CN1629237A - Water-repellent film-forming composition and coating method using it - Google Patents
Water-repellent film-forming composition and coating method using it Download PDFInfo
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- CN1629237A CN1629237A CN 200410095943 CN200410095943A CN1629237A CN 1629237 A CN1629237 A CN 1629237A CN 200410095943 CN200410095943 CN 200410095943 CN 200410095943 A CN200410095943 A CN 200410095943A CN 1629237 A CN1629237 A CN 1629237A
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Abstract
The invention provided a water-repellent film-forming composition that has good coating workability and exhibits water repellency over a prolonged period of time and to provide a coating method using the water-repellent film-forming composition. The water-repellent film-forming composition contains an emulsion (A) having an alkylalkoxysilane (a), an organopolysiloxane (b) having an alkoxy group and an emulsifier (c) as the active components, and an organic solvent (B) having a water solubility of 5% or more and has a nonvolatile content in a range of 2-50 %. It is preferable that the emulsion (A) further comprises an alkoxysilane (d1) having an aminoalkyl group and/or an organopolysiloxane (d2) having an aminoalkyl group.
Description
Technical field
The present invention relates to the method that forms the composition of water-repellent film and use it to apply.
Background technology
Therefore inorganic substrate weather resistance such as concrete are good, and because its unique texture can obtain distinctive attractive in appearancely, used by the exterior material as for example buildings widely.This class inorganic substrate exists so-called because long-term exposure and the problem of deterioration easily.For example on concrete surface, the mortar of use makes water-repellancy reduce owing to long-term exposure causes neutralisation etc., and weather resistance also reduces, and further also can produce the water and the muriate that for example bring from the outside simultaneously and invade to the inner disadvantageous situation of this class of reinforcing bar.As its countermeasure, in patent documentation 1, put down in writing a kind of water-resisting agent of silicone that on concrete surface, applies concrete is carried out the method for modification.
Yet in this method, the waterproof persistence is insufficient, the time can produce so-called water-resisting agent drippage etc. in coating and make coating be difficult to the problem of carrying out.
[patent documentation 1] spy opens 2002-60283 number
The present inventor has carried out conscientiously research in order to solve the above problems, found that, by making it contain specific organic solvent in specific silicane emulsion, and the composition of making after its effective constituent concentration adjusted can address the above problem, and finished the present invention thus.
Promptly the present invention relates to:
1. composition that forms water-repellent film, comprising with alkylalkoxy silane (a), the organopolysiloxane (b) with alkoxyl group and emulsifying agent (c) is organic solvent (B) more than 5% as the emulsion (A) of effective constituent and water solubility, and wherein nonvolatile element is in 2～50% scope.
2. as the composition of the 1 formation water-repellent film of being put down in writing, wherein emulsion (A) also comprises organoalkoxysilane (d1) with aminoalkyl group and/or the organopolysiloxane (d2) with aminoalkyl group.
3. the composition of the formation water-repellent film put down in writing as in 1 or 2 wherein forms the composition of water-repellent film with respect to 100 weight parts, the content of organic solvent (B) is in the scope of 1～10 weight part.
4. the composition of each formation water-repellent film of putting down in writing as in 1 to 3 wherein also contains thickening material (C).
5. as the composition of the 4 formation water-repellent films of being put down in writing, wherein thickening material (C) is the thickening material of derivatived cellulose class.
6. the composition of each formation water-repellent film of putting down in writing as in 1 to 5, its viscosity is in the scope of 50～1000cps.
7. the composition of each formation water-repellent film of putting down in writing as in 1 to 6 wherein also contains the titanium oxide (D) with photocatalytic activity.
8. coating method, its be with as 1 to 7 in the composition of each formation water-repellent film of putting down in writing be coated on coated.
9. as 8 coating methods of being put down in writing, wherein coated thing is the inorganic substrate that is selected from tile wall, concrete and wallboard material (siding material).
10. coating method, it is after forming the composition of water-repellent films with the 8 or 9 coating methods coatings of being put down in writing, to apply varnish colour again.
11. as 10 coating methods of being put down in writing, wherein varnish colour contains the organic silicic acid salt compound.
12. as 9 to 11 in each coating method of putting down in writing, wherein contain in the varnish colour have dimaleoyl imino the light-cured type resin as resinous principle.
13. a coating method, after it is characterized in that forming the composition of water-repellent films with the 8 or 9 coating methods coatings of being put down in writing, coating contains the Liniment of the titanium oxide with photocatalytic activity again.
14. be coated with membrane product by what each method of putting down in writing in 8 to 13 made.
Embodiment
The composition of formation water-repellent film of the present invention comprises with alkylalkoxy silane (a), the organopolysiloxane (b) with alkoxyl group and emulsifying agent (c) emulsion (A) as effective constituent.
In abovementioned alkyl organoalkoxysilane (a), as this alkyl, what can enumerate is the aliphatic alkyl of straight chain/chain, ester ring type or aromatic series alkyl etc., and this alkyl can partly be replaced by halogen atoms such as fluorine, chlorine, bromine and iodine.Suitable in the present invention is that carbonatoms is 1～20 alkyl, as this alkyl, what can enumerate is, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, 2,2, a straight chain and/or a catenate alkyl such as 4-tri-methyl-amyl, n-nonyl, positive decyl, dodecyl; Cyclopentyl, cyclohexyl, 4-ethyl cyclohexyl, suberyl, the cycloalkyl of removing first Camphanyl, methyl cyclohexane thiazolinyl etc.; Vinyl, allyl group, just-thiazolinyl of 5-hexenyl, 4 vinyl cyclohexene base and 3-norbornene etc.; The aryl of phenyl, xenyl, naphthyl, anthryl, phenanthryl etc.; Adjacent-,-, the alkylaryl of right-tolyl, xylyl and ethylphenyl etc.; Benzyl, α-and the aralkyl of beta-phenyl ethyl etc. etc.Wherein preferably carbonatoms is 1～12 not substituted type alkyl and phenyl.
As alkoxyl group, suitable is that carbonatoms is 1～6 alkoxyl group, for example methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy, pentyloxy, hexyloxy etc.This alkoxyl group can be replaced by halogen atom.
What the organopolysiloxane with alkoxyl group (b) among the present invention can be enumerated is to contain the material of catenate structure example shown in following general formula (I).
[changing 1]
R
xSi(OR
1)
y(OH)
zO
(4-x-y-z)/2????(I)
(R in the formula represents according to different situations carbonatoms that can be replaced by halogen, identical or different to be 1～20 alkyl, R
1Represent that identical or different carbonatoms is 1～6 alkyl, x represents the numerical value of 0≤x≤3, is preferably the numerical value of 0.6≤x≤1.8, and y represents the numerical value of 0≤y≤3, is preferably the numerical value of 0.01≤y≤2.0, and z represents the numerical value of 0≤z≤3.But the total of x, y and z is below 3.5.)
As carbonatoms is that 1～20 alkyl and carbonatoms are 1～6 alkoxyl group, can use the cited same group of group in the explanation with abovementioned alkyl organoalkoxysilane (a).
Above-mentioned organopolysiloxane (b) can pass through, and for example makes METHYL TRICHLORO SILANE and be that 1～8 alkyl trichlorosilane or phenyl-trichloro-silicane and ethanol react in water and obtains according to the different situations carbonatoms.
As emulsifying agent (c), can use present known emulsifying agents such as anionic emulsifier, cationic emulsifier, non-ionic emulsifier, amphoteric emulsifier ad lib, preferred especially non-ionic emulsifier, the preferably for example adduct of alkyl polyglycol ether, alkylaryl polyglycol ether, alkylamine and oxyethane or propylene oxide, alkyl polyglucoside, polyvinyl alcohol.
In the present invention, above-mentioned emulsion (A) contains as composition (a) and (b) that must composition and (c), to form the waterproof persistence of filming in order prolonging, preferably also to contain organoalkoxysilane (d1) with aminoalkyl group and/or organopolysiloxane (d2) with aminoalkyl group.
What have that the organoalkoxysilane (d1) of aminoalkyl group can enumerate is material shown in following general formula (II).
R
2 aR
3 bSi(OR
4)
4-a-b?????????????(II)
(the R in the formula
2The identical or different carbonatoms that expression can be replaced by halogen is 1～20 alkyl, methyl preferably, R
3The identical or different carbonatoms that expression can be replaced by halogen is 1～30 aminoalkyl group, R
4Represent that identical or different carbonatoms is 1～6 alkyl or hydrogen atom, a is the numerical value of 0≤a≤2, and b is the numerical value of 1≤b≤3, but the total of a and b is below 3).
R
2Can use the group identical with R.As R
3The preferred aminoalkyl group of group, that can enumerate is H
2NCH
2-, H
2N (CH
2)
2-, H
2N (CH
2)
3-, H
2N (CH
2)
2NH (CH
2)
2-, H
2N (CH
2)
2NH (CH
2)
3-, H
3CNH (CH
2)
3-, C
2H
5NH (CH
2)
3-, H
3CNH (CH
2)
2-, C
2H
5NH (CH
2)
2-, H
2N (CH
2)
4-, H
2N (CH
2)
5-, H (NHCH
2CH
2)
3-, C
4H
9NH (CH
2)
2NH (CH
2)
2-, cyclohexyl-NH (CH
2)
3-, cyclohexyl-NH (CH
2)
2-, (CH
3)
2N (CH
2)
3-, (CH
3)
2N (CH
2)
2-, (C
2H
5)
2N (CH
2)
3-and (C
2H
5)
2N (CH
2)
3-Ji etc.
Organopolysiloxane (d2) with aminoalkyl group, what be fit to use is the material shown in following general formula (III) that contains a chain structure.
[changing 2]
R
5 cR
6 d(OR
7)
eSiO
(4-c-d-e)/2(III)
(R in the formula
5Expression and the same group of R, R
6Expression and R
3Same group, R
7Expression and R
1Same group, and c represents the numerical value of 0≤c≤1, and d represents the numerical value of 0≤d≤3, and e represents the numerical value of 0≤e≤3, wherein the total of c, d and e is below 3).
Specially suitable R
5Be methyl, R
6Be aminopropyl or (amino-ethyl) aminopropyl, R
7Be methyl or ethyl.
Above-mentioned organopolysiloxane (d2) with aminoalkyl group can by make above-mentioned have the organoalkoxysilane (d1) of aminoalkyl group and have alkoxyl group and/or the organopolysiloxane of hydroxyl and alkali-free nitrogen between balance or condensation make.
Above-mentioned emulsion (A) is by emulsification in abovementioned alkyl organoalkoxysilane (a), organopolysiloxane (b) and the organoalkoxysilane with aminoalkyl group (d1) that contains as required and organopolysiloxane (d2) employing water with aminoalkyl group and the emulsifying agent (c) is formed.
Can carry out emulsification by general method as emulsification method.For example earlier only a part of water and emulsifying agent (c) are mixed, add composition (b) then, and add composition (d1) and/or (d2) as required, add composition (a) again and carry out emulsification, add remaining water dilution then.In addition, also can be with composition (a) and composition (b), and after with composition (d1) and/or (d2) mixing as required, it be joined in the mixture of emulsifying agent (c) and water.Emulsification is preferably carried out in pressure mulser, colloidal mill or high speed stator rotor stirrer.
It is organic solvent (B) more than 5% that the composition of formation water-repellent film of the present invention is included under 20 ℃ solubleness to water.Thus, said composition is permeated to the direction of the inorganic substrate degree of depth, thereby can improve waterproof effect.As the solubleness to water is organic solvent (B) more than 5%, and what can enumerate for example is, ketones solvents such as methylethylketone, methyl iso-butyl ketone (MIBK), isophorone, pimelinketone; Esters solvents such as ritalin, vinyl acetic monomer, propyl acetate, N-BUTYL ACETATE, isobutyl acetate, amyl acetate-n; Alcoholic solvents such as methyl alcohol, ethanol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, isopropylcarbinol, amylalcohol, n-hexyl alcohol, hexalin, 2-Ethylhexyl Alcohol, n-Octanol, benzylalcohol, hexylene glycol; Ether solvents such as diox, tetrahydrofuran (THF), butyl glycol ether, ethylene glycol uncle butyl ether, glycol hexyl ether, 2-Rutgers 612, butoxy ethanol, butylcarbitol, テ キ サ ノ-Le ethyl isobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methyl-3-methoxybutanol, propylene glycol methyl ether acetate etc., these can be used alone, but also also mix together.
With respect to the composition of 100 weight parts formation water-repellent film, the content of above-mentioned organic solvent (B) is preferably in the scope of 1～10 weight part.The amount of organic solvent (B) is if surpass 10 weight parts, and then the stain resistance of the water-repellent film that is formed by said composition will become insufficient.
In addition, in the composition of above-mentioned formation water-repellent film, preferably contain thickening material (C), can use used thickening material in general coating purposes ad lib as this thickening material (C), what can enumerate for example is, the derivatived cellulose class of carboxymethyl cellulose, methylcellulose gum, Natvosol and so on; The mineral-type of silicate, montmorillonite, colloidal aluminum oxide and so on; The partial esterification thing of polyvinyl alcohol, Polyvinylpyrolidone (PVP), sodium polyacrylate, acrylate copolymer, polyethers dialkyl, vinyl methyl ether-copolymer-maleic anhydride, sodiun alginate etc.Wherein the thickening material of derivatived cellulose class can make the coat operations of the composition that forms water-repellent film become well, therefore is fit to.
In addition, preferably contain titanium oxide (D) in the composition of formation water-repellent film of the present invention with photocatalytic activity.
Above-mentioned titanium oxide (D) with photocatalytic activity is the semiconductor grain with band gap, when being subjected to energy and being positioned at this light more than band gap (for example the ultraviolet ray of sunlight and artificial lighting light etc.) irradiation,, can give play to by its strong oxidation capacity and decompose the functions such as pollution substance that are in contact with it because move to the semiconductor surface particle surface in electronics and hole that optical excitation generates.This titanium oxide has 3 kinds of crystal formations that belong to tetragonal rutile-type, Detitanium-ore-type and belong to rhombic brookite type, generally is the titanium oxide of Detitanium-ore-type but conduct has the titanium oxide of photocatalytic activity.In addition, also comprise and make the colloidal water dispersion that obtains behind above-mentioned example compound modified.
The composition that contains the formation water-repellent film of the present invention of this titanium oxide with photocatalytic activity (D) in coating, when coated face is the inorganic based face, the composition of performance water-repellancy soaks into the inside to inorganic substrate, make the inside of inorganic substrate become water-repellancy thus, on the other hand, form the layer that contains the titanium oxide (D) that has photocatalytic activity in a large number on the top layer of inorganic substrate, can make the inorganic substrate surface have the photocatalytic activity of didirtresistance and pollution substance decomposability etc. thus.
For the composition that 100 weight parts form water-repellent film, the content with titanium oxide (D) of photocatalytic activity is preferably in about 1～50 weight part.
Organic polymer and dispersion, pigment, dispersion agent, surface tension adjustment agent, weighting agent, thickening material, buffer substance, mould inhibitor, antiseptic-germicide, algicide, sterilant, spices, sanitas and the defoamer that can also further contain in addition, silicone resin, fluoropolymer, polyolefin-wax, silicon wax, urethane, vinylformic acid, polyester, epoxy compounds etc. in the composition of formation water-repellent film of the present invention.
Nonvolatile element in the composition of the formation water-repellent film that obtains according to the method described above is in 2～50% scope.Nonvolatile element is if less than 2% then becomes insufficient by the water-repellancy of filming that said composition forms, and on the other hand if surpass 50%, then the operability that applies when the coating said composition becomes bad, and is therefore not preferred.In addition, in the present invention, the viscosity of the composition of above-mentioned formation water-repellent film is if then can make the operability of coating become well in the scope of 50～1000cps, and is therefore preferred.
The value that obtains when in the present invention, viscosity is meant and with BROOKFIELD type viscometer 20 ℃ sample is measured.
The present invention also provides a kind of coating method that applies the composition of above-mentioned formation water-repellent film on coated thing.
As coated thing, what can enumerate is metal, plastics, inorganic substrate etc. and filming of applying on these base materials etc., goes for works, bridge, furniture, car body, car repair various uses such as film.
In the method for the invention, as coated thing, what be fit to is the inorganic substrate with water vapour permeability, what specifically can enumerate is, for example concrete, wallboard material, tile wall, light weight cellular concrete, mortar, brick, timber, stone material etc., wherein, can give play to good especially effect if tile wall, concrete, wallboard material are used method of the present invention.In addition, so-called in the present invention tile wall is meant the wall that is formed by ceramic tile and its purpose position of mating formation, ceramic tile generally be by the mixture of porcelain base soil at high temperature molten sintering make, for example with clay product, feldspar and silica are the ceramic tile of main component, and the purpose position is that cementitious material and sand are made by mortar generally.
This tile wall is formed by ceramic tile and purpose position, owing to formed by diverse material, for example outward appearance, water-absorbent etc. have bigger gap in nature, but as if the composition by above-mentioned formation water-repellent film, can easily apply, bring into play this performance that this is filmed.
As the coating amount of the composition of above-mentioned formation water-repellent film, suitable is at 0.05～0.2Kg/m
2/ time scope in, preferably at 0.07～0.15Kg/m
2/ time scope in.This coating method has no particular limits, and can be undertaken by for example methods such as spraying method, rolling method, spread coating, curtain Tu Fa.
When coated thing was tile wall, as coating method, what can enumerate was to apply the method at the purpose position of ceramic tile and this ceramic tile simultaneously, only apply the method at the purpose position of ceramic tile.If use the composition of formation water-repellent film of the present invention, do not need to make ceramic tile and this purpose position to become wet look simultaneously, just can make it have water-repellancy, also can only apply the purpose position that water-repellancy is had special requirement.Specifiable is for example only to select the purpose position to apply by above-mentioned coating method, perhaps can adopt aforesaid method to apply the purpose position of ceramic tile and this ceramic tile simultaneously, after dipping said composition on the purpose position of this ceramic tile, remove the method that is coated in the said composition on this ceramic tile etc.As removing the method that is coated in the said composition on the ceramic tile, can enumerate be wiping should the surface, method such as water spray processing.The composition that utilizes this formation water-repellent film greater than the character to the degree of impregnation of ceramic tile self, can realize only the purpose position coating of this ceramic tile being formed the composition of water-repellent film to the degree of impregnation at purpose position as mentioned above.
In the method for the invention, adopt the compositions-treated of above-mentioned formation water-repellent film after, can repeat to apply the waterproof finishing agent of present known silicon class, zirconium class further by above-mentioned coating method.
As next process, when on the applicator surface of the composition that above-mentioned existing waterproof finishing agent or varnish colour described later or the Liniment that contains the titanium oxide with photocatalytic activity is repeated be coated in formation water-repellent film of the present invention, the composition of this formation water-repellent film is under 20 ℃ drying temperature for example at dry suitable after the coating, carries out in the scope between about 2 hours to 10 days.
After the present invention also provides a kind of composition that applies above-mentioned formation water-repellent film to coated thing, further apply the coating method of varnish colour.
As this varnish colour, can use present known varnish colour.
As the resinous principle that becomes carrier components, what can enumerate is the resin of at present known crosslinked or non-crosslinked type, for example acrylic resin, acrylic silicon resin, vibrin, silicone resin, fluoro-resin, urethane resin etc.In addition, also comprise it is made up the resin that post-modification forms aptly, or the resin that mixes.
As varnish colour, operable be for example will be in above-mentioned example resinous principle aqueous medium or organic solvent (for example with the fragrant same clan, ester class, ketone, alcohols, ethers, aliphatic hydrocarbon etc. these use separately or with the organic solvent that combines more than 2 kinds etc.) in the coating that forms of dissolving or dispersion.
In the method for the invention, as above-mentioned resinous principle, preferably use light-cured type resin with maleoyl amido.The maleoyl amido be by illumination can 2 yuan of changes functional group, the resin that contains this group can photocuring.As light source can be natural lights such as sunlight, owing to be cured in the forming process of filming out of doors, therefore all favourable to storage stability and solidified nature two aspects.In addition, varnish colour is owing to contain the maleoyl amido, has so-called varnish and films and be difficult to the advantage of being made dirty.
As the method for introducing the maleoyl amido, what can enumerate for example is, will have the polymerizability unsaturated monomer of maleoyl amido and the method that other monomer carries out copolymerization.
In addition, make surface that this varnish films since rainfall etc. through hydrophilization behind the certain hour, thereby varnish is filmed has stain resistance, above-mentioned varnish colour preferably comprises organic silicate compound.As the organic silicic acid salt compound for realizing that this purpose is used, what can enumerate is the compound shown in for example following general formula.
R in the formula
8Represent that identical or different hydrogen atom or carbonatoms are 1～10 alkyl or aryl.As abovementioned alkyl, what can enumerate is the alkyl of straight or brancheds such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl for example, as aryl suitable be phenyl etc.
Thus, as the concrete example of above-mentioned organic silicic acid salt compound, what can enumerate is for example tetrahydroxy silane, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, tetraphenoxy-silicane alkane, dimethoxy diethoxy silane etc.These can use separately, also can make up more than 2 kinds and use.
In addition, can also use the chain or the straight catenate condenses that form between the above-mentioned organic silicic acid salt compound, its condensation degree is suitable in 2～100 scope generally.
In addition, when varnish colour is under the situation of water system, as the organic silicic acid salt compound, the organic silicic acid salt compound of alkoxyl group in above-mentioned organic silicic acid salt compound and/or its condenses or hydroxyl and polyalkylene glycols compound generation partial reaction and modification is owing to the favorable solubility of water, therefore can use aptly.
As the polyalkylene glycols compound of properties-correcting agent, can enumerate be as shown in the formula
R
9O-(R
10O)n-H
Shown compound, R in the formula
9Be hydrogen atom, alkyl or aryl, R
10Be the alkylidene group of carbonatoms 2～4, n is 2～60.What specifically can enumerate is, for example polyalkylene glycols such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol; Alkoxyl group polyalkylene glycols such as methoxy poly (ethylene glycol), oxyethyl group polyoxyethylene glycol, oxyethyl group polypropylene glycol, oxyethyl group polytetramethylene glycol; Polyoxyalkylene alkyl phenyl ethers such as polyoxygenated ethylidene nonylplenyl ether, polyoxygenated ethylidene octyl phenyl ether etc., particularly suitable is polyoxyethylene glycol, polyoxygenated ethylidene nonylplenyl ether.
For the resin solid state component of per 100 weight part varnish colours, the content of above-mentioned organic silicic acid salt compound is generally in the scope of 0.1～50 weight part, preferably in the scope of 1～20 weight part.
Above-mentioned varnish colour general suitable be the resin solid state component in 20～60 weight % scopes, specially suitable is in the scope of 30～50 weight %, coating amount is about 0.05～0.12Kg/m in addition
2/ time, preferably at 0.08～0.10Kg/m
2/ time scope in.The dry coating thickness of varnish colour is in the scope of 10～100 μ m, preferably in the scope of 20～70 μ m.In order to obtain the thickness of this dry coating, can in the scope of above-mentioned coating amount, repeat coating for several times.This coating method has no particular limits, and what can enumerate is to be undertaken by for example methods such as spraying method, rolling method, spread coating, flow coat method.If coating amount reduces with next protective capability of filming in this scope, if surpass this scope, then when the inorganic based face was used as coated, this substrate surface became wet look sometimes.
As if the above-mentioned varnish colour of use and according to coating method of the present invention; particularly when inorganic substrate is used as coated; the composition that this inorganic substrate inside is formed water-repellent film soaks into and becomes water-repellancy; and improved water-repellancy; and the surface of inorganic substrate by varnish film protect, can make it further have functions such as stain resistance.
It is a kind of behind the composition of coated the above-mentioned formation water-repellent film of coating that the present invention also provides, and further coating contains the coating method of the Liniment of the titanium oxide with photocatalytic activity.
Titanium oxide with photocatalytic activity can use same material in the explanation with above-mentioned (D).
As the composition beyond the titanium oxide that has photocatalytic activity in above-mentioned Liniment, what can enumerate is carrier components and various additive, thinners etc. such as mineral-type resin such as silicone resin.
The coating amount of above-mentioned Liniment is wished at 0.1～10g/m according to the solid state component meter of this Liniment
2Scope in, preferably at 0.3～5g/m
2Scope in apply.
This coating method has no particular limits, and what can enumerate is to be undertaken by for example methods such as spraying method, rolling method, spread coating, flow coat method.When coated face is the ceramic tile wall, the method of coating can be the method that applies the purpose position of ceramic tile face and this ceramic tile simultaneously, also can be after applying the purpose position of ceramic tile face and this ceramic tile simultaneously and make that Liniment is immersed on the purpose position of this ceramic tile by aforesaid method, the method for removing the Liniment that is coated in ceramic tile surface again by the method for for example above-mentioned explanation.
As if the above-mentioned Liniment of use and according to coating method of the present invention, particularly when inorganic substrate is used as coated, the composition that this inorganic substrate inside is formed water-repellent film soaks into and becomes water-repellancy, and improved water-repellancy, and can form photocatalyst layer on the surface, can when keeping interior waterproof, can photocatalytic activities such as stain resistance, pollution substance decomposability be arranged the table of discovery mask.
[embodiment]
The present invention is described in detail below by enumerating embodiment.In addition, " part " in the literary composition and " % " represent the meaning of " weight part " and " weight % " respectively.
The manufacturing of emulsion
Preparation example 1～3
Each composition shown in the following table 1 is mixed according to the proportioning shown in following, carry out emulsification with high speed stator rotor whipping appts and obtain emulsion (A1)～(A3).
Table 1
| Emulsion | A1 | A2 | A3 |
| The iso-octyl triethoxyl silane | 38％ | 36％ | 43.2％ |
| Siloxanes (annotating 1) | 10％ | 10％ | 12％ |
| Emulsifying agent (annotating 2) | 2％ | 2％ | 2.4％ |
| Aminoalkyl group silane (annotating 3) | 2％ | 2.4％ | |
| Water | 50％ | 50％ | 40％ |
(annotating 1) siloxanes: molecular-weight average, empirical formula with 760g/ mole are (CH
3)
0.7(iso-octyl)
0.3Si (OCH
3)
1.3O
0.85Shown compound.
(annotating 2) emulsifying agent: isotrideyl alcohol-(16)-polyglycol ether.
(annotating 3) aminoalkyl group silane: N-(2-aminoethyl)-3-aminopropyl trimethoxysilane.
Embodiment 1～14 and comparative example 1～3
Form the preparation of the composition (I-1)～(I-17) of water-repellent film
Mix each composition by the proportioning shown in the table 2 and make the composition (I-1)～(I-17) that forms water-repellent film.
[table 2]
| Form the composition of water-repellent film | Embodiment | Comparative example | |||||||||||||||
| ??1 | ?2 | ?3 | ??4 | ?5 | ??6 | ?7 | ??8 | ??9 | ??10 | ??11 | ??12 | ??13 | ??14 | ??1 | ??2 | ??3 | |
| ??I-1 | ?I-2 | ?I-3 | ??I-4 | ?I-5 | ??I-6 | ?I-7 | ??I-8 | ??I-9 | ??I-10 | ??I-11 | ??I-12 | ??I-13 | ??I-14 | ??I-15 | ??I-16 | ??I-17 | |
| Emulsion (A1) | ??20 | ||||||||||||||||
| Emulsion (A2) | ?20 | ?20 | ??20 | ?20 | ??40 | ?20 | ??20 | ??20 | ??20 | ??20 | ??20 | ??20 | ??20 | ??20 | ??20 | ||
| Emulsion (A3) | ??40 | ||||||||||||||||
| Ethylene glycol monobutyl ether (annotating 4) | ??3 | ?3 | ?6 | ??1.5 | ?0.5 | ??8 | ??12 | ??3 | ??3 | ??3 | ??3 | ??3 | ??30 | ??1.3 | |||
| Butylcarbitol (annotating 5) | ?3 | ||||||||||||||||
| Propylene glycol monobutyl ether (annotating 6) | ??3 | ||||||||||||||||
| Propylene glycol monophenyl ether (annotating 7) | ??3 | ||||||||||||||||
| Natvosol | ??0.1 | ??0.4 | ??0.8 | ??1.2 | |||||||||||||
| " TKC-304 " (annotating 8) | ??30 | ||||||||||||||||
| Water | ??77 | ?77 | ?77 | ??77 | ?174 | ??8.5 | ?79.5 | ??72 | ??68 | ??76.9 | ??76.6 | ??76.2 | ??75.8 | ??47 | ??77 | ??950 | ??2.3 |
| Add up to | ??100 | ?100 | ?100 | ??100 | ?200 | ??50 | ?100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??100 | ??1000 | ??43.6 |
| Nonvolatile element (%) | ??10 | ?10 | ?10 | ??10 | ?5 | ??40 | ?10 | ??10 | ??10 | ??10.1 | ??10.4 | ??10.8 | ??11.2 | ??12.7 | ??10 | ??1 | ??55 |
| Quantity of solvent (%) | ??3 | ?3 | ?3 | ??3 | ?3 | ??3 | ?0.5 | ??8 | ??12 | ??3 | ??3 | ??3 | ??3 | ??3 | ??3 | ??3 | ??3 |
| Viscosity (cps) | ??30 | ?30 | ?30 | ??30 | ?30 | ??60 | ?30 | ??40 | ??45 | ??60 | ??400 | ??800 | ??1200 | ??30 | ??30 | ??20 | ??100 |
(annotating 4) ethylene glycol monobutyl ether: water solubility, infinity
(annotating 5) butylcarbitol: water solubility, infinity
(annotating 6) propylene glycol monobutyl ether: water solubility 6.4%
(annotating 7) propylene glycol monophenyl ether: water solubility 1.1%
(annotating 8) " TKC-304 " (trade(brand)name, テ イ カ Co., Ltd. makes, the aqueous dispersion of Detitanium-ore-type photocatalytic titanium oxide, solid component concentration 9%).
The preparation of varnish colour
Preparation example 4
In the 2L flask of stirrer, thermometer, dropping funnel, nitrogen ingress pipe is housed, the methacrylic ester that contains the maleoyl amido, the 5g methacrylic acid that 900g N-BUTYL ACETATE, 220g methyl methacrylate, 44g n-BMA, 87g n-butyl acrylate, 58g hydroxyethyl methylacrylate, 87g be shown below of packing into, after carrying out sufficient nitrogen replacement, be warming up to 75 ℃.When the interior temperature of flask arrives 75 ℃, drip the initiator solution of the 100g N-BUTYL ACETATE that is dissolved with the 5g Diisopropyl azodicarboxylate, the beginning polymerization.Make the 5g Diisopropyl azodicarboxylate be dissolved in methacrylic ester that contains the maleoyl amido that 220g methyl methacrylate, 44g n-BMA, 87g n-butyl acrylate, 58g hydroxyethyl methylacrylate, 87g be shown below and the monomer mixture in the 5g methacrylic acid with in this flask, dripping in 3 hours then, be warming up to 85 ℃ and slaking then 2 hours, further 90 ℃ of following slakings 2 hours.
Then, the inclusion of flask is precipitated in a large amount of methyl alcohol, obtaining weight is that 999g (percent polymerization 99.7%), hydroxyl value are that 50mgKOH/g, acid number are the polymkeric substance of 6.5mgKOH/g.It is dissolved in the solution of dimethylbenzene/N-BUTYL ACETATE=50/50 (weight ratio), makes the solid state component of this polymkeric substance reach 40%, obtain water white solution.In this polymers soln that obtains of 100 weight parts, add 7.3 parts of " コ ロ ネ-ト HX " (trade(brand)names as solidifying agent, Japan's Port リ ウ レ Application (strain) is made, isocyanate curing agent), 2.9 parts of xylene solutions as the 0.1wt% of the dibutyl tin laurate of curing catalyst, make hydroxyl value/nco value become 1.0, make and contain light-cured type resin with maleoyl amido varnish colour (B1) as resinous principle.
Preparation example 5
With with respect to 100 parts of " ア レ ス レ Application Network リ ヤ-" (trade(brand)names, Northwest paint company is made, acrylic resin/cured with isocyanates type organic solvent class coating) resin solid state component, " ethyl silicate 40 " (trade(brand)name, コ Le コ-ト company makes, the tetraethyl orthosilicate condenses) solid state component is that 20 parts proportioning is mixed it, adjusts the varnish colour (B2) that contains the organosilicon acid esters.
The manufacturing of ceramic tile panel test substrate
Along using epoxy adhesive that it is fitted on the slabstone between the ceramic tile of per 2 length of side 10cm of direction in length and breadth, at this moment making the joint gap between each ceramic tile is 2mm.In this seam, insert filleting mortar (ダ Application ト-メ ジ Off イ Star ト, ダ Application ト-Co., Ltd. makes), maintain after 14 days it is tested substrate as the ceramic tile panel with the height that is lower than ceramic tile surface 2mm.
The manufacturing of trial target
Embodiment 15
On concrete, with the composition (I-1) of brush, with 100g/m with above-mentioned formation water-repellent film
2/ time coating amount apply, obtain trial target after dry at normal temperatures 7 days.
Embodiment 16～34, and this is than example 4～6
In embodiment 15, except the composition that will form water-repellent film and coated according to as shown in table 3 the combination, all the other are according to obtaining each trial target with embodiment 15 same methods.In addition, in coated of table 3, (1) is concrete surface, and (2) are the wallboard materials, and (3) are above-mentioned ceramic tile panel test substrates.
Embodiment 35
On the test board that in embodiment 16, obtains, further use brush with 30g/m
2Coating amount coating " TKC-304 " (trade(brand)name, テ イ カ Co., Ltd. makes, the aqueous dispersion of Detitanium-ore-type photocatalytic titanium oxide, solid component concentration 9%), obtain trial target after dry 7 days.
Embodiment 36
On the test board that in embodiment 16, obtains, further use brush with 100g/m
2Coating amount coating " ア Network ア プ リ ズ system " (trade(brand)name, Northwest paint company is made, water-based silicon class varnish colour, solid state component 45%), obtain trial target after dry 7 days.
Embodiment 37
On the test board that in embodiment 16, obtains, further use brush with 100g/m
2Coating amount coating contain the varnish colour (B2) of organosilicon acid esters, obtain trial target after dry 7 days.
Embodiment 38
On the test board that in embodiment 16, obtains, further use brush with 100g/m
2Coating amount coating contain light-cured type resin with maleoyl amido varnish colour (B1) as resinous principle, obtain trial target after dry 7 days.
Comparative example 7
On concrete, with 100g/m
2/ time coating amount coating with the composition (I-18) of hexyl Trimethoxy silane with the formation water-repellent film of dilution with toluene to 10%, obtain the trial target of comparative example 7 after dry 7 days at normal temperatures.
According to following test method above-mentioned each trial target that obtains is tested.Test-results is shown in following table 3.
Table 3
| Embodiment | |||||||||||||||
| 15 | ?16 | ?17 | ?18 | ?19 | ?20 | ?21 | ?22 | ?23 | ?24 | ?25 | ?26 | ?27 | ?28 | ||
| Applicator surface | (1) | ?(1) | ?(1) | ?(1) | ?(1) | ?(1) | ?(1) | ?(1) | ?(1) | ?(1) | ?(1) | ?(1) | ?(1) | ?(1) | |
| Form the composition of water-repellent film | I-1 | ?I-2 | ?I-3 | ?I-4 | ?I-5 | ?I-6 | ?I-7 | ?I-8 | ?I-9 | ?I-10 | ?I-11 | ?I-12 | ?I-13 | ?I-14 | |
| The top coated operation | " TKC-304 " (annotating 8) | ||||||||||||||
| “アクアプリズム” | |||||||||||||||
| Varnish colour (B1) | |||||||||||||||
| Varnish colour (B2) | |||||||||||||||
| Evaluation test | The wet look of initial stage outward appearance | ◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ |
| Water contact angle/° | 114 | ?118 | ?121 | ?109 | ?114 | ?110 | ?112 | ?115 | ?118 | ?117 | ?109 | ?114 | ?111 | ?50 | |
| Water contact angle behind the SWOM/° | 104 | ?110 | ?112 | ?100 | ?104 | ?102 | ?103 | ?102 | ?103 | ?107 | ?101 | ?111 | ?100 | ?32 | |
| Adhesivity | ◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?△ | ?◎ | |
| Stain resistance | ◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?○ | ?◎ | ?◎ | ?◎ | ?○ | ?◎ | |
| The coating operability | ○ | ?○ | ?○ | ?○ | ?○ | ?◎ | ?○ | ?○ | ?○ | ?◎ | ?◎ | ?◎ | ?◎ | ?○ | |
| Water-repellancy | ◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?○ | ?◎ | ?○ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | |
Table 3 is continuous
| Comparative example | |||||||||||||||
| 29 | ?30 | ?31 | ?32 | ?33 | ?34 | ?35 | ?36 | ?37 | ?38 | ?4 | ?5 | ?6 | ?7 | ||
| Applicator surface | (2) | ?(2) | ?(2) | ?(3) | ?(3) | ?(3) | ?(1) | ?(1) | ?(1) | ?(1) | ?(1) | ?(1) | ?(1) | ?(1) | |
| The waterproof finishing agent kind | I-2 | ?I-11 | ?I-14 | ?1-2 | ?I-11 | ?I-14 | ?I-2 | ?I-2 | ?I-2 | ?I-2 | ?I-15 | ?I-16 | ?I-17 | ?I-18 | |
| Working procedure of coating | " TKC-304 " (annotating 8) | ?★ | |||||||||||||
| “アクアプリズム” | ?★ | ||||||||||||||
| Varnish colour (B1) | ?★ | ||||||||||||||
| Varnish colour (B2) | ?★ | ||||||||||||||
| Evaluation test | The wet look of initial stage outward appearance | ◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?○ | ?○ | ?○ | ?◎ | ?◎ | ?◎ | ?◎ |
| Water contact angle/° | 117 | ?118 | ?52 | ?113 | ?111 | ?48 | ?40 | ?88 | ?41 | ?83 | ?115 | ?110 | ?120 | ?105 | |
| Water contact angle behind the SWOM/° | 110 | ?105 | ?28 | ?107 | ?102 | ?30 | ?28 | ?83 | ?30 | ?81 | ?104 | ?85 | ?108 | ?28 | |
| Adhesivity | ◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?○ | ?○ | ?○ | ?◎ | ?◎ | ?○ | ?◎ | |
| Stain resistance | ◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?△ | ?◎ | ?× | |
| The coating operability | ○ | ?◎ | ?○ | ?○ | ?◎ | ?○ | ?◎ | ?◎ | ?◎ | ?◎ | ?△ | ?△ | ?× | ?○ | |
| Water-repellancy | ◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?◎ | ?△ | ?× | ?◎ | ?○ | |
The wet look of (* 1) initial stage outward appearance
Each trial target and each applicator surface of not applying by visual comparison, are judged that according to following benchmark trial target has or not variable color.
◎: trial target and each applicator surface that does not apply are as broad as long
Zero: trial target and each applicator surface that does not apply are almost as broad as long
△: the color of trial target is denseer slightly than each applicator surface that does not apply
*: the color of trial target is denseer than each applicator surface that does not apply significantly
(* 2) water contact angle
Water droplet is dropped in each trial target surface, measure the angle (water contact angle) on the border of each trial target surface and water droplet with the goniometry device, big more its surface that then shows of value has good more water-repellancy.
Water contact angle after (* 3) sunlight weather meter (sunshine weather meter) test
The exposure in the trier (sunlight weather meter) of JISB7753 regulation of each trial target was measured water contact angle after 1000 hours.The variation of the water contact angle before and after exposing is more little, and the persistence of the function that then showing respectively films is had is good more.
(* 4) adhesivity
After above-mentioned accelerated test finishes, the surface of each trial target put into parting tool draw lattice after, peel after sticking adhesive tape, judge according to following benchmark.
◎: do not peel off fully
Zero: peel off a bit along drawing lattice
△: have significantly and peel off
*: peel off fully
(* 5) stain resistance
After each trial target being carried out the outdoor exposure test in 1 year,, judge according to following benchmark by the visual valuation trial target.
◎: almost do not see pollution
Zero: find to have slight pollution
△: see pollution
*: pollute significantly
(* 7) coat operations
Each composition that forms water-repellent film is coated on the vertical surface of each applicator surface, judges according to following benchmark.
◎: do not drip, best in quality
Zero: do not drip, quality is poor slightly
△: find part drippage, inferior quality
*: find drippage, quality is obviously poor
(* 8) water-repellancy
Pervious test method according to JIS K 5400 records is estimated water-repellancy, judges according to following benchmark.
◎: permeable amount is below 0.5ml
Zero: permeable amount is greater than 0.5ml, below the 1ml
△: permeable amount is greater than 1ml, below the 3ml
*: permeable amount is greater than 3ml
[invention effect]
Use the composition of formation water-repellent film of the present invention, can form that coat operations is very good, good the filming of water proofing property. The composition of this formation water-repellent film is particularly suitable for the protection of inorganic based face. In addition, be coated on the inorganic based face by the composition that will form water-repellent film, further apply again varnish paint or contain the coating agent of photochemical catalyst, can make the composition of this formation water-repellent film deeply infiltrate into inside, make its inside have water proofing property, the top layer has the functions such as stain resistance, photocatalytic activity, beautiful outward appearance that can the long term maintenance inorganic substrate.
Claims (14)
1. composition that forms water-repellent film, comprising with alkylalkoxy silane (a), the organopolysiloxane (b) with alkoxyl group and emulsifying agent (c) is organic solvent (B) more than 5% as the emulsion (A) of effective constituent and water solubility, and wherein nonvolatile element is in 2～50% scope.
2. the composition of the formation water-repellent film of claim 1 record, wherein emulsion (A) also comprises organoalkoxysilane (d1) with aminoalkyl group and/or the organopolysiloxane (d2) with aminoalkyl group.
3. the composition of formation water-repellent films of claim 1 or 2 records wherein forms the composition of water-repellent film with respect to 100 weight parts, the content of organic solvent (B) is in the scope of 1～10 weight part.
4. the composition of the formation water-repellent film of each record in the claim 1 to 3 wherein also contains thickening material (C).
5. the composition of the formation water-repellent film of claim 4 record, wherein thickening material (C) is the thickening material of derivatived cellulose class.
6. the composition of the formation water-repellent film of each record in the claim 1 to 5, its viscosity is in the scope of 50～1000cps.
7. the composition of the formation water-repellent film of each record in the claim 1 to 6 wherein also contains the titanium oxide (D) with photocatalytic activity.
8. coating method, it is that composition with the formation water-repellent film of each record in the claim 1 to 7 is coated on coated.
9. the coating method of claim 8 record, wherein coated thing is the inorganic substrate that is selected from tile wall, concrete and wallboard material.
10. coating method, it is after coating methods coating with claim 8 or 9 records forms the composition of water-repellent film, to apply varnish colour again.
11. the coating method of claim 10 record, wherein varnish colour contains the organic silicic acid salt compound.
12. the coating method of each record in the claim 9 to 11, wherein contain in the varnish colour have dimaleoyl imino the light-cured type resin as its resinous principle.
13. a coating method, it is characterized in that coating methods coating with claim 8 or 9 records forms the composition of water-repellent film after, coating contains the Liniment of the titanium oxide with photocatalytic activity again.
14. the coated articles that the method by each record in the claim 8 to 13 makes.
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