CA2175848C - Water repellent surface treatment with integrated primer - Google Patents
Water repellent surface treatment with integrated primer Download PDFInfo
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- CA2175848C CA2175848C CA002175848A CA2175848A CA2175848C CA 2175848 C CA2175848 C CA 2175848C CA 002175848 A CA002175848 A CA 002175848A CA 2175848 A CA2175848 A CA 2175848A CA 2175848 C CA2175848 C CA 2175848C
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Classifications
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
Abstract
A composition for producing a water repellent surface on a substrate such as glass, plastic, metal, organic polymer coated substrates or inorganic coated substrates includes a perfluoroalkylalkylsilane selected from compounds having the general formula RmR'nSiX4-m-n where R is a perfluoroalkylalkyl radical, R' is a vinyl or an alkyl radical, m+n is less than 4, and X is a halogen, alkoxy or an acyloxy radical and a completely hydrolyzable silane or siloxane selected from silanes and siloxanes. The nonwetting property, as measured by contact angle of a drop of water on the substrate surface treated with the foregoing compound, is more durable than the nonwetting property of a surface treated with the same perfluoroalkylalkylsilane without the completely hydrolyzable silane or siloxane.
Description
2~.'~~~~-~
WA'.CER REE'ELLENT SURFACE TREATMENT
WITH INTEGRATED 'PRIMER
BACKGROUND
Fiel(~ of f ha Tntrcnt.ion The present invention relates generally to the art of surface treatment and, more particularly, to the art of producing a water repellent surface on various substrates, and most particularly to improving the durability of such water repellent surfaces.
relevant Art U.S. Patent No. 5,314,731 to Yoneda et al. describes a surface-treated substrate having at least two treated surface layers wherein the first outermost layer is obtained by treatment with a compo,snd containing at least one Si-NCO
group capable of forming ;~ surface having a contact angle of at least 70° against. water- and the second underlayer is obtained by treatment with at least one reactive silane compound selected from isocyanate silane compounds and hydrolyzable silane compounds.
w 2175848 U.S. Paten.t Nos. 4,983,459 and 4,997,684 to Franz et al. disclose an article and method respectively for providing a durable nonwea ting surface on glass by treatment with a perfluoroalkylalkyl s~ilane and a fluorinated olefin telomer.
In Lf.S. Patent No. 5,308,705 Franz et al. describe providing nonwEa ting surface properties to substrates other than glass by t:reatme:nt with a perfluoroalkylalkyl silane and a fluorinated olefin telomer.
In Li.S. Patent No. 5,328,768 Goodwin discloses a to glass substratE: the ~;urface of which is treated with first a silica primer 7_ayer and second a perfluoroalkylalkyl silane.
SUMMARY OF THE INVENTION
The present invention provides a substrate surface is with high water. repel.lency and high lubricity. The durability of the water and dirt: repellency of a substrate surface is improved by applying to the substrate surface a perfluoro-alkylalkylsilane compound and a hydrolyzable silane or siloxane compound. The hydrolyzable silane or siloxane zo compound is a compound capable of hydrolytic condensation to form silica ge=L and functions as an integral primer compound.
The surface treatment: of the present invention provides enhanced durability t:o the water and dirt repellent surface without requiring a :separate primer layer. High water 2s repellency and lubric:ity are provided by perfluoroalkylalkyl-silane. The h~,rdrolyzable silane or siloxane also provides for reactive dryin<1 of the solvent. The perfluoroalkylalkylsilane and hydrolyzab:Le silane or siloxane surface treatment of the present invent:LOn al:~o provides enhanced abrasion resistance 3o to the substrate surface. Increased resistance to humidity, ultraviolet radiation and mechanical abrasion are provided by 2m~s~a the silane or ;~iloxane compound capable of hydrolytic condensation to silica gel.
DESCRIPTION OF THE PREFERRED EMBODIMENT
s Durability of rain and soil repellency provided by application of a perfluoroalkylalkylsilane to a substrate surface is enh;~nced by mixing a silane, siloxane or mixture of silane and/or ;siloxane compounds capable of hydrolysis to silica gel with a perfluoroalkylalkylsilane prior to io application. In accordance with the present invention, a mixture of a perfluoroalkylalkylsilane and silane, siloxane or mixture of sil;~ne and/or siloxane compounds capable of hydrolysis to ~~ilica gel is applied to the surface of glass to form a coating which is more durable than would have been is formed without the silane, siloxane or mixture of silane and/or siloxan~~ compounds capable of hydrolysis to silica gel.
Per:Eluoroalkylalkylsilane and hydrolyzable silane and/or siloxan~~ are applied to the surface of a substrate to produce the article of the present invention preferably as a 2o colloidal suspension or solution, preferably in an aprotic solvent, preferably an alkane or mixture of alkanes, or a fluorinated solvent. The preferred solution of the present invention is applied to a substrate surface by any conventional technique such as dipping, flowing, wiping or 2s spraying. The silane reacts with the substrate surface, and excess solution is removed, providing a durable, non-wetting, lubricating surface with improved abrasion resistance. The present invention provides the. durability benefits of a primer without the additional step of applying a separate primer 30 layer. The use of t:he completely hydrolyzable silane and/or siloxane improves the humidity, ultraviolet light, and abrasion resistance of the silane surface treatment as measured by the Cl.evelan.d Condensing Cabinet, QW (with FS40 or B313 lamps), and wet sled abrasion tests, indicating a longer useful procluct lifetime.
Suitable silanes capable of hydrolysis to silica gel s have the general formula SiX'9wherein X'is a hydrolyzable radical generally selected from the group of halogens, alkoxy and acyloxy radicals.
Preferred silanes are those wherein X is preferably chloro, bromo, iodo, methoxy, ethoxy and acetoxy. Preferred io hydrolyzable silanes include tetrachlorosilane, tetramethoxy-silane and tetraacetoxysilane.
Suitable silo:xanes have the general formula SiYOZX"QY_ZZ, wherein X" is selected from the group of halogen, alkoxy and acyloxy radicals, y is two or more, and z is one or is more and 4y-2z is greater than zero. Preferred hydrolyzable siloxanes include hexach:Lorodisiloxane, octachlorotrisiloxane, and higher oligomer chlo:rosiloxa~nes.
The hydrolyzable silanes or siloxanes serve two functions. One is to become part of the coating and impart 2o resistance to weathering and abrasion. Another function is to dry the solvent. 'Typica:l hydrocarbon solvents can contain 50 to 200 ppm of water. Other solvents can be much higher in water content. For example, a solvent containing 200 ppm water would have enough water present to partially hydrolyze 2s the perfluoroalkyl~alkyls:ilane at 0.5 weight percent concentration. The comp:Letely hydrolyzable silane or siloxane is capable of eliminatin<~ or reducing the water content of the ,solvent prior to p~~rfluo~roalkylalkylsilane addition.
Otherwise, partially hydrolyzed perfluoroalkylalkylsilane 3o could result in insufficient coating deposition or very poor durability.
A
WA'.CER REE'ELLENT SURFACE TREATMENT
WITH INTEGRATED 'PRIMER
BACKGROUND
Fiel(~ of f ha Tntrcnt.ion The present invention relates generally to the art of surface treatment and, more particularly, to the art of producing a water repellent surface on various substrates, and most particularly to improving the durability of such water repellent surfaces.
relevant Art U.S. Patent No. 5,314,731 to Yoneda et al. describes a surface-treated substrate having at least two treated surface layers wherein the first outermost layer is obtained by treatment with a compo,snd containing at least one Si-NCO
group capable of forming ;~ surface having a contact angle of at least 70° against. water- and the second underlayer is obtained by treatment with at least one reactive silane compound selected from isocyanate silane compounds and hydrolyzable silane compounds.
w 2175848 U.S. Paten.t Nos. 4,983,459 and 4,997,684 to Franz et al. disclose an article and method respectively for providing a durable nonwea ting surface on glass by treatment with a perfluoroalkylalkyl s~ilane and a fluorinated olefin telomer.
In Lf.S. Patent No. 5,308,705 Franz et al. describe providing nonwEa ting surface properties to substrates other than glass by t:reatme:nt with a perfluoroalkylalkyl silane and a fluorinated olefin telomer.
In Li.S. Patent No. 5,328,768 Goodwin discloses a to glass substratE: the ~;urface of which is treated with first a silica primer 7_ayer and second a perfluoroalkylalkyl silane.
SUMMARY OF THE INVENTION
The present invention provides a substrate surface is with high water. repel.lency and high lubricity. The durability of the water and dirt: repellency of a substrate surface is improved by applying to the substrate surface a perfluoro-alkylalkylsilane compound and a hydrolyzable silane or siloxane compound. The hydrolyzable silane or siloxane zo compound is a compound capable of hydrolytic condensation to form silica ge=L and functions as an integral primer compound.
The surface treatment: of the present invention provides enhanced durability t:o the water and dirt repellent surface without requiring a :separate primer layer. High water 2s repellency and lubric:ity are provided by perfluoroalkylalkyl-silane. The h~,rdrolyzable silane or siloxane also provides for reactive dryin<1 of the solvent. The perfluoroalkylalkylsilane and hydrolyzab:Le silane or siloxane surface treatment of the present invent:LOn al:~o provides enhanced abrasion resistance 3o to the substrate surface. Increased resistance to humidity, ultraviolet radiation and mechanical abrasion are provided by 2m~s~a the silane or ;~iloxane compound capable of hydrolytic condensation to silica gel.
DESCRIPTION OF THE PREFERRED EMBODIMENT
s Durability of rain and soil repellency provided by application of a perfluoroalkylalkylsilane to a substrate surface is enh;~nced by mixing a silane, siloxane or mixture of silane and/or ;siloxane compounds capable of hydrolysis to silica gel with a perfluoroalkylalkylsilane prior to io application. In accordance with the present invention, a mixture of a perfluoroalkylalkylsilane and silane, siloxane or mixture of sil;~ne and/or siloxane compounds capable of hydrolysis to ~~ilica gel is applied to the surface of glass to form a coating which is more durable than would have been is formed without the silane, siloxane or mixture of silane and/or siloxan~~ compounds capable of hydrolysis to silica gel.
Per:Eluoroalkylalkylsilane and hydrolyzable silane and/or siloxan~~ are applied to the surface of a substrate to produce the article of the present invention preferably as a 2o colloidal suspension or solution, preferably in an aprotic solvent, preferably an alkane or mixture of alkanes, or a fluorinated solvent. The preferred solution of the present invention is applied to a substrate surface by any conventional technique such as dipping, flowing, wiping or 2s spraying. The silane reacts with the substrate surface, and excess solution is removed, providing a durable, non-wetting, lubricating surface with improved abrasion resistance. The present invention provides the. durability benefits of a primer without the additional step of applying a separate primer 30 layer. The use of t:he completely hydrolyzable silane and/or siloxane improves the humidity, ultraviolet light, and abrasion resistance of the silane surface treatment as measured by the Cl.evelan.d Condensing Cabinet, QW (with FS40 or B313 lamps), and wet sled abrasion tests, indicating a longer useful procluct lifetime.
Suitable silanes capable of hydrolysis to silica gel s have the general formula SiX'9wherein X'is a hydrolyzable radical generally selected from the group of halogens, alkoxy and acyloxy radicals.
Preferred silanes are those wherein X is preferably chloro, bromo, iodo, methoxy, ethoxy and acetoxy. Preferred io hydrolyzable silanes include tetrachlorosilane, tetramethoxy-silane and tetraacetoxysilane.
Suitable silo:xanes have the general formula SiYOZX"QY_ZZ, wherein X" is selected from the group of halogen, alkoxy and acyloxy radicals, y is two or more, and z is one or is more and 4y-2z is greater than zero. Preferred hydrolyzable siloxanes include hexach:Lorodisiloxane, octachlorotrisiloxane, and higher oligomer chlo:rosiloxa~nes.
The hydrolyzable silanes or siloxanes serve two functions. One is to become part of the coating and impart 2o resistance to weathering and abrasion. Another function is to dry the solvent. 'Typica:l hydrocarbon solvents can contain 50 to 200 ppm of water. Other solvents can be much higher in water content. For example, a solvent containing 200 ppm water would have enough water present to partially hydrolyze 2s the perfluoroalkyl~alkyls:ilane at 0.5 weight percent concentration. The comp:Letely hydrolyzable silane or siloxane is capable of eliminatin<~ or reducing the water content of the ,solvent prior to p~~rfluo~roalkylalkylsilane addition.
Otherwise, partially hydrolyzed perfluoroalkylalkylsilane 3o could result in insufficient coating deposition or very poor durability.
A
Preferred perfluoroalhylalkylsilanes have the general formula RmR'nSlX9_m_~, wherein R is a perfluoroalkylalkyl radical; m is typically one, but may also be two or three, n is typically zero or one, but may also be two and m+n is less than 4; R' is a vinyl or an alkyl radical, preferably methyl, ethyl., vinyl or propyl; and X is preferably a radical such as halogen, acyloxy, and/or alkoxy. Preferred perfluoroalkyl moieties in the perfluoroalkylalkyl radicals range from CF3 to C3pF6.~, preferably CsFl3 to ClgF3~, and most preferably CgFl~ to C121.~'25% the alkyl moiety is preferably ethyl. R' is pre:Eerabl;r methyl or ethyl. Preferred radicals for X include hydrolyzable chloro, bromo, iodo, methoxy, ethoxy and acetox~r radicals. Preferred perfluoroalkylalkyl-silanes in accordance w_Lth the present invention include perfluoroalkyleth;rltrichlorosilane, perfluoroalkylethyl-trimethoxysilane, perfluoroalkylethyltriacetoxysilane, perfluoroalkyleth~rldich:Loro(methyl)silane and perfluoroalkyl-ethyldiethoxy(methyl)si~~Lane.
These preferred perfluoroalkylethylsilanes appear to react with bonding sites at the substrate surface on a molecular basis. Strong surface bonding of the perfluoro-alkylethylsilanes produces a durable substrate surface which exhibits a high contact angle with a drop of water, indicating high water repellE~ncy.
Suitab7Le solvents include hexane, heptane, mineral spirits, acetone, toluene and naphtha. Preferred solvents are alkanes or halogenated hydrocarbon solvents such as trichlorotrifluoroethane, and methylene chloride, and perfluorinated organic compounds such as perfluorocarbons.
Concentrations of about 0.005 to 50, preferably about 0.05 to 5, percent of silane are, preferred. The solvent may be evaporated simply by drying in air at ambient temperature, or excess solution preferably may be removed by wiping. ' A
These preferred perfluoroalkylethylsilanes appear to react with bonding sites at the substrate surface on a molecular basis. Strong surface bonding of the perfluoro-alkylethylsilanes produces a durable substrate surface which exhibits a high contact angle with a drop of water, indicating high water repellE~ncy.
Suitab7Le solvents include hexane, heptane, mineral spirits, acetone, toluene and naphtha. Preferred solvents are alkanes or halogenated hydrocarbon solvents such as trichlorotrifluoroethane, and methylene chloride, and perfluorinated organic compounds such as perfluorocarbons.
Concentrations of about 0.005 to 50, preferably about 0.05 to 5, percent of silane are, preferred. The solvent may be evaporated simply by drying in air at ambient temperature, or excess solution preferably may be removed by wiping. ' A
The silanes may also be crosslinked to form a more durable coating. Preferably, curing is accomplished by heating the silane treated surface. Typically, curing temperatures of a.t lea~;t 150°F (about 66°C) are preferred, particularly above 200°F (about 93°C). A cure cycle of about 200°F (about 93°Cj for about 30 minutes is suitable. Higher temperatures and shorter heating times may be more efficient.
A cure cycle of 2 to 5 minutes at 400 to 500°F (about 204 to 260°C) may be preferred, particularly about 3 minutes at about io 470°F (about 243°c~) . A fluorinated olefin telome:r may also be included in the silane composition as described in U.S. Patent No. 5, 308, 705, preferably of the general formula Cm,F2m~+~CH=CHZ, where m'is from 1. to 30, preferably 1 to 16, more preferably 4 to 10. The substrate ~;urfaces may, in the alternative, be is contacted with pe:rfluoroalkylalkylsilane in vapor form.
The contact angles recited herein are measured by the sessile drop method using a modified captive bubble iridicator manufactured by Lord Manufacturing, Inc., equipped with Gaertner Sci.entifi.c goniometer optics. The surface to be 2o measured is placed in a horizontal position, facing upward, in front of a light source:. A drop of water is placed on top of the surface in front of: the light source so that the profile of the sessile drop can be viewed and the contact angle measured through the goniometer telescope equipped with 2s circular protractor graduation.
Weathering chambers include the Cleveland Condensing Cabinet (CCC) and QUV Tester (products of The Q-Panel Company, Cleveland, OH). The CC:C chamber was operated at a vapor temperature of 160°F (60°C) in an indoor ambient environment 3o which resulted in constant water condensation on the test surface. The QiJ~~ Tester is operated with cycles of 8 hours UV
A
z175~48 (either B313 or FS40 lamps) at black panel temperature of 65-70°C and 4 hours condensing humidity at 50°C.
The present invention will be further understood from the descriptions of specific examples which follow.
EXAMPLE I
A solution was prepared by mixing one gram of tetrachlorosilane and. one gram of perfluoroalkylalkylsilane in 40 grams of tri.chlorotrifluoroethane (Freon~ TF solvent, a to product of DuPc>nt). The perfluoroalkylalkylsilane comprised perfluoroalkyleahyltrichlorosilanes, wherein the perfluoroalkyl moieties comprised primarily C6F13 to C18F3~. For comparison, a control. solution was mixed without the tetrachlorosilane. The solutions were applied to the atmosphere surface of 3.9 millimeter thick Solex~ float glass (product of PPCi Industries, Inc.) with a cotton pad. Coupons were cured at 200°F (93°C) for one hour. The excess silane was removed from the gla:~s surfaces by solvent washing. Coupons were weathered in the: CCC and QW-FS40 weathering cabinets.
2o Coating efficiency was measured by the contact angle of a sessile drop oj_ water. The results are shown in the following table.
Table I
Hours Primer ~lcZPrimer Hours Primer No Primer 927 Ei7 60 1332 91 89 21'5 ~ ~-8 _8_ EXAMPLE II
Foux- solutions were prepared, each of which was 0.5 percent by weicfht perfluorohexylethyltrichlorosilane in Isopar s L solvent (product of: Exxon), a mixture of alkanes. The solutions had t:etrachlorosilane concentrations of 0.0, 0.2, 0.45, and 0.79 percent by weight. The order of addition was Isopar L, tetrachlorosilane and perfluoroalkylethyl-trichlorosilane~ to utilize the reactive drying of the solvent io by the hydrolyzable t:etrachlorosilane. These four solutions were coated on the tin surface of coupons of 0.182 inch (4.6 millimeter) th:LCk cle=ar float glass. Samples were tested in the CCC chambe:r. Coating efficiency was measured by the contact angle of a sessile drop of water. It can be seen in 15 the following l~.able t=hat increasing the concentration of hydrolyzable s:ilane within this range improves the durability of the perfluo:roalky:Lalkylsilane surface treatment.
2o CCC Contact Anale (°) Primer Concentration (Percent by Weight) Hours _0 0.2 0.45 0.79 0 1.15 115 114 114 642 __ __ __ 47 30 ~ EXAMPLE III
Four solutions were prepared, each of which was 2.5 percent by weight of the perfluoroalkylethyltrichlorosilane described in Example I and 2.5 percent by weight perfluoroalkylethylene in Fluorinert~ FC-77 solvent (a product of 3M). The solutions had tetrachlorosilane concentrations of 0.0, 1.0, 2.0 and 5.0 percent by weight. These four solutions were coated on the tin surface of coupons of 0.187 inch (4.7 millimeter) thick clear float glass. Coupons were cured at 300°F (149°C) for 15 minutes. Samples were tested in the CCC
and QUVB-313 chambers. Coating efficiency was measured by contact angle of a sessile drop of water. Results are given in the following tab7~_es .
io Table IIIA
CCC Contact ngle () A
Primer Concentration (Percent Weight) by Hours _~ 1 Q. 2.Q 50 2o Table IIIB
QUVB-313 Contact Anale () Primer Concentration (Percent Weight) by Hours _0 1.0 2.0 5.0 0 1.13 114 117 116 566 1.07 111 111 109 3o EXAMPLE IV
Solutions were prepared comprising 0.5 percent by weight perflucroalkylethyltrichlorosilane with and without 0.5 percent by weight tetrachlorosilane in Isopar L solvent.
Three perfluoroalkylethyltrichlorosilanes were employed:
1H,1H,2H,2H-tridecafluorooctyltrichlorosilane ("octyl"), 1H,1H,2H,2H-heF~tadeca.fluorodecyltrichlorosilane ("decyl"), or a mixture of pe:rfluoroalkylethyltrichlorosilanes described in Example I. Tempered Solex~ glass coupons and clear float glass coupons that ha.d undergone a heat treatment which s simulates a bending cycle (without bending significantly) were used in this study. The Solex glass was 0.157 inch (4 millimeters) thick, the clear float was 0.090 inch (2.3 millimeters) tYiick, a.nd the tin surfaces were treated.
Samples were tested i.n the QWB-313 chamber and on a Wet Sled io Abrader (Sheen Instruments LTD, Model 903). The Wet Sled Abrader was cu:~tom modified with an aluminum block which held two automotive windshield wiper blades. The wet sled abrasion test thus configured has an unusually high pressure wiper arm loading and is done partially wet and partially dry. These is wiper strokes are much more severe than normally used in vehicles. Coating efficiency was measured by the contact angle of a ses:~ile drop of water. The plus sign "+" refers to the presence oi= tetrachlorosilane in the coating formulations in the following tables.
Table IVA
OUVB- 313 Contact Angle (1 Hours octv:L_ oc decyl decyl+ mix mix+
',!1.
0 116 :112 111 115 111 118 163 102 :105 87 112 102 116 352 9!~ 95 84 107 100 111 496 8:2 88 74 102 89 106 827 7~ 85 60 89 82 103 , , Fable IVB
6Vet d Abrasion ContactAnode() Sle ~vcles octvl, octv~l+ dec;~ decyl+ mix mix+
200* 86 104 79 108 86 108 600* 52 99 78 106 79 105 *These data (at 200 and 600 cycles) were obtained with a io slurry of 0.5 ~~ercent by weight Hi-Sil~ 233 synthetic precipitated silica in water. The data for 5000 cycles were obtained using deionized water only.
EXAMPLE V
i5 A control solution was prepared by mixing 95 grams of FC-77 solvent, 2.5 grams of perfluoroalkylethyltri-chlorosilanes I:perflu.oroalkyl = C6F13 to ClgF3~) , and 2.5 grams of perfluoroalk:ylethylene. A primer-containing solution was prepared by mi~:ing 18.8 grams of FC-77 solvent, 5 grams of 2o perfluoroalkylE:thyltrichlorosilanes, 5.0 grams of perfluoro-alkylethylene ~;perf luoroalkyl = C6F13 to ClgF3~ ) , and 2 grams of tetrachlorosilane. A primer only solution was prepared from 198.4 grams of FC-77 solvent and 1.6 grams of tetrachloro-silane. These solutions were applied to the tin surface of 25 4.9 millimeter thick clear float glass with a cotton pad.
Selected coupons werE: coated with primer solution prior to coating with e_Lther control solution or the solution containing per:=luoroalkylalkylsilane and tetrachlorosilane.
Coupons were cured at. 300°F (149°C) for 15 minutes. The excess 3o silane was removed from the glass surfaces by solvent washing.
Coupons were wf~athered in the CCC. Coating efficiency was measured by the contact angle of~a sessile drop of water.
Table V
.
CCC Contact rle !1 Anc No x~rimer layer Primer l ayer ~iours No integral Integral No integralIntegral primer primer primer primer 918 :?9 39 31 41 The solution containing a silane hydrolyzable to silica led to i5 more durable coatings whether or not the glass was preprimed with a silica layer separately with a solution of a hydrolyzable si.lane.
The above examples are offered to illustrate the 2o present invention. Various perfluoroalkylalkylsilanes, hydrolyzable si.lanes, solvents and concentrations may be applied by any conventional technique, and optimally cured at suitable tempex-atures; for adequate times to provide durable non-wetting surfaces to any of a variety of glass and plastic 25 substrates, as well as other inorganic surfaces such as metals, cerami(a, enamels, and metal or metal oxide films.
The treated substrates of the present invention are especially suitable in automobile and aircraft parts, as well as in building components, lenses and CRT plates.
A cure cycle of 2 to 5 minutes at 400 to 500°F (about 204 to 260°C) may be preferred, particularly about 3 minutes at about io 470°F (about 243°c~) . A fluorinated olefin telome:r may also be included in the silane composition as described in U.S. Patent No. 5, 308, 705, preferably of the general formula Cm,F2m~+~CH=CHZ, where m'is from 1. to 30, preferably 1 to 16, more preferably 4 to 10. The substrate ~;urfaces may, in the alternative, be is contacted with pe:rfluoroalkylalkylsilane in vapor form.
The contact angles recited herein are measured by the sessile drop method using a modified captive bubble iridicator manufactured by Lord Manufacturing, Inc., equipped with Gaertner Sci.entifi.c goniometer optics. The surface to be 2o measured is placed in a horizontal position, facing upward, in front of a light source:. A drop of water is placed on top of the surface in front of: the light source so that the profile of the sessile drop can be viewed and the contact angle measured through the goniometer telescope equipped with 2s circular protractor graduation.
Weathering chambers include the Cleveland Condensing Cabinet (CCC) and QUV Tester (products of The Q-Panel Company, Cleveland, OH). The CC:C chamber was operated at a vapor temperature of 160°F (60°C) in an indoor ambient environment 3o which resulted in constant water condensation on the test surface. The QiJ~~ Tester is operated with cycles of 8 hours UV
A
z175~48 (either B313 or FS40 lamps) at black panel temperature of 65-70°C and 4 hours condensing humidity at 50°C.
The present invention will be further understood from the descriptions of specific examples which follow.
EXAMPLE I
A solution was prepared by mixing one gram of tetrachlorosilane and. one gram of perfluoroalkylalkylsilane in 40 grams of tri.chlorotrifluoroethane (Freon~ TF solvent, a to product of DuPc>nt). The perfluoroalkylalkylsilane comprised perfluoroalkyleahyltrichlorosilanes, wherein the perfluoroalkyl moieties comprised primarily C6F13 to C18F3~. For comparison, a control. solution was mixed without the tetrachlorosilane. The solutions were applied to the atmosphere surface of 3.9 millimeter thick Solex~ float glass (product of PPCi Industries, Inc.) with a cotton pad. Coupons were cured at 200°F (93°C) for one hour. The excess silane was removed from the gla:~s surfaces by solvent washing. Coupons were weathered in the: CCC and QW-FS40 weathering cabinets.
2o Coating efficiency was measured by the contact angle of a sessile drop oj_ water. The results are shown in the following table.
Table I
Hours Primer ~lcZPrimer Hours Primer No Primer 927 Ei7 60 1332 91 89 21'5 ~ ~-8 _8_ EXAMPLE II
Foux- solutions were prepared, each of which was 0.5 percent by weicfht perfluorohexylethyltrichlorosilane in Isopar s L solvent (product of: Exxon), a mixture of alkanes. The solutions had t:etrachlorosilane concentrations of 0.0, 0.2, 0.45, and 0.79 percent by weight. The order of addition was Isopar L, tetrachlorosilane and perfluoroalkylethyl-trichlorosilane~ to utilize the reactive drying of the solvent io by the hydrolyzable t:etrachlorosilane. These four solutions were coated on the tin surface of coupons of 0.182 inch (4.6 millimeter) th:LCk cle=ar float glass. Samples were tested in the CCC chambe:r. Coating efficiency was measured by the contact angle of a sessile drop of water. It can be seen in 15 the following l~.able t=hat increasing the concentration of hydrolyzable s:ilane within this range improves the durability of the perfluo:roalky:Lalkylsilane surface treatment.
2o CCC Contact Anale (°) Primer Concentration (Percent by Weight) Hours _0 0.2 0.45 0.79 0 1.15 115 114 114 642 __ __ __ 47 30 ~ EXAMPLE III
Four solutions were prepared, each of which was 2.5 percent by weight of the perfluoroalkylethyltrichlorosilane described in Example I and 2.5 percent by weight perfluoroalkylethylene in Fluorinert~ FC-77 solvent (a product of 3M). The solutions had tetrachlorosilane concentrations of 0.0, 1.0, 2.0 and 5.0 percent by weight. These four solutions were coated on the tin surface of coupons of 0.187 inch (4.7 millimeter) thick clear float glass. Coupons were cured at 300°F (149°C) for 15 minutes. Samples were tested in the CCC
and QUVB-313 chambers. Coating efficiency was measured by contact angle of a sessile drop of water. Results are given in the following tab7~_es .
io Table IIIA
CCC Contact ngle () A
Primer Concentration (Percent Weight) by Hours _~ 1 Q. 2.Q 50 2o Table IIIB
QUVB-313 Contact Anale () Primer Concentration (Percent Weight) by Hours _0 1.0 2.0 5.0 0 1.13 114 117 116 566 1.07 111 111 109 3o EXAMPLE IV
Solutions were prepared comprising 0.5 percent by weight perflucroalkylethyltrichlorosilane with and without 0.5 percent by weight tetrachlorosilane in Isopar L solvent.
Three perfluoroalkylethyltrichlorosilanes were employed:
1H,1H,2H,2H-tridecafluorooctyltrichlorosilane ("octyl"), 1H,1H,2H,2H-heF~tadeca.fluorodecyltrichlorosilane ("decyl"), or a mixture of pe:rfluoroalkylethyltrichlorosilanes described in Example I. Tempered Solex~ glass coupons and clear float glass coupons that ha.d undergone a heat treatment which s simulates a bending cycle (without bending significantly) were used in this study. The Solex glass was 0.157 inch (4 millimeters) thick, the clear float was 0.090 inch (2.3 millimeters) tYiick, a.nd the tin surfaces were treated.
Samples were tested i.n the QWB-313 chamber and on a Wet Sled io Abrader (Sheen Instruments LTD, Model 903). The Wet Sled Abrader was cu:~tom modified with an aluminum block which held two automotive windshield wiper blades. The wet sled abrasion test thus configured has an unusually high pressure wiper arm loading and is done partially wet and partially dry. These is wiper strokes are much more severe than normally used in vehicles. Coating efficiency was measured by the contact angle of a ses:~ile drop of water. The plus sign "+" refers to the presence oi= tetrachlorosilane in the coating formulations in the following tables.
Table IVA
OUVB- 313 Contact Angle (1 Hours octv:L_ oc decyl decyl+ mix mix+
',!1.
0 116 :112 111 115 111 118 163 102 :105 87 112 102 116 352 9!~ 95 84 107 100 111 496 8:2 88 74 102 89 106 827 7~ 85 60 89 82 103 , , Fable IVB
6Vet d Abrasion ContactAnode() Sle ~vcles octvl, octv~l+ dec;~ decyl+ mix mix+
200* 86 104 79 108 86 108 600* 52 99 78 106 79 105 *These data (at 200 and 600 cycles) were obtained with a io slurry of 0.5 ~~ercent by weight Hi-Sil~ 233 synthetic precipitated silica in water. The data for 5000 cycles were obtained using deionized water only.
EXAMPLE V
i5 A control solution was prepared by mixing 95 grams of FC-77 solvent, 2.5 grams of perfluoroalkylethyltri-chlorosilanes I:perflu.oroalkyl = C6F13 to ClgF3~) , and 2.5 grams of perfluoroalk:ylethylene. A primer-containing solution was prepared by mi~:ing 18.8 grams of FC-77 solvent, 5 grams of 2o perfluoroalkylE:thyltrichlorosilanes, 5.0 grams of perfluoro-alkylethylene ~;perf luoroalkyl = C6F13 to ClgF3~ ) , and 2 grams of tetrachlorosilane. A primer only solution was prepared from 198.4 grams of FC-77 solvent and 1.6 grams of tetrachloro-silane. These solutions were applied to the tin surface of 25 4.9 millimeter thick clear float glass with a cotton pad.
Selected coupons werE: coated with primer solution prior to coating with e_Lther control solution or the solution containing per:=luoroalkylalkylsilane and tetrachlorosilane.
Coupons were cured at. 300°F (149°C) for 15 minutes. The excess 3o silane was removed from the glass surfaces by solvent washing.
Coupons were wf~athered in the CCC. Coating efficiency was measured by the contact angle of~a sessile drop of water.
Table V
.
CCC Contact rle !1 Anc No x~rimer layer Primer l ayer ~iours No integral Integral No integralIntegral primer primer primer primer 918 :?9 39 31 41 The solution containing a silane hydrolyzable to silica led to i5 more durable coatings whether or not the glass was preprimed with a silica layer separately with a solution of a hydrolyzable si.lane.
The above examples are offered to illustrate the 2o present invention. Various perfluoroalkylalkylsilanes, hydrolyzable si.lanes, solvents and concentrations may be applied by any conventional technique, and optimally cured at suitable tempex-atures; for adequate times to provide durable non-wetting surfaces to any of a variety of glass and plastic 25 substrates, as well as other inorganic surfaces such as metals, cerami(a, enamels, and metal or metal oxide films.
The treated substrates of the present invention are especially suitable in automobile and aircraft parts, as well as in building components, lenses and CRT plates.
Claims (20)
1. A composition for producing a water repellent surface on a substrate comprising a mixture of:
a perfluoroalkylalkylsilane selected from compounds having the general formula R m R'n SiX4-m-n, wherein R is a perfluoroalkylalkyl radical, R' is a vinyl or an alkyl radical, m is 1, 2 or 3, n is 0, 1 or 2 and m+n is less than 4, and X is selected from the group consisting of halogen and acyloxy radicals, and a further compound selected from the group consisting of siloxanes capable of hydrolysis to a silica gel and a mixture of said siloxanes and silanes capable of hydrolysis to a silica gel.
a perfluoroalkylalkylsilane selected from compounds having the general formula R m R'n SiX4-m-n, wherein R is a perfluoroalkylalkyl radical, R' is a vinyl or an alkyl radical, m is 1, 2 or 3, n is 0, 1 or 2 and m+n is less than 4, and X is selected from the group consisting of halogen and acyloxy radicals, and a further compound selected from the group consisting of siloxanes capable of hydrolysis to a silica gel and a mixture of said siloxanes and silanes capable of hydrolysis to a silica gel.
2. A composition according to claim 1, wherein the perfluoroalkyl moiety of said perfluoroalkylalkyl radical is selected from CF3 to C30F61.
3. A composition according to claim 1, wherein R' is selected from the group consisting of methyl, ethyl, vinyl and propyl.
4. A composition according to claim 1, wherein X is selected from the group consisting of chloro, bromo, iodo and acetoxy.
5. A composition according to claim 1, wherein said perfluoroalkylalkylsilane is selected from the group consisting of perfluoroalkylethyltrichlorosilane, perfluoroalkylethyltriacetoxysilane and perfluoroalkylethyldichloro(methyl)silane.
6. A composition according to claim 1, wherein said silane capable of hydrolysis to a silica gel has the general formula SiX'4, wherein X' is selected from the group consisting of halogen, alkoxy and acyloxy radicals.
7. A composition for producing a water repellent surface on a substrate comprising a mixture of:
a perfluoroalkylalkylsilane selected from compounds having the general formula R m R'n SiX4-m-n, wherein R is a perfluoroalkylalkyl radical, R' is a vinyl or an alkyl radical, m is 1, 2 or 3, n is 0, 1 or 2 and m+n is less than 4, and X is selected from the group consisting of halogen, alkoxy and acyloxy radicals, and a mixture of a silane capable of hydrolysis to a silica gel, wherein said silane has the general formula SiX'4, wherein X' is halogen, and a siloxane capable of hydrolysis to a silica gel.
a perfluoroalkylalkylsilane selected from compounds having the general formula R m R'n SiX4-m-n, wherein R is a perfluoroalkylalkyl radical, R' is a vinyl or an alkyl radical, m is 1, 2 or 3, n is 0, 1 or 2 and m+n is less than 4, and X is selected from the group consisting of halogen, alkoxy and acyloxy radicals, and a mixture of a silane capable of hydrolysis to a silica gel, wherein said silane has the general formula SiX'4, wherein X' is halogen, and a siloxane capable of hydrolysis to a silica gel.
8. A composition according to claim 7, wherein said silane capable of hydrolysis to a silica gel is silicon tetrachloride.
9. A composition according to claim 1, wherein said siloxane capable of hydrolysis to a silica gel has the general formula Si y O z X"4y-2z wherein X" is selected from the group of halogen, alkoxy and acyloxy radicals, y is two or more and z is one or more and 4y-2z is greater than zero.
10. A composition for producing a water repellent surface on a substrate comprising a mixture of:
a perfluoroalkylalkylsilane selected from compounds having the general formula R m R'n SiX4-m-n, wherein R is a perfluoroalkylalkyl radical, R' is a vinyl or an alkyl radical, m is 1, 2 or 3, n is 0, 1 or 2 and m+n is less than 4, and X is selected from the group consisting of halogen, alkoxy and acyloxy radicals;
a further compound selected from the group consisting of siloxanes, and a mixture of siloxanes and silanes wherein the silanes and siloxanes are capable of hydrolysis to a silica gel, and a fluorinated olefin telomer having the general formula C m,F2m'+1CH=CH2 where m' is from 1 to 30.
a perfluoroalkylalkylsilane selected from compounds having the general formula R m R'n SiX4-m-n, wherein R is a perfluoroalkylalkyl radical, R' is a vinyl or an alkyl radical, m is 1, 2 or 3, n is 0, 1 or 2 and m+n is less than 4, and X is selected from the group consisting of halogen, alkoxy and acyloxy radicals;
a further compound selected from the group consisting of siloxanes, and a mixture of siloxanes and silanes wherein the silanes and siloxanes are capable of hydrolysis to a silica gel, and a fluorinated olefin telomer having the general formula C m,F2m'+1CH=CH2 where m' is from 1 to 30.
11. A composition according to claim 1 wherein said mixture of the perfluoroalkylalkylsilane and said other compound capable of hydrolysis to a silica gel are in a solvent selected from the group consisting of alkanes, minerals spirits, acetone, toluene, naphtha, halogenated hydrocarbons, perfluorinated organic solvents, and mixtures thereof.
12. A composition according to claim 11, wherein the perfluoroalkyl moiety of said perfluoroalkylalkyl radical is CF3 to C30F61.
13. A composition according to claim 11, wherein R' is selected from the group consisting of methyl, ethyl, vinyl and propyl.
14. A composition according to claim 11, wherein X is selected from the group consisting of chloro, bromo, iodo and acetoxy.
15. A composition according to claim 11, wherein said solvent is selected from the group consisting of hexane, heptane, mineral spirits, acetone, toluene, naphtha, trichlorotrifluoroethane, methylene chloride, perfluorocarbons and mixtures thereof.
16. A composition according to claim 11, wherein said silane capable of hydrolysis to a silica gel has the general formula SiX'4, wherein X' is selected from the group consisting of halogen, alkoxy and acyloxy radicals.
17. A composition according to claim 16, wherein the silane capable of hydrolysis to silica gel is silicon tetrachloride.
18. A composition according to claim 11, further comprising a fluorinated olefin telomer having the general formula C m.F2m'+1CH=CH2 where m' is 1 to 30.
19. A composition according to claim 1, wherein the mixture consists essentially of the perfluoroalkylalkylsilane and the further compound.
20. A composition according to claim 1, wherein the mixture consists essentially of the perfluoroalkylalkylsilane and the further compound in a solvent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US46146495A | 1995-06-05 | 1995-06-05 | |
| US461,464 | 1995-06-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2175848A1 CA2175848A1 (en) | 1996-12-06 |
| CA2175848C true CA2175848C (en) | 2000-01-11 |
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ID=23832663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002175848A Expired - Fee Related CA2175848C (en) | 1995-06-05 | 1996-05-06 | Water repellent surface treatment with integrated primer |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPH08333545A (en) |
| KR (1) | KR100194250B1 (en) |
| CN (1) | CN1072700C (en) |
| CA (1) | CA2175848C (en) |
| TW (1) | TW415923B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8286561B2 (en) | 2008-06-27 | 2012-10-16 | Ssw Holding Company, Inc. | Spill containing refrigerator shelf assembly |
| US9074778B2 (en) | 2009-11-04 | 2015-07-07 | Ssw Holding Company, Inc. | Cooking appliance surfaces having spill containment pattern |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19731416C1 (en) * | 1997-07-22 | 1998-09-17 | Vetrotech Saint Gobain Int Ag | Fire protection glazing filled with hardened hydrated alkali poly:silicate avoiding localised delamination in fire |
| GB0206930D0 (en) | 2002-03-23 | 2002-05-08 | Univ Durham | Method and apparatus for the formation of hydrophobic surfaces |
| JP2012097267A (en) * | 2003-09-17 | 2012-05-24 | Kazufumi Ogawa | Water and oil repellency composite film-forming solution, manufacturing method of water and oil repellency composite film using the solution, and water and oil repellency composite film using the method |
| JP5343271B2 (en) * | 2003-09-17 | 2013-11-13 | 小川 一文 | Water repellent and oil repellent antifouling glass plate, production method thereof, automobile and electromagnetic cooker using the same |
| CN100396751C (en) * | 2005-06-21 | 2008-06-25 | 广州市白云化工实业有限公司 | Organic silicon fluoro water proofing agent and its preparation method |
| US11786036B2 (en) | 2008-06-27 | 2023-10-17 | Ssw Advanced Technologies, Llc | Spill containing refrigerator shelf assembly |
| WO2010042668A1 (en) | 2008-10-07 | 2010-04-15 | Ross Technology Corporation | Spill resistant surfaces having hydrophobic and oleophobic borders |
| EP2547832A4 (en) | 2010-03-15 | 2016-03-16 | Ross Technology Corp | Plunger and methods of producing hydrophobic surfaces |
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| CN104829641B (en) * | 2015-05-12 | 2018-01-19 | 傅筠 | A kind of fluorine-containing organic silicon monomer and preparation method thereof |
| KR101912605B1 (en) * | 2017-03-10 | 2018-10-30 | 경기대학교 산학협력단 | Super-Hydrophobic Particle and Composite having the Same |
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| CN110981225A (en) * | 2019-12-20 | 2020-04-10 | 苏州浩纳新材料科技有限公司 | Hydrophobic rainproof coating for glass, preparation method and application method |
| CN111501354B (en) * | 2020-05-23 | 2022-11-04 | 苏州大学 | Oil-proof antifouling self-cleaning functional fabric and preparation method thereof |
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Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6051103A (en) * | 1983-08-30 | 1985-03-22 | Shin Etsu Chem Co Ltd | Antifouling treatment |
| JPH0759699B2 (en) * | 1987-10-05 | 1995-06-28 | ダイキン工業株式会社 | Water and oil repellent composition |
| US5308705A (en) * | 1990-04-03 | 1994-05-03 | Ppg Industries, Inc. | Water repellent surface treatment |
| US5523161A (en) * | 1990-04-03 | 1996-06-04 | Ppg Industries, Inc. | Water repellent surface treatment with integrated primer |
| JPH04144940A (en) * | 1990-10-05 | 1992-05-19 | Asahi Glass Co Ltd | Water repellent and oil repellent composition |
| JP2500149B2 (en) * | 1991-01-23 | 1996-05-29 | 松下電器産業株式会社 | Water- and oil-repellent coating and method for producing the same |
| JP2555797B2 (en) * | 1991-05-13 | 1996-11-20 | トヨタ自動車株式会社 | Water repellent glass and method for manufacturing the same |
| JP3155025B2 (en) * | 1991-05-17 | 2001-04-09 | 旭硝子株式会社 | Surface-treated building / building article and method of manufacturing the article |
| JP2874391B2 (en) * | 1991-06-05 | 1999-03-24 | 日産自動車株式会社 | Manufacturing method of water-repellent glass |
| JPH05170486A (en) * | 1991-12-25 | 1993-07-09 | Central Glass Co Ltd | Water repellent for glass surface and water-repellent glass |
| JPH06293782A (en) * | 1993-04-07 | 1994-10-21 | Mitsubishi Kasei Corp | Coating composition |
| CA2175849C (en) * | 1995-06-01 | 2003-07-15 | George B. Goodwin | Autophobic water repellent surface treatment |
-
1996
- 1996-05-06 CA CA002175848A patent/CA2175848C/en not_active Expired - Fee Related
- 1996-05-20 TW TW085105930A patent/TW415923B/en not_active IP Right Cessation
- 1996-06-03 CN CN96107924A patent/CN1072700C/en not_active Expired - Lifetime
- 1996-06-04 KR KR1019960019762A patent/KR100194250B1/en not_active IP Right Cessation
- 1996-06-04 JP JP8141488A patent/JPH08333545A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8286561B2 (en) | 2008-06-27 | 2012-10-16 | Ssw Holding Company, Inc. | Spill containing refrigerator shelf assembly |
| US8596205B2 (en) | 2008-06-27 | 2013-12-03 | Ssw Holding Company, Inc. | Spill containing refrigerator shelf assembly |
| US9179773B2 (en) | 2008-06-27 | 2015-11-10 | Ssw Holding Company, Inc. | Spill containing refrigerator shelf assembly |
| US9074778B2 (en) | 2009-11-04 | 2015-07-07 | Ssw Holding Company, Inc. | Cooking appliance surfaces having spill containment pattern |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1072700C (en) | 2001-10-10 |
| JPH08333545A (en) | 1996-12-17 |
| CA2175848A1 (en) | 1996-12-06 |
| KR970001503A (en) | 1997-01-24 |
| KR100194250B1 (en) | 1999-06-15 |
| CN1141941A (en) | 1997-02-05 |
| TW415923B (en) | 2000-12-21 |
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