Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From silicon reactant having at least one...
Reexamination Certificate
2002-03-26
2003-11-11
Gorr, Rachel (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From silicon reactant having at least one...
C528S049000, C528S070000, C556S414000, C556S417000, C556S420000, C556S421000, C554S106000, C428S425600, C428S425100, C427S387000, C252S389320, C252S008620, C252S182150
Reexamination Certificate
active
06646088
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to chemical compositions comprising one or more urethane oligomers and coating compositions comprising at least one solvent and the chemical compositions of the present invention. When applied as a coating, these urethane-based chemical compositions impart durable stain-release characteristics. This invention also relates to articles comprising a substrate and on this substrate is a cured coating derived from the coating compositions of the present invention. The cured coating can impart stain-release characteristics to the substrate and resist being worn-off due to wear and abrasion. In another aspect, this invention relates to a process for imparting stain-release characteristics to substrates.
BACKGROUND OF THE INVENTION
The use of certain fluorochemical compositions on fibers and fibrous substrates, such as textiles, paper, and leather, to impart oil- and water-repellency and soil- and stain-resistance is well known in the art. 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)), fluoroaliphatic alcohols (U.S. Pat. No. 4,468,527 (Patel)), fluorine-containing addition polymers, copolymers, and macromers (U.S. Pat. No. 2,803,615 (Ahlbrecht et al.); U.S. Pat. No. 3,068,187 (Bolstad et al.); U.S. Pat. No. 3,102,103 (Albrecht et al.); 3,341,497 (Sherman et al.); U.S. Pat. No. 3,574,791 (Sherman et al.); U.S. Pat. No. 3,916,053 (Sherman et al.); U.S. Pat. No. 4,529,658 (Schwartz et al.); U.S. Pat. No. 5,216,097 (Allewnert et al.); U.S. Pat No. 5,276,175 (Dams et al.); U.S. Pat. No. 5,725,789 (Huber et al.); U.S. Pat. No. 6,037,429 (Linert et al.)), fluorine-containing phosphate esters (U.S. Pat. Nos. 3,094,547 (Heine et al.); U.S. Pat. No. 5,414,102 (Pohmer et al.); U.S. Pat. No. 5,424,474 (Pohmer et al.)), fluorine-containing urethanes (U.S. Pat. No. 3,987,182 (Gold); U.S. Pat. No. 3,987,227 (Schultz et al.); U.S. Pat. No. 4,504,401 (Matsuo et al.); U.S. Pat. No. 4,958,039 (Pechhold)), fluorochemical allophanates (U.S. Pat. No. 4,606,737 (Stem)) fluorochemical biurets (U.S. Pat. No. 4,668,406 (Chang)), fluorochemical oxazolidinones (U.S. Pat. No. 5,025,052 (Crater et al.)), and fluorochemical piperazines (U.S. Pat. No. 5,451,622 (Boardman)).
Certain of these fluorochemical compositions, such as the fluorine-containing addition copolymers of U.S. Pat. No. 6,037,429 (Linert et al.), may be used on hard surfaces, including for example, ceramics, stone, masonry, wood. U.S. Pat. No. 5,414,102 (Pohmer et al.) and U.S. Pat. No. 5,424,474 (Pohmer et al.) suggest that certain fluorine-containing phosphate esters can be used on hard surfaces, such as, ceramics, stone, masonry, wood, and plastics to repel water, grease, oil, and dirt. These previously known fluorochemical compositions typically have been coated on hard substrates by means of aqueous emulsions.
In coating on hard surfaces, durability of the coating of fluorochemical compositions is a concern. In many cases the fluorochemical compositions exhibit poor durability because the majority of the coated hard surface area is exposed to wear and abrasion from use, cleaning, and the elements. Due to this exposure, the coated composition can be worn-off leaving the hard surface unprotected. Certain fluorine-containing urethanes have been found to provide superior abrasion durability and especially good water- and oil-repellency and stainproofing properties (U.S. Pat. No. 4,504,401 (Matsuo et al.)). These previously known fluorine-containing urethane compositions can be solvent- or water-based. In practice, all of the previously known fluorine-containing urethanes rely on perfluoroalkyl groups having an average of eight carbon atoms to achieve the desired repellency and stainproofing properties.
Although urethanes have been found to be especially durable, improved long-term durability is still needed for many hard surface applications. In particular in the widely used siliceous surfaces, such as ceramic and masonry, a coating composition is needed that imparts longer lasting repellency and stain-proofing and is capable of withstanding repeated abrading and washing.
As indicated above, both solvent- and water-based fluorine-containing urethane compositions have been used to provide water- and oil-repellency to hard surfaces. Since organic solvents pose health, safety, and environmental concerns, the water-based compositions are particularly desirable. However, the previously known compositions are typically aqueous dispersions or emulsions, not solutions; therefore, they require a high temperature cure to impart good repellency properties. In many cases, for example in floors and walls, high temperature curing is not practical or possible. For this reason there is a continuing need for urethanes that do not require costly and energy consuming high temperature cure conditions to impart good repellency properties. Therefore, urethane compositions, including those containing fluorine, that display increased water solubility are needed to eliminate the need for high temperature cure conditions, as well as to increase the ease of preparation and to provide more stable aqueous solutions.
SUMMARY OF THE INVENTION
The inventors recognized the need for shelf-stable chemical compositions, including those containing fluorine, that can successfully impart long-term durability, uniform oil- and water-repellency and soil- and stain-resistance. These chemical compositions should be water and organic solvent soluble and should not require high temperatures for curing.
In one aspect, this invention relates to chemical compositions comprising one or more urethane oligomers of at least two repeating units selected from the group consisting of fluorine-containing urethane oligomers and long-chain hydrocarbon-containing urethane oligomers. These urethane oligomers comprise the reaction product of (a) one or more polyfunctional isocyanate compounds; (b) one or more polyols; (c) one or more monoalcohols selected from the group consisting of fluorochemical monoalcohols, optionally substituted long-chain hydrocarbon monoalcohols, and mixtures thereof; (d) one or more silanes; and optionally (e) one or more water-solubilizing compounds comprising one or more water-solubilizing groups and at least one isocyanate-reactive hydrogen containing group.
The silanes are of the following formula (I):
X—R
1
—Si—(Y)
3
formula (I)
wherein:
X is —NH
2
; —SH; —OH; —N═C═O; or —NRH where R is a phenyl, straight or branched aliphatic, alicyclic, or aliphatic ester group;
R
1
is an alkylene, heteroalkylene, aralkylene, or heteroaralkylene bridging group; and
each Y is independently a hydroxyl; a hydrolyzable moiety selected from the group consisting of alkoxy, acyloxy, heteroalkyoxy, heteroacyloxy, halo, and oxime; or a non-hydrolyzable moiety selected from the group consisting of phenyl, alicyclic, straight-chain aliphatic, and branched-chain aliphatic, wherein at least one Y is a hydrolyzable moiety.
As used herein, the term “oligomer” means a polymer molecule that consists of at least two repeating (polymerized) units, but up to only a few (for example, from 2 to about 20) repeating units. Each repeating unit comprises a urethane group that is derived or derivable from the reaction of at least one polyfunctional isocyanate compound and at least one polyol. The oligomer is terminated with (i) one or more perfluoroalkyl groups, one or more perfluoroheteroalkyl groups, or one or more long-chain hydrocarbyl groups; and (ii) one or more silyl groups.
The chemical compositions of the present invention, comprising one or
Cote Linda G.
Fan Wayne W.
Johnson Mitchell T.
Lien Larry A.
Martin Steven J.
3M Innovative Properties Company
Gorr Rachel
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