CN103709915A - Surface treatment method and surface-treated article - Google Patents

Surface treatment method and surface-treated article Download PDF

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CN103709915A
CN103709915A CN201310459881.9A CN201310459881A CN103709915A CN 103709915 A CN103709915 A CN 103709915A CN 201310459881 A CN201310459881 A CN 201310459881A CN 103709915 A CN103709915 A CN 103709915A
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surface treatment
polymkeric substance
treatment method
water
mole
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佐藤伸一
山根祐治
小池则之
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Shin Etsu Chemical Co Ltd
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    • 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
    • C09D171/02—Polyalkylene oxides
    • 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
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • 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
    • C09D171/02—Polyalkylene oxides
    • C09D171/03—Polyepihalohydrins
    • 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
    • C09D183/02—Polysilicates
    • 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
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

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  • Engineering & Computer Science (AREA)
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  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
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  • Surface Treatment Of Optical Elements (AREA)

Abstract

The invention provides a surface treatment method and a surface-treated article. The surface treatment agent employed in the surface treatment method contains polymer composite containing oxyfluoride alkylene and/or partial Hydrolytic condensation compound of the polymer composite containing oxyfluoride alkylene, wherein the polymer composite containing oxyfluoride alkylene contains a polymer containing linear chain oxyfluoride alkylene with isopropenyl oxygroup silylation at single end (herein after refer to single-end hydrolyzed polymer) represented by formula (1) and a polymer containing linear chain oxyfluoride alkylene with isopropenyl oxygroup silylation at two ends (herein after refer to two-end hydrolyzed polymer) represented by formula (2). Relative to the total mole of the single-end hydrolyzed polymer and the two-end hydrolyzed polymer, the content of the two-end hydrolyzed polymer is less than 10 mol% (other than 0mol%).

Description

Surface treatment method and surface treated article
Technical field
The present invention relates to utilize wet type coating method coating surface treatment agent on base material a kind of comprising, then make the surface treatment method of base material of the step of its sclerosis, relate in particular to a kind of article that use the surface treatment method of following surface treatment agent and utilize this surface treatment agent to process, sclerosis after described surface treatment agent is coated on base material is fast, even if with its sclerosis of chien shih in short-term, also can provide the sclerosis tunicle of adhesion excellence and water-repellent oil-repellent, low kinetic friction, excellent scratch resistance.
Background technology
In recent years, in order to make outward appearance or visual good, the requirement that the surface at indicating meter is difficult to adhere to the technology of fingerprint or easily remove the technology of dirt improves year by year, and the material that can tackle these requirements is developed in expectation.Especially the surface of touch panel display is owing to easily adhering to fingerprint dirt, so with regard to preventing the viewpoint of impaired property and the fingerprint property wiped, the surperficial water-repellent oil-repellent layer of coated touch panel display is more satisfactory is that kinetic friction coefficient is low.Therefore, require to develop excellent scratch resistance and the low water-repellent oil-repellent layer of kinetic friction coefficient, developing for the kinds of surface treatment agent of this kind of water-repellent oil-repellent layer is set.
Patent documentation 1 has been recorded the represented fluorine amino containing silane compound of following formula, realizes the high water-repellent oil-repellent to glass.But the perfluor oxyalkylene chain of this compound is short, cannot fully show oilness, release property, didirtresistance.
Figure BDA0000390233960000011
(in formula, R 2, R 3for the alkyl of carbon number 1～4, R 1for-CH 2cH 2cH 2-or-CH 2cH 2nHCH 2cH 2cH 2-, the integer that h is 0～8, i is 2 or 3)
Patent documentation 2 has been recorded the represented PFPE upgrading amino containing silane that contains branch-like long-chain perfluor oxyalkylene of following formula.The water-repellent oil-repellent angle of this PFPE upgrading amino containing silane is high, but owing to thering is branched structure on main chain, so the dirt property wiped or oilness insufficient.
Figure BDA0000390233960000021
(in formula, X is water-disintegrable base, R 4for monovalence alkyl, R 6for hydrogen atom or monovalence alkyl, R 5expression can be inserted with the alkylidene group of NH base; J is 14～49 integer, and k is 2 or 3)
Patent documentation 3 has been recorded the represented PFPE upgrading silane that contains straight chain shape perfluor oxyalkylene of following formula.The lens of processing through this PFPE upgrading silane or the slipperiness of anti-reflective film, release property and antifriction consumption are excellent, but because two ends are fixed on base material, so oilness is insufficient.
Figure BDA0000390233960000022
(in formula, Rf is divalence straight chain type holo-fluorine polyester, and R is alkyl or the phenyl of carbon number 1～4, and X is water-disintegrable base, 1 integer that is 0～2, and the integer that m is 1～5, a is 2 or 3)
Patent documentation 4 has been recorded the PFPE upgrading silane shown in following formula as the treatment agent that improves oilness.But this compound is owing to not having endways containing fluorine-based, so water-repellent oil-repellent, low kinetic friction, release property are poor.
(Z 2Q) βRf(QZ 1A α) 2-β
(in formula, Rf represents the group that comprises divalent perfluor ether residue, and Q represents divalent organic radical, Z 1and Z 2represent organopolysiloxane residue, A represents to have the univalent perssad of terminal-reactive silylation; α is 1～8 integer, β be greater than 0 and be less than 2 number)
Patent documentation 5 has been recorded a kind of surface treatment agent of the polymer composition that contains fluorine-containing oxyalkylene, and the polymer composition of described fluorine-containing oxyalkylene is the composition that contains following polymkeric substance: with-(CF 2) d-(OC 2f 4) e(OCF 2) f-O (CF 2) d-as backbone structure and in single end have water-disintegrable silylation containing the polymkeric substance of straight chain shape fluorine oxyalkylene and with-(CF 2) d-(OC 2f 4) e(OCF 2) f-O (CF 2) d-as backbone structure and in two ends have water-disintegrable silylation containing the polymkeric substance of straight chain shape fluorine oxyalkylene; The described polymer composition that contains fluorine-containing oxyalkylene is characterised in that: with respect to the total mole of the water-disintegrable polymkeric substance of single end and the water-disintegrable polymkeric substance of two ends, the content of the water-disintegrable polymkeric substance of two ends be 0.1 % by mole above and be less than 10 % by mole.
[prior art document]
[patent documentation]
The clear 58-167597 communique of [patent documentation 1] Japanese Patent Laid-Open
[patent documentation 2] Japanese Patent Laid-Open 2000-143991 communique
[patent documentation 3] Japanese Patent Laid-Open 2003-238577 communique
[patent documentation 4] Japanese Patent Laid-Open 2007-297589 communique
[patent documentation 5] Japanese Patent Laid-Open 2012-72272 communique
Summary of the invention
In recent years, coating manufacturer expectation provides can be after coating on base material, harden and show the finish materials of described surface property (that is, scuff resistance and the low kinetic friction of excellence) with the short period of time.Surface treatment agent is coated to be had the dry type coating methods such as vacuum evaporation and dip coated, sprays the wet type coating methods such as coating in the method on base material.
Described patent documentation 5 has been recorded: the described surface treatment agent that is Trimethoxy silane base by the end of polymkeric substance by vacuum evaporation is coated substrate surface, then under 40 ℃, the environment of humidity 80%, harden 2 hours, the sclerosis tunicle with excellent scuff resistance and low kinetic friction is provided thus.But if utilize wet type coating method that this surface treatment agent is coated to substrate surface,, in short period of time sclerosis then, generation cannot obtain the problem of the sclerosis tunicle with excellent surface property.Think that its reason is: in the situation that being coated with by vacuum evaporation, due to the SiO of evaporation substrate surface 2layer, can provide with the sclerosis of short period of time the sclerosis tunicle with excellent surface property, but in the situation that utilizing wet type coating method to be coated with, coating time Mo evaporation SiO 2layer.
Therefore, the object of the present invention is to provide a kind of surface treatment method of base material, it comprises the step of utilizing wet type coating method coating surface treatment agent on base material, even and if the setting time after coating is short, the surface treatment method of described base material also can provide has excellent surface property, particularly excellent scuff resistance and the sclerosis tunicle of low kinetic friction.
The present inventors are active research in order to solve described problem, found that, the surface treatment agent of the partial hydrolysis condenses of the polymer composition that contains fluorine-containing oxyalkylene by use and/or the polymer composition of this fluorine-containing oxyalkylene, the polymer composition of wherein said fluorine-containing oxyalkylene with specifically allocate than contain following formula (1) represented in single end have iso-propenyloxysilane base containing the polymkeric substance of straight chain shape fluorine oxyalkylene, and following formula (2) represented in two ends have iso-propenyloxysilane base containing the polymkeric substance of straight chain shape fluorine oxyalkylene, can be after utilizing the coating of wet type coating method, sclerosis with the short period of time provides the sclerosis tunicle with excellent scuff resistance and low kinetic friction, thereby complete the present invention.
; the invention provides a kind of surface treatment method and there are the surperficial article that the method utilized is processed; described surface treatment method is to comprise utilizing wet type coating method coating surface treatment agent on base material, then makes the surface treatment method of base material of the step of its sclerosis
The partial hydrolysis condenses of the polymer composition that described surface treatment agent contains fluorine-containing oxyalkylene and/or the polymer composition of this fluorine-containing oxyalkylene,
The polymer composition of described fluorine-containing oxyalkylene comprises following formula (1)
Figure BDA0000390233960000041
(in formula, Rf base is-(CF 2) d-(OC 2f 4) e(OCF 2) f-O (CF 2) d -, A is that end is-CF 31 valency of base is containing fluorine-based, and Q is divalent organic radical, and Z is the divalent～8 valency organopolysiloxane residue with siloxane bond, R is alkyl or the phenyl of carbon number 1～4, X is different propenyloxy group, and a is 2 or 3, the b integer that is 1～7, c is 2～5 integer, d is respectively 0 or 1～5 integer independently, the integer that e is 0～80, the integer that f is 0～80, and the integer of e+f=5～100, repeating unit is bond randomly)
Represented polymkeric substance (hereinafter referred to as the water-disintegrable polymkeric substance of single end) and following formula (2) containing straight chain shape fluorine oxyalkylene
Figure BDA0000390233960000051
(in formula, RF, Q, Z, R, X, a, b, c are identical with described formula (1))
The represented polymkeric substance (hereinafter referred to as the water-disintegrable polymkeric substance of two ends) containing straight chain shape fluorine oxyalkylene, and with respect to the total mole of the water-disintegrable polymkeric substance of described single end and the water-disintegrable polymkeric substance of described two end, the content of the water-disintegrable polymkeric substance of two ends is less than 10 % by mole (but not being 0 % by mole).
[effect of invention]
According to the present invention, comprise in the surface treatment method that utilizes wet type coating method base material of the step of coating surface treatment agent on base material, can to various article surfaces, give excellent water-repellent oil-repellent, low kinetic friction and scuff resistance with the sclerosis of short period of time.
Embodiment
In method of the present invention, the partial hydrolysis condenses of the polymer composition that surface treatment agent contains fluorine-containing oxyalkylene and/or the polymer composition of this fluorine-containing oxyalkylene.In the polymer composition of this fluorine-containing oxyalkylene, the contained water-disintegrable polymkeric substance of single end and the water-disintegrable base of end (the represented group of X in formula (1) and formula (2)) of the water-disintegrable polymkeric substance of two ends are different propenyloxy group.Thus, comprise in the surface treatment method that utilizes wet type coating method base material of the step of coating surface treatment agent on base material, the sclerosis tunicle with excellent scuff resistance and low kinetic friction can be provided with the sclerosis of short period of time.
In the polymer composition of described fluorine-containing oxyalkylene, total mole with respect to the water-disintegrable polymkeric substance of single end and the water-disintegrable polymkeric substance of two ends, the content of the water-disintegrable polymkeric substance of two ends is less than 10 % by mole (but not being 0 % by mole), be preferably 0.1 % by mole～9.8 % by mole, especially be preferably 1 % by mole～9 % by mole, more preferably 1 % by mole～5 % by mole.Surface treatment agent of the present invention passes through the content of the water-disintegrable polymkeric substance of two ends in described scope, can form the film of excellent scratch resistance.
In addition, surface treatment agent of the present invention can pass through the polymkeric substance general-(CF of described fluorine-containing oxyalkylene 2) d-(OC 2f 4) e(OCF 2) f-O (CF 2) d-as backbone structure, and form the low film of kinetic friction coefficient.In described formula, d is respectively 0 or 1～5 integer independently, the integer that e is 0～80, and the integer that f is 0～80, and the integer of e+f=5～100, repeating unit is bond randomly.E+f is preferably 10～80, and more preferably 15～60.If e+f is greater than described higher limit, there is the possibility of adhesion or hardening variation, if be less than described lower value, cannot give full play to the feature of fluorine oxyalkylene.
In described formula (1), A is that end is-CF 31 valency of base, containing fluorine-based, is preferably the straight chain shape perfluor base of carbon number 1～6, is wherein preferably CF 3base.
In described formula (1) and formula (2), R is alkyl or the phenyl of carbon number 1～4, is wherein preferably methyl.A is 2 or 3, with regard to reactive, to regard to the viewpoint of the adhesion of base material, be preferably 3.B is 1～7, is preferably 1～3 integer, and c is 2～5, is preferably 2～3 integer.
In described formula (1) and formula (2), Q is the concatenating group of Rf base and Z base.Be preferably and can comprise the alkyl that the free intoxicated amine key of choosing, ehter bond, ester bond or vinyl bonds form the carbon number 2～12 of 1 above key in cohort.For example can enumerate following radicals.
Figure BDA0000390233960000071
In described formula (1) and formula (2), 2 for have siloxane bond divalent～8 valency, be preferably divalent～4 valency organopolysiloxane residue, and be 2～13 of Siliciumatom numbers, be preferably chain or the ring-type organopolysiloxane residue of 2～5 of Siliciumatom numbers.Wherein, can comprise 2 Siliciumatoms by sila alkylidene group (silalkylene) structure of alkylidene group bond, comprise Si-(CH 2) n-Si (integer that in described formula, n is 2～6).The polymer composition of fluorine-containing oxyalkylene of the present invention can, by having siloxane bond in molecule, carry out the coating of antifriction consumption, excellent scratch resistance.
This organopolysiloxane residue be preferably there is carbon number 1～8, more preferably 1～4 alkyl or the group of phenyl.In addition, the alkylidene group in sila alkylene base key is preferably carbon number 2～6, is preferably 2～4 alkylidene group.Z as above can enumerate the group shown in following.
Figure BDA0000390233960000091
The polymer composition of the fluorine-containing oxyalkylene using in the present invention can and then contain following formula (3)
A-Rf-A (3)
(in formula, Rf and A with for described formula (1) and formula (2) and the group of recording is identical) polymkeric substance of represented fluorine-containing oxyalkylene is (hereinafter referred to as without functional initiator L
The polymkeric substance of the fluorine-containing oxyalkylene using in the present invention contains in the described situation without functional initiator, more satisfactory is with respect to the water-disintegrable polymkeric substance of described single end, the water-disintegrable polymkeric substance of two ends, and this is without the total mole of functional initiator, the ratio of the water-disintegrable polymkeric substance of single end is more than 80 % by mole, be preferably more than 85 % by mole, more preferably 90 % by mole above (but not being 100 % by mole), and the ratio of the water-disintegrable polymkeric substance of two ends is less than 10 % by mole (but not being 0 % by mole), be preferably 0.1 % by mole～9.8 % by mole, especially be preferably 1 % by mole～9 % by mole, more preferably 1 % by mole～5 % by mole.Ratio without functional initiator should be less than 20 % by mole, is preferably 1 % by mole～15 % by mole, more preferably 5 % by mole～10 % by mole.
The polymer composition of described fluorine-containing oxyalkylene for example can by following (i)～(and) step manufacture.
(i) by two ends being there is to the end of carboxylic acid group's perfluor oxygen compound, undertaken partially fluorinatedly, manufacture the mixture of the polymkeric substance (hereinafter referred to as two end carboxylic acid polyalcohols) that the polymkeric substance (hereinafter referred to as single end carboxylic acid polyalcohol) that comprises single end and have carboxylic acid group's fluorine-containing oxyalkylene and two ends have carboxylic acid group's fluorine-containing oxyalkylene.In this reaction, end-CF 3the importing rate of base can, by adjusting the amount of the fluorine gas of supplying with, be controlled to fluoridize suitably and adjust.The mixture obtaining in this step can comprise the polymkeric substance (hereinafter referred to as without functional initiator) that end does not have carboxylic acid group's fluorine-containing oxyalkylene.
(ii) mixture that comprises single end carboxylic acid polyalcohol and two end carboxylic acid polyalcohols is offered to adsorption treatment and/or molecular distillation and process, obtain with high density and contain the polymer composition of polymkeric substance that single end has carboxylic acid group's fluorine-containing oxyalkylene.As long as the method that adsorption treatment and/or molecular distillation are processed is according to known method.By this step, the two end water-disintegrable polymkeric substance of capable of regulating for the total of the water-disintegrable polymkeric substance of single end and the water-disintegrable polymkeric substance of two ends mole contain ratio.
(iii) the end carboxylic acid group in this polymer composition is upper, via amido linkage, ehter bond, ester bond or vinyl bonds, imports the group that end has aliphatics unsaturated group.As long as introduction method is according to known method.For example, first the polymer composition containing end carboxylic acid group is offered to the reduction of using metal hydride or the catalytic hydrogenation (catalytic hydrogenation) of using noble metal catalyst, make the polymer composition containing terminal hydroxyl shown in following (in formula, Rf 1base is-(OC 2f 4) e(OCF 2) fo-, e and f are as mentioned above).
CF 3-Rf 1-CF 2CH 2OH
HOH 2CCF 2Rf 1-CF 2CH 2OH
CF 3-Rf 1-CF 3
Then, on the terminal hydroxyl of the polymkeric substance by above-mentioned gained, import aliphatics unsaturated group.As long as aliphatics unsaturated group is to the importing of terminal hydroxyl according to known method.By this step, manufacture as described below import endways have the polymer composition containing end aliphatics unsaturated group of the thiazolinyls such as allyl group (in formula, Rf 1as mentioned above).
CF 3-Rf 1-CF 2CH 2OCH 2CH＝CH 2
CH 2＝CHCH 2OCH 2CF 2-Rf 1-CF 2CH 2OCH 2CH＝CH 2
CF 3-Rf 1-CF 3
(iv) then, make the end aliphatics unsaturated group and the silicoorganic compound with most SiH bases of described polymkeric substance, for example, carry out addition reaction with the silicoorganic compound with Z～8 SiH bases.The polymkeric substance that reacts to obtain by this has most remaining SiH bases in molecule.Then, make this remaining SiH base and an end therein there is aliphatics unsaturated group and carry out addition reaction at the silicoorganic compound that another end has a different propenyloxy group.Addition reaction needs only with known reaction conditions, and as long as for example, under the existence of addition reaction catalyst (platinum family compound).By this step, can obtain the polymer composition of fluorine-containing oxyalkylene of the present invention.
In surface treatment agent of the present invention, the partial hydrolysis condenses of the polymer composition of described fluorine-containing oxyalkylene, refer to and utilize in advance known mode, the different propenyloxy group of end of the polymkeric substance that the polymer composition of described fluorine-containing oxyalkylene is had carries out partial hydrolysis, makes its condensation and the compound that obtains.
In surface treatment agent of the present invention, can optionally add hydrolytic condensation catalyzer, such as: organo-tin compound (dibutyl tin dimethoxy compound, dibutyl tin laurate etc.), organic titanic compound (tetra-n-butyl titanic acid ester etc.), organic acid (acetic acid, methylsulfonic acid, fluorine upgrading carboxylic acid etc.), mineral acid (hydrochloric acid, sulfuric acid etc.).In these compounds, be desirably especially acetic acid, tetra-n-butyl titanic acid ester, dibutyl tin laurate, fluorine upgrading carboxylic acid etc.Addition is so long as catalytic amount.Conventionally, with respect to polymer composition and/or its partial hydrolysis condenses 100 mass parts of fluorine-containing oxyalkylene, described addition is 0.01 mass parts～5 mass parts, particularly 0.1 mass parts～1 mass parts.
Surface treatment agent of the present invention can and then contain solvent.This solvent can illustration: fluorine upgrading aliphatic hydrocarbon series solvent (PF 5070, PFO etc.), fluorine upgrading aromatic hydrocarbons series solvent (two phenylfluoroform (m-xylenehexafluoride), phenylfluoroform (benzotrifluoride), 1, 3 trifluoromethylbenzenes etc.), fluorine upgrading ether series solvent (methyl perfluor butyl ether, ethyl perfluor butyl ether, perfluor (2-butyl tetrahydrofuran) etc.), fluorine upgrading alkylamine series solvent (perfluor tributylamine, perfluor three amylamines etc.), hydrocarbon system solvent (sherwood oil (petroleum benzine), mineral spirits (mineral spirit), toluene, dimethylbenzene etc.), ketone series solvent (acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.).Wherein, with regard to the aspects such as solvability, wetting quality, more satisfactory is solvent (that is, fluorous solvent) through fluorine upgrading.Two phenylfluoroforms, perfluor (2-butyl tetrahydrofuran), perfluor tributylamine, ethyl perfluor butyl ether between being particularly preferably.
Described solvent can mix two or more, be preferably the polymer composition that makes fluorine-containing oxyalkylene with and partial hydrolysis condenses dissolve equably.In addition, the polymer composition that is dissolved in the fluorine-containing oxyalkylene in solvent with and the optimum concn of partial hydrolysis condenses as long as suitably adjust according to treatment process, be preferably 0.01 % by weight～10 % by weight, be particularly preferably 0.05 % by weight～5 % by weight.
The invention provides a kind of surface treatment method that comprises the base material of the step of utilizing wet type coating method to be coated with described surface treatment agent on base material.Wet type coating method is such as having dipping, injection, rotary coating, blade coating etc.Method of the present invention is particularly preferably to be used dip coated and sprays coating.Use described wet type coating method that surface treatment agent is coated to the method on base material, such as used device etc. as long as according to existing known method.
Method of the present invention comprises the step that makes surface treatment agent sclerosis after the described application step of utilizing wet type coating method.In the situation that using wet type coating method, the setting time of surface treatment agent is generally 12 hours～and 24 hours.In method of the present invention, setting time was preferably below 6 hours, was particularly preferably 1 hour～4 hours, was especially preferably 1 hour～3 hours.Method of the present invention, by using described surface treatment agent, even if the short period of time as above hardens, also can provide and have excellent surface property, particularly excellent low kinetic friction and the sclerosis tunicle of scuff resistance.
In method of the present invention, the stiffening temperature of surface treatment agent is preferably the temperature, the particularly temperature in the scope of 50 ℃～80 ℃ in the scope in room temperature to 100 ℃.In addition, the situation of hardening under humidification can promote reaction, so preferably, especially should carry out under the humidity in the scope in 60%～90%RH.In addition, the thickness of sclerosis tunicle is suitably to select according to the kind of base material, is generally 0.1nm～100nm, is in particular 1nm～20nm.
There is no particular restriction to utilize method of the present invention to carry out surface-treated base material, can be paper, cloth, metal with and the base material of the various materials such as oxide compound, glass, plastics, pottery, quartz.Method of the present invention can be given water-repellent oil-repellent, low kinetic friction and scuff resistance to described substrate surface.Especially be suitable as through SiO 2the method that process on the glass of processing or the surface of quartz base plate is used.
The article that become the object that uses the inventive method can be enumerated: auto navigation (car navigation), mobile phone, digital camera (digital camera), Digital Video (digital video camera), personal digital assistant (Personal Digital Assistant, PDA), portable audio player (portable audio player), automobile audio (car audio), game machine, ophthalmic lens, camera lens (camera lens), optical filtering (lens filter), sunglasses (sunglass), the medical devices such as gastrophotor (gastrocamera), duplicating machine, PC (Personal Computer, PC), liquid-crystal display, organic electroluminescent (Electro-Luminescence, EL) indicating meter, plasma display, touch panel display, protective membrane, the optical articles such as anti-reflective film.The method of the application of the invention is carried out surface treatment, can prevent from adhering to fingerprint and sebum at described article surface, and then can give anti-impaired property.Treatment process of the present invention is especially useful in order to give water-repellent oil-repellent layer to touch panel display, anti-reflective film etc.
In addition, method of the present invention can be suitable for: to the drying of the health of bathing pool, wash stand and so on (sanitafy) goods, antifouling coating; Antifouling coating to the window glass of automobile, electric car, aircraft etc. or chilled glass, headlamp cover etc.; Drying, antifouling coating to outer wall with building materials; The greasy dirt of building materials for kitchen use is prevented with coating; The drying of call box, antifouling and paster are prevented to coating, scribble prevent coating; To artistic products etc. give water-repellancy, fingerprint adheres to the coating preventing; The fingerprint of CD, DVD etc. is adhered to and prevents coating; Nano impression is bestowed in the various steps such as releasing agent with mould etc.
[embodiment]
Below represent embodiment and comparative example, and the present invention will be described in more detail, but the present invention is not limited to following embodiment.
the polymer composition of fluorine-containing oxyalkylene
The polymer composition of the fluorine-containing oxyalkylene using in embodiment 1 is the composition that comprises following polymkeric substance:
(1a) and X represented by following formula (4) 1for following formula (a) represented group, X 2the water-disintegrable polymkeric substance of single end for fluorine atom: 91 % by mole;
(1b) and X represented by following formula (4) 1and X 2be the water-disintegrable polymkeric substance of two ends of the represented group of following formula (a): 1 % by mole; And
(1c) and X represented by following formula (4) 1and X 2be fluorine atom without functional initiator: 8 % by mole.
X 1-CF 2-O-(CF 2O) p(CF 2CF 2O) q-CF 2-X 2 (4)
Figure BDA0000390233960000142
Figure BDA0000390233960000141
The polymer composition of the fluorine-containing oxyalkylene using in embodiment 2 is the composition that comprises following polymkeric substance:
(2a) and X represented by following formula (5) 1for following formula (b) represented group, X 2the water-disintegrable polymkeric substance of single end for fluorine atom: 91 % by mole;
(2b) and X represented by following formula (5) 1and X 2be the water-disintegrable polymkeric substance of two ends of the represented group of following formula (b): 1 % by mole; And
(2c) and X represented by following formula (5) 1and X 2be fluorine atom without functional initiator: 8 % by mole.
X 1-CF 2-O-(CF 2O) p(CF 2CF 2O) q-CF 2-X 2 (5)
Figure BDA0000390233960000143
Figure BDA0000390233960000151
In comparative example 1 and comparative example 2, the polymer composition that use is the fluorine-containing oxyalkylene of Trimethoxy silane base as the end of being recorded in the embodiment of Japanese Patent Laid-Open 2012-72272 communique.
The polymer composition of the fluorine-containing oxyalkylene using in comparative example 1 comprises: 1 % by mole, the water-disintegrable polymkeric substance of two ends that represented 91 % by mole, the water-disintegrable polymkeric substance of single end, the following formula (3b) of following formula (3a) is represented and following formula (3c) represented without 8 % by mole of functional initiators (identical with the composition using in the embodiment 1 recording in Japanese Patent Laid-Open 2012-72272 communique).
F 3C(OC 2F 4) p(OCF 2) q-OCF 2CH 2OC 3H 6Si(OCH 3) 3 (3a)
(CH 3O) 3SiC 3H 6OCH 2-CF 2-(OC 2F 4) p(OCF 2) q-OCF 2CH 2OC 3H 6Si(OCH 3) 3 (3b)
F 3C(OC 2F 4) p(OCF 2) q-OCF 3 (3c)
The polymer composition of the fluorine-containing oxyalkylene using in comparative example 2 is the composition that comprises following polymkeric substance:
(4a) and X represented by following formula (6) 1for following formula (c) represented group, X 2the water-disintegrable polymkeric substance of single end for fluorine atom: 91 % by mole;
(4b) and X represented by following formula (6) 1and X 2be the water-disintegrable polymkeric substance of two ends of the represented group of following formula (c): 1 % by mole; And
(4c) and X represented by following formula (6) 1and X 2be fluorine atom without functional initiator: 8 % by mole.
X 1-CF 2-O-(CF 2O) p(CF 2CF 2O) q-CF 2-X 2 (6)
Figure BDA0000390233960000162
Figure BDA0000390233960000161
the preparation of surface treatment agent
The mode that becomes 0.3wt% with concentration makes the polymer composition of described each fluorine-containing oxyalkylene prepare surface treatment agent in two phenylfluoroforms (m-xylenehexafluoride) between being dissolved in.
[embodiment 1, embodiment 2 and comparative example 1, comparative example 2]
the surface treatment of base material
Will be in most surface to SiO 2carry out after 10nm processes the glass (Gorilla that healthy and free from worry (Cofning) company manufactures) form and clean with neutral lotion, with Virahol, carrying out the ultrasonic cleaning of 10 minutes, and dry (hereinafter referred to as glass coupon).Described each surface treatment agent that is 0.3wt% by concentration is added to respectively in Glass Containers, and described glass coupon is flooded 30 seconds in each surface treatment agent, with the speed of 200mm/ minute, lifts.Then, each test piece is placed 1 hour in the controlled thermohygrostat of 80 ℃/80%RH, make surface treatment agent sclerosis and formation sclerosis tunicle.
Utilize following method evaluation to be formed at the surface physical property of the surperficial sclerosis tunicle of glass coupon.Show the result in table 1.
[evaluation of water-repellent oil-repellent]
Use contact angle meter DropMaster (consonance interface science company manufactures), measure sclerosis tunicle to the contact angle of water and the contact angle to oleic acid.
[mensuration of kinetic friction coefficient]
Use surface property trier 14FW (new eastern scientific company manufacture), with following condition, measure the kinetic friction coefficient to Bemcot (Asahi Kasei Corporation's manufacture).
Contact area: 35mm * 35mm
Bear a heavy burden: 200g
[evaluation of antifriction consumption]
Use frictional testing machines (Rubbing Tester) (new eastern scientific company manufacture), with following condition, utilize Steel Wool (steel wool) to come the surface of friction hardening tunicle.Every friction 1000 times, measures the water contact angle on the sclerosis tunicle surface after friction, and the water contact angle of measuring sclerosis tunicle can keep 100 ° of above friction number of times as abrasion durability times.The mensuration of water contact angle is to use contact angle meter DropMaster (consonance interface science company manufactures) to carry out.Described testing circumstance condition is 25 ℃, humidity 40%.
Steel Wool: BONSTAR#0000 (Japanese Steel Wool limited-liability company manufacture)
Miles of relative movement (one way) 30mm
Translational speed 1800mm/ minute
Bear a heavy burden: 1kg/cm 2
[table 1]
As shown in table 1, as the use that embodiment recorded of Japanese Patent Laid-Open 2012-72272 communique comprises in the method for end for the surface treatment agent of the polymer composition of the fluorine-containing oxyalkylene of Trimethoxy silane base, after utilizing the application step of wet type coating method, the sclerosis by the short period of time cannot obtain the sclerosis tunicle with sufficient scuff resistance.On the other hand, use in the method for the present invention that comprises the surface treatment agent that end is the polymer composition of the fluorine-containing oxyalkylene of iso-propenyloxysilane base, even if setting time is short, also can provide the sclerosis tunicle with excellent scuff resistance.
[utilizability in industry]
According to method of the present invention, comprise in the surface treatment method that utilizes wet type coating method base material of the step of coating surface treatment agent on base material, even if the setting time of surface treatment agent is short, the sclerosis tunicle of water-repellent oil-repellent, low kinetic friction, antifriction consumption, particularly scuff resistance (Steel Wool weather resistance) excellence also can be provided.Therefore, surface treatment method of the present invention can be used in aptly and use dip coated, in the surface treatment step of the base material that sprays the wet type coating methods such as coating.Especially, surface treatment method of the present invention forms the method for water-repellent oil-repellent layer as the surface at optical articles such as touch panel display, anti-reflective films and useful.

Claims (13)

1. a surface treatment method, it is the surface treatment method that comprises the base material of the step of utilizing wet type coating method coating surface treatment agent on base material then to make its sclerosis, described surface treatment method is characterised in that: the partial hydrolysis condenses of the polymer composition that described surface treatment agent contains fluorine-containing oxyalkylene and/or the polymer composition of described fluorine-containing oxyalkylene, and the polymer composition of described fluorine-containing oxyalkylene comprises:
Following formula (1) represented containing the polymkeric substance of straight chain shape fluorine oxyalkylene, hereinafter referred to as the water-disintegrable polymkeric substance of single end:
Figure FDA0000390233950000011
In formula, Rf base is-(CF 2) d-(OC 2f 4) e(OCF 2) f-O (CF 2) d-, A is that end is-CF 31 valency of base is containing fluorine-based, and Q is divalent organic radical, and Z is the divalent～8 valency organopolysiloxane residue with siloxane bond, R is alkyl or the phenyl of carbon number 1～4, X is different propenyloxy group, and a is 2 or 3, the b integer that is 1～7, c is 2～5 integer, d is respectively 0 or 1～5 integer independently, the integer that e is 0～80, the integer that f is O～80, and the integer of e+f=5～100, repeating unit is bond randomly; And
Following formula (2) represented containing the polymkeric substance of straight chain shape fluorine oxyalkylene, hereinafter referred to as the water-disintegrable polymkeric substance of two ends:
In formula, Rf, Q, Z, R, X, a, b, c are identical with described formula (1), and with respect to the total mole of the water-disintegrable polymkeric substance of described single end and the water-disintegrable polymkeric substance of described two end, the content of the water-disintegrable polymkeric substance of described two end is less than 10 % by mole but be not 0 % by mole.
2. surface treatment method according to claim 1, is characterized in that, the polymer composition of described fluorine-containing oxyalkylene and then contain:
The polymkeric substance of the fluorine-containing oxyalkylene that following formula (3) is represented, hereinafter referred to as without functional initiator:
A-Rf-A (3)
In formula, Rf and A are same as described above, and with respect to the water-disintegrable polymkeric substance of single end, the water-disintegrable polymkeric substance of two ends and without the total mole of functional initiator, the ratio of the water-disintegrable polymkeric substance of described single end be 80 % by mole above but be not 100 % by mole, and the ratio of the water-disintegrable polymkeric substance of described two end is less than 10 % by mole but be not 0 % by mole.
3. surface treatment method according to claim 1 and 2, is characterized in that: described surface treatment agent and then contain fluorous solvent.
4. surface treatment method according to claim 2, it is characterized in that: with respect to the water-disintegrable polymkeric substance of single end, the water-disintegrable polymkeric substance of two ends and without the total of functional initiator, the described ratio without functional initiator is less than 20 % by mole but be not 0 % by mole.
5. according to the surface treatment method described in claim 1 or 3, it is characterized in that: Z is that Siliciumatom is straight chain shape or the ring-type organopolysiloxane residue of 2～5.
6. surface treatment method according to claim 1 and 2, is characterized in that: Q is for comprising the alkyl that selects free amido linkage, ehter bond, ester bond and vinyl bonds to form the carbon number 2～12 of 1 above key in cohort.
7. article, is characterized in that: comprise and utilize the surface that in claim 1 to 6, the surface treatment method described in any one is processed.
8. an optical article, is characterized in that: comprise and utilize the surface that in claim 1 to 6, the surface treatment method described in any one is processed.
9. a touch panel, is characterized in that: comprise and utilize the surface that in claim 1 to 6, the surface treatment method described in any one is processed.
10. an anti-reflective film, is characterized in that: comprise and utilize the surface that in claim 1 to 6, the surface treatment method described in any one is processed.
11. 1 kinds through SiO 2the glass of processing, is characterized in that: comprise and utilize the surface that in claim 1 to 6, the surface treatment method described in any one is processed.
12. 1 kinds of chilled glasses, is characterized in that: comprise and utilize the surface that in claim 1 to 6, the surface treatment method described in any one is processed.
13. 1 kinds of quartz base plates, is characterized in that: comprise and utilize the surface that in claim 1 to 6, the surface treatment method described in any one is processed.
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