Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2001-03-09
2004-06-22
Anthony, Joseph D. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S199000, C525S276000, C526S243000, C526S248000, C526S242000, C428S411100, C428S357000, C523S200000, C524S539000, C524S168000, C524S462000
Reexamination Certificate
active
06753380
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to fluorochemical compositions comprising one or more compounds or oligomers having at least one fluorine-containing repeatable unit and at least one fluorine-containing terminal group. This invention also relates to articles comprising a substrate and the fluorochemical composition, which may be applied as coatings or incorporated as melt additives the fluorochemical compositions impart oil and water repellency to the substrate. In other aspects, this invention relates to processes for imparting oil and water repellency characteristics to substrates and articles.
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. Nos. 2,803,615; 3,068,187; 3,102,103; 3,341,497; 3,574,791; 3,916,053; 4,529,658; 5,216,097; 5,276,175; 5,725,789; 6,037,429), fluorine-containing phosphate esters (U.S. Pat. Nos. 3,094,547; 5,414,102; 5,424,474), fluorine-containing urethanes (U.S. Pat. Nos. 3,987,182; 3,987,227; 4,504,401; 4,958,039), fluorochemical allophanates (U.S. Pat. No. 4,606,737) fluorochemical biurets (U.S. Pat. No. 4,668,406), fluorochemical oxazolidinones (U.S. Pat. No. 5,025,052), and fluorochemical piperazines (U.S. Pat. No. 5,451,622).
It has long since been well documented that the fluorochemical segment, F(CF
2
)
n
—, of essentially any oil- and water-repellency imparting compound, oligomer, or polymer must have six or more carbon atoms; that is n must be equal to or greater than 6 (Philips, R. W. and Dettre, R. H.,
J. Col. and Interface Sci
., 56 (2), (1976)). However, the use of such prior art fluorochemical compositions having fluorochemical segments with n>6, has been cited as a potential concern. Many previously known oil- and water-repellency imparting compounds or oligomers contain perfluorooctyl moieties. These surfactants ultimately degrade to perfluorooctyl-containing compounds. It has been reported that certain perfluorooctyl-containing compounds may tend to bio-accumulate in living organisms; this tendency has been cited as a potential concern regarding some fluorochemical compounds. For example, see U.S. Pat. No. 5,688,884 (Baker et al.). As a result, there is a desire for fluorine-containing compositions which are effective in providing desired oil and water repellency, and/or stain-release or stain resistance properties, and which eliminate more effectively from the body (including the tendency of the composition and its degradation products).
SUMMARY OF THE INVENTION
In one aspect, this invention relates to chemical compositions comprising one or more compounds or oligomers having at least one fluorine-containing repeatable unit and at least one fluorine-containing terminal group. These compounds or oligomers comprise the condensation reaction product of (a) one or more polyols; (b) one or more polyacyl compounds (such as carboxylic acids, esters, acyl halides); and (c) one or more monofunctional fluorine-containing compounds comprising a functional group that is reactive with the hydroxyl group of the polyol (a) or with the acyl group of the polyacyl compound (b); wherein at least a portion of the polyol compounds further comprise at least one fluorine-containing group selected from the group consisting of perfluoroalkyl, perfluoroheteroalkyl, and perfluoroheteroalkylene. Optionally, the fluorochemical oligomers further comprise water-solubilizing groups and/or polymerizable groups.
As used herein, the term “oligomer” means a polymer molecule consisting of only a few, i.e. up to an average of 10, but preferably up to an average of 5, repeating (polymerized) or repeatable units. Each repeating unit comprises an ester group that is derived or derivable from the reaction of at least one polyol having an average of greater than one, preferably two or more hydroxyl moieties; and at least one polyacyl compound having an average of greater than one, preferably two or more acyl moieties, wherein at least a portion of the polyol compounds further comprises at least one fluorine-containing moiety, selected from the group consisting of perfluoroalkyl, perfluoroalkylene, perfluoroheteroalkyl, and perfluoroheteroalkylene. The oligomer is terminated with one or more perfluoroalkyl groups, one or more perfluoroheteroalkyl groups, or mixtures thereof.
Certain preferred embodiments of the fluorochemical compositions of the present invention include those compositions comprising terminal and pendant R
f
groups having from 1 to 12 carbons, preferably 6 or fewer carbons, and more preferably three to five carbons. Even with R
f
groups that are relatively short (i.e. a carbon chain length of less than eight carbon atoms), these fluorochemical compositions, surprisingly, impart excellent oil and water repellency and stain release or stain resistance and exhibit high dynamic water and hexadecane contact angles. Although compositions comprising low fluorine content are less expensive, R
f
groups shorter than eight carbons typically have been overlooked by those of skill in the art because they have been believed to impart inferior oil and water repellency and stain resistance.
When the compounds further comprise water-solubilizing groups, the fluorochemical compositions of the present invention exhibit water solubility or water dispersability, while at the same time providing surprisingly good water-repellency and stain-release properties. These embodiments include, for example, those chemical compositions comprising a ester oligomer containing one or more solubilizing groups. The solubilizing groups include carboxylate, sulfate, sulfonate, phosphate, phosphonate, ammonium, quaternary ammonium, and the like, and mixtures thereof. These embodiments are particularly well suited for uniform topical treatments on a variety of substrates where the use of organic solvents is undesirable.
When the compounds further comprise polymerizable groups, the coatings derived from the fluorochemical compositions of the present invention exhibit increased durability. That is the repellency and stain-resistant properties remain even after abrasion, scrubbing, washing, exposure to wear, and the like.
Another embodiment of the present invention relates to a coating composition comprising a solution comprising the fluorochemical composition of the present invention and a solvent. In this embodiment, the fluorochemical composition is dissolved or dispersed in the solvent. When applied to a substrate, this coating composition provides a uniform distribution of the chemical composition on the substrate without altering the appearance of the substrate. This invention further relates to a method for imparting water- and oil-repellency, stain-release, or stain-resistance characteristics to a substrate, comprised of one or more surfaces, comprising the steps of:
(a) applying the coating composition of the present invention onto one or more surfaces of the substrate wherein the coating composition comprises:
(i) at least one solvent; and
(ii) the fluorochemical composition of the invention; and
(b) curing the coating composition.
The fluorochemical compositions of the present invention can be applied as coatings to a wide variety of substrates, for example, by topical application, to impart oil- and water-r
3M Innovative Properties Company
Anthony Joseph D.
Kokko Kent S.
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