CN104471003A - Hydrophobic coating - Google Patents
Hydrophobic coating Download PDFInfo
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- CN104471003A CN104471003A CN201380039302.3A CN201380039302A CN104471003A CN 104471003 A CN104471003 A CN 104471003A CN 201380039302 A CN201380039302 A CN 201380039302A CN 104471003 A CN104471003 A CN 104471003A
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- composition
- silane
- hydrolysis
- season
- coating
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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
- 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
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
Disclosed is a composition capable of yielding a hydrophobic coating. The composition comprises: (a) hydrophobic colloidal particles; (b) first hydrolyzed quaternary silane having four hydroxyl ligands and/or its oligomer; (c) second hydrolyzed quaternary silane having at least two hydroxyl ligands and at least one hydrophobic ligand and/or its oligomer; and (d) solvent.
Description
Invention field
The present invention relates to and put on surface to form the composition of hydrophobic coating thereon.Especially, the present invention relates to and comprise hydrophobicity micelle, the silane of hydrolysis and the such composition of solvent.
Background of invention
The tubing system of arid, bad irrigation and deficiency just causes the reason of certain areas water shortage.Water shortage can cause serious social concern, such as health problem, and it is the direct result of the cleaning applications insufficient when there is not enough water gagings.
Make an effort to limited amount water clean surface.In fact, have studied the surface cleaning of attempting to simulate lotus leaf surface.Such as, taro leaves has been used as the template of the polystyrene structure that can play lotus leaf effect.This class formation may be used for the coating with super-hydrophobicity.Therefore, needing the goods with the surface being difficult to soak, namely there are the goods of water repellent surface, because they have self-cleaning property when there is low water gaging.In addition, after applying, this type coating obtains and makes clean more easily and faster surface for consumers.
Although need hydrophobicity and particularly super hydrophobic surface, causing the composition forming this type of surface may be difficult to manufacture and can cause forming the surface with poor self-cleaning property, such as, is the direct result at its too low characterisation contact angle.In addition, the feasible method of the super-hydrophobic coating forming the outward appearance not changing the surface processed is not provided for.
Hydrophobic coating exploitation being caused being formed to the surface of the high contact angle had water resistant is interesting all the more.
US 6, 210, 750 (SAMSUNG CORNING CO LTD) disclose the waterproof glass prepared by a kind of method, the method comprises: (a) organoalkoxysilane by being hydrolyzed in the basic conditions in the presence of water and in polycondensation organic solvent, then process described colloidal silica suspension in acid condition and prepare colloidal silica suspension, to obtain the silica dispersion comprising crosslinked spherical silicon dioxide granule and linear polysiloxane, (b) merge described silica dispersion and the mixed solvent that is made up of acetic acid and alcohol to obtain coating composition, c () applies described coating composition to form silicon dioxide layer from it on glass substrate surface, d silicon dioxide layer described in () thermal treatment to provide silica membrane on described glass baseplate, (e) on described silica membrane, water-resisting agent is applied to provide waterproof glass.
H.M. Shang
deng people, " Optically transparent superhydrophobic silica-based films ",
thin Solid Films, 2005,
472, 37-43 discloses the optically transparent super-hydrophobic silica base film obtained by sol-gel processing and self-assembly (SA).By conscientiously controlling hydrolysis and the condensation reaction of various silica precursor during sol-gel processing, the surfaceness needed is obtained by regulating the microstructure of sol-gel, and reacted by Surface condensation, the modification of surface chemistry is completed by introducing individual layer.
In disclosing at above-mentioned two, teach the additional step (such as by the Surface condensation of fluorohydrocarbon) in the after-applied surface modification treatment with silica membrane coating thus the water-repellancy of realization needs.
B.J. Basu
deng people, " Effect of microstructure and surface roughness on the wettability of superhydrophobic sol-gel nanocomposite coatings ",
j. Sol-Gel Sci. Technol., 2010,
56, 278-286 discloses the sol-gel nano-composite coating by spraying the precursor mixture manufacture comprising the hydrophobic modified Nano particles of silicon dioxide be dispersed in sol-gel matrix (adopting acid catalyzed tetraethoxysilane or Union carbide A-162 preparation).
Above-mentioned openly teaching uses thickness for 15-20 μm and/or have the film of relatively a large amount of silica particles.This type of character may be not suitable for wherein needing application that is transparent or at least translucent coating.
The present inventor has had recognized the need to be formed and has not changed the coating that they apply the outward appearance on surface thereon.In addition, the present inventor have recognized the need to for the formation of this type coating and can from easily obtain and/or safety material formulation composition thus said composition can be used by family consumer.Therefore, the present invention relates to the composition for obtaining the hydrophobic coating comprising the micelle be cross-linked by the hydrolysising silane of particular type.By merge described micelle, hydrolysising silane and solvent preparation solidify to form the coating of needs composition and prepare coating of the present invention.Such composition can adopt the preparation of comparatively safe solvent (as alcohol and/or aqueous solvent) and usually can solidify to obtain at least translucent and normally transparent and/or persistent coating.
Test and definition
hydrophobicity
For purposes of the present invention, " hydrophobicity " attracted to and the part tended to by oil (the having precedence over water) molecule that dissolves or molecule for describing, or has the surface being greater than the contact angle of 90o for water." high hydrophobicity (Ultrahydrophobic) " used herein refers to have being greater than the contact angle of 110 ° and being less than the slide angle of 45 ° for water." super-hydrophobicity (Superhydrophobic) " used herein refers to the contact angle of at least 140 ° and the slide angle being less than 20 ° that have for water.Contact angle used herein refers to that water/vapor interface meets the angle of the solid surface at 25 DEG C of temperature.Such angle can adopt protractor or other water-drop-shaped analytical systems to measure.Slide angle used herein refers to the pitch angle on the surface that 5 μ l water droplets slide at 25 DEG C.
oligopolymer
For purposes of the present invention, " oligopolymer " refers to by several monomeric unit, such as 2 to 100, more preferably the molecule of 2 to 60 monomeric unit formations.
hydrolysis
For purposes of the present invention, " hydrolysis " refer to and to react with water." hydrolyzable " herein refers to the compound that can react with water." hydrolysis " refers to that described compound is the reaction product of another compound (precursor) and water.
pH
PH value mentioned in this article is measured at the temperature of 25 DEG C.
transmittance
The value of the transmittance quoted herein measures and following measurement under 550 nm wavelength:
-by transmittance be 89.0% uncoated slide glass be used as base material.
-composition is spread upon described slide glass side on to provide about 2.86 × 10
-4mg/mm
2uniform coating.
-by described coating curing 10 min or until its formation adhesive film.
-slide glass of described coating to be placed in ultraviolet-visible spectrometer (such as Perkin-Elmer Lambda 650S) and to measure transmittance at 25 DEG C.
Transmittance is used as the measuring of transparency in this article, and therefore should not exist under 550 nm any assess the chromophoric situation of absorbancy under measure.
granularity
Granularity used herein refers to particle dia, unless otherwise indicated.Diameter refer to average maximum detection span on when not forming the ball of strict difinition particle or agglomerate from.For polydispersion sample, diameter refers to and such as uses dynamic light scattering (see international standard ISO 13321) and instrument as Zetasizer Nano
tMthe z-mean particle size that (Malvern Instruments Ltd, UK) measures.
" primary particle size " refers to the particle dia under non-agglomeration state.
refractive index
Refractive index is quoted under the wavelength of the temperature of 25 DEG C and 589 nm.
miscellaneous
Except in an embodiment, or when otherwise clearly representing, representing in this specification sheets that the amount of material or reaction conditions, the physical properties of material and/or whole numerals of purposes can optionally be interpreted as and to be modified by word " about ".
Unless otherwise indicated, otherwise all amounts all with the weighing scale of total composition.
It should be noted when specifying the scope of any value, any specific higher limit can be combined with any specific lower value.
In order to avoid trouble, word " comprise " refer to " comprising " and nonessentially to refer to " by ... form " or " by ... composition ".In other words, cited step or option need not be exhaustive.
Although the claim that may occur not multinomial subordinate or have the fact of redundancy (redundancy), the disclosure of the present invention occurred in this article is considered to contain in the mode of multinomial subordinate each other the whole embodiments occurred in claim.
When a certain feature is for particular aspects of the present invention open (such as composition of the present invention), this type of openly is also considered to be applicable to any other aspect of the present invention (such as method of the present invention), adds necessary change.
Summary of the invention
In first aspect, the invention provides the composition that can obtain hydrophobic coating, said composition comprises:
A) hydrophobicity micelle;
B) there is the season silane and/or its oligopolymer of the first hydrolysis of four hydroxy iigands;
C) there is the season silane and/or its oligopolymer of the second hydrolysis of at least two hydroxy iigands and at least one hydrophobic ligand; With
D) solvent.
In a second aspect of the present invention, provide the method for forming hydrophobic coating from the teeth outwards, the method comprise the composition of any embodiment of first aspect is applied to described surface and dry described composition to obtain described hydrophobic coating.
In a third aspect of the present invention, provide and obtained and/or obtainable hydrophobic coating by any embodiment of the method for second aspect.
In a fourth aspect of the present invention, provide the method for the composition of any embodiment for the preparation of first aspect, wherein said method comprises the steps:
Formed comprise water, the first season silane precursor and the second season silane precursor reaction mixture;
(ii) be hydrolyzed in described reaction mixture first and second season silane precursor with provide described first and second season silane and/or its oligopolymer; With
(iii) described reaction mixture and described hydrophobicity micelle are merged.
Every other aspect of the present invention more easily can be found out after detailed description civilian under consideration and embodiment.
Describe in detail
Unique restriction about the hydrophobicity micelle type that can use in the present invention is that the hydrophobicity micelle of the type may be used in the composition of applicable human consumer use to form hydrophobic coating.The present inventor has been found that to there is the hydrophobicity that particle improves final coating composition in the present compositions.When being not wishing to be bound by theory, contriver believes that this may due to the structure of described particle imparting coating and their intrinsic hydrophobic surface properties.
The example of suitable hydrophobicity micelle comprises the micelle of such as metal-salt, particularly metal oxide.Suitable metal oxide comprises such as silicon-dioxide (SiO
2), titanium dioxide (TiO
2), aluminum oxide (Al
2o
3), zirconium dioxide (ZrO
2), tindioxide (SnO
2), zinc oxide (ZnO), ferric oxide (Fe
2o
3) and its mixture.More preferably there is the metal oxide on hydrophobic modified surface.
Particularly preferably be hydrophobic modified silicon dioxide granule, due to the consistency that they and silane are good.
The Exemplary silica basal granule attached bag being applicable to using in the present invention is containing at least 25 % by weight silicon-dioxide (i.e. silicon oxide), the preferably silicon-dioxide of at least 50 % by weight, the most preferably silicon-dioxide of at least 75 % by weight to 100 % by weight, based on particle total weight and comprise the four corner wherein contained.
Exemplary hydrophobic modified silicon-dioxide comprises those that comprise at least one following group:
Or
。
In one usually preferred embodiment, the silica-based particles used is by silicon-dioxide (i.e. pyrogenic silica) prepared by hydrophobic modified pyrolysis method.Be not wishing to be bound by theory, the present inventor believes the ability that the layered structure of pyrogenic silica contributes to composition and prepares hydrophobic coating.
This type of silicon-dioxide in such as U.S. Patent No. 7,282, in 236 describe and by supplier if Evonik Degussa GmbH is with title Aerosil
?r812, R812S, R202, MS202, R974, R972 and R805 are commercially available.Particularly preferably be the silicon-dioxide comprising the group represented by formula (I), formula (III) or its combination.Such as with title Aerosil
?r805 sells octyl group silane type and comprises the silicon-dioxide of the group represented by formula (III), such as, with title Aerosil
?r812S sells hexamethyldisilazane type and comprises the silicon-dioxide of the group represented by (I).
The size of the micelle used in the present invention is not particularly limited and eliminates (save) described particle must be colloid.But, preferably the size of described particle lower than 500 nm to avoid final coating too opaque.More preferably, described granularity is 1 to 250 nm.In addition or or, the primary particle size of described particle is 0.1 to 100 nm, more preferably 1 to 50 nm, most preferably 3 to 13 nm.
Described composition preferably comprises 0.1 to 10 % by weight, more preferably 0.25 to 5 % by weight, the most preferably micelle of amount of 1 to 3 % by weight, based on composition total weight and comprise the four corner contained herein.
The season silane of the first hydrolysis in the present invention is the silane with four hydroxy iigands.First hydrolysis season silane two or more silanol groups condensation can form oligopolymer together.But this condensation should not cause excessive polymerization, otherwise described silane may can not disperse well and even may precipitate.
Usually, described first hydrolysis season silane can from having formula (R
1)
4the silane precursor hydrolysis first season of Si.R
1representative can be hydrolyzed into the part of hydroxyl.R
1such as can be selected from alkoxyl group, halogen etc.
Use in the present invention the first season silane precursor example comprise comprise tetraethoxysilane (also referred to as tetraethyl orthosilicate or TEOS), tetramethoxy-silicane (also referred to as positive quanmethyl silicate or TMOS), tetrapropoxysilane (also referred to as positive silicic acid orthocarbonate or TPOS), four butoxy silanes (also referred to as positive silicic acid four butyl ester or TBOS), four bromo-silicanes, tetrachloro silicane or its mixture those.In a more preferred embodiment, described first season, silane precursor comprised TEOS, TBOS or its mixture.
The season silane precursor being such as applicable to using in the present invention comprises from the TEOS of Shanghai Chemical Reagent Co. Ltd (China) and/or the TBOS from Sigma-Aldrich (Germany).
The season silane of the second hydrolysis in the present invention is the silane with at least two hydroxy iigands and at least one hydrophobic ligand.Described second hydrolysis season silane two or more silanol groups condensation can form oligopolymer together.In addition or or, second hydrolysis season silane silanol groups can be hydrolyzed with first season silane silanol groups condensation to form the oligopolymer mixed.But this condensation should not cause excessive polymerization, otherwise described silane may not disperse well and even may precipitate.
Described second hydrolysis season silane one or more hydrophobic ligand preferably independently selected from alkyl, thiazolinyl, fluoroalkyl, fluorine thiazolinyl, aryl, fluoro aryl and its combination.Therefore, second hydrolysis season silane can by having formula (R
1)
4-msi (R
2)
mthe second season silane precursor hydrolysis, wherein:
-each R
1independently selected from alkoxyl group and halogen;
-R
2be selected from alkyl, thiazolinyl, fluoroalkyl, fluorine thiazolinyl, aryl, fluoro aryl and its combination; With
-m=1 or 2.
In order to provide maximum hydrophobicity, preferably R
2comprise at least 2 carbon atoms, more preferably at least 3 carbon atoms, also more preferably at least 4 carbon atoms, even more preferably at least 5 carbon atoms, most preferably at least 6 carbon atoms.Compared with Long carbon chain may but negative impact silane stability and/or can be detrimental to the ability that it is condensed into gel or film.Therefore, preferably R
2comprise and be less than 30 carbon atoms, more preferably less than 25, be most preferably less than 20 carbon atoms.For similar reason, in addition or or, preferably described second hydrolysis silane on only have a part to be hydrophobic, i.e. m=1.
In the most preferred embodiment, R
2for alkyl, particularly C
5-C
20alkyl.
Use in the present invention the second season silane precursor example comprise containing, for example those of lower material: phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl-trichloro-silicane, benzyl Trimethoxy silane, benzyl triethoxyl silane, benzyl trichlorosilane, styroyl Trimethoxy silane, styroyl triethoxyl silane, phenylethyltrichlorosilane, butyl trimethoxy silane, butyl triethoxyl silane, butyl trichlorosilane, cyclohexyl trimethoxy silane, cyclohexyltriethyloxysilane, cyclohexyl trichlorosilane, hexadecyl trimethoxy silane, hexadecyl, hexadecyl trichlorosilane, (ten three fluoro-1, 1, 2, 2-tetrahydro-octyl) Trimethoxy silane, (ten three fluoro-1, 1, 2, 2-tetrahydro-octyl) triethoxyl silane, (ten three fluoro-1, 1, 2, 2-tetrahydro-octyl) trichlorosilane, amyltrimethoxysilane, amyl triethoxysilane, trichlorine pentylsilane, hexyl Trimethoxy silane, hexyl triethoxyl silane, trichlorine hexyl silane, heptyl Trimethoxy silane, heptyl triethoxyl silane, trichlorine heptyl silane, octyl group Trimethoxy silane, octyltri-ethoxysilane, trichlorine octyl group silane, decyl Trimethoxy silane, decyl triethoxyl silane, trichlorine decyl silane, dodecyltrimethoxysilane, dodecyl triethoxysilane, trichlorine dodecyl silane, octadecyl trimethoxysilane, octadecyltriethoxy silane, trichlorine octadecylsilane, or its mixture.
More preferably, described second season, silane precursor was selected from amyltrimethoxysilane, amyl triethoxysilane, trichlorine pentylsilane, hexyl Trimethoxy silane, hexyl triethoxyl silane, trichlorine hexyl silane, heptyl Trimethoxy silane, heptyl triethoxyl silane, trichlorine heptyl silane, octyl group Trimethoxy silane, octyltri-ethoxysilane, trichlorine octyl group silane, decyl Trimethoxy silane, decyl triethoxyl silane, trichlorine decyl silane, dodecyltrimethoxysilane, dodecyl triethoxysilane, trichlorine dodecyl silane, hexadecyl trimethoxy silane, hexadecyl, hexadecyl trichlorosilane, octadecyl trimethoxysilane, octadecyltriethoxy silane, trichlorine octadecylsilane, or its mixture.
Such as, the silane precursor second season being applicable to using in the present invention comprises hexyl Trimethoxy silane, dodecyltrimethoxysilane, trichlorine dodecyl silane, and/or octadecyltriethoxy silane, they are all commercially available from Tokyo Chemical Industry Co., Ltd (Japan).
The present inventor finds that the silane comprising the first hydrolysis in the present compositions can provide and has excellent stability, such as scratch resistance and/or wear-resisting in coating.But the silane relative hydropathic of described first hydrolysis, therefore the present inventor has been found that the silane needing to introduce owing to there is one or more hydrophobic ligand and relatively more hydrophobic second hydrolysis.Surprisingly, even if the relative hydrophobicity of the silane of described first hydrolysis, but the present inventor has been found that the silane of the first hydrolysis of even vast scale also may be used for described composition and do not lose the ability that it obtains hydrophobic coating.Such as, the silane of the first hydrolysis in the composition and the weight ratio of the second silane be hydrolyzed can be at least 1:1, more preferably at least 2:1, also more preferably at least 3:1, most preferably at least 4:1.But, in order to the hydrophobicity of final coating maximizes, the silane of preferably the first hydrolysis in the composition and the weight ratio of the second silane be hydrolyzed for being not more than 100:1, more preferably no more than 50:1, also more preferably no more than 20:1, be most preferably not more than 10:1.
The present inventor also has been found that the silane of the total amount that needs are relatively low is to provide not only hydrophobicity but also firmly composition.In addition, excessive in the composition silane can cause too early polycondensation and/or the precipitation of described silane.Such as, described composition can comprise no more than 10 % by weight, more preferably no more than 7 % by weight, also more preferably no more than 5 % by weight, even more preferably no more than 2 % by weight, even also more preferably no more than 1 % by weight, the most preferably silane of the first hydrolysis of the no more than total amount of 0.2 % by weight and the silane of the second hydrolysis that account for described composition.Minimum (amount of silane of the first hydrolysis adds the amount of the silane of the second hydrolysis) of total silane be described composition preferably at least 0.001 % by weight, more preferably at least 0.005 % by weight, also more preferably at least 0.01 % by weight, most preferably at least 0.02 % by weight.
Except described micelle and silane, described composition also comprises solvent.Solvent forms the surplus of described composition usually, but optional composition as tinting material, sanitas etc. can also be present in as described in composition.Described composition can comprise such as 50 to 99.9 % by weight, and more preferably 70 to 99 % by weight, also more preferably 80 to 98 % by weight, the most preferably solvent of amount of 90 to 97 % by weight.
Preferably volatile solvent (namely there is the solvent can measuring vapour pressure at 25 DEG C).Preferably there is the solvent of the vapour pressure at least equaling pure water at 25 DEG C.Volatile solvent is preferred, because the tendency of its rapid evaporation, so leave the coating being made up of (or at least basic comprising) the silane of silica-based particles, the first hydrolysis and the silane of the second hydrolysis.Described silane can be polymerized and experience so-called sol-gel transition during drying process.Be not wishing to be bound by theory, the present inventor believes that the polymerization of silane in final coating composition partly may contribute to the stability of its excellence.
Occasionally, some solvents can remain in described coating, and thus prevent less desirable opaqueness in these cases, preferably use the solvent of the refractive index had close to silane.Therefore, preferably described solvent has 1.2 to 1.6, more preferably the refractive index of 1.3 to 1.5.
Particularly preferred solvent is polar organic solvent, more preferably C
1-C
4alcohol, due to its relative safety and high volatile volatile.Described solvent most preferably comprises methyl alcohol, ethanol, propyl alcohol, Virahol or its mixture.
In addition or or, described solvent can comprise water, preferred amount is described composition weight at least 5%, more preferably at least 10%, also more preferably at least 15%, most preferably at least 20%.But glassware for drinking water has poor with consistency that is hydrophobic particles, therefore preferably the amount of water is not more than 80% of described composition weight in described composition, more preferably no more than 70%, also more preferably no more than 50%, is most preferably not more than 30%.
Advantageously, polar organic solvent can be used for the consistency improving hydrophobic particles and water.Therefore, in one embodiment, described solvent comprises polar organic solvent (particularly C
1-C
4alcohol) and water.More preferably, described solvent with 100:1 to 1:10, even more preferably 20:1 to 1:2, also more preferably 10:1 to 1:1 the solvent of most preferably 5:1 to 2:1: the weight ratio of water comprises polar organic solvent and water.
In certain embodiments, particularly when described composition is used as hard-surface cleaning compositions, preferably comprise and comprise tensio-active agent in the formulation.Therefore, described composition preferably comprises tensio-active agent.Described tensio-active agent can be anionic, non-ionic type, cationic, amphoteric, amphoteric ion type or its mixture.But we find cationic surfactant particularly in composition used in the present invention, and do not affect the ability that described composition forms hydrophobic coating.Therefore, described tensio-active agent preferably comprises cationic surfactant, and more preferably, in described composition, the tensio-active agent of at least 50% gross weight is cationic surfactant, and also more preferably at least 75 % by weight, most preferably 80 to 100 % by weight.
Preferred cationic surfactant is quaternary ammonium salt.More preferably, described cationic surfactant has formula N
+r
3r
4r
5r
6, wherein R
3, R
4, R
5and R
6be (C independently
1to C
30) alkyl or benzyl.Preferably, R
3, R
4, R
5and R
6one, two or three are (C independently
4to C
30) alkyl and other R one or more
3, R
4, R
5and R
6group is (C
1-C
6) alkyl or benzyl.
Most preferred cationic surfactant is selected from hexadecyl-trimethylammonium bromide (CTAB), hexadecyl-trimethyl ammonium chloride (CTAC), Shan Yuji-trimethyl ammonium chloride (BTAC), stearyl trimethyl ammonium chloride (STAC), Benzyldimethyltetradecyla-mmonium chloride (BDMTAC) and its mixture.
Aniorfic surfactant can destroy the ability that described composition forms hydrophobic coating usually.Therefore, preferably described tensio-active agent (when it is present) is substantially free of aniorfic surfactant.More preferably, the tensio-active agent being less than the gross weight of 10% in described composition is aniorfic surfactant, and also more preferably less than 5 % by weight, most preferably in described composition, the tensio-active agent of 0 to 1% is aniorfic surfactant.
Usually, described composition comprises the tensio-active agent of the amount of 0.01 to 4 % by weight.But even for cationic surfactant, in some cases, high-content can disturb described composition to form the ability of hydrophobic coating.Therefore, what preferably described composition comprised described composition weight is less than 1%, more preferably less than 0.7%, even more preferably less than 0.5%, and the most preferably tensio-active agent of 0.05 to 0.3%.
In some embodiments, described composition can be substantially free of tensio-active agent.More preferably, what such composition comprised described composition weight is less than 0.01%, the most preferably tensio-active agent of 0 to 0.001%.
Composition of the present invention can have any suitable pH.But the stability that we have been surprised to find described composition is best, if they are not too acid.Therefore, preferably, the pH of described composition is 5 to 10, more preferably 6 to 8.
Composition of the present invention is for the preparation of hydrophobic coating.Method for manufacturing hydrophobic coating from the teeth outwards preferably includes and described composition is put on surface and makes the step of said composition drying.Described silane can be polymerized (further) and experience so-called sol-gel transition during drying process.Do not wish to be subject to theoretical constraint, the present inventor believes that the polymerization of the silane in final coating composition partly may contribute to the stability of its excellence.
Usually, after drying, what described coating comprised this coating wt is less than 30%, more preferably less than 20%, also more preferably less than 10%, and the most preferably solvent of 0.001 to 5%.
Described coating is hydrophobic.In some cases, such as described coating can be high hydrophobicity, or even super-hydrophobicity.More preferably, described coating can have at least 145 ° of water or the even contact angle of 150 to 160 °.In addition or or, described coating can have and is less than 15 ° or the even slide angle of 0.1 to 10 ° to water.
Described coating is generally at least translucent and normally transparent.Such as, described coating has at least 80%, and more preferably at least 85%, the most preferably value of transmittance of 87 to 95%.
Composition of the present invention is preferably applicable to treatment of hard surfaces, particularly helps hard-surface cleaning or antiscale.For purposes of the present invention, " crust " refers to and comprises hard material such as glass, glazed ceramics, metal, stone, plastics, paint, timber or its any surface of combining.Usually, in resident family, described crust comprises glass, kitchen, bathroom, toilet, furniture, floor etc.
When by described compositions-treated crust, any general fashion for the treatment of of hard surfaces is acceptable.Usually, be that described composition is sprayed on described crust by the mode of described compositions-treated crust, or by crust described in the cleaning piece wiping being impregnated with described composition, or described composition is poured on described crust, or its combination.Preferably, the mode for the treatment of of hard surfaces for described composition is sprayed on crust, and/or by being impregnated with the cleaning piece wiping crust of described composition.When spraying for the treatment of crust, how to spray described composition and not limiting.Usually, the spray bottle for hard-surface cleaning product is favourable.When adopting wiping treatment of hard surfaces, cleaning piece comprises woven or non-woven, natural or synthetic sponge or sponge sheet, and " squeegee " material, paper handkerchief etc. is suitable.Described cleaning piece can be done dipping or more preferably flood with wet form.
But, by any particular theory or explain constraint, we believe described composition make its pass through to deposit hydrolysis season silane and/or its oligopolymer and hydrophobic particles work on crust, thus form the hydrophobic layer being attached to crust.Described layer can improve the ability of resistance to dirt deposits and/or spot or at least make this type of material be easier to removing.
Therefore, after with described compositions-treated surface, the method for the treatment of crust optionally can also comprise the step making dirt and/or grime.Therefore, dirt or spot can easily be removed when method according to the present invention cleans described crust subsequently.Meanwhile, composition of the present invention is also preferred puts on described crust in clean period subsequently.Optionally, adopt described compositions-treated crust, rinse step can be carried out by preferred water afterwards.
Therefore, the most preferred method for the treatment of crust comprises:
I. described hydrophobic coating is formed on said surface;
II. make dirt and/or grime in described coating; Then
III. clean described surface is to remove described dirt and/or spot.
The present invention can also provide other other benefits, clean, the lower surface corrosion of clean, the less effort of such as long duration, clean period less noise and/or anti-scraping property.Other aspects of the present invention are included in hard-surface cleaning operation and obtain the method for these other benefits one or more and/or described composition in the method manufactured a product for providing the purposes of any one or more these type of benefits of the present invention.
Dirt of the present invention and spot can comprise dirt and the spot of any type usually run in resident family, and organic or inorganic is originated, and no matter naked eyes are visible or invisible, comprises dirty solid fragment and/or with bacterium or other pathogenic agent.Especially, method and composition according to the present invention may be used for processing the surface being easy to meet with fat or grease soils and spot.
Composition of the present invention can be prepared in any convenient manner.Suitably, but described composition is prepared by a method comprising the following steps:
Formed comprise water, the first season silane precursor and the second season silane precursor reaction mixture;
(ii) be hydrolyzed in described reaction mixture first and second season silane precursor to provide the season silane and/or its oligopolymer of described first and second hydrolysis; With
(iii) merge described reaction mixture and described hydrophobicity micelle.
When formed comprise water and season silane precursor reaction mixture time, for mixing water and season silane precursor order do not limit.Water can be added season silane precursor, or season silane precursor is added to the water.Normally, stir for obtain water and season silane precursor well blend.
Similarly, the order merging described reaction mixture and described hydrophobicity micelle is not limited.But, in preferred embodiments, step (iii) before the step (ii) or period carry out, because described micelle can interact with greater or lesser degree and silane by this way during hydrolytic process.Especially, when described micelle comprises silicon-dioxide, this may cause some bondings of silane and the described micelle be hydrolyzed, because we have found that if prepare composition by this way, then the weather resistance of final coating improves (although having slight loss of clarity).Therefore, in particularly preferred embodiments, described method comprises the steps:
A) providing package containing hydrophobic modified micelle silicon-dioxide, the first season silane precursor, the second season silane precursor and the reaction mixture of water; Then
B) be hydrolyzed in described reaction mixture described first and second season silane precursor to provide the season silane and/or its oligopolymer of described first and second hydrolysis.
Silane excessive in described reaction mixture may cause too early polycondensation and/or the precipitation of silane.Such as, described mixture can comprise the first season silane precursor and the second season silane precursor, total amount is no more than 10% of described mixture weight, more preferably no more than 7%, also more preferably no more than 5%, even more preferably no more than 2%, most preferably no more than 1%.Minimum (first season, the amount of silane precursor added the amount of the silane precursor second season) of total silane is preferably at least 0.001% of described mixture weight, and more preferably at least 0.005%, also most preferably at least 0.01%, most preferably at least 0.02%.
In described mixture the first season silane precursor and the second season silane precursor weight ratio can be such as at least 1:1, more preferably at least 2:1, also more preferably at least 3:1, most preferably at least 4:1.In addition or or, in described mixture the first season silane precursor and the second season silane precursor weight ratio such as can be not more than 100:1, more preferably no more than 50:1, also more preferably no more than 20:1, be most preferably not more than 10:1.
The season hydrolysis of silane precursor can at described mixture for carrying out time acid or alkaline.In order to avoid excessive polymerization, described mixture is preferably acid.More preferably, the pH value of described mixture is 2 to 7, most preferably is 3 to 5.The pH of described mixture is lower, and the season hydrolysis of silane precursor is faster.Acid for the pH for regulating described mixture does not limit, such as, can use hydrochloric acid, sulfuric acid, citric acid, oxalic acid or its combination.
If described mixture is acid during hydrolysing step, then after this hydrolysing step, preferably by the pH regulator to 5 of described mixture to 10, more preferably 6 to 8.
Described reaction mixture can comprise polar organic solvent in addition.
Described composition can any packaged, but preferably packs as conventional crust process or cleaning product.Preferably be packaged as spray application device.Also can be pump decollator (no matter spraying or non-spraying pump) and topple over applying (bottle etc.).Also described composition can be adopted to flood cleaning piece.
There is provided embodiment hereafter to help to understand the present invention.There is provided described embodiment and the scope of non-limiting claim.
Embodiment
material
-Aerosil
?r812S is the silicon dioxide granule (average primary particle size 7 nm) of the hexamethyldisilazane-modification of being supplied by Evonic AG.
-RHODORSIL
?bP9400 is the alkyl polysiloxane oligopolymer from Bluestar Silicones.
-HTS is the hexyl Trimethoxy silane from Tokyo Chemical Industry Co., Ltd..
-DTS is the dodecyl Trimethoxy silane from Tokyo Chemical Industry Co., Ltd..
-TEOS is the tetraethyl orthosilicate from Sinopharm Chemical Reagent Co..
-CTAB is the hexadecyl-trimethylammonium bromide from Rhodia.
-CTAC is the hexadecyl-trimethyl ammonium chloride from Clariant.
-BTAC is the mountain Yu base-trimethyl ammonium chloride from KCI Limited.
-STAC is the stearyl trimethyl ammonium chloride from Clariant.
Unless stated otherwise, every other material is analytical pure rank.
the preparation of particle-silane dispersion
By cohydrolysis and condensation two silane precursor-TEOS with have the silane (HTS or DTS) of hydrophobic ligand-prepare colloidal sol.Described silane is scattered in alcohol (ethanol and/or Virahol) solvent and water under room temperature (25 DEG C) stirs 30 min.Then, under stirring at room temperature 3 h, hydrochloric acid (36.5 wt%) is added in described solution to cause the hydrolysis of silane and condensation and to prepare matrix sol composition.
By hydrophobicity pyrogenic silica particle (Aerosil under sonication 15 min
?r812S) matrix colloidal sol (as above preparing) is added into.Unless otherwise indicated, otherwise use ammonia (25 wt%) by preparation hydrolysising silane/silica dispersion pH regulator to about 7 ~ 8 prepare use.
When tensio-active agent comprises in the composition, described dispersion can be added into after as above preparing.
the preparation of coating
Select slide glass as model base material.By transfer pipet for dispersion being dripped at described slide glass with controllable amounts.After described dispersion drips on the target surface, with the end of transfer pipet, described composition is sprawled on said surface to guarantee even spread.For spraying, the triggering device-sprayer being widely used in home care or personal care product is used for described composition to be applied on the surface.After described dispersion spraying on the target surface, paper handkerchief or cloth are used for wiping target surface thus make coating uniform and remove excessive dispersion.
After applying on the substrate by described dispersion, solvent is at room temperature evaporated (conventional evaporation time is 10-15 min).Expect that described silane experiences further polycondensation on substrate surface during drying to form durable coating, make silicon dioxide granule embed in gained network simultaneously.
coating standard
-by the analysis system 100 (DSA 100, Kr ü ss) of droplet profile for measuring contact angle and slide angle.Use and put on the deionized water drop of about 5 μ L of 5 differences of each film, the DSA 100 of tilting table maximum load in the visual field with maximum 90 ° is used for slide angle test, the slide angle of whole 5 drops is averaged.
-the visible transmission ratio of coating is measured by UV-visible spectrometer (Perkin-Elmer Lambda 650S).
As M.H. Blees
deng people(
thin Solid Film,
359, 1) described in, use the drawing test method with Scotch 600 adhesive tape (3M) to measure the weather resistance of film.
embodiment 1
This embodiment confirms existence and the impact of amount on coating performance with the silane of hydrophobic ligand (HTS).
In this article, before the coating non-pyrogenic silica particle is not added into described composition.
The composition that the colloidal sol of test listed by table 1 and the contact angle of coating prepared by this colloidal sol.
Table 1
| Sample | TEOS (wt%) | HTS (wt%) | Water (wt%) | HCl * (wt%) | Virahol (wt%) | Contact angle **(degree) |
| 1 | 5.9 | 0.00 | 10.6 | 1.2 | To 100 | 24.0 ± 0.9 |
| 2 | 5.8 | 0.96 | 10.5 | 1.2 | To 100 | 114.5 ± 1.4 |
| 3 | 5.8 | 1.9 | 10.4 | 1.2 | To 100 | 106.0 ± 1.2 |
| 4 | 5.7 | 2.8 | 10.3 | 1.2 | To 100 | 106.0 ± 2.1 |
| 5 | 5.7 | 3.7 | 10.2 | 1.2 | To 100 | 107.1 ± 2.3 |
| 6 | 5.6 | 4.6 | 10.1 | 1.2 | To 100 | 101.5 ± 1.0 |
* the amount provided is the amount of the 36.5 wt% aqueous solution.
The error that * provides is 95% fiducial interval.
This data presentation, there is not (sample 1) under HTS, described coating is not hydrophobic.Add even a small amount of HTS (sample 2) to make to form hydrophobic coating.The amount (sample 3 to 6) of further raising HTS does not improve the hydrophobicity of film, in fact may reduce hydrophobicity a little.
embodiment 2
This embodiment confirms the impact (again, before the coating do not add pyrogenic silica particle to described composition) of the amount of water on coating performance.
The composition that the colloidal sol of test enumerated by table 2 and the contact angle of coating prepared from this colloidal sol.
Table 2
| Sample | TEOS (wt%) | HTS (wt%) | Water (wt%) | HCl * (wt%) | Virahol (wt%) | Contact angle **(degree) |
| 7 | 6.5 | 1.06 | 0.0 | 1.4 | To 100 | 96.0 ± 0.8 |
| 8 | 5.8 | 0.96 | 10.5 | 1.2 | To 100 | 114.5 ± 1.4 |
| 9 | 5.3 | 0.86 | 18.8 | 1.1 | To 100 | 105.6 ± 0.9 |
| 10 | 4.8 | 0.78 | 25.8 | 1.0 | To 100 | 110.0 ± 2.1 |
| 11 | 4.4 | 0.73 | 31.7 | 0.9 | To 100 | 101.8 ± 1.7 |
* the amount provided is the amount of the 36.5 wt% aqueous solution.
The error that * provides is 95% fiducial interval.
These data illustrate does not add extra water (namely except the water in hydrochloric acid soln), causes being formed just hydrophobic a little film (sample 7).The water (sample 8 to 10) adding the amount of about 10 to about 26 wt% provides more hydrophobic film.But the water yield is increased to the hydrophobicity not improving described film higher than 30 % by weight (samples 11) further, in fact may reduce hydrophobicity a little.
embodiment 3
This embodiment confirms the impact of amount for coating performance of hydrophobic particles.
The composition provided in employing table 3 prepares matrix colloidal sol.
Table 3
| Matrix colloidal sol | TEOS (wt%) | Ethanol (wt%) | HCl * (wt%) | DTS (wt%) | Water (wt%) |
| A | 0.18 | To 100 | 0.075 | 0.034 | 0.38 |
| B | 0.12 | To 100 | 0.075 | 0.022 | 0.25 |
| C | 0.059 | To 100 | 0.075 | 0.011 | 0.13 |
| D | 0.030 | To 100 | 0.075 | 0.006 | 0.063 |
* the amount provided is the amount of the 36.5 wt% aqueous solution.
Then, by described matrix colloidal sol for the preparation of the hydrophobicity pyrogenic silica particle (Aerosil with different content
?r812S) dispersion.Contact angle and the transparency of the coating be made up of these dispersions are summarized in table 4.
Table 4
| Sample | Matrix colloidal sol | Pyrogenic silica (wt%) | Contact angle *(degree) | Transmittance (%) |
| 12 | A | 0.00 | 108.6 ± 0.9 | 92 |
| 13 | A | 0.25 | 122.3 ± 3.2 | 82 |
| 14 | A | 0.50 | 133.9 ± 2.2 | 82 |
| 15 | A | 1.00 | 152.7 ± 2.1 | 85 |
| 16 | A | 1.50 | 150.7 ± 3.0 | 78 |
| 17 | A | 2.00 | 148.5 ± 2.7 | 87 |
| 18 | A | 2.50 | 153.3 ± 4.5 | 89 |
| 19 | B | 0.00 | 107.1 ± 1.0 | 90 |
| 20 | B | 0.25 | 141.2 ± 2.2 | 86 |
| 21 | B | 0.50 | 139.8 ± 1.9 | 88 |
| 22 | B | 1.00 | 135.5 ± 3.3 | 89 |
| 23 | B | 1.50 | 149.9 ± 2.4 | 85 |
| 24 | B | 2.00 | 147.4 ± 1.5 | 90 |
| 25 | B | 2.50 | 155.2 ± 2.7 | 89 |
| 26 | C | 0.00 | 107.4 ± 1.1 | 88 |
| 27 | C | 0.25 | 140.3 ± 5.0 | 88 |
| 28 | C | 0.50 | 143.7 ± 3.7 | 87 |
| 29 | C | 1.00 | 150.6 ± 2.1 | 87 |
| 30 | C | 1.50 | 153.9 ± 1.1 | 87 |
| 31 | C | 2.00 | 155.5 ± 3.1 | 89 |
| 32 | C | 2.50 | 156.7 ± 1.7 | 87 |
| 33 | D | 0.00 | 108.7 ± 0.9 | 91 |
| 34 | D | 0.25 | 128.8 ± 4.1 | 89 |
| 35 | D | 0.50 | 143.2 ± 3.2 | 89 |
| 36 | D | 1.00 | 152.0 ± 3.0 | 84 |
| 37 | D | 1.50 | 150.8 ± 1.7 | 88 |
| 38 | D | 2.00 | 152.5 ± 4.0 | 86 |
| 39 | D | 2.50 | 152.9 ± 2.5 | 88 |
* the error provided is 95% fiducial interval.
This data presentation is when adding described colloidal sol by silicon dioxide granule, and these particles greatly improve the hydrophobicity of final coating.When only adding the silicon dioxide granule of 0.25 wt %, the contact angle of the coating prepared by matrix sol B reaches higher than 140 °.General trend is that contact angle increases along with the amount increase of the pyrogenic silica added.When silicon dioxide granule content is higher than 1.0 wt%, most of coating demonstrates super-hydrophobicity and has low-down slide angle (lower than 8 °).When in described dispersion, silicon dioxide granule content is 2 to 2.5 wt%, contact angle is increased to close to or more than 150 °, when glass only tilts to about 2 to 5 °, 5 μ l water droplets are rolled off from surface.
The quantitative characteristic of the transparency of coating is the transmittance of coating under 550 nm wavelength.The transmittance of uncoated slide glass is 89.0%.Therefore, the data presentation in table 4 goes out all coatings and all has close or total transparency.The transmittance of these coatings is 78% to 92%.Surprisingly, some samples demonstrate the visible transmission ratio larger than blank glass.But some samples illustrate the transmittance than blank glass difference.Usually, the coating be made up of the dispersion based on sol B, C or D demonstrates best transparency.This may because the total silane amount in higher matrix Sol A causes the agglomerate obtaining the crosslinked polysilane of high-content and the silicon dioxide granule of large-size.
embodiment 4
This embodiment confirms that type of solvent is on the impact of coating performance.
The composition provided in employing table 5 prepares matrix colloidal sol.
Table 5
| Matrix colloidal sol | TEOS(μl) | Ethanol (ml) | Virahol (ml) | HCl * (μl) | DTS (μl) | Water (μ l) |
| E | 20 | 20 | -- | 10 | 4 | 40 |
| F | 20 | -- | 20 | 10 | 4 | 40 |
* the amount provided is the amount of the 36.5 wt% aqueous solution.
Then, by described matrix colloidal sol for the preparation of the hydrophobicity pyrogenic silica particle (Aerosil with different content
?r812S) dispersion.Contact angle and the transparency of the coating be made up of these dispersions are summarized in table 6.
Table 6
| Sample | Matrix colloidal sol | Pyrogenic silica (wt%) | Contact angle *(degree) | Transmittance (%) |
| 40 | E | 0.25 | 131.3 ± 3.5 | 86 |
| 41 | E | 0.50 | 137.3 ± 2.7 | 88 |
| 42 | E | 1.00 | 146.5 ± 2.2 | 89 |
| 43 | E | 1.50 | 149.9 ± 1.7 | 85 |
| 44 | E | 2.00 | 147.4 ± 2.0 | 90 |
| 45 | E | 2.50 | 155.2 ± 2.1 | 89 |
| 46 | F | 0.25 | 135.2 ± 4.1 | 86 |
| 47 | F | 0.50 | 141.0 ± 2.3 | 88 |
| 48 | F | 1.00 | 141.8 ± 5.1 | 89 |
| 49 | F | 1.50 | 142.0 ± 2.1 | 86 |
| 50 | F | 2.00 | 152.7 ± 1.9 | 87 |
| 51 | F | 2.50 | 150.3 ± 2.1 | 88 |
* the error provided is 95% fiducial interval.
Data acknowledgement ethanol in this table and Virahol based solvent are all applicable to providing the dry dispersion obtaining the coating with excellent hydrophobicity and the transparency.
embodiment 5
This embodiment confirms the weather resistance of the coating be made up of various hydrophobicity pyrogenic silica dispersion.
The composition of described dispersion provides in table 7.
Table 7
| Sample | Aerosil ? R812S (wt%) | RHODORSIL ? BP9400 (wt%) | TEOS (wt%) | DTS (wt%) | Ethanol (wt%) | HCl * (wt%) | Water (wt%) |
| 52 | 1.5 | -- | -- | -- | To 100 | -- | -- |
| 53 | 1.5 | 0.8 | -- | -- | To 100 | -- | -- |
| 54 | 1.5 | -- | 0.029 | 0.006 | To 100 | 0.069 | 0.062 |
* the amount provided is the amount of the 36.5 wt% aqueous solution.
Pull-out test (pull-off test) result being applied to the coating be made up of above-mentioned dispersion is provided in table 8.
Table 8
。
As can be the data from table 8 found out, the initial contact angle of these three coatings is all about 150 °.Observe after first time pull-out test, lose whole hydrophobicity by the coating only having the dispersion of silicon-dioxide to make in alcohol (sample 52).For the coating be made up of the silicon-dioxide in alcohol and silicone (sample 53), after first time pull-out test, described coating still demonstrates hydrophobicity, but increases along with drawing number of times, and the contact angle of coating reduces gradually.About third time pull-out test after, contact angle is reduced to about 80 °, and drawing subsequently has little impact to contact angle.For the super-hydrophobic coating be made up of the dispersion of silicon-dioxide in the alcosol of silane (sample 54), observe the contact angle of first time pull-out test on coating and there is little impact.After second time drawing, described coating still demonstrates the high contact angle of 134 °.Even after the 5th drawing, the contact angle of coating is kept above 100 °.Therefore, the coating (sample 54) be made up of the silane being hydrolyzed demonstrates excellent weather resistance.
embodiment 6
This embodiment confirms the stability in storage of the dispersion of hydrophobicity pyrogenic silica.
Composition and the pH of described dispersion are provided in table 9.
Table 9
| Sample | Aerosil ? R812S (wt%) | HTS (wt%) | TEOS (wt%) | Virahol (wt%) | Ethanol (wt%) | HCl * (wt%) | Water (wt%) | Ammonia (wt%) | pH |
| 55 | 2.0 | 0.94 | 5.7 | To 100 | --- | 1.2 | 9.3 | --- | 3 |
| 56 | 2.0 | 0.91 | 5.5 | To 100 | --- | 1.2 | 10 | 1.6 | 7 |
| 57 | 2.0 | 0.93 | 5.7 | --- | To 100 | 1.2 | 11 | --- | 3 |
| 58 | 2.0 | 0.90 | 5.5 | --- | To 100 | 1.1 | 13 | 1.7 | 7 |
* the amount provided is the amount of the 36.5 wt% aqueous solution.
The section store of each dispersion in sealed vessel, under some of them container remains on the constant temperature of 25 DEG C, under other remain on the constant temperature of 37 DEG C.Take out sample 1 and 3 months and evaluate the ability of outward appearance and formation super-hydrophobic coating.Result display in table 10, uses following mark:
√-good appearance; Form super-hydrophobic coating.
-slight sedimentation or visible agglomerate; Form super-hydrophobic coating.
×-significantly sedimentation; The coating hydrophobicity reduced.
Table 10
。
Result in table 10 demonstrates after all samples at room temperature even stores three months all has satisfactory stability.After 3 months, the sedimentation in the composition with pH 3 is obvious, but these compositions still have rational outward appearance and keep being formed the ability of super-hydrophobic coating.The sample with pH 7 demonstrates best stability, no matter in room temperature or at 37 DEG C.
embodiment 7
This embodiment confirms the consistency of some dispersion and cationic surfactant.
The composition of dispersion is provided in table 11.
Table 11
| Sample | Aerosil ?R812S (wt%) | DTS (wt%) | TEOS (wt%) | Virahol (wt%) | CTAB (wt%) | HCl * (wt%) | Water (wt%) |
| 59 | 1.0 | 0.007 | 0.036 | To 100 | 0.0 | 0.046 | 39 |
| 60 | 1.0 | 0.007 | 0.036 | To 100 | 0.1 | 0.045 | 39 |
| 61 | 1.0 | 0.007 | 0.035 | To 100 | 0.5 | 0.045 | 38 |
| 62 | 1.0 | 0.007 | 0.035 | To 100 | 1.0 | 0.045 | 38 |
| 63 | 1.0 | 0.007 | 0.035 | To 100 | 1.5 | 0.045 | 38 |
| 64 | 1.0 | 0.007 | 0.035 | To 100 | 2.0 | 0.045 | 38 |
* the amount provided is the amount of the 36.5 wt% aqueous solution.
Contact angle and the outward appearance of the film be made up of these compositions are provided in table 12.
Table 12
| Sample | Contact angle *(degree) | Film appearance |
| 59 | 150 ± 3 | Homogeneous transparent |
| 60 | 149 ± 2 | Homogeneous transparent |
| 61 | 141 ± 4 | Some obvious oyster white regions |
| 62 | 15 ± 11 | There is the transparency gap in different oyster white region |
| 63 | 12 ± 2 | There is the transparency gap in different oyster white region |
| 64 | 8 ± 2 | There is the transparency gap in different oyster white region |
* the error provided is 95% fiducial interval.
Result in table 12 demonstrates, and for containing the sample lower than 1.0% CTAB, can make hydrophobic film.The content increasing cationic surfactant increasingly makes this film unstable and destroys its hydrophobicity.
embodiment 8
This embodiment confirms the composition being applicable to cleaning of hard surfaces.
Composition provides in table 13.
Table 13
| Composition (wt%) | Sample 65 | Sample 66 | Sample 67 | Sample 68 |
| Aerosil ?R812S | 1.000 | 1.000 | 1.000 | 1.000 |
| DTS | 0.007 | 0.007 | 0.007 | 0.007 |
| TEOS | 0.036 | 0.036 | 0.036 | 0.036 |
| Virahol | To 100 | To 100 | To 100 | To 100 |
| HCl * | 0.045 | 0.045 | 0.045 | 0.045 |
| Water | 39 | 39 | 39 | 39 |
| CTAB | 0.1 | -- | -- | -- |
| CTAC | -- | 0.1 | -- | -- |
| BTAC | -- | -- | 0.1 | -- |
| STAC | -- | -- | -- | 0.1 |
* the amount provided is the amount of the 36.5 wt% aqueous solution.
Find that sample 65-58 all forms transparent super-hydrophobic coating.
In the first and second clean operations, comparative sample 65-68 and be purchased hard surface cleaner clean-up performance.For first time clean operation, above-mentioned sample has than being purchased sanitising agent performance poor a little, but still provides acceptable result.In second time clean operation, even if the performance of above-mentioned sample is no better than, to be purchased sanitising agent also equally good with it.
Claims (19)
1. can obtain the composition of hydrophobic coating, said composition comprises:
A) hydrophobicity micelle;
B) there is the season silane and/or its oligopolymer of the first hydrolysis of four hydroxy iigands;
C) there is the season silane and/or its oligopolymer of the second hydrolysis of at least two hydroxy iigands and at least one hydrophobic ligand; With
D) solvent.
2. composition as claimed in claim 1, wherein said micelle is hydrophobic modified silicon dioxide granule, preferably hydrophobic modified pyrogenic silica particle.
3. composition as claimed in claim 2, wherein said silicon dioxide granule comprises at least one following group:
Or
。
4. the composition as described in aforementioned any one of claim, wherein said first hydrolysis season silane can from having formula (R
1)
4the silane precursor hydrolysis first season of Si, wherein each R
1independently selected from alkoxyl group and halogen.
5. composition according to claim 4, wherein said first season, silane precursor comprised tetraethoxysilane, tetramethoxy-silicane, tetrapropoxysilane, four butoxy silanes, four bromo-silicanes, tetrachloro silicane or its mixture.
6. as the composition described in aforementioned any one of claim, wherein said second hydrolysis season silane can from having formula (R
1)
4-msi (R
2)
mthe second season silane precursor hydrolysis, wherein:
-each R
1independently selected from alkoxyl group and halogen;
-R
2be selected from alkyl, thiazolinyl, fluoroalkyl, fluorine thiazolinyl, aryl, fluoro aryl and its combination; With
-m=1 or 2.
7. composition, wherein R as claimed in claim 6
2comprise at least 2 carbon atoms, preferably R
2for C
3-C
30.
8. the composition as described in claim 6 or claim 7, wherein m=1.
9. the composition as described in aforementioned any one of claim, the silane of wherein said first hydrolysis and the weight ratio of the second silane be hydrolyzed are at least 1:1, preferred 2:1 to 50:1.
10. the composition as described in aforementioned any one of claim, wherein said composition comprise account for said composition 0.1 to 10 % by weight the hydrophobicity micelle of amount.
11. compositions as described in aforementioned any one of claim, wherein said composition comprises the silane of the first hydrolysis of the total amount accounting for said composition 0.001 to 10 % by weight and the silane of the second hydrolysis.
12. compositions as described in aforementioned any one of claim, wherein said solvent comprises polar organic solvent, and preferably wherein said polar organic solvent comprises C
1-C
4alcohol.
13. compositions as described in aforementioned any one of claim, wherein said solvent comprises water, and preferably wherein said solvent comprises the water of the amount accounting for said composition 5 to 50 % by weight.
14. methods forming hydrophobic coating from the teeth outwards, the method comprises and the composition of any one of claim 1 to 13 is put on this surface and by dry for said composition to obtain hydrophobic coating.
The method of 15. treatment of hard surfaces, it comprises:
I. hydrophobic coating is formed on said surface by the method for claim 14;
II. make dirt and/or grime in described coating; Then
III. by described surface cleaning to remove described dirt and/or spot.
16. methods as claimed in claim 15, wherein Step II I comprises the composition described in any one of claim 1 to 13 is put on described surface.
17. hydrophobic coatings obtained by the method for claim 14, wherein said coating have at least 110 ° the contact angle to water, be less than the slide angle to water of 45 ° or both.
The preparation method of 18. compositions as described in any one of claim 1 to 13, wherein the method comprises the steps:
Formed comprise water, the first season silane precursor and the second season silane precursor reaction mixture;
(ii) be hydrolyzed in described reaction mixture first and second season silane precursor to provide the season silane and/or its oligopolymer of described first and second hydrolysis; With
(iii) described reaction mixture and described hydrophobicity micelle are merged.
19. methods as claimed in claim 18, wherein before the step (ii) or period carry out step (iii).
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| EP12184348 | 2012-09-14 | ||
| EP12184348.6 | 2012-09-14 | ||
| PCT/EP2013/064362 WO2014019809A1 (en) | 2012-08-02 | 2013-07-08 | Hydrophobic coating |
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|---|---|
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| CN110520492A (en) * | 2017-06-29 | 2019-11-29 | 住友化学株式会社 | Composition |
| KR20200023269A (en) * | 2017-06-29 | 2020-03-04 | 스미또모 가가꾸 가부시키가이샤 | Composition |
| TWI784014B (en) * | 2017-06-29 | 2022-11-21 | 日商住友化學股份有限公司 | The composition and the film formed by hardening it |
| KR102583115B1 (en) | 2017-06-29 | 2023-09-27 | 스미또모 가가꾸 가부시키가이샤 | composition |
| WO2020007254A1 (en) * | 2018-07-02 | 2020-01-09 | Evonik Operations Gmbh | Surface coating composition with long durability |
| CN112368346A (en) * | 2018-07-02 | 2021-02-12 | 赢创运营有限公司 | Surface coating composition with long durability |
| CN112368346B (en) * | 2018-07-02 | 2022-05-31 | 赢创运营有限公司 | Surface coating composition with long durability |
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