Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Processes of preparing a desired or intentional composition...
Reexamination Certificate
1999-12-14
2002-05-21
Sanders, Kriellion A. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Processes of preparing a desired or intentional composition...
C544S221000, C544S222000, C428S426000, C428S496000, C428S535000
Reexamination Certificate
active
06391948
ABSTRACT:
This invention relates to fluorochemical triazine compounds, compositions containing the fluorochemical triazine compounds, the process for preparing the fluorochemical compounds and compositions, substrates treated with the fluorochemical compounds, melt extrusion of fibers and films containing the fluorochemical compounds and compositions, and coating, polish and marine antifouling compositions to provide oil and water repellency to substrates.
Organofluorine compounds or fluorochemicals are substances containing portions that are fluorocarbon in nature and have properties such as hydrophobicity, oleophobicity, and chemically inertness, and portions that are organic or hydrocarbon in nature and which may be chemically reactive in organic reactions. Some fluorochemicals are familiar to the general public, such as SCOTCHGARD™ brand carpet protector, which imparts oil and water repellency and stain- and soil-resistance to carpet. Other fluorochemicals have other industrial uses, such as reducing the surface tension of liquids, reducing evaporation and inflammability of volatile organic liquids, and improving the leveling of organic polymer coatings.
The use of various fluorochemical compositions on fibers and fibrous substrates, such as textiles, paper, and leather, to impart oil and water repellency is known; see, for example, Banks, Ed., Organofluorine Chemicals and Their Industrial Applications, Ellis Horwood Ltd., Chichester, England, 1979, pp. 226-234. Such fluorochemical compositions include, for example, fluorochemical guanidines (U.S. Pat. No. 4,540,497, Chang et al.), compositions of cationic and non-cationic fluorochemicals (U.S. Pat. No. 4,566,981, Howells), compositions containing fluorochemical carboxylic acid and epoxidic cationic resin (U.S. Pat. No. 4,426,466, Schwartz), fluoroaliphatic carbodiimides (U.S. Pat. No. 4,215,205, Landucci), and fluoroaliphatic alcohols (U.S. Pat. No. 4,468,527, Patel).
Fluorochemical compositions can be applied to various fibrous substrates by methods which include, for example, spraying, padding, and finish bath immersion. Textile fibers and yams can also be treated by incorporation of the fluorochemical in fiber spin finishes and by melt extrusion of a blend of a synthetic organic fiber-forming polymer and a fluorochemical composition. Such melt extrusion is described, for example, by Mares, F., et al., “Modification of Fiber Surfaces by Monomeric Additives, Part I: Extrusion Techniques,” Textile Research Journal, Vol. 47, No. 8, pp. 551-561 and Mares, F., et al., “Modification of Fiber Surfaces by Monomeric Additives, Part II: Absorption of Fluorocarbon Additives by Polyethylene Terephthalate”, Textile Research Journal, Vol. 48, No. 4, pp. 218-229, and in U.S. Pat. No. 3,899,563 (Oxenrider et al.)
Fluorochemical triazine compounds, and processes for preparing the same have been described, for example, in U.S. Pat. No. 3,128.272 (Wear et al.) which describes compounds of the formula:
where X and Y are amino or hydrazino radicals, Rf is a perfluorinated alkyl radical and QW is a linking group. The compounds may be reacted with formaldehyde to yield polymethylol derivatives, which in turn may be condensed to thermosetting crosslinked polymeric products.
SUMMARY OF THE INVENTION
This invention provides fluorochemical triazine compounds comprising fluoroaliphatic radical-containing, tris thia-, aza- or oxa-alkylene triazine compounds, said compounds comprising one or more triazine moieties of the formula,
Where A is a triazine ring of the formula
each B is an oxalkylene or thiaalkylene moiety,
each Q is a divalent linking group,
R
f
is a fluorinated aliphatic group,
Y is a functional group capable of further reaction, and
Z is —Q—Rf or Y.
This invention further provides coating compositions comprising aqueous suspensions or emulsions, or organic solvent solutions, of the fluorochemical triazine compositions, which compositions are useful in the surface treatment of hard surfaces, such as glass, wood, stone, tile, grout, concrete, metal, fiberglass, plastics such as polyacrylates and polycarbonates, and the like to impart oil and water repellency and anti-soiling properties thereto. This invention further provides compositions comprising aqueous suspensions or emulsions, or organic solvent solutions, of the fluorochemical triazine compositions, which compositions are useful in the surface treatment of fibrous substrates, such as textile fibers (or filaments) during their manufacture, and useful also in the surface treatment of finished or fabricated fibrous substrates such as textiles, carpets, paper and leather, to impart oil and water repellency and anti-soiling properties thereto. The present invention also provides coated substrates comprising the cured coatings of this invention, applied to the substrate.
Advantageously, coatings of the present invention generally cure, under ambient condition and without heating, to a tack-free state in fifteen minutes or less and pass the “pen test” (described below) within 45 minutes.
This invention also provides fibers, films, and molded articles prepared by melt extrusion and molded articles prepared by, e.g., injection molding of a blend or mixture of (a) fiber- or film-forming synthetic organic polymers and (b) fluorochemical triazines which fibers, films, and molded articles have low surface energy, oil and water repellency, and anti-soiling properties.
DETAILED DESCRIPTION OF THE INVENTION
Two classes of fluoroaliphatic radical-containing triazine compounds of this invention can be represented by the Formulas I and II
where each X is an oxygen or alkylamino of the formula —NR— each W is an oxygen, sulphur, alkylamino of the formula —NR′—, or urethane group of the formula —NR′—CO—O—, where R′ is a lower alkyl or 1 to 4 carbon atoms, each n and m is independently an integer of from 1 to 20, preferably 2 to 12, Q is a linking group, Y is a reactive functional group, R
f
is a fluoroaliphatic radical, and Z is R
f
or Y.
In each of the above fluorochemical triazines of general Formulas I and II, where there are a plurality of R
f
and Y groups or moieties, each can be the same or different. Also Formulas II and I represent individual compounds or mixtures of compounds, for example, as they are obtained as products from reactions used in their preparation. In addition, small amounts of by-products, with and without the fluoroaliphatic radical R
f
, and not represented by Formulas I and II, can also be present in small amounts in said mixtures or reaction products because of the reaction conditions involved in their preparation. The presence of such small amounts of by-products, generally less than 10 weight percent, does not affect the usefulness of the fluorochemical triazine mixtures or compounds of this invention.
The fluoroaliphatic radical, R
f
, is a fluorinated, stable, inert, non-polar, preferably saturated, monovalent moiety which is both oleophobic and hydrophobic. It can be straight chain, branched chain, or, if sufficiently large, cyclic, or combinations thereof, such as alkylcycloaliphatic radicals. Though not preferred, the skeletal chain in the fluoroaliphatic radical can include catenary oxygen, hexavalent sulfur, and/or trivalent nitrogen hetero atoms bonded only to carbon atoms of the skeletal chain, such hetero atoms providing stable linkages between fluorocarbon portions of R
f
not interfering with the inert character of the R
f
radical. While R
f
can have a large number of carbon atoms, compounds where R
f
is not more than 20 carbon atoms will be adequate and preferred since large radicals usually represent a less efficient utilization of fluorine than is possible with smaller R
f
radicals of less than 20 carbon atoms. Generally R
f
will have 3 to 20 carbon atoms, preferably 4 to about 12, and will contain 40 to 78 weight percent, preferably 50 to 78 weight percent, fluorine. The terminal portion of the R
f
group preferably has at least three fully fluorinated carbon atoms, e.g., CF
3
CF
2
CF
2
—, and the preferred compounds are those in wh
Behr Frederick E.
Clark Gregory D.
Hall Gregory K.
Roberts Gary P.
Vander Louw Steven J.
3M Innovative Properties Company
Kokko Kent S.
Sanders Kriellion A.
LandOfFree
Triazine compounds and use thereof does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Triazine compounds and use thereof, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Triazine compounds and use thereof will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2890861