in RaIn via Z1Base connection is that there are 2 or more for the Si atom of straight-chain, but link in this way via Z base for straight-chain The number of Si atom is up to 5.In addition, " RaIn via Z base connection be straight-chain Si atom number " in RaMiddle company Become-the Z of straight-chain1The repetition number of-Si- is equal.
For example, following be illustrated in RaIn via Z1Base (following to be represented simply as " Z ") is linked with an example of Si atom.
In above-mentioned formula, * means that the position ... in conjunction with the Si of main chain means to combine the regulation group other than ZSi, changes When 3 valence links of Yan Zhi, Si atom are all ..., it is intended that the position that the repetition of ZSi terminates.In addition, the number in the upper right corner of Si Refer to the frequency of occurrence via the Si that the connection of Z base is straight-chain counted from *.In other words, with Si2Terminate in the duplicate chain of ZSi “RaIn via Z1Base connection is the number of the Si atom of straight-chain " it is 2, equally, with Si3、Si4And Si5Terminate ZSi to repeat Chain in, " RaIn via Z1Base connection is the number of the Si atom of straight-chain " it is respectively 3,4 and 5.In addition, such as from above-mentioned Formula is it is found that in RaIn, ZSi chain is there are multiple, but they do not need all equal lengths, can be respectively random length.
In a preferred manner, as shown in following, " RaIn via Z1Base connection is the number of the Si atom of straight-chain " It is 1 (levoform) or 2 (right formula) in whole chains.
In a kind of mode, RaIn be 1 or 2 via the number of Si atom that the connection of Z base is straight-chain, preferably 1.
In formula, R72At each occurrence independently, the group that indicates hydroxyl or can hydrolyze.
When using in the present specification, above-mentioned " group that can be hydrolyzed " refers to the group that hydrolysis can occur.Make Example for the group that can be hydrolyzed can enumerate-OR ,-OCOR ,-O-N=C (R)2,-N (R)2,-NHR, halogen (this In a little formulas, R indicates the alkyl of substituted or non-substituted carbon atom number 1~4) etc., preferably-OR (alkoxy).In the example of R Packet: the non substituted alkyls such as methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group are included；Chloromethyl etc. replaces alkyl.These In, optimizing alkyl, particularly non substituted alkyl, more preferable methyl or ethyl.Hydroxyl is not particularly limited, and can be can hydrolyze Group occur hydrolysis generate hydroxyl.
It is preferred that R72For-OR, (in formula, R indicates substituted or non-substituted C1-3Alkyl, more preferably expression methyl).
In formula, R73At each occurrence independently, hydrogen atom or low alkyl group are indicated.The low alkyl group is preferably carbon original The alkyl of subnumber 1~20, the more preferably alkyl of carbon atom number 1~6, further preferably methyl.
In formula, p1 is at each occurrence 0~3 integer independently；Q1 at each occurrence independently, be 0~ 3 integer；R1 is at each occurrence 0~3 integer independently.Wherein, the sum of p1, q1 and r1 are 3.
In a preferred manner, in RaIn end Ra' (R is not presenta' when be Ra) in, above-mentioned q1 is preferably 2 or more, For example, 2 or 3, more preferably 3.
In a preferred manner, RaAt least one of terminal part can be-Si (- Z1- SiR72 qR73 r)2Or-Si (- Z1- SiR72 qR73 r)3, preferably-Si (- Z1- SiR72 qR73 r)3.In formula, (- Z1- SiR72 qR73 r) unit be preferably (- Z1- SiR72 3).In further preferred mode, RaTerminal part can all-Si (- Z1- SiR72 qR73 r)3, preferably All-Si (- Z1- SiR72 3)3。
In above-mentioned formula (C1) and (C2), at least there is 1 R72。
R in above-mentioned formulabAt each occurrence independently, the group that indicates hydroxyl or can hydrolyze.
Above-mentioned RbPreferably hydroxyl ,-OR ,-OCOR ,-O-N=C (R)2,-N (R)2,-NHR, halogen (these formulas In, R indicates the alkyl of substituted or non-substituted carbon atom number 1~4), preferably-OR.R includes methyl, ethyl, propyl, isopropyl The non substituted alkyls such as base, normal-butyl, isobutyl group；Chloromethyl etc. replaces alkyl.In these, optimizing alkyl, particularly non-substituted Alkyl, more preferable methyl or ethyl.Hydroxyl is not particularly limited, and the hydroxyl that hydrolysis generates occurs for the group that can be can hydrolyze Base.More preferable Rc is that (in formula, R indicates substituted or non-substituted C to-OR1-3Alkyl, more preferably expression methyl).
In above-mentioned formula, RcAt each occurrence independently, hydrogen atom or low alkyl group are indicated.The low alkyl group is preferably The alkyl of carbon atom number 1~20, the more preferably alkyl of carbon atom number 1~6, further preferably methyl.
In formula, k1 is at each occurrence 0~3 integer independently；11 at each occurrence independently, be 0~ 3 integer；M1 at each occurrence independently, 0~3 integer.Wherein, the sum of k1,11 and m1 is 3.
Above-mentioned formula (C1) and (C2) compound represented can obtain as follows: for example, will correspond to Rf1-PFPE1Partial Perfluoro polyether derivant is as raw material, after end imports hydroxyl, the group with unsaturated bond is imported in end, makes the tool There is the group of unsaturated bond to react with the silyl derivative with halogen atom, further in end in the silicyl Hydroxyl is imported, reacts the group with unsaturated bond imported with silyl derivative.Such as it can operate to obtain as follows.
Preferred formula (C1) and (C2) compound represented are following formula (C1 ") and (C2 ") compound represented.
Rf1-PFPE1-X7-SiRa 3…(C1”)
Ra 3Si-X7-PFPE1-X7-SiRa 3…(C2”)
[in formula:
PFPE1Independently, it is group shown in following formula:
-(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-
(in formula, a, b, c and d independently, be 0~200 integer, the sum of a, b, c and d be at least 1, with subscript a, B, it c or d and is arbitrary in formula by the presence of each repetitive unit that bracket brackets sequence.)；
Rf1At each occurrence independently, the carbon atom number 1 that expression can be replaced by 1 or 1 or more fluorine atom~ 16 alkyl；
X7Expression-CH2O(CH2)2-、-CH2O(CH2)3Or-CH2O(CH2)6-；
RaAt each occurrence independently, expression-Z1-SiR71 p1R72 q1R73 r1；
Z1Indicate C1-6Alkylidene；
R71At each occurrence independently, R is indicateda’；
Ra’With RaMeaning is identical；
RaIn, via Z1Base connection is that the Si of straight-chain is up to 5；
R72At each occurrence independently, the group that indicates hydroxyl or can hydrolyze；
R73At each occurrence independently, hydrogen atom or low alkyl group are indicated；
P1 is at each occurrence 0~2 integer independently；
Q1 is 1~3 integer at each occurrence independently, preferably 3；
R1 is at each occurrence 0~2 integer independently；
Wherein, in a RaIn, the sum of p1, q1 and r1 are 3.]
Above-mentioned formula (C1) and (C2) compound represented can for example be manufactured such as operations described below.By following formula (C1-4) or (C2-4) compound represented and HSiR93 k1Rb 11Rc m1(in formula, R93It is former for halogen atom, such as fluorine atom, chlorine atom, smelly element Son or iodine atom, preferably chlorine atom, RbAt each occurrence independently, the group that indicates hydroxyl or can hydrolyze, RcEvery It is secondary when occurring independently, indicate that hydrogen atom or low alkyl group, the integer that k1 is 1~3,11 and m1 are 0~2 independently Integer, the sum of k1,11 and m1 are 3.) compound represented reaction, obtain formula (C1-5) or (C2-5) compound represented.
(Rf1-PFPE1)γ’-X7’-(R92- CH=CH2)γ…(C1-4)(CH2=CH-R92)γ-X7’-PFPE1-X7’-(R92CH =CH2)γ…(C2-4)
[in formula:
PFPE1Independently, it is group shown in following formula:
-(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-
(in formula, a, b, c and d independently, be 0~200 integer, the sum of a, b, c and d be at least 1, with subscript a, B, it c or d and is arbitrary in formula by the presence of each repetitive unit that bracket brackets sequence.)；
Rf1At each occurrence independently, the carbon atom number 1 that expression can be replaced by 1 or 1 or more fluorine atom~ 16 alkyl；
X7’Independently, the organic group of singly-bound or 2~10 valences is indicated；
γ is 1~9 integer independently；
γ ' is 1~9 integer independently；
R92For singly-bound or the organic group of divalent.]
(Rf1-PFPE1)γ’-X7’-(R92-CH2CH2-SiR93 k1Rb 11Rc m1)γ…(C1-5)
(Rc m1Rb 11R93 k1Si-CH2CH2-R92)γ-X7’-PFPE1-*
*X7’-(R92-CH2CH2-SiR93 k1Rb 11Rc m1)γ…(C2-5)
[in formula, Rf1、PFPE1、R92、R93、Rb、Rc、γ、γ’、X7’, k1,11 and m1 it is identical as above-mentioned meaning.]
By obtained formula (C1-5) or (C2-5) compound represented and Hal-J-R84- CH=CH2(in formula, Hal is indicated Halogen atom (such as I, Br, Cl, F etc.), J indicate Mg, Cu, Pd or Zn, R94Indicate the organic group of singly-bound or divalent.) shown in Compound reaction, obtains formula (C1-6) or (C2-6) compound represented.
(Rf1-PFPE1)γ’-X7’-(R92-CH2CH2-SiRb 11Rc m1(R94- CH=CH2)k1)γ... (C1-6) ((CH=CH2- R94)k1Rc m1Rb 11Si-CH2CH2-R92)γ-X7’-PFPE1-*
*X7’-(R92-CH2CH2-SiRb 11Rc m1(R94- CH=CH2)k1)γ…(C2-6)
[in formula, Rf1、PFPE1、R92、R94、Rb、Rc、γ、γ’、X7’, k1,11 and m1 it is identical as above-mentioned meaning.]
By obtained formula (C1-6) or (C2-6) compound represented and HSiM3(in formula, M is that halogen is former independently Son, R72Or R73, R72At each occurrence independently, the group that indicates hydroxyl or can hydrolyze, R73Distinguish at each occurrence It is independent, indicate hydrogen atom or low alkyl group.) reaction, as needed, above-mentioned halogen atom is made to be transformed to R72Or R73, can obtain Formula (C1 " ') or (C2 " ') compound represented.
(Rf1-PFPE1)γ’-X7’-(R92-CH2CH2-SiRb 11Rc m1(R94-CH2CH2-SiR72 q1R73 r1)k1)γ
…(C1”’)
((R72 q1R73 r1Si-CH2CH2-R94)k1Rc m1Rb 11Si-CH2CH2-R92)γ-X7’-PFPE1-*
*X7’-(R92-CH2CH2-SiRb 11Rc m1(R94-CH2CH2-SiR72 q1R73 r1)k1)γ…(C2”’)
[in formula, Rf1、PFPE1、R72、R73、R92、R94、Rb、Rc、γ、γ’、X7’, k1,11 and m1 it is identical as above-mentioned meaning；
Q1 is at each occurrence 1~3 integer independently；
R1 is at each occurrence 0~2 integer independently.]
In formula (C1 " ') or (C2 " '), from X7’To R92-CH2CH2Part correspond to formula (C1) or (C2) in X7,- R94-CH2CH2Correspond to the Z in formula (C1) or (C2).
Formula (D1) and (D2):
(Rf1-PFPE1)δ’-X9-(CRd k2Re 12Rf m2)δ…(D1)
(Rf m2Re 12Rd k2C)δ-X9-PFPE1-X-(CRd k2Re 12Rf m2)δ…(D2)
In above-mentioned formula (D1) and (D2), Rf1And PFPE1It is identical as the record meaning about above-mentioned formula (A1) and (A2).
In above-mentioned formula, X9Independently, the organic group of singly-bound or 2~10 valences is indicated.The X is in formula (D1) and (D2) institute The perfluoropolyether portion of water-repellancy and surface slip etc. will be mainly provided in the compound shown (that is, Rf1-PFPE1Portion or-PFPE1- Portion) and provide with the combination of substrate can the linker that links of part (that is, with δ and group for being bracketed by bracket).Therefore, As long as the group that the X can be stabilized with formula (D1) and (D2) compound represented, can be arbitrary organic group Group.
In above-mentioned formula, the integer that δ is 1~9, the integer that δ ' is 1~9.These δ and δ ' can change according to the valence mumber of X.? In formula (D1), the sum of δ and δ ' are identical as the valence mumber of X.For example, the sum of δ and δ ' are 10, such as can when X is the organic group of 10 valences It is 9 and δ ' be 1, δ be 5 and δ ' is that 5 or δ is 1 and δ ' is 9 to be δ.In addition, X9For divalent organic group when, δ and δ ' are 1. In formula (D2), δ is from X9Valence mumber subtract 1 obtained value.
Above-mentioned X9Preferably 2~7 valences, more preferably 2~4 valences, the further preferably organic group of divalent.
In a kind of mode, X9For the organic group of 2~4 valences, δ is that 1~3, δ ' is 1.
In another way, X9For the organic group of divalent, δ 1, δ ' is 1.At this point, formula (D1) and (D2) such as following formula Shown in (D1 ') and (D2 ').
Rf1-PFPE1-X9-CRd k2Re 12Rf m2…(D1’)
Rf m2Re 12Rd k2C-X9-PFPE1-X9-CRd k2Re 12Rf m2…(D2’)
As above-mentioned X9Example, be not particularly limited, for example, can enumerate with about X1The identical base of documented group Group.
X as a preferred method,5It can be-Xc- CO-NR14- XdOr-Xc- CO-N (- Xd)2It is shown Group.XcAnd XdWith about above-mentioned X1Be recorded as same position.
Preferred specific X9It can enumerate:
Singly-bound,
- CH2O(CH2)2,
- CH2O(CH2)3,
- CH2O(CH2)6,
- 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,
- CH2OCH2CHFCF2OCF2,
- CH2OCH2CHFCF2OCF2CF2,
- CH2OCH2CHFCF2OCF2CF2CF2,
- CH2OCH2CHFCF2OCF(CF3)CF2OCF2,
- CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2,
- CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2?
- CH2OCF2CHFOCF2CF2CF2- C (O) NH-CH2,
- 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,
(CH2)2- Si (CH3)2(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 above-mentioned formula, RdAt each occurrence independently, expression-Z2- CR81 p2R82 q2R83 r2。
In formula, Z2At each occurrence independently, the organic group of oxygen atom or divalent is indicated.
Above-mentioned Z2Preferably C1-6Alkylidene ,-(CH2)g- O- (CH2)h(in formula, the integer that g is 0~6, for example, 1 ~6 integer, the integer that h is 0~6, for example, 1~6 integer) or-phenylene-(CH2)i(in formula i be 0~6 it is whole Number), more preferably C1-3Alkylidene.These groups can be for example selected from fluorine atom, C1-6Alkyl, C2-6Alkenyl and C2-6Alkynyl In 1 or 1 or more substituent group replace.
In formula, R81At each occurrence independently, R is indicatedd’。Rd’With RdMeaning is identical.
RdIn, via Z2Base connection is that the C of straight-chain is up to 5.In other words, in above-mentioned RdIn, R81At least there is 1 When, RdIn via Z2Base connection is that there are 2 or more for the C atom of straight-chain, but in this way via Z2Base connection is the C of straight-chain The number of atom is up to 5.In addition, " RdIn via Z2Base connection is the number of the C atom of straight-chain " in RdIn with connection For-the Z of straight-chain2The repetition number of-C- is equal.This and the R in formula (C1) and (C2)aIt is related record it is same.
In a preferred manner, " RdIn via Z2Base connection is the number of the C atom of straight-chain " it is 1 in whole chains A (levoform) or 2 (right formula).
In a kind of mode, RdIn via Z2Base connection is that the number of the C atom of straight-chain is 1 or 2, preferably 1 It is a.
In formula, R82Expression-Y-SiR85 n2R86 3-2n。
Y independently, indicates the organic group of divalent at each occurrence.
In a preferred manner, Y C1-6Alkylidene ,-(CH2)g’- O- (CH2)h’(in formula, g ' be 0~6 it is whole Number, for example, 1~6 integer, the integer that h ' is 0~6, for example, 1~6 integer) or-phenylene-(CH2)i’(formula In, i ' be 0~6 integer).These groups can be for example selected from fluorine atom, C1-6Alkyl, C2-6Alkenyl and C2-6In alkynyl 1 or 1 or more substituent group replace.
In a kind of mode, Y can be C1-6Alkylidene ,-O- (CH2)h’Or-phenylene-(CH2)i’?.Y is above-mentioned When group, light patience, particularly ultraviolet resistance can become higher.
Above-mentioned R5At each occurrence independently, the group that indicates hydroxyl or can hydrolyze.
When using in the present specification, above-mentioned " group that can be hydrolyzed " refers to the group that hydrolysis can occur.Make Example for the group that can be hydrolyzed can enumerate-OR ,-OCOR ,-O-N=C (R)2,-N (R)2,-NHR, halogen (this In a little formulas, R indicates the alkyl of substituted or non-substituted carbon atom number 1~4) etc., preferably-OR (alkoxy).In the example of R, Non substituted alkyl including methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group etc.；The substitution alkyl of chloromethyl etc..This In a little, optimizing alkyl, particularly non substituted alkyl, more preferable methyl or ethyl.Hydroxyl is not particularly limited, and can be being capable of water The hydroxyl that hydrolysis generates occurs for the group of solution.
It is preferred that R85For-OR, (in formula, R indicates substituted or non-substituted C1-3Alkyl more preferably indicates ethyl or methyl, spy It is not methyl).
Above-mentioned R86At each occurrence independently, hydrogen atom or low alkyl group are indicated.The low alkyl group is preferably carbon original The alkyl of subnumber 1~20, the more preferably alkyl of carbon atom number 1~6, further preferably methyl.
N2 is in each (- Y-SiR85 n2R86 3-n2) independent in unit, indicate 1~3 integer, preferably 2 or 3, more preferably It is 3.
Above-mentioned R83At each occurrence independently, hydrogen atom or low alkyl group are indicated.The low alkyl group is preferably carbon original The alkyl of subnumber 1~20, the more preferably alkyl of carbon atom number 1~6, further preferably methyl.
In formula, p2 is at each occurrence 0~3 integer independently；Q2 at each occurrence independently, be 0~ 3 integer；R2 is at each occurrence 0~3 integer independently.Wherein, the sum of p2, q2 and r2 are 3.
In a preferred manner, in RdIn end Rd’(R is not presentd’When, it is Rd) in, above-mentioned q2 is preferably 2 or more, For example, 2 or 3, more preferably 3.
In a preferred manner, RdAt least one of terminal part can be-C (- Y-SiR85 q2R86 r2)2Or-C (- Y-SiR85 q2R86 r2)3, preferably-C (- Y-SiR85 q2R86 r2)3.In formula, (- Y-SiR85 q2R86 r2) unit be preferably (- Y-SiR85 3).In further preferred mode, RdTerminal part can all-C (- Y-SiR85 q2R86 r2)3, excellent Select all-C (- Y-SiR85 3)3。
In above-mentioned formula, ReAt each occurrence independently, expression-Y-SiR85 n2R86 3-n2.Wherein, Y, R85、R86And n2 With above-mentioned R82In record meaning it is identical.
In above-mentioned formula, Rf independently, indicates hydrogen atom or low alkyl group at each occurrence.The low alkyl group is preferably The alkyl of carbon atom number 1~20, the more preferably alkyl of carbon atom number 1~6, further preferably methyl.
In formula, k2 is at each occurrence 0~3 integer independently；L2 at each occurrence independently, be 0~ 3 integer；M2 is at each occurrence 0~3 integer independently.Wherein, the sum of k2, l2 and m2 are 3.
In a kind of mode, at least one k2 is 2 or 3, preferably 3.
In a kind of mode, k2 is 2 or 3, preferably 3.
In a kind of mode, l2 is 2 or 3, preferably 3.
In above-mentioned formula (D1) and (D2), at least one q2 is that 2 or 3 or at least one l is 2 or 3.In other words, in formula at least There are 2-Y-SiR85 n2R86 3-n2Base.
Silane compound shown in formula (D1) or formula (D2) containing perfluor (poly-) ether can be by combining well known side Method manufacture.For example, formula (D1 ') compound represented that X is divalent does not limit, it can be such as following manufactures.
At HO-X-C (YOH)3(in formula, X and Y are the organic group of divalent independently.) shown in lead in polyalcohol Enter group containing double bonds (preferably allyl) and halogen (preferably bromine), obtains Hal-X-C (Y-O-R-CH= CH2)3(in formula, Hal is halogen, such as Br, and R is organic group, such as alkylidene of divalent.) shown in halogenation containing double bonds Object.Then, make the halogen and R of endPFPE- OH (in formula, RPFPEFor the group containing holo-fluorine polyester.) shown in contain perfluor The alcohol of polyether-based reacts, and obtains RPFPE- O-X-C (Y-O-R-CH=CH2)3.Then, make-the CH=CH of end2With HSiCl3With alcohol or HSiR85 3Reaction, can obtain RPFPE- O-X-C (Y-O-R-CH2- CH2- SiR85 3)3。
Contain perfluor (poly-) ether shown in above-mentioned formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) Silane compound be not particularly limited, can have 5 × 102~1 × 105Number-average molecular weight.Above-mentioned number-average molecular weight is preferred It is 1,000~30,000, more preferably 2,000~15,000, further preferably 3,000~8,000.
In addition, in the present invention, " number-average molecular weight " by19F-NMR measurement.
Then, perfluor (poly-) ether modified compound shown in above-mentioned formula (E1) is illustrated.
In above-mentioned formula, PFPE2It is and above-mentioned PFPE1Same perfluor (poly-) ether is independently shown in following formula Group.
(OC6F12)a(OC5F10)b(OC4F8)c(OC3F6)d(OC2F4)e(OCF2)f-
In formula, a, b, c, d, e and f are 0 or more 200 integer below independently, and the sum of a, b, c, d, e and f are at least 1.It is preferred that a, b, c, d, e and f are independently, it is 0 or more 100 integer below.It is preferred that the sum of a, b, c, d, e and f are 5 or more, More preferably 10 or more, for example, 10 or more and 100 or less.In addition, being bracketed with a, b, c, d, e or f and by bracket each The presence sequence of repetitive unit is arbitrary in formula.
These repetitive units can be straight-chain, or branched, preferably straight-chain.Such as-(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))-in any number of, preferably-(OCF2CF2CF2CF2)-.(OC3F6)-can be with For-(OCF2CF2CF2)-,-(OCF (CF3)CF2)-and-(OCF2CF(CF3))-in it is any number of, preferably- (OCF2CF2CF2)-.In addition ,-(OC2F4)-can be-(OCF2CF2)-and-(OCF (CF3))-in it is any number of, it is excellent It is selected as-(OCF2CF2)-.
In a kind of mode, above-mentioned PFPE2For-(OC3F6)d(in formula, d is 1 or more 200 or less, preferably 5 or more 200 or less, 10 or more 200 integers below are more preferably).It is preferred that PFPE2For-(OCF2CF2CF2)d(in formula, d is 1 or more 200 or less, preferably 5 or more 200 or less, more preferable 10 or more 200 integer below) or-(OCF (CF3)CF2)d(in formula, d For 1 or more 200 or less, preferably 5 or more 200 or less, more preferable 10 or more 200 integer below).More preferable PFPE2For- (OCF2CF2CF2)d(d is 1 or more 200 or less, preferably 5 or more 200 or less, more preferable 10 or more 200 below whole in formula Number).
In another way, PFPE2For-(OC4F8)c(OC3F6)d(OC2F4)e(OCF2)f(c and d points in formula It is not independent, be 0 or more 30 integer below, e and f independently, be 1 or more 200 or less, preferably 5 or more 200 or less, it is more excellent 10 or more 200 integers below are selected, the presence sequence with subscript c, d, e or f and each repetitive unit for being bracketed by bracket exists It is arbitrary in formula).It is preferred that PFPE2For-(OCF2CF2CF2CF2)c(OCF2CF2CF2)d(OCF2CF2)e(OCF2)f?. In a kind of mode, PFPE2It can be-(OC2F4)e(OCF2)f(in formula, e and f independently, be 1 or more 200 or less, It is preferred that 5 or more 200 or less, more preferable 10 or more 200 integer below, with subscript e or f and each repetition for being bracketed by bracket The presence sequence of unit is arbitrary in formula).
In another way in turn, PFPE2For-(R6- R7)qShown in group.In formula, R6For OCF2Or OC2F4, excellent It is selected as OC2F4.In formula, R7For selected from OC2F4、OC3F6、OC4F8、OC5F10And OC6F12In group, or to be independently selected from these The combination of 2 or 3 groups of group.It is preferred that R7For selected from OC2F4、OC3F6And OC4F8In group, or to be independently selected from this The combination of 2 or 3 groups of a little groups.As being independently selected from OC2F4、OC3F6And OC4F82 or 3 groups combination, do not have It is particularly limited to, such as-OC can be enumerated2F4OC3F6,-OC2F4OC4F8,-OC3F6OC2F4,- OC3F6OC3F6,-OC3F6OC4F8,-OC4F8OC4F8,-OC4F8OC3F6,-OC4F8OC2F4,- OC2F4OC2F4OC3F6,-OC2F4OC2F4OC4F8,-OC2F4OC3F6OC2F4,-OC2F4OC3F6OC3F6,- OC2F4OC4F8OC2F4,-OC3F6OC2F4OC2F4,-OC3F6OC2F4OC3F6,-OC3F6OC3F6OC2F4And- OC4F8OC2F4OC2F4Etc..The integer that above-mentioned q is 2~100, preferably 2~50 integer.In above-mentioned formula, OC2F4、OC3F6、 OC4F8、OC5F10And OC6F12It can be any of linear chain or branched chain, preferably straight chain.In this approach, PFPE2Preferably- (OC2F4- OC3F6)qOr-(OC2F4- OC4F8)q?.
In above-mentioned formula, Rf2Indicate the alkyl for the carbon atom number 1~16 that can be replaced by 1 or 1 or more fluorine atom.
" carbon atom number 1 in the alkyl of the above-mentioned carbon atom number 1~16 that can be replaced by 1 or 1 or more fluorine atom ~16 alkyl " can may be branch for straight chain, preferably the carbon atom number 1~6, particularly carbon atom of linear chain or branched chain The alkyl of number 1~3, the more preferably alkyl of the carbon atom number 1~3 of straight chain.
Above-mentioned Rf2It is preferred that the alkyl for the carbon atom number 1~16 that can be replaced by 1 or 1 or more fluorine atom, more preferably For CF2H-C1-15Fluorianted alkylene, the further preferably perfluoroalkyl of carbon atom number 1~16.
The perfluoroalkyl of the carbon atom number 1~16 can may be branch for straight chain, preferably the carbon of linear chain or branched chain The perfluoroalkyl of atomicity 1~6, particularly carbon atom number 1~3, the more preferably perfluoroalkyl of the carbon atom number 1~3 of straight chain, Specifically-CF3,-CF2CF3Or-CF2CF2CF3。
In above-mentioned formula, Z2Indicate the organic group of singly-bound or divalent.
Above-mentioned Z2In the organic group of divalent be preferably
(CR18 2)k7(O)k8(NR19)k9,
[in formula:
R18It independently, is hydrogen atom or fluorine atom；
R19Independently, hydrogen atom, phenyl or C are indicated1-6Alkyl；
The integer that k7 is 1~20；
The integer that k8 is 0~10；
The integer that k9 is 0~10；
Wherein, the presence sequence with k7, k8 or k9 and each repetitive unit for being bracketed by bracket is any in formula 's.].
Preferred Z2For
(CF2)k7’Or-(CF2)k7’(O)k8’?
[in formula:
The integer that k7 ' is 1~6；
The integer that k8 ' is 1~3；
Wherein, the presence sequence for each repetitive unit for having k7 ' or k8 ' and being bracketed by bracket is any in formula 's.].
In above-mentioned formula, x is 1 or 2, and when x is 1, A is-COOR3,-PO (OR3)2,-SO2(OR3) or-SO (OR3), x is When 2, A is-PO (OR3)-.In addition, when x is 2,2 Rf2- PFPE2It can be the same or different.
In above-mentioned formula, R3For hydrogen atom or alkyl.
As above-mentioned alkyl, the preferably alkyl of carbon atom number 1~6, the preferably alkyl of carbon atom number 1~3, more preferably may be used Think methyl.
In a preferred manner, 1 x, A are-COOR3。
In a kind of preferred mode, x 1, A are-COOH.
In another preferred mode, x 1, A are-COOCH3。
It is above-mentioned containing perfluor (poly-) ether that perfluor (poly-) ether modified compound shown in above-mentioned formula (E1) can be synthesis The unreacted reactant of raw material compound when silane compound is also possible to the compound in addition added.In addition the compound added It can be compound identical with compound used in synthesis, be also possible to different compounds.
Perfluor (poly-) ether modified compound shown in above-mentioned formula (E1) is not particularly limited, and can have 5 × 102~1 × 105Number-average molecular weight.Above-mentioned number-average molecular weight is preferably 1,000~30,000, more preferably 2,000~15,000, into one Step preferably 3,000~8,000.
In a preferred manner, contain shown in above-mentioned formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) or (D2) There is the number of the number-average molecular weight of the silane compound of perfluor (poly-) ether with perfluor (poly-) ether modified compound shown in formula (E1) The difference of average molecular weight is within 2,000, within preferably 1,500, within more preferable 1,000, within further preferably 500.
In composition of the invention, the above-mentioned silane compound containing perfluor (poly-) ether and above-mentioned perfluor (poly-) ether are modified The ratio of the content of compound is 99.99: 0.01~70: 30, preferably 99.5: 0.5~80: 20, more preferably 99: 1~90: 10.By being set as such range, perfluor (poly-) ether modified compound can efficiently be catalyzed the silicon containing perfluor (poly-) ether Hydride compounds are reacted with substrate.
In a kind of mode, the above-mentioned silane compound containing perfluor (poly-) ether in the present composition and above-mentioned complete The ratio of the content of fluorine (poly-) ether modified compound is 99.99: 0.01~97: 3, preferably 99.9: 0.1~98: 2.In another party The above-mentioned silane compound containing perfluor (poly-) ether and above-mentioned perfluor (poly-) ether modified compound in formula, in the present composition The ratio of the content of object is 95: 5~70: 30, preferably 92: 8~80: 20.
In addition to the above-mentioned silane compound containing perfluor (poly-) ether and above-mentioned perfluor (poly-) ether change in the present composition Other than property compound, other ingredients can also be contained.It as such other ingredients, is not particularly limited, such as can enumerate Other surface treatment compounds, (non-reacted) the fluoropolyether compound that can be used as fluorine-containing oil understanding are preferably complete Fluorine (poly-) ether compound (hereinafter also referred to as " fluorine-containing oil "), (non-reacted) organosilicon compound that can be used as silicone oil understanding Object (hereinafter also referred to as " silicone oil "), catalyst etc..
It as above-mentioned fluorine-containing oil, is not particularly limited, such as following general formula (3) compound represented (perfluor can be enumerated (poly-) ether compound).
Rf5(OC4F8)a’(OC3F6)b’(OC2F4)c’(OCF2)d’- Rf6…(3)
In formula, Rf5Indicate the C that can be replaced by 1 or 1 or more fluorine atom1-16Alkyl (preferably C1―16Perfluor Alkyl), Rf6Indicate the C that can be replaced by 1 or 1 or more fluorine atom1-16Alkyl (preferably C1-16Perfluoroalkyl), Fluorine atom or hydrogen atom, Rf5And Rf6It more preferably independently, is C1-3Perfluoroalkyl.
A ', b ', c ' and d ' respectively indicate 4 kinds of number of repeat unit for constituting perfluor (poly-) ether of main framing of polymer, phase It mutually independently, is 0 or more 300 integer below, the sum of a ', b ', c ' and d ' at least 1, preferably 1~300, more preferably 20~ 300.It is arbitrary in formula with subscript a ', b ', c ' or d ' and by the presence sequence for each repetitive unit that bracket brackets.This In a little repetitive units ,-(OC4F8)-can 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))-in it is any number of, preferably- (OCF2CF2CF2CF2)-.(OC3F6)-can be-(OCF2CF2CF2)-,-(OCF (CF3)CF2)-and-(OCF2CF (CF3))-in any number of, preferably-(OCF2CF2CF2)-.(OC2F4)-can be-(OCF2CF2)-and-(OCF (CF3))-in any number of, preferably-(OCF2CF2)-.
As the example of perfluor (poly-) ether compound shown in above-mentioned general formula (3), can enumerate following general formula (3a) and Any one of (3b) compound represented (can be one kind or two or more mixture).
Rf5(OCF2CF2CF2)b”- Rf6…(3a)
Rf5(OCF2CF2CF2CF2)a”(OCF2CF2CF2)b”(OCF2CF2)c”(OCF2)d”- Rf6…(3b)
In these formulas, Rf5And Rf6As described above；B " is 1 or more 100 integer below in formula (3a)；In formula (3b), A " and b " is 1 or more 30 integer below independently, and c " and d " are 1 or more 300 integer below independently.It has down It marks a ", b ", c ", d " and is arbitrary in formula by the presence sequence for each repetitive unit that bracket brackets.
Above-mentioned fluorine-containing oil can have 1,000~30,000 average molecular weight.It is sliding thereby, it is possible to obtain high surface Property.
In composition of the invention, relative to above-mentioned silane compound and above-mentioned perfluor (poly-) containing perfluor (poly-) ether Ether modified compound total 100 mass parts (respectively two or more when for the total of them, below similarly), such as can be with Contain fluorine-containing oil with 0~500 mass parts, preferably 0~400 mass parts, more preferable 5~300 mass parts.
General formula (3a) compound represented and general formula (3b) compound represented can be used alone respectively, can also combine It uses.Compared with general formula (3a) compound represented, when using general formula (3b) compound represented, available higher surface Slip, so it is preferred that.When they are applied in combination, the matter of general formula (3a) compound represented and general formula (3b) compound represented Amount is than preferably 1: 1~1: 30, more preferably 1: 1~1: 10.According to such mass ratio, surface slip and friction can be obtained The surface-treated layer of the balancing good of durability.
In a kind of mode, fluorine-containing oil contains a kind or a kind or more shown in general formula (3b) of compound.In this mode In, the above-mentioned silane compound containing perfluor (poly-) ether and above-mentioned perfluor (poly-) ether modified compound in surface treating agent Total mass ratio with formula (3b) compound represented is preferably 4: 1~1: 4.
In a preferred manner, when forming surface-treated layer by vacuum vapour deposition, contain perfluor (poly-) ether with above-mentioned Silane compound compared with the average molecular weight of above-mentioned perfluor (poly-) ether modified compound, the average mark of fluorine-containing oil can be increased Son amount.By being formed as such average molecular weight, superior friction durability and surface slip can be obtained.
In addition, fluorine-containing oil can (in formula, Rf ' be C for general formula R f '-F from the viewpoint of not5-16Perfluoroalkyl.) institute The compound shown.Furthermore it is possible to be chlorotrifluoroethylene oligomer.It is obtaining and Rf1For C1-16Perfluoroalkyl it is above-mentioned containing complete The aspect of the high-affinity of the silane compound of fluorine (poly-) ether, preferably Rf '-F compound represented and chlorotrifluoroethylene oligomerization Object.
Fluorine-containing oil helps to improve the surface slip of surface-treated layer.
As above-mentioned silicone oil, it is 2,000 straight-chain below or cricoid silicone oil that siloxanes key, which can be used for example,.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, hydrogenated methyl silicone oil.As modified silicon oil, it can enumerate and common silicone oil is utilized into alkyl, aralkyl, polyethers, advanced The modified obtained silicone oil such as aliphatic ester, fluoro-alkyl, amino, epoxy group, carboxyl, alcohol.Cricoid silicone oil, such as can enumerate Ring shape dimethylsiloxane oil etc..
In composition of the invention, relative to above-mentioned silane compound and above-mentioned perfluor (poly-) containing perfluor (poly-) ether Total 100 mass parts (being the total of them when for two or more, below similarly) of ether modified compound, for example, can with 0~ 300 mass parts, preferably 0~200 mass parts contain such silicone oil.
Silicone oil helps to improve the surface slip 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 silane compound containing perfluor (poly-) ether, promotes at surface Manage the formation of layer.
Composition of the invention can be the form of a kind of solution (or suspension or dispersion liquid), or be also possible to divide The solution of other above-mentioned silane compound containing perfluor (poly-) ether and above-mentioned perfluor (poly-) ether modified compound will make With preceding mixed form.
Composition of the invention can be impregnated in porous mass, for example porous ceramic material, metallic fiber, for example by steel Silk flosssilk wadding is collected as in the material of cotton like, is formed as pellet.The pellet for example can be used in vacuum evaporation.
It is durable that composition of the invention can assign water-repellancy, group oiliness, soil resistance, waterproofness and high friction to substrate Property, therefore surface treating agent use can be work perfectly well as.It, can be with specifically, composition of the invention is not particularly limited It is work perfectly well as soil resistance coating agent or waterproofness coating agent uses.
Then, article of the invention is illustrated.
Article of the invention includes substrate and the layer formed on the surface of the substrate by the present composition (surface treatment Layer).The article can for example be manufactured by such as operations described below.
Firstly, preparing substrate.The substrate being able to use in the present invention, such as can be by glass, sapphire glass, resin (can be natural or synthetic resin, for example general plastic material, can be plate, film, other form), metal (can be with For the complex of the metal simple-substance of aluminium, copper, iron etc. or alloy etc.), ceramics, semiconductor (silicon, germanium etc.), fiber (fabric, non-woven fabrics Deng), fur, leather, timber, pottery chinaware, stone material etc., the arbitrary suitable material such as building component constitute.
As above-mentioned glass, preferably soda-lime glass, alkali alumina silicate glass, pyrex, alkali-free glass, crystal glass Glass, quartz glass, the soda-lime glass particularly preferably through chemical strengthening, the alkali alumina silicate glass through chemical strengthening and chemistry knot Pyrex after conjunction.
As resin, preferred acrylic resins, polycarbonate.
For example, it can be used for optical part for constituting the material on the surface of substrate when the article to be manufactured is optical component Material, such as glass or transparent plastic.In addition, the article to be manufactured be optical component when, can the surface of substrate (most Outer layer) it is formed with certain layer (or film), such as hard conating, anti-reflection layer.Anti-reflection layer can be used single layer anti-reflection layer and Multilayer anti-reflection layer it is any.As SiO can be enumerated in the example for the inorganic matter that anti-reflection layer uses2、SiO、 ZrO2、TiO2、TiO、Ti2O3、Ti2O5、Al2O3、Ta2O5、CeO2、MgO、Y2O3、SnO2、MgF2、WO3Deng.These inorganic matters can be with Individually or by these two or more combination (such as mixture) use.When being formed as multilayer anti-reflection layer, preferably at it Outermost layer uses SiO2And/or SiO.It, can be in substrate when the article to be manufactured is the optical glass component of touch panel The a part on the surface of (glass) has transparent electrode, the film such as using tin indium oxide (ITO), indium zinc oxide.In addition, Substrate can have insulating layer, adhesive layer, protective layer, adornment frame layer (I-CON), sprayed film according to its specific specification etc. Layer, hard coat film, light polarizing film, phase difference film and LCD assembly etc..
The shape of substrate is not particularly limited.Additionally, it should which the surface region for forming the substrate of surface-treated layer is substrate At least part on surface can be suitably determined according to the purposes for the article to be manufactured and specific specification etc..
As such substrate, the substrate that at least by script there is the material of hydroxyl to be formed in its surface portion can be. As such material, glass can be enumerated, forms the metal of natural oxide film or heat oxide film on surface furthermore it is possible to enumerate (especially base metal), ceramics, semiconductor etc..Alternatively, as resin etc. have hydroxyl but it is insufficient when or originally do not have When having hydroxyl, hydroxyl can be imported to the surface of substrate, or increase hydroxyl by implementing certain pre-treatment to substrate.As this The example of the pre-treatment of sample can enumerate corona treatment (such as corona discharge), ion beam irradiation.Corona treatment energy It is enough that substrate surface is imported or increases hydroxyl, also, can also be suitably used for keeping substrate surface purifying (removing foreign matter etc.). In addition, another example as such pre-treatment, the method that can be listed below: will be with carbon-to-carbon unsaturation combination base Interfacial Adsorption agent is using LB method (Langmuir-Blodgett method) or chemiadsorption etc., in substrate surface in advance with unimolecule The form of film is formed, and disconnects unsaturated bond under the atmosphere containing aerobic, nitrogen etc. later.
In addition, alternatively, can be at least its surface portion as such substrate and have by other reactive groups, for example The substrate for thering are the organo-silicon compound of more than one Si-H base, the material containing alkoxy silane to be formed.
Then, the film of aforementioned present invention composition is formed on the surface of this substrate, after carrying out as needed to the film Reason, forms surface-treated layer by the present composition as a result,.
The film of the present composition is formed, and the present invention can be applied in a manner of covering the surface the surface to substrate Composition implement.Covering method is not particularly limited.For example, being able to use wet cladding process and dry 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 (in general, vacuum evaporation), sputtering, CVD and similar side can be enumerated Method.As the concrete example of vapour deposition method (in general, vacuum vapour deposition), resistance heating, electron beam can be enumerated, using the height of microwave etc. Frequency heating, ion beam and similar method.As the concrete example of CVD method, can enumerate plasma-CVD, optics CVD, Hot CVD and similar method.
In addition, can also be covered using ordinary pressure atmospheric plasma method.
When using wet cladding process, composition of the invention is applied to substrate surface after capable of being diluted with solvent.From this hair , it is preferable to use following solvent from the viewpoint of the stability of bright composition and the volatility of solvent: C5-12Perfluorinated polyether Hydrocarbon (for example, perflexane, perfluoromethylcyclohexane (PFMCH) and perfluor -1,3- dimethyl cyclohexane)；Poly- fluoro aromatic hydrocarbon (example Such as, bis- (trifluoromethyl) benzene)；Poly- fluorinated aliphatic hydrocarbon is (for example, C6F13CH2CH3(for example, manufactured by Asahi Glass Co., Ltd ASAHIKLIN (registered trademark) AC-6000), 1,1,2,2,3,3,4- seven fluorine pentamethylene is (for example, ZEON Co., Ltd., Japan ZEORORA (registered trademark) H of manufacture)；Hydrofluorocarbon (HFC) (for example, 1,1,1,3,3- 3-pentafluorobutane (HFC-365mfc))； Hydrochlorofluorocarazeotropic (for example, HCFC-225 (ASAHIKLIN (registered trademark) AK225))；Hydrofluoroether (HFE) is (for example, the third first of perfluor Ether (C3F7OCH3) (for example, Novec (trade (brand) name) 7000 of Sumitomo 3M Co., Ltd. manufacture), perfluor fourth methyl ether (C4F9OCH3) (for example, Novec (trade (brand) name) 7100 of Sumitomo 3M Co., Ltd. manufacture), perfluor fourth ether (C4F9OC2H5) (for example, Sumitomo 3M Co., Ltd. manufacture Novec (trade (brand) name) 7200), the own methyl ether (C of perfluor2F5CF(OCH3)C3F7) (for example, Sumitomo 3M plants of formula meeting The Novec (trade (brand) name) 7300 of society's manufacture) etc. alkyl perfluoroalkyl ethers (perfluoroalkyl and alkyl can be linear chain or branched chain Shape) or CF3CH2OCF2CHF2(for example, ASAHIKLIN manufactured by Asahi Glass Co., Ltd (registered trademark) AE-3000)), 1, 2- bis- chloro- 1,3,3,3- tetrafluoro-1-propenes (for example, the manufacture of three well Dupon Fluoro Chemical companies Vertrel (registered trademark) SION) etc..These solvents can be used alone or combine two or more and use as mixture. In addition, such as the dissolubility in order to adjust the silane compound containing perfluor (poly-) ether and perfluoropolyether-modified compound, Also it can be mixed with other solvents.
When using dry cladding process, composition of the invention is used directly for dry cladding process, or can also be in benefit With above-mentioned solvent dilution later for drying cladding process.
Film formed preferably in film the present composition with for hydrolyze and the catalyst of dehydrating condensation together with it is existing Mode is implemented.Briefly, when using wet cladding process, after the present composition being diluted with solvent, will Before substrate surface, catalyst is added in the dilution of the present composition.It, can be with when using dry cladding process By the present composition for being added to catalyst be directly deposited (in general, vacuum evaporation) processing, or can be used iron, The partical substance for being impregnated with the present composition added with catalyst in the metal porous body of copper etc. be deposited (in general, Vacuum evaporation) processing.
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 that can more specifically implement such as operations described below.
As described above after the film that substrate surface forms the present composition, to the film (hereinafter also referred to as " precursor Film ") supply moisture.The supply method of moisture is not particularly limited, and can be used for example and utilizes precursor film (and substrate) and surrounding The method of the moisture condensation or vapor (steam) of the temperature difference of atmosphere blowed etc..
The supply of moisture can such as 0~250 DEG C, preferably 60 DEG C or more, be more preferably 100 DEG C or more, it is excellent It is selected as implementing under 180 DEG C or less, further preferably 150 DEG C of atmosphere below.By supplying moisture, energy in the temperature range Enough carry out hydrolysis.Pressure at this time is not particularly limited, and briefly can be set to normal pressure.
Then, which is heated under the drying atmosphere more than 60 DEG C on the surface of the substrate.Dry heat Method is not particularly limited, and precursor film is configured in the temperature more than 60 DEG C, preferably greater than 100 DEG C together with substrate and is, for example, At 250 DEG C or less, preferably 180 DEG C temperature below and the atmosphere of unsaturated water vapor pressure.Pressure at this time is without spy It does not limit, briefly can be set to normal pressure.
Under such atmosphere, between the silane compound containing perfluor (poly-) ether of the invention, after hydrolysis with Rapid dehydration is condensed the group that Si is combined each other.In addition, between such compound and substrate, after the hydrolysis of the compound It is reacted rapidly between group and the reactive group for being present in substrate surface in conjunction with Si, is present in the reactivity of substrate surface When being hydroxyl dehydrating condensation occurs for group.As a result, being formed between silane compound and substrate containing perfluor (poly-) ether Key.
Above-mentioned moisture supply and dry heat can continuously be implemented by using overheated steam.
It can implement to post-process such as aforesaid operations.Such post-processing can in order to further increase friction durability and reality It applies, but needing to pay attention to it not is necessary to manufacture article of the invention.For example, composition of the invention is applied to substrate It, can also be only to stand as former state after surface.
Such as aforesaid operations, the surface-treated layer of the film from the present composition is formed on the surface of substrate, manufactures this hair Bright article.Thus obtained surface-treated layer has high friction durability.In addition, the surface-treated layer is in addition to high friction Other than durability, according to the composition of used composition, it is possible to have water-repellancy, dial oiliness, soil resistance (such as prevents from referring to The attachment of the pollution of line etc.), surface slip (or lubricity, the property wiped of the pollution such as fingerprint, the excellent touching to finger Sense) etc., it can be used as functional film and suitably utilize.
In other words, the invention further relates to the optical materials in outermost layer with above-mentioned solidfied material.
As optical material, other than the optical material in relation to display etc. illustrated by aftermentioned, can 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 are aobvious Show device (FED；Field Emission Display) etc. display or these displays protection board or surface to them Implement the optical material of antireflection film processing.
Article with the surface-treated layer obtained through the invention is not particularly limited, and can be optical component.Optics The example of component can be listed below article: the lens of glasses etc.；Front protecting plate, the antireflection of the display of PDP, LCD etc. Plate, polarizer, anti-dazzle tabula rasa；The touch surface plate of the equipment such as portable phone, portable information terminal；Blue light (Blu-ray (registration Trade mark)) disk, DVD disc, CD-R, MO etc. CD disk；Optical fiber etc..
In addition, the article with the surface-treated layer obtained through the invention may be Medical Devices or medical material.
The thickness of surface-treated layer is not particularly limited.It is resistance to from optical property, surface slip, friction when for optical component From the aspect of long property and soil resistance, preferably surface-treated layer with a thickness of 1~50nm, preferably 1~30nm, more preferably 1 The range of~15nm.
More than, the article for using the present composition to obtain is elaborated.In addition, composition of the invention Purposes, application method and manufacturing method of article etc. are not limited to foregoing illustrative content.
Embodiment
For composition of the invention, it is specifically described by embodiment below, but the present invention is not limited to These embodiments.In addition, chemical formula as shown below all indicates average composition in the present embodiment, the weight of perfluoropolyether is constituted Multiple unit (CF2CF2CF2O presence sequence) is arbitrary.
Synthesis example 1
The synthesis of perfluoropolyether-modified methyl ester compound
In the reactor, it is packed into methanol 240g, triethylamine 19.6g, under stream of nitrogen gas, in 5 DEG C of dropwise addition average compositions CF3CF2CF2O(CF2CF2CF2O)32CF2CF2Perfluoropolyether-modified acid fluorine compounds 500g shown in COF is warming up to room later Temperature is stirred.Then, after adding perflexane 300g and stirring, be transferred to separatory funnel, after standing, point take perfluor oneself Alkane layer.Then, cleaning operation is carried out using 3 equivalent aqueous hydrochloric acid solutions.Then, anhydrous magnesium sulfate 30g is added in perflexane layer, After stirring, it is separated by filtration insoluble matter.Then, volatile ingredient is distilled off under reduced pressure, obtains that there is methyl esters in end as a result, Following perfluoropolyether-modified methyl ester body (A) 476g of base.
Perfluoropolyether-modified methyl ester compound (A):
CF3CF2CF2O(CF2CF2CF2O)32CF2CF2CO2CH3
Synthesis example 2
The synthesis of perfluoropolyether-modified carboxylic acid compound
In the reactor, it is packed into pure water 100g, triethylamine 20.4g, under stream of nitrogen gas, in 5 DEG C of dropwise addition average compositions CF3CF2CF2O(CF2CF2CF2O)32CF2CF2Perfluoropolyether-modified acid fluorine compounds 500g shown in COF is warming up to room later Temperature is stirred.Then, after adding perflexane 400g and stirring, be transferred to separatory funnel, after standing, point take perfluor oneself Alkane layer.Then, cleaning operation is carried out using 3 equivalent aqueous hydrochloric acid solutions.Then, anhydrous magnesium sulfate 30g is added in perflexane layer, After stirring, it is separated by filtration insoluble matter.Then, volatile ingredient is distilled off under reduced pressure, obtains that there is carboxylic acid in end as a result, Following perfluoropolyether-modified carboxylic acid compound (B) 476g of base.
Perfluoropolyether-modified carboxylic acid compound (B):
CF3CF2CF2O(CF2CF2CF2O)32CF2CF2CO2H
Synthesis example 3
The synthesis of perfluoropolyether-modified phosphate compound
In the reactor, it is packed into bis- (trifluoromethyl) the benzene 200g of 1,3-, phosphoryl chloride phosphorus oxychloride 54.5g, under stream of nitrogen gas, with 5 DEG C Average composition CF is added dropwise3CF2CF2O(CF2CF2CF2O)32CF2CF2CH2Perfluoropolyether-modified alcoholic compound 200g shown in OH, it Afterwards, it is warming up to room temperature, is stirred.Then, after adding perflexane 400g and stirring, pure water 100g is added dropwise, is stirred. Later, it is transferred to separatory funnel, after standing, point takes perflexane layer.Then, cleaning behaviour is carried out using 3 equivalent aqueous hydrochloric acid solutions Make.Then, anhydrous magnesium sulfate 10g is added in perflexane layer, after stirring, is separated by filtration insoluble matter.Then, it steams under reduced pressure Volatile ingredient is removed in distillation, obtains the following perfluoropolyether-modified phosphate compounds (C) for having phosphate in end as a result, 202g。
Phosphate compound (C) containing holo-fluorine polyester:
CF3CF2CF2O(CF2CF2CF2O)32CF2CF2CH2OP (=O) (OH)2
Embodiment 1
Perfluoropolyether-modified methyl ester compound (A) obtained in above-mentioned synthesis example 1 and following shown perfluoropolyether are changed Property silane compound (X) with 2 ﹕ 98 of molar ratio mixing, be dissolved in Novec7200 (manufacture of 3M company), be 20wt%'s with concentration Mode prepares surface treating agent 1.
Perfluoropolyether-modified silane compound (X)
CF3CF2CF2O(CF2CF2CF2O)32CF2CF2CH2OCH2CH2CH2Si(OCH3)3
By the surface treating agent 1 of above-mentioned preparation in chemically reinforced glass (manufacture of Coming company, " Gorilla " glass, thickness Degree 0.7mm) on carry out vacuum evaporation.The treatment conditions of vacuum evaporation are set as pressure 3.0 × 10-3Pa, firstly, utilizing electron ray Silica with the thickness of 7nm, is deposited vapor deposition mode on the surface of the chemically reinforced glass, forms silicon dioxide film, Then, surface treating agent 2mg is deposited to every 1 piece of chemically reinforced glass (55mm × 100mm).Later, the change of evaporation film will be had Strengthened glass is learned to stand 24 hours under the atmosphere of 20 DEG C of temperature and humidity 65%.Evaporation film solidifies as a result, forms surface treatment Layer.
(embodiment 2~9)
By perfluoropolyether-modified compound (A)~(C) and perfluoropolyether-modified silane compound (X)~(Z) with following tables Combination with molar ratio 2: 98 mixing, surface treating agent is made, in addition to this, operates similarly to Example 1, preparation surface treatment Agent forms surface-treated layer.
Perfluoropolyether-modified silane compound (Y)
CF3CF2CF2O(CF2CF2CF2O)32CF2CF2CON(CH3)CH2CH2CH2Si(OCH3)3
Perfluoropolyether-modified silane compound (Z)
CF3CF2CF2O(CF2CF2CF2O)32CF2CF2CH2OCH2CH2CH2Si[CH2CH2CH2Si(OCH3)3]3
[table 1]
Embodiment Perfluoropolyether-modified compound Perfluoropolyether-modified silane compound
Embodiment 1 (A) (X)
Embodiment 2 (A) (Y)
Embodiment 3 (A) (Z)
Embodiment 4 (B) (X)
Embodiment 5 (B) (Y)
Embodiment 6 (B) (Z)
Embodiment 7 (C) (X)
Embodiment 8 (C) (Y)
Embodiment 9 (C) (Z)
Comparative example 1~3
Other than above-mentioned perfluoropolyether-modified silane compound (X)~(Z) is used alone, grasp similarly to Example 1 Make, prepare surface treating agent, forms surface-treated layer.
[table 2]
Comparative example Perfluoropolyether-modified silane compound
Comparative example 1 (X)
Comparative example 2 (Y)
Comparative example 3 (Z)
Comparative example 4
Surface treatment is made by mixing with molar ratio 2: 98 in acetic acid and above-mentioned perfluoropolyether-modified silane compound (X) Agent operates similarly to Example 1 in addition to this, prepares surface treating agent, forms surface-treated layer.
To the surface-treated layer formed in above-described embodiment 1~9, comparative example 1~4 in substrate surface, pass through rubber friction Endurance test, evaluation friction durability.Specifically, the sample item horizontal arrangement that will form surface-treated layer, makes rubber (manufacture of KOKUYO Co., Ltd., KESHI-70, planar dimension 1cm × 1.6cm) is contacted with the surface of surface-treated layer, on it Apply 500gf load, later, apply load in the state of make rubber with 20mm/ seconds speed back and forth.Number of rounds is every The static contact angle (degree) of 500 measurement water.The measured value of contact angle stops evaluation when being lower than 100 degree.It is most followed by the expression of table 3 Number of rounds when feeler is more than 100 degree.
[table 3]
Rubber is durable (secondary)
Embodiment 1 3,500
Embodiment 2 4,000
Embodiment 3 7,000
Embodiment 4 3,000
Embodiment 5 4,000
Embodiment 6 7,000
Embodiment 7 2,500
Embodiment 8 3,500
Embodiment 9 6,500
Comparative example 1 1,500
Comparative example 2 2,000
Comparative example 3 5,000
Comparative example 4 1,500
Confirmed according to the above results, with 1~3 phase of comparative example that the silane compound containing perfluor (poly-) ether is used alone Than the Examples 1 to 9 that the silane compound containing perfluor (poly-) ether and perfluoropolyether-modified compound is applied in combination has height Rubber patience.Although the present invention is not limited by any theory system, it is believed that when making surface-treated layer, perfluor Polyether-modified compound (A)~(C) plays a role as acid catalyst, improves the silane chemical combination for containing perfluor (poly-) ether Object (X)~(Z) and substrate surface reactivity, as a result, obtaining excellent rubber durability.In addition it confirms, and uses The comparative example 4 for being purely by way of the acetic acid that catalyst functions is compared, and the implementation of perfluoropolyether-modified carboxylic acid compound (B) is used Example 4 has high rubber patience.Although the present invention is without being bound by any theory, it is believed that this is because: since acid has There is holo-fluorine polyester, so that its own can aid in the function of surface-treated layer.
Industrial utilizability
The present invention can be suitably used for the surface in various substrates, particularly the optical component for requiring permeability Form surface-treated layer.

Claims (35)

1. a kind of composition, which is characterized in that contain:
It is at least one kind of shown in any general formula in the following general formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) to contain There is the silane compound of perfluor (poly-) ether；With at least one kind of compound shown in following formula (E1),
(Rf1-PFPE1)β’-X5-(SiR1 n1R2 3-n1)β …(B1)
(R2 3-n1R1 n1Si)β-X5-PFPE1-X5-(SiR1 n1R2 3-n1)β …(B2)
(Rf1-PFPE1)γ’-X7-(SiRa k1Rb l1Rc m1)γ …(C1)
(Rc m1Rb l1Ra k1Si)γ-X7-PFPE1-X7-(SiRa k1Rb l1Rc m1)γ …(C2)
(Rf1-PFPE1)δ’-X9-(CRd k2Re l2Rf m2)δ …(D1)
(Rf m2Re l2Rd k2C)δ-X9-PFPE1-X-(CRd k2Re l2Rf m2)δ …(D2)
In formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2):
PFPE1At each occurrence independently, it is group shown in following formula:
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f-
In formula, a, b, c, d, e and f are 0 or more 200 integer below independently, and the sum of a, b, c, d, e and f are at least 1, band There are a, b, c, d, e or f and be arbitrary in formula by the presence sequence for each repetitive unit that bracket brackets,
Rf1At each occurrence independently, the carbon atom number 1~16 that can be replaced by 1 or 1 or more fluorine atom is indicated Alkyl；
R1At each occurrence independently, the group that indicates hydroxyl or can hydrolyze；
R2At each occurrence independently, the alkyl of hydrogen atom or carbon atom number 1~22 is indicated；
R11At each occurrence independently, hydrogen atom or halogen atom are indicated；
R12At each occurrence independently, hydrogen atom or low alkyl group are indicated；
N1 is in each (- SiR1 n1R2 3-n1) in unit independently, be 0~3 integer；
Wherein, in formula (A1), (A2), (B1) and (B2), at least one n1 be 1~3 integer；
X1Independently, the organic group of singly-bound or 2~10 valences is indicated；
X2At each occurrence independently, the organic group of singly-bound or divalent is indicated；
T is at each occurrence 1~10 integer independently；
α is 1~9 integer independently；
α ' is 1~9 integer independently；
X5Independently, the organic group of singly-bound or 2~10 valences is indicated；
β is 1~9 integer independently；
β ' is 1~9 integer independently；
X7Independently, the organic group of singly-bound or 2~10 valences is indicated；
γ is 1~9 integer independently；
γ ' is 1~9 integer independently；
RaAt each occurrence independently, expression-Z1- SiR71 p1R72 q1R73 r1；
Z1At each occurrence independently, the organic group of oxygen atom or divalent is indicated；
R71At each occurrence independently, R is indicateda’；
Ra’With RaMeaning is identical；
RaIn, via Z1Group connection is that the Si of straight-chain is up to 5；
R72At each occurrence independently, the group that indicates hydroxyl or can hydrolyze；
R73At each occurrence independently, hydrogen atom or low alkyl group are indicated；
P1 is at each occurrence 0~3 integer independently；
Q1 is at each occurrence 0~3 integer independently；
R1 is at each occurrence 0~3 integer independently；
Wherein, in formula (C1) and (C2), at least one q1 be 1~3 integer；
RbAt each occurrence independently, the group that indicates hydroxyl or can hydrolyze；
RcAt each occurrence independently, hydrogen atom or low alkyl group are indicated；
K1 is at each occurrence 1~3 integer independently；
L1 is at each occurrence 0~2 integer independently；
M1 is at each occurrence 0~2 integer independently；
X9Independently, the organic group of singly-bound or 2~10 valences is indicated；
δ is 1~9 integer independently；
δ ' is 1~9 integer independently；
RdAt each occurrence independently, expression-Z2- CR81 p2R82 q2R83 r2；
Z2At each occurrence independently, the organic group of oxygen atom or divalent is indicated；
R81At each occurrence independently, R is indicatedd’；
Rd’With RdMeaning is identical；
RdIn, via Z2Group connection is that the C of straight-chain is up to 5；
R82At each occurrence independently, expression-Y-SiR85 n2R86 3-n2；
Y independently, indicates the organic group of divalent at each occurrence；
R85At each occurrence independently, the group that indicates hydroxyl or can hydrolyze；
R86At each occurrence independently, hydrogen atom or low alkyl group are indicated；
N2 is in each (- Y-SiR85 n2R86 3-n2) in unit independently, indicate 1~3 integer；
Wherein, in formula (D1) and (D2), at least one n2 be 1~3 integer；
R83At each occurrence independently, hydrogen atom or low alkyl group are indicated；
P2 is at each occurrence 0~3 integer independently；
Q2 is at each occurrence 0~3 integer independently；
R2 is at each occurrence 0~3 integer independently；
ReAt each occurrence independently, expression-Y-SiR85 n2R86 3-n2；
RfAt each occurrence independently, hydrogen atom or low alkyl group are indicated；
K2 is at each occurrence 0~3 integer independently；
L2 is at each occurrence 0~3 integer independently；
M2 is at each occurrence 0~3 integer independently；
Wherein, in formula (D1) and (D2), at least one q2 is that 2 or 3 or at least one l2 is 2 or 3,
(Rf2-PFPE2-Z2)X-A …(E1)
In formula (E1):
PFPE2At each occurrence independently, it is group shown in following formula:
(OC6F12)a(OC5F10)b(OC4F8)c(OC3F6)d(OC2F4)e(OCF2)f?
In formula, a, b, c, d, e and f are 0 or more 200 integer below independently, and the sum of a, b, c, d, e and f are at least 1, band There are a, b, c, d, e or f and be arbitrary in formula by the presence sequence for each repetitive unit that bracket brackets,
Rf2At each occurrence independently, the carbon atom number 1~16 that can be replaced by 1 or 1 or more fluorine atom is indicated Alkyl；
Z2Indicate the organic group of singly-bound or divalent；
X is 1 or 2；
When x is 1, A is-COOR3,-PO (OR3)2,-SO2(OR3) or-SO (OR3)；
When x is 2, A is-PO (OR3)-；
R3For hydrogen atom or alkyl.
2. composition as described in claim 1, it is characterised in that:
Rf1For the perfluoroalkyl of carbon atom number 1~16.
3. composition as claimed in claim 1 or 2, it is characterised in that:
PFPE1For following formula (a), (b) or (c):
(OC3F6)d(a)
In formula (a), d is 1 or more 200 integer below,
(OC4F8)c(OC3F6)d(OC2F4)e(OCF2)f(b)
In formula (b), c and d are 0 or more 30 integer below independently；
E and f are 1 or more 200 integer below independently；
C, the sum of d, e and f are 10 or more 200 integers below；
It is arbitrary in formula with subscript c, d, e or f and by the presence sequence for each repetitive unit that bracket brackets,
(R6- R7)q(c)
In formula (c), R6For OCF2Or OC2F4；
R7For selected from OC3F6、OC4F8、OC5F10And OC6F12In group, or be 2 or 3 groups in these groups Combination；
The integer that q is 2~100.
4. composition according to any one of claims 1 to 3, it is characterised in that:
X1、X5、X7And X9For the organic group of divalent, α, β, γ and δ are that 1, α ', β ', γ ' and δ ' are 1.
5. composition as described in any one of claims 1 to 4, it is characterised in that:
X1、X5、X7And X9It independently, is-(R31)p’(Xa)q’Shown in group,
Formula-(R31)p’(Xa)q’In:
R31Independently, singly-bound ,-(CH are indicated2)s’Or adjacent phenylene, metaphenylene or to phenylene, formula- (CH2)s’In, s ' be 1~20 integer；
XaExpression-(Xb)l’, formula-(Xb)l’In, l ' be 1~10 integer；
XbAt each occurrence independently, it indicates selected from-O- ,-S-, adjacent phenylene, metaphenylene or to phenylene ,-C (O) O- ,-Si (R33)2,-(Si (R33)2O)m’- Si (R33)2,-CONR34,-O-CONR34,-NR34? With-(CH2)n’In group, formula-(Si (R33)2O)m’- Si (R33)2In, the integer that m ' is 1~100, formula- (CH2)n’In, n ' be 1~20 integer；
R33At each occurrence independently, phenyl, C are indicated1-6Alkyl or C1-6Alkoxy；
R34At each occurrence independently, hydrogen atom, phenyl or C are indicated1-6Alkyl；
P ' is 0,1 or 2；
Q ' is 0 or 1；
Wherein, at least one of p ' and q ' are 1, the presence sequence with p ' or q ' and each repetitive unit for being bracketed by bracket It is arbitrary in formula；
R31And XaFluorine atom, C can be selected from1-3Alkyl and C1-31 or 1 or more substituent group in fluoro-alkyl replaces.
6. such as composition according to any one of claims 1 to 5, it is characterised in that:
X1、X5、X7And X9Independently, it is selected from:
Singly-bound,
- CH2O(CH2)2,
- CH2O(CH2)3,
- CH2O(CH2)6,
- 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,
- CH2OCH2CHFCF2OCF2,
- CH2OCH2CHFCF2OCF2CF2,
- CH2OCH2CHFCF2OCF2CF2CF2,
- CH2OCH2CHFCF2OCF(CF3)CF2OCF2,
- CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2,
- CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2?
- CH2OCF2CHFOCF2CF2CF2- C (O) NH-CH2,
- 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,
(CH2)2- Si (CH3)2(CH2)2,
- CONH- (CH2)3,
- CON (CH3)-(CH2)3,
- CON (Ph)-(CH2)3, in formula, Ph refer to phenyl,
- CONH- (CH2)6,
- CON (CH3)-(CH2)6,
- CON (Ph)-(CH2)6, in formula, Ph refer 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,
7. such as composition according to any one of claims 1 to 6, it is characterised in that:
K1 is 3, RaIn, q1 3.
8. such as composition according to any one of claims 1 to 7, it is characterised in that:
L2 is 3, n2 3.
9. such as composition according to any one of claims 1 to 8, it is characterised in that:
Y is C1-6Alkylidene ,-(CH2)g’- O- (CH2)h’Or-phenylene-(CH2)i’, formula-(CH2)g’- O- (CH2)h’In, the integer that g ' is 0~6, the integer that h ' is 0~6, formula-phenylene-(CH2)i’In, i ' be 0~6 it is whole Number.
10. composition according to any one of claims 1 to 3, it is characterised in that:
X1、X5、X7And X9It independently, is the organic group of 3~10 valences.
11. composition as claimed in claim 10, it is characterised in that:
X1、X5、X7And X9Independently, it is selected from:
In formula, in each group, at least one in T be formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) in PFPE1In conjunction with following group:
- 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 refer to phenyl and
At least one in other T is former with carbon in formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) The combination of sub or Si atom-(CH2)n, remaining T independently, be methyl, phenyl, carbon atom number 1~6 alkoxy, from Base or ultraviolet radiation absorption base, formula-(CH are captured by base2)nIn, the integer that n is 2~6,
R41It independently, is the alkyl of hydrogen atom, phenyl, the alkoxy of carbon atom number 1~6 or carbon atom number 1~6,
R42Independently, hydrogen atom, C are indicated1-6Alkyl or C1-6Alkoxy.
12. the composition as described in any one of claim 1~11, it is characterised in that:
Contain the silanization of perfluor (poly-) ether shown in formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) or (D2) The number-average molecular weight for closing object is 1,000~30,000.
13. the composition as described in any one of claim 1~12, it is characterised in that:
Silane compound containing perfluor (poly-) ether is at least one kind of compound shown in any formula in formula (A1) and (A2).
14. the composition as described in any one of claim 1~12, it is characterised in that:
Silane compound containing perfluor (poly-) ether is at least one kind of compound shown in any formula in formula (B1) and (B2).
15. the composition as described in any one of claim 1~12, it is characterised in that:
Silane compound containing perfluor (poly-) ether is at least one kind of compound shown in any formula in formula (C1) and (C2).
16. the composition as described in any one of claim 1~12, it is characterised in that:
Silane compound containing perfluor (poly-) ether is at least one kind of compound shown in any formula in formula (D1) and (D2).
17. the composition as described in any one of claim 1~16, it is characterised in that:
Rf2For the perfluoroalkyl of carbon atom number 1~16.
18. the composition as described in any one of claim 1~17, it is characterised in that:
PFPE2For following formula (a), (b) or (c):
(OC3F6)d(a)
In formula (a), d is 1 or more 200 integer below,
(OC4F8)c(OC3F6)d(OC2F4)e(OCF2)f(b)
In formula (b), c and d are 0 or more 30 integer below independently；
E and f are 1 or more 200 integer below independently；
C, the sum of d, e and f are 10 or more 200 integers below；
It is arbitrary in formula with subscript c, d, e or f and by the presence sequence for each repetitive unit that bracket brackets,
(R6- R7)q(c)
In formula (c), R6For OCF2Or OC2F4；
R7For selected from OC3F6、OC4F8、OC5F10And OC6F12In group, or 2 or 3 bases to be independently selected from these groups The combination of group；
The integer that q is 2~100.
19. the composition as described in any one of claim 1~18, it is characterised in that:
Z2In the organic group of divalent be
(CR18 2)k7(O)k8(NR19)k9,
In formula:
R18It independently, is hydrogen atom or fluorine atom；
R19Independently, hydrogen atom, phenyl or C are indicated1-6Alkyl；
The integer that k7 is 1~20；
The integer that k8 is 0~10；
The integer that k9 is 0~10；
Wherein, it is arbitrary in formula with k7, k8 or k9 and by the presence sequence for each repetitive unit that bracket brackets.
20. the composition as described in any one of claim 1~18, it is characterised in that:
Z2For-(CF2)k7’Or-(CF2)k7’(O)k8’?
In formula:
The integer that k7 ' is 1~6；
The integer that k8 ' is 1~3；
Wherein, it is arbitrary in formula with k7 ' or k8 ' and by the presence sequence for each repetitive unit that bracket brackets.
21. the composition as described in any one of claim 1~20, it is characterised in that:
A is-COOR3。
22. the composition as described in any one of claim 1~21, it is characterised in that:
The number-average molecular weight of formula (E1) compound represented is 1,000~30,000.
23. the composition as described in any one of claim 1~21, it is characterised in that:
Contain the silanization of perfluor (poly-) ether shown in formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) or (D2) The difference for closing the number-average molecular weight of object and the number-average molecular weight of formula (E1) compound represented is within 2000.
24. the composition as described in any one of claim 1~23, it is characterised in that:
Also containing a kind or a kind or more of other ingredients in fluorine-containing oil, silicone oil and catalyst.
25. composition as claimed in claim 24, it is characterised in that:
The compound that fluorine-containing oil is a kind or a kind or more shown in formula (3):
Rf3(OC4F8)a1(OC3F6)b1(OC2F4)c1(OCF2)d1- Rf4 (3)
In formula (3):
Rf3Indicate the alkyl for the carbon atom number 1~16 that can be replaced by 1 or 1 or more fluorine atom；
Rf4Indicate alkyl, fluorine atom or the hydrogen atom of the carbon atom number 1~16 that can be replaced by 1 or 1 or more fluorine atom；
A1, b1, c1 and d1 respectively indicate the number of repeat unit for constituting 4 kinds of perfluor (poly-) ether of main framing of polymer, mutually solely It is vertical, it is 0 or more 300 integer below, the sum of a1, b1, c1 and d1 are at least 1, with subscript a1, b1, c1 or d1 and by bracket The presence sequence of each repetitive unit bracketed is arbitrary in formula.
26. the composition as described in any one of claim 1~25, it is characterised in that:
Also contain solvent.
27. the composition as described in any one of claim 1~26, it is characterised in that:
It is surface treating agent.
28. the composition as described in any one of claim 1~27, it is characterised in that:
It is used as soil resistance coating agent or waterproofness coating agent.
29. a kind of pellet containing composition described in any one of claim 1~28.
30. a kind of formed comprising substrate and on the surface of the substrate using composition described in any one of claim 1~28 Layer article.
31. article as claimed in claim 30, it is characterised in that:
Substrate is glass.
32. article as claimed in claim 30, it is characterised in that:
Substrate is selected from sapphire glass, soda-lime glass, alkali alumina silicate glass, pyrex, alkali-free glass, crystal glass With the glass in quartz glass.
33. the article as described in any one of claim 30~32, it is characterised in that:
It is optical component.
34. the article as described in any one of claim 30~33, it is characterised in that:
It is display.
35. the condensation accelerator of silane compound of the one kind containing perfluor (poly-) ether, it is characterised in that:
Contain at least one kind of compound shown in following formula (E1):
(Rf2-PFPE2-Z2)X-A …(E1)
In formula (E1):
Rf2Independently, the alkyl for the carbon atom number 1~16 that can be replaced by 1 or 1 or more fluorine atom is indicated；
PFPE2Independently, expression-(OC6F12)a(OC5F10)b(OC4F8)c(OC3F6)d(OC2F4)e? (OCF2)f, wherein a, b, c, d, e and f are 0 or more 200 integer below, the sum of a, b, c, d, e and f are at least independently It is 1, is arbitrary in formula with a, b, c, d, e or f and by the presence sequence for each repetitive unit that bracket brackets；
Z2Indicate the organic group of singly-bound or divalent；
X is 1 or 2；
When x is 1, A is-COOR3,-PO (OR3)2,-SO2(OR3) or-SO (OR3)；
When x is 2, A is-PO (OR3)-；
R3For hydrogen atom or alkyl.
CN201780054313.7A 2016-09-08 2017-08-30 Composition containing the silane compound containing perfluor (poly-) ether Pending CN109689786A (en)

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