WO1999029636A1 - Emulsions aqueuses contenant un hydrolysat de silane fluorocarbone, et matieres revetues de ces emulsions - Google Patents

Emulsions aqueuses contenant un hydrolysat de silane fluorocarbone, et matieres revetues de ces emulsions Download PDF

Info

Publication number
WO1999029636A1
WO1999029636A1 PCT/US1998/026019 US9826019W WO9929636A1 WO 1999029636 A1 WO1999029636 A1 WO 1999029636A1 US 9826019 W US9826019 W US 9826019W WO 9929636 A1 WO9929636 A1 WO 9929636A1
Authority
WO
WIPO (PCT)
Prior art keywords
silane
aqueous emulsion
fiuorocarbon
silicate
hydrolysate
Prior art date
Application number
PCT/US1998/026019
Other languages
English (en)
Inventor
Robert Allen Halling
Tatsuhiro Takahashi
Satoko Iwato
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Publication of WO1999029636A1 publication Critical patent/WO1999029636A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

Definitions

  • the present invention relates to fiuorocarbon silane hydrolysate-containing aqueous emulsions. More specifically, it relates both to fiuorocarbon silane hydrolysate-containing aqueous emulsions which, when coated and dried on a substrate, are able to provide a water-repelling surface that is clear, smooth, and has an improved heat resistance; as well as to materials obtained by coating and drying this aqueous emulsion on the surface of a substrate.
  • Si(OR)4 a substituted silicon alkoxide in which some of the alkoxyl groups have been substituted with fluoroalkyl groups, an alcohol, water, and an acid or a base in order to produce water-repellent glass by forming a water-repellent clear film on the surface of a glass substrate.
  • this has the drawback that a high concentration cannot be achieved because silicon alkoxide which has been partially substituted with fluoroalkyl groups does not readily dissolve in an alcohol/water-type solvent.
  • this aqueous solution consists of a silicone alkoxide- and alcohol-containing solution in which an acid or a base has been included, the reaction proceeds over time, during the course of which the viscosity rises; hence, the storage stability is poor.
  • the fact that alcohol is used makes this method environmentally undesirable.
  • U.S. Patent 5,550,184 discloses emulsions of hydrolyzable alkoxysilane compounds which are able to confer water and oil repellency to a substrate without requiring a special curing operation.
  • these emulsions are clear immediately after being coated onto a glass sheet, it was found that when thick coatings of these emulsions dry, liquid drops form, making it difficult to maintain the transparency of the glass sheet.
  • improvements are also desirable in the heat resistance of the coated surface.
  • the present invention provides a stable aqueous emulsion containing a fiuorocarbon silane hydrolysate and a silicate which resolves the above-mentioned problems and confers excellent water repellency while maintaining the clarity and smoothness of the coated surface, as well as giving a coated surface which has excellent heat resistance.
  • the present invention comprises an aqueous emulsion comprising a) at least one hydrolysate of a fiuorocarbon silane having the formula
  • Rf is a perfluoroalkyl group having from 3 to 18 carbon atoms, or a mixture thereof; each R is independently an alkyl group having from 1 to 3 carbon atoms; p is from 2 to 4; and n is from 2 to 10; said hydrolysate generated in the presence of a surfactant, and b) a silicate having the formula
  • each R is independently selected from the group consisting of OCH3, OCH 2 CH 3 and (OCH 2 CH 2 ) m OCH3 wherein m is 1 to 10.
  • the present invention also comprises a water-repellent material which is obtained by coating and drying this aqueous emulsion on a substrate.
  • fiuorocarbon silane hydrolysate-containing aqueous emulsions according to the present invention for resolving the above-described problems contain at least one hydrolysate of a fiuorocarbon silane having the formula
  • Rf is a perfluoroalkyl group having from 3 to 18 carbon atoms, or a mixture thereof; each R' is independently an alkyl group having from 1 to 3 carbon atoms; p is from 2 to 4; and n is from 2 to 10, said hydrolysate generated in the presence of a surfactant, and a silicate having the formula Si-R4 (2)
  • each R is independently selected from the group consisting of OCH3, OCH 2 CH 3 and (OCH 2 CH 2 ) m OCH3 wherein m is 1 to 10.
  • the fiuorocarbon silane hydrolysate-containing aqueous emulsions according to the present invention are those in which the content of the fiuorocarbon silane in the aqueous emulsion is from 0.1 to 20% by weight, and the molar fraction of the silicate with respect to the fiuorocarbon silane is from 0.3 to 10. Two or more hydrolyzed fiuorocarbon silanes may be mixed and used together.
  • aqueous emulsions of the present invention use is made of, from among hydrolyzable alkoxysilane compounds, those fiuorocarbon silanes where Rf is a perfluoroalkyl group having from 3 to 18 carbon atoms. These are preferably perfluoroalkyl groups in which Rf represents mixed perfluoroalkyl groups having an average of from 3 to 12 carbon atoms. R' is a C1-C3 alkyl.
  • R' is methyl
  • p is 2
  • n is from 2 to 4.
  • the preferable fiuorocarbon silane hydrolysates are hydrolysates of perfluoroalkylethyltris(2-(2- methoxyethoxy)ethoxy)silanes; when n is 3, the preferable fiuorocarbon silane hydrolysates are hydrolysates of 2-perfluoroalkylethyltris(2-(2-(2- methoxyethoxy)ethoxy)ethoxy)-silanes.
  • This type of fiuorocarbon silane is produced by known methods. See Kirk-Othmer, Encyclopedia of Chemical Technology, third edition, vol. 20, and Mehrota, R. C, Pure Appl. Chem., 13,
  • the preferred method is by reacting the corresponding perfluoroalkyl trichlorosilane with the proper ether alcohol, such as, diethylene glycol monomethyl ether or triethylene glycol monomethyl ether.
  • the fluorinated trichloro silane starting materials for the above reaction can be prepared by one of several recognized procedures: for example see, McBee, E. T., J. Am. Chem. Soc, 79, 2329 (1957); Adv. Organomet. Chem, 17, 407 (1979); U.S. Patent No. 3,012,006; U.S. Patent No. 4,089,882 or U.S. Patent No. 4,549,003
  • the aqueous emulsions of the present invention contain an ingredient that copolymerizes with the above-described fiuorocarbon silane hydrolyzate.
  • R represents one or more groups selected from among OCH3,
  • OCH 2 CH3 and (OCH 2 CH 2 ) m OCH3 wherein m is being from 1 to 10, are used in the present invention because they hydrolyze and dissolve in water.
  • the disemulsion of oil-soluble Si(OCH3)4 or Si(OCH CH3)4 in water has hitherto been carried out only in water/alcohol systems, but it was discovered that this generally also hydrolyzes and dissolves in water with at least three hours of stirring. From the standpoint of being able to shorten the stirring time with the hydrolyzed fiuorocarbon silane aqueous emulsion and thus enabling easy preparation, water-soluble silicates having the formula
  • Surfactants are employed to form the stable aqueous emulsions of the fiuorocarbon silane hydrolysate which are used in the aqueous emulsions of the present invention. Emulsions are achieved by emulsifying the hydrolyzable alkoxysilane in water in the presence of an effective amount of surfactant of sufficiently high HLB value to simultaneously retain said hydrolyzable alkoxysilane compound in a substantially totally hydrolyzed state and inhibit said resulting hydrolyzed alkoxysilane compound from self-condensation.
  • Surfactants suitable for use herein are chosen from nonionic, cationic, anionic and amphoteric types.
  • Preferred surfactants are those that have an HLB ("The HLB System” published by ICI America's Inc., Wilmington, Del.; Adamson, A. W., "Physical Chemistry of Surfaces," 4 th . Ed., John Wily & Sons, N.Y., 1982, p. 475) value greater than 12, and preferably greater than 16.
  • HLB The HLB System
  • Surfactants with HLB values from 12 to 16 may be used, but, usually require significantly greater quantities to achieve emulsions of adequate stability. Mixtures of emulsifiers that each meet the above HLB requirements may be used if they are compatible with one another.
  • Suitable emulsifiers include, but are not limited to, alkylbenzenesulfonates, linear alkyldiphenyletherdisulfonates, alpha-olefin sulfonates, ethoxylated alkyl alcohol ethers, ethoxylated alkyl alcohol ether sulfates, ethoxylated alkylphenols, ethoxylated alkylphenol ether sulfates, ethoxylated perfluoroalkylalkanols, Cg_ ⁇ g alkyltrimethylammonium salts, Cg. ⁇ g alkyldimethylammonium salts, ethoxylated
  • Cg_ ⁇ g amine salts and alpha-trimethylamino fatty acid betains and perfluoroalkyl amphoteric surfactants of the type Rf-CH2CH(OR")CH2N(CH3)2CH 2 CO2(inner salt) where R" is H or acetyl, and quaternary salts of the type
  • nonionic surfactants such as Rf-CH 2 CH-O-(CH 2 CH O) ⁇ i-H, or C 9 Hi9-C6H4-O-(CH 2 CH O) 5 o-H
  • cationic surfactants such as R f -CH 2 CH 2 SCH 2 CH(OH)CH 2 N(CH 3 ) + Cl-
  • anionic surfactants such as C ⁇ 2 H 2 5(OCH 2 CH 2 )4 ⁇ S ⁇ 3-NH4 + and C12H27-C6H4-
  • the Rf in the above surfactants is a perfluoroalkyl group, usually having 3 to 18 carbon atoms.
  • the fiuorocarbon silane content within the aqueous emulsion is at least 0.1% by weight, preferably from 2 to 20% by weight, and most preferably from 7 to 15% by weight. When this is less than 0.1% by weight, the water repellency is inadequate, and when this is greater than 20% by weight, it becomes difficult to obtain a stable aqueous emulsion.
  • the weight ratio within the aqueous emulsion of the fiuorocarbon silane and the surfactant employed in the formation of the hydrolysate is from 1 : 1 to 10:1, preferably from 10:2 to 10:5, and most preferably 10:3.
  • the ratio of the S'irfactant is too low, it becomes impossible to keep the aqueous emulsion stable, and when the ratio is too high, hydrophilic groups tend to remain on the substrate even after drying, making it impossible to provide good water repellency.
  • the molar fraction of the silicate with respect to the fiuorocarbon silane is at least 0.1, preferably from 0.3 to 10, and even more preferably from 0.4 to 2.
  • the ratio of fiuorocarbon silane contained is too high, the clarity of the coated surface is lost. If the ratio of the silicate content is too high, the aqueous emulsion gels, resulting in a loss in stability.
  • the stability of the aqueous emulsion is influenced not only by the fiuorocarbon silane concentration and the molar fraction of silicate with respect to the fiuorocarbon silane, but also by the pH of the aqueous emulsion and the type of surfactant employed.
  • a nonionic surfactant any pH is suitable for the stability of the aqueous emulsion.
  • the pH of the aqueous emulsion can also affect the durability of the coating and then a pH of less than 7 is usually better.
  • the pH of the aqueous emulsion is less than 4 when a nonionic surfactant is used.
  • a high pH will negate its surfactant properties and usually the pH of the aqueous emulsion is less than 7, and preferably less than 4.
  • a high pH is usually needed to avoid interaction with the surfactant, and preferably the pH of the aqueous emulsion is greater than 7, more preferably greater than 10.
  • the ratios in which the ingredients are included within the aqueous emulsion are set as desired while taking into account all of these conditions.
  • aqueous emulsions in which 1) the fiuorocarbon silane content is from 0.1 to 20% by weight, the molar fraction of silicate with respect to fiuorocarbon silane is from 0.1 to 0.5, and the pH has been adjusted to less than 4, and in particular to from 2 to 3, and the weight ratio of fiuorocarbon silane and surfactant used to generate the hydrolysate is from 1:1 to 10:1; 2) aqueous emulsions in which the fiuorocarbon silane content is from 0.1 to 1.0% by weight, the molar fraction of silicate with respect to fiuorocarbon silane is from 0.1 to 1, the pH has been adjusted to less than 4, and in particular to from 2 to 3, and the weight ratio of the fiuorocarbon silane and the surfactant used to generate the
  • C9Hi9-C6H4-O-(CH2CH2 ⁇ )5Q-H is used, as long as an aqueous emulsion is used that has a fiuorocarbon silane content of from 0.1 to 20% by weight, a silicate molar fraction with respect to fiuorocarbon silane of from 0.1 to 5, and a weight ratio of fiuorocarbon silane to surfactant used to generate the hydrolysate is from 1:1 to 10:1, this may have any pH.
  • aqueous emulsions in which the fiuorocarbon silane content is from 0.1 to 20% by weight, the molar fraction of silicate with respect to fiuorocarbon silane is from 0.1 to 5, the pH has been adjusted to less than 4, and in particular to from 2 to 3, and the weight ratio of fiuorocarbon silane to surfactant used to generate the hydrolysate is from 1 :1 to 10:1; and 2) aqueous emulsions in which the fiuorocarbon silane content is from 0.1 to 10% by weight, the molar fraction of silicate with respect to fiuorocarbon silane is from 0.1 to 1, the pH has been adjusted to from 4 to 7, and the weight ratio of the fiuorocarbon silane and the surfactant used to generate the hydrolysate is from 1 : 1 to 10: 1.
  • an anionic surfactant represented by the formula Cl2tl25(OCH2CH2)4 ⁇ S ⁇ 3NH4 s use( i- desirable examples are 1) aqueous emulsions in which the fiuorocarbon silane content is from 0.1 to 20% by weight, the molar fraction of silicate with respect to the fiuorocarbon silane is from 0.1 to 5, the pH has been adjusted to less than 4, and in particular to from 2 to 3, and the weight ratio of the fiuorocarbon silane and the surfactant used to generate the hydrolysate is from 1 : 1 to 10: 1 ; 2) aqueous emulsions in which the fiuorocarbon silane content is from 0.1 to 10% by weight, the molar fraction of silicate with respect to the fiuorocarbon silane is from 0.5 to 1 , the pH has been adjusted to from 4 to 7, and the weight ratio of the fiuorocarbon silane and the surfactant used to generate the hydrolysate is from 1:1 to 10:1; and 3)
  • Adjustment of the pH is carried out using a suitable acid or alkali, such as hydrochloric acid or ammonia water.
  • the aqueous emulsions of the present invention can include additives such as pigments, biocides, ultraviolet light absorbers, and antioxidants, within a range that does not affect the properties of the aqueous emulsion.
  • the aqueous emulsions of the present invention are applied and dried on a substrate such as a polymer substrate having pendant active hydrogen groups, such as polyesters and polyamides, wood, brick, concrete, stone, glass, ceramic tiles, aluminum sheet, stainless-steel sheet, natural and synthetic fibers, leather and like.
  • aqueous emulsion onto the substrate is carried out by a known method such as dipping, spraying or spin coating.
  • a dipping method is preferable so as not to lose the clarity. Heating may also be carried out in order to accelerate the drying step. Drying is generally carried out for 1 to 24 hours within a temperature range of from 100 to 300°C.
  • the substrate onto which the aqueous emulsion has been applied and dried is washed with water after it has dried, thereby removing the remaining surfactant.
  • the aqueous emulsions of the present invention are useful in providing oil and water repellant surfaces when coated and dried on a substrate.
  • the coated surface is clear, smooth, and has excellent heat resistance.
  • the coated substrates are useful in situations where the glass, fabrics, construction materials, and polymeric surfaces require oil and water repellency and clear coatings.
  • aqueous emulsion of the hydrolysate of the fiuorocarbon silane and the surfactant were prepared as in U.S. 5,550,184 wherein the fiuorocarbon silane was emulsified in water with an effective amount of the indicated surfactant to retain the fiuorocarbon silane in a substantially totally hydrolyzed state. Additional components were added to the emulsions as depicted in the examples below.
  • the fiuorocarbon silane hydrolysate used was a hydrolysate of a compound having the formula Rf-(CH2)2-Si ⁇ -(O-CH2CH2)2-OCH3 ⁇ 3 wherein
  • the surfactant used was a nonionic surfactant having the formula Rf-CH 2 CH 2 -O-(CH CH 2 O) ⁇ ⁇ -H.
  • the content within the aqueous emulsion was set at 30 parts by weight per 100 parts by weight of the fiuorocarbon silane.
  • the silicate used was tetraethoxyorthosilicate (TEOS) or tetrakis [2-(2-methoxyethoxy)ethyl] silicate (Si(DEGM)4).
  • Adjustment of the pH was carried out by adding hydrochloric acid while using a pH meter.
  • the stability of the aqueous emulsion thus prepared was measured by the method described below. The aqueous emulsion was prepared, and one week later was examined to determine whether gelation or precipitation had occurred. Only in cases where it was free-flowing like water was it regarded as stable.
  • test pieces were fabricated using a glass substrate (commercial glass slides "Preclin Glass” trade name), manufactured by Matsunami Co. measuring 2.5 x 7.5 cm, and 1.2 mm thick. Because this glass is a washed glass, it was used directly in testing.
  • the application of the aqueous emulsion was carried out by means of dip coating. In dip coating the glass slide was lowered at a speed of 300 mm/min., held in the immersed state for 10 minutes, then drawn out at a speed of 10 mm/min. Drying after application was carried for 60 minutes at 200°C.
  • a drop of pure water was added to the surface of the coated substrate, and the contact angle was measured with a contact angle analyzer (manufactured by Kyowa Kaimen Kagaku).
  • Comparative Example A In Comparative Example 1, an aqueous emulsion containing no silicate but containing the fluorocarbon silane of working Examples 1-7 was prepared. Using the aqueous emulsion thus obtained, test pieces were fabricated and tested in the same manner as in Working Examples 1-7. The stability of the aqueous emulsion, and the clarity and water repellency of the coated surface are given in Table 1.
  • TEOS tetraethoxyorthosilicate
  • Si(DEGM)4 tetrakis [2-(2-methoxyethoxy)ethyl]silicate
  • Working Examples 1, 2, 4, 6 and 7 showed that the aqueous emulsions of the present invention have excellent stability, in addition to which the glass on which the aqueous emulsions of the present invention had been coated and dried were imparted with an excellent water repellency while maintaining the clarity of the glass. Moreover, Working Examples 1 and 2 showed that the water repellency of the glass surface was maintained even after 100 hours in a 300°C oven, and that some degree of water repellency continued to remain even after 5 hours in a 350°C oven.
  • Working Example 3 showed that when the ratio of the silicate with respect to the fluorocarbon silane is low, the clarity tended to suffer.
  • Working Example 5 showed that when the ratio of the silicate with respect to the fluorocarbon silane is high, the aqueous emulsion tended to become somewhat unstable.
  • the fluorocarbon silane hydrolysate used was a hydrolysate of a compound having the formula Rf-(CH 2 ) 2 -Si ⁇ -(O-CH 2 CH 2 ) 2 -
  • the silicate was tetrakis [2-(2-methoxyethoxy)ethyl] silicate (Si(DEGM)4), and the surfactant was a nonionic surfactant having the formula
  • Comparative Examples B and C In Comparative Examples B and C, aqueous emulsions containing no silicate but containing the fluorocarbon silane hydrolysate of working Examples 8-9 were prepared. Using the aqueous emulsion thus obtained, test pieces were fabricated in the same manner as in Working Examples 8 and 9. The stability of the aqueous emulsion, and the clarity and water repellency of the coated surface are shown in Table 2.
  • coated surfaces obtained by coating and drying the fluorocarbon silane hydrolysate-containing aqueous emulsions of the present invention onto a substrate were clear and smooth, and were able to provide excellent water repellency and heat resistance.
  • by adjusting both the molar ratio of fluorocarbon silane hydrolysate and silicate within the aqueous emulsion and the pH according to the type of surfactant used stable aqueous emulsions having good storability were obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Wood Science & Technology (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne des émulsions aqueuses renfermant 1) un hydrolysat de silane fluorocarboné, généré en présence d'un tensioactif, et 2) un silicate, qui permet d'obtenir une surface revêtue à la fois claire et lisse, présentant une excellente hydrophobicité et une résistance thermique satisfaisante une fois ledit silicate appliqué sur un substrat. L'invention concerne également les matières revêtues des émulsions aqueuses susmentionnées.
PCT/US1998/026019 1997-12-10 1998-12-08 Emulsions aqueuses contenant un hydrolysat de silane fluorocarbone, et matieres revetues de ces emulsions WO1999029636A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US98789897A 1997-12-10 1997-12-10
US08/987,898 1997-12-10

Publications (1)

Publication Number Publication Date
WO1999029636A1 true WO1999029636A1 (fr) 1999-06-17

Family

ID=25533675

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/026019 WO1999029636A1 (fr) 1997-12-10 1998-12-08 Emulsions aqueuses contenant un hydrolysat de silane fluorocarbone, et matieres revetues de ces emulsions

Country Status (1)

Country Link
WO (1) WO1999029636A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001018135A1 (fr) * 1999-09-02 2001-03-15 Nanogate Gmbh Procede et matieres
WO2001090267A2 (fr) * 2000-05-19 2001-11-29 E.I. Du Pont De Nemours And Company Emulsion et composition hydrofuge
WO2001094477A1 (fr) * 2000-06-02 2001-12-13 Baco Consumer Products Limited Film de cuisson
WO2002031062A3 (fr) * 2000-10-06 2002-07-04 Du Pont Emulsion et produit revetu de celle-ci
US6592659B1 (en) 2001-11-15 2003-07-15 3M Innovative Properties Company Compositions for aqueous delivery of fluorinated silanes
US6709504B2 (en) 2000-05-19 2004-03-23 E. I. Du Pont De Nemours And Company Emulsion and water-repellent composition
US6977307B2 (en) 2001-01-19 2005-12-20 3M Innovative Properties Company Water soluble or water dispersible fluorochemical silanes for rendering substrates oil and water repellent
US7166329B2 (en) 2001-01-19 2007-01-23 3M Innovative Properties Company Method of rendering substrates oil and water repellent with a fluorochemical oligomeric silane
CN1325416C (zh) * 2005-10-14 2007-07-11 浙江大学 玻璃疏水镀膜液
US7470741B2 (en) 2002-06-03 2008-12-30 3M Innovative Properties Company Fluorochemical composition and method of treatment of a substrate therewith to render substrate oil- and/or water repellent
US7723452B2 (en) 2003-12-23 2010-05-25 3M Innovative Properties Company Composition of an oligomeric fluorosilane and surface treatment of retroreflective sheet
CN108841324A (zh) * 2018-06-26 2018-11-20 王春林 一种无卤阻燃硅烷水性涂料及其制备和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0513727A2 (fr) * 1991-05-13 1992-11-19 Toyota Jidosha Kabushiki Kaisha Verre hydrophobe et son procédé de fabrication
US5552476A (en) * 1994-03-04 1996-09-03 E. I. Du Pont De Nemours And Company Hydrolyzed silane emulsions and their use as surface coatings

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0513727A2 (fr) * 1991-05-13 1992-11-19 Toyota Jidosha Kabushiki Kaisha Verre hydrophobe et son procédé de fabrication
US5552476A (en) * 1994-03-04 1996-09-03 E. I. Du Pont De Nemours And Company Hydrolyzed silane emulsions and their use as surface coatings

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001018135A1 (fr) * 1999-09-02 2001-03-15 Nanogate Gmbh Procede et matieres
US6709504B2 (en) 2000-05-19 2004-03-23 E. I. Du Pont De Nemours And Company Emulsion and water-repellent composition
WO2001090267A2 (fr) * 2000-05-19 2001-11-29 E.I. Du Pont De Nemours And Company Emulsion et composition hydrofuge
WO2001090267A3 (fr) * 2000-05-19 2002-06-06 Du Pont Emulsion et composition hydrofuge
KR100741256B1 (ko) * 2000-05-19 2007-07-19 이 아이 듀폰 디 네모아 앤드 캄파니 에멀젼 및 발수성 조성물
WO2001094477A1 (fr) * 2000-06-02 2001-12-13 Baco Consumer Products Limited Film de cuisson
WO2002031062A3 (fr) * 2000-10-06 2002-07-04 Du Pont Emulsion et produit revetu de celle-ci
US6649273B2 (en) 2000-10-06 2003-11-18 E. I. Du Pont De Nemours And Company Emulsion and coated product thereof
CN1322069C (zh) * 2000-10-06 2007-06-20 纳幕尔杜邦公司 乳液及其涂布产品
KR100746459B1 (ko) * 2000-10-06 2007-08-03 이 아이 듀폰 디 네모아 앤드 캄파니 에멀젼 및 그의 코팅된 생성물
US6977307B2 (en) 2001-01-19 2005-12-20 3M Innovative Properties Company Water soluble or water dispersible fluorochemical silanes for rendering substrates oil and water repellent
US7166329B2 (en) 2001-01-19 2007-01-23 3M Innovative Properties Company Method of rendering substrates oil and water repellent with a fluorochemical oligomeric silane
US6592659B1 (en) 2001-11-15 2003-07-15 3M Innovative Properties Company Compositions for aqueous delivery of fluorinated silanes
US7470741B2 (en) 2002-06-03 2008-12-30 3M Innovative Properties Company Fluorochemical composition and method of treatment of a substrate therewith to render substrate oil- and/or water repellent
US7723452B2 (en) 2003-12-23 2010-05-25 3M Innovative Properties Company Composition of an oligomeric fluorosilane and surface treatment of retroreflective sheet
CN1325416C (zh) * 2005-10-14 2007-07-11 浙江大学 玻璃疏水镀膜液
CN108841324A (zh) * 2018-06-26 2018-11-20 王春林 一种无卤阻燃硅烷水性涂料及其制备和应用
CN108841324B (zh) * 2018-06-26 2020-06-05 王春林 一种无卤阻燃硅烷水性涂料及其制备和应用

Similar Documents

Publication Publication Date Title
CA2405277C (fr) Emulsion et composition hydrofuge
AU693529B2 (en) Hydrolyzed silane emulsions and their use as surface coatings
US5274159A (en) Destructable fluorinated alkoxysilane surfactants and repellent coatings derived therefrom
CA2423203C (fr) Emulsion et produit revetu de celle-ci
JP3574222B2 (ja) 表面処理方法
US6592659B1 (en) Compositions for aqueous delivery of fluorinated silanes
RU2130957C1 (ru) Способ придания масло- и водоотталкивающих свойств поверхности пористых керамических материалов, фосфорные моноэфиры и способ их получения
WO1999029636A1 (fr) Emulsions aqueuses contenant un hydrolysat de silane fluorocarbone, et matieres revetues de ces emulsions
US7399875B2 (en) Fluorosilane condensation products, their preparation and use for surface modification
WO2002030848A1 (fr) Compositions comprenant des polyether silanes fluores servant a rendre des substrats oleofuges et hydrofuges
US20040060476A1 (en) Composition for treating substrate and process of treatment
JPS58172246A (ja) ガラスの表面処理剤
US6709504B2 (en) Emulsion and water-repellent composition
JP4028057B2 (ja) 耐熱性撥水コーティング層を有する材料
JP2013129695A (ja) 撥水膜形成用組成物、撥水膜付き基体および輸送機器用物品
EP1197538A2 (fr) Compostion aqueuse de revêtement
US6448428B1 (en) Fluorine-containing organic silicon compound and method for its production
JP2001335693A (ja) フルオロカーボンシラン加水分解物含有水性エマルジョンおよび耐油防汚性・耐熱撥水性の被覆物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN JP KR