Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2001-05-08
2002-11-19
Pezzuto, Helen L. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S243000, C526S246000, C526S248000, C526S253000, C526S304000, C526S307300, C526S307500, C526S307700, C526S312000, C526S320000, C526S325000, C526S329400, C526S329600, C526S333000
Reexamination Certificate
active
06482911
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to fluorochemical polymers for use in providing stain release properties to a substrate material. In another aspect, this invention relates to fluorochemical polymers that contain pendant fluoroaliphatic and cationogenic groups. This invention also relates to fluorochemical polymers with improved stain release durability when applied to a substrate material.
BACKGROUND OF THE INVENTION
The treatment or modification of fabrics to improve their properties is routine practice in the textile industry. Fabrics can be treated to reduce their oleophilicity and facilitate stain release during laundering. Such treatments include fluorochemical-based polymers containing both fluorinated oleophobic and non-fluorinated hydrophilic fractions.
Fluorochemicals include substances containing portions which are fluorocarbon in nature and portions which are organic hydrocarbon in nature. Such fluorochemicals are common and have various industrial uses including reducing the surface tension of liquids, reducing evaporation and flammability of volatile organic liquids, and improving the leveling of organic polymer coatings.
The utility of organofluorine compounds as surface-active agents and surface-treating agents is due in large part to the extremely low free-surface energy of a C
6
-C
12
fluorocarbon group, according to H. C. Fielding, “Organofluorine Compounds and Their Applications” R. E. Banks, Ed., Society of Chemical Industry at p. 214 (1979).
SUMMARY OF THE INVENTION
Generally, the present invention relates to fluorochemical polymers for use in providing stain release properties to a substrate material. One embodiment is a polymer that includes, i) a perfluoroaliphatic monomer of the formula
where R
f
is a C
1
-C
20
perfluorinated group, A is divalent linking group,
group, z is 1 to 12, m is 1 to 6, n is 1 to 12, R
1
is H or CH
3
—, and R
2
is H, CH
3
— or C
2
H
5
—; ii) a hydrophilic monomer of the formula
where B is a divalent linking group, R
3
is H or CH
3
, p is 1 to 25, R
4
is C
1
-C
12
alkyl, aryl, aralkyl or alkaryl; iii) a cationogenic monomer of the formula
where L is —(C
q
H
2q
)—Y, and salts thereof, i.e. —(C
q
H
29
q)—Y
+
X
−
q is 1 to 8, Y is a cationogenic group, X
−
is an anion, R
5
is H or CH
3
—, and R
6
and R
7
are independently C
1
-C
12
alkyl or C
1
-C
2
hydroxyalkyl; and iv) a N-hydroxyalkylacrylamide monomer of the formula
where z is 1 to 12, and R
11
is H or CH
3
—; and/or v) a diacrylate monomer of the formula
where R
12
is H or CH
3
—, and R
13
includes —(CH
2
CH
2
O)
p
—, where p is 1 to 25.
An embodiment of the present invention includes polymers described above where monomer (i) is present in the amount of 20 to 70 percent by weight, monomer (ii) is present in the amount of 25 to 60 percent by weight, monomer (iii) is present in the amount of 1 to 20 percent by weight, and monomer (iv) is present in the amount of 1 to 10 percent by weight.
Another embodiment of the present invention includes polymers described above where monomer (i) is present in the amount of 45 to 70 percent by weight, monomer (ii) is present in the amount of 25 to 50 percent by weight, monomer (iii) is present in the amount of 1 to 10 percent by weight, and monomer (iv) is present in the amount of 1 to 8 percent by weight.
A further embodiment of the present invention includes polymers described above where monomer (i) is present in the amount of 50 to 65 percent by weight, monomer (ii) is present in the amount of 35 to 40 percent by weight, monomer (iii) is present in the amount of 1 to 5 percent by weight, and monomer (iv) is present in the amount of 1 to 5 percent by weight.
An embodiment of the present invention includes polymers described above where monomer (i) is present in the amount of 20 to 70 percent by weight, monomer (ii) is present in the amount of 25 to 60 percent by weight, monomer (iii) is present in the amount of 1 to 20 percent by weight, and monomer (v) is present in the amount of 0.001 to 5 percent by weight.
In an additional embodiment, monomer (i) is present in the amount of 45 to 65 percent by weight, monomer (ii) is present in the amount of 30 to 50 percent by weight, monomer (iii) is present in the amount of 1 to 10 percent by weight, and monomer (v) is present in the amount of 0.01 to 2 percent by weight.
In yet a further embodiment, monomer (i) is present in the amount of 50 to 60 percent by weight, monomer (ii) is present in the amount of 35 to 45 percent by weight, monomer (iii) is present in the amount of 1 to 5 percent by weight, and monomer (v) is present in the amount of 0.1 to 1 to percent by weight.
Yet another embodiment, of the present invention includes a composition for imparting oil, water and stain repellency and stain-release properties to a substrate including an aqueous, substantially organic solvent free, solution or dispersion of the polymers described above.
Advantageously, the polymers of the present invention may be applied to substrates, such as textiles, to provide stain resistance, stain release and or oil-repellency without the use of other common textile additives such as permanent press resins, and the like. However, such additives may be added where desired. Such additives may be admixed with the polymers of the invention and applied to the substrate, or may be applied separately.
An additional advantage of the present invention is that aqueous solutions of the polymers described herein maintain a water-like viscosity characteristic which allows the materials to be conveniently handled and transferred even at wt solids at or above 15%. This allows for more efficient conveyance of polymer solutions, since a higher percent solids aqueous formulation necessarily requires the transportation of less water.
The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. As used herein, the term polymer shall be inclusive of oligomers. The detailed description which follows more particularly exemplifies these embodiments.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention is believed to be applicable to fluorochemical polymers for use in providing stain-resistant and/or stain-release properties to a substrate material. In particular, the present invention is directed to fluorochemical polymers that contain pendant fluoroaliphatic and cationogenic groups. While the present invention is not so limited, an appreciation of various aspects of the invention will be gained through a discussion of the examples provided below.
It is to be understood that the recitation of numerical ranges by endpoints includes all numbers and fractions subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).
It is to be understood that all numbers and fractions thereof are presumed to be modified by the term “about.”
It is to be understood that “a” as used herein includes both the singular and plural.
The general definitions used herein have the following meanings within the scope of the present invention.
The term “alkyl” refers to straight or branched hydrocarbon radicals, such as methyl, ethyl, propyl, butyl, octyl, isopropyl, tert-butyl, sec-pentyl, and the like. Alkyl groups can either be unsubstituted or substituted with one or more substituents, e.g., halogen, alkoxy, aryl, arylalkyl, aralkoxy and the like. Alkyl groups include, for example, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 6 carbon atoms.
The term “alkenyl” refers to straight or branched unsaturated hydrocarbon radicals having one or more double bonds, such as ethylene, propylene, butylene, 1,3-pentadiene, 1,4-pentadiene, and the like. Alkenyl groups can either be unsubstituted or substituted with one or more substituents, e.g., haloalkyl, halogen, alkoxy, aryl, arylalkyl, aralkoxy and the like. Alkenyl groups include, for example, 2 to 12 carbon atoms, or 2 to 9 carbon atoms.
The term “alkylene” refers to a divalent straight or branched saturated hydrocarbon radical such a
Cote Linda G.
Eilers Deborah J.
Jariwala Chetan P.
3M Innovative Properties Company
Kokko Kent S.
Pezzuto Helen L.
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