Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
2000-06-12
2003-07-01
Niland, Patrick D. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C523S200000
Reexamination Certificate
active
06586522
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to compositions that exhibit water and oil repellency characteristics. This invention further relates to fibers, films, fabrics, coatings, and molded or blown articles comprising the compositions. In other aspects, this invention also relates to processes for imparting water and oil repellency characteristics to substrates, to a topical treatment composition for use in at least one such process, and to certain novel fluorochemical additives for use in the compositions and processes.
BACKGROUND OF THE INVENTION
Synthetic polymeric fibers have been used to make a variety of products, including carpets, drapery material, upholstery, and clothing. Often, however, such fibers (and the resulting products) have suffered from an inherent lack of water and oil repellency. Since fluorochemical groups are characteristically hydrophobic and oleophobic, various fluorochemicals have been developed for application to the polymeric fibers to impart water and oil repellency (as well as soil resistance) thereto. These fluorochemicals have most often been applied topically (for example, by spraying, padding, or finish bath immersion), but some fluorochemicals have also been useful as polymer melt additives.
In order for a fluorochemical to have utility as a polymer melt additive, it must be sufficiently thermally stable and non-volatile to withstand typical melt processing conditions. It must also be compatible with the polymer at the melt processing temperatures (to enable blending) and should preferably be able to migrate to the polymer surface as the temperature is lowered, so as to minimize the amount of fluorochemical needed to modify surface properties. This preference for migration capability has tended to limit the size of the fluorochemical molecule that can be utilized, effectively eliminating high molecular weight polymeric fluorochemicals from consideration.
Since some synthetic polymers such as polyesters require extremely high melt processing temperatures (for example, in the range of about 250-300° C.), it has been difficult to find fluorochemicals that are not only compatible with such polymers and capable of migration within them, but that are also sufficiently thermally stable. Although useful topical fluorochemical treatments have been developed, such treatments have often lacked the durability needed for some applications (for example, clothing, carpets, and upholstery), have tended to provide uneven or non-uniform coverage, and have often involved the use of environmentally unfriendly solvents. Even if water-based topical treatments are utilized, expenses are incurred for the purchase and maintenance of coating equipment.
Thus, there remains a need in the art for fluorochemicals that can successfully function as melt additives for high-melting polymers such as polyesters. Such fluorochemicals should not only be compatible with the polymers and able to meet the stringent thermal stability requirements, but should also be able to impart durable, uniform water and oil repellency properties to the polymers for, preferably, about the same cost as topical treatments.
SUMMARY OF THE INVENTION
Briefly, in one aspect, this invention provides a water- and oil-repellent composition comprising
(a) a repellency-imparting, fluorochemical composition comprising at least one fluorine-containing aromatic ester oligomer comprising
(1) at least two polymerized (repeat) units derived or derivable from the reaction of at least one dicarboxylic acid (or a derivative thereof, for example, a dicarboxylic acid halide, a dicarboxylic acid anhydride, or a dicarboxylic acid ester) and at least one polyol, with the proviso that at least one of the dicarboxylic acid (or derivative) and the polyol is aromatic or heteroaromatic (that is, either the carbonyl moiety of the carboxylic acid groups of the dicarboxylic acid, or the hydroxyl groups of the polyol, or both are bonded directly to at least one aromatic or heteroaromatic ring (“directly ring-bonded”)) and
(2) fluorochemical endgroups derived or derivable from the reaction of
(i) the dicarboxylic acid (or derivative) and at least one fluorine-containing monoalcohol or
(ii) the polyol and at least one fluorine-containing monocarboxylic acid (or derivative); and
(b) a treatable substrate; with the proviso that,
when the treatable substrate comprises a mixture of at least two polymers, the mixture is non-stratifying.
As used herein, the term “oligomer” means a polymer molecule consisting of only a few (for example, from 2 to about 20) polymerized (repeat) units, and the term “non-stratifying” means that the polymers in a polymer mixture are sufficiently compatible that a melt blend thereof does not phase separate to form two or more polymeric layers of different composition. Preferably, the polyol is a diol, and the treatable substrate comprises at least one thermoplastic or thermoset polymer (more preferably, a thermoplastic polymer; even more preferably, a thermoplastic polymer having a melting point above about 150° C.; most preferably, a polyester).
It has been discovered that the above-described, aromatic ester oligomer-containing, fluorochemical composition can be used to impart water and oil repellency, soil resistance, solvent resistance, and release properties to a variety of substrates. The substrates can be treated either by topical (external) application of the fluorochemical composition or by using the fluorochemical composition as a melt (internal) additive. Surprisingly, in spite of its higher molecular weight component(s), the aromatic ester oligomer-containing fluorochemical composition provides repellency properties comparable to or better than those imparted by the corresponding monomeric composition (containing only aromatic ester monomer(s) or compound(s)). Such repellency properties can thus be achieved without the need for careful molecular weight control.
In addition, certain preferred embodiments of the fluorochemical composition (for example, those comprising aromatic ester oligomer(s) having sulfonamido-linked fluorochemical endgroups) exhibit exceptionally high thermal stabilities (being stable at temperatures up to, for example, about 300° C.). These embodiments are thus particularly well-suited for use as melt additives for thermoplastic polymers and, in particular, meet the need in the art for fluorochemicals that can successfully function as melt additives for high-melting polymers such as polyesters and polyamides. The preferred fluorochemical compositions are not only compatible with such high-melting polymers and able to meet their stringent thermal stability requirements, but they are also able to impart durable, uniform water and oil repellency properties to the polymers for about the same cost as topical treatments.
In other aspects, this invention also provides fiber, fabric, film, a coating, and a molded or blown article comprising the water- and oil-repellent composition of the invention; processes for imparting repellency characteristics to a substrate, for example, by bulk addition or by topical treatment; a topical treatment composition comprising (a) the above-described repellency-imparting, fluorochemical composition and (b) at least one liquid, organic or aqueous vehicle; and a novel repellency-imparting, fluorochemical composition comprising at least one fluorine-containing, aromatic ester compound or oligomer comprising (a) at least one repeat or repeatable unit derived or derivable from the reaction of at least one dicarboxylic acid (or a derivative thereof) and at least one polyol, with the proviso that at least one of the dicarboxylic acid (or derivative) and the polyol (that is, either the dicarboxylic acid or the polyol or both) is aromatic or heteroaromatic and (b) sulfonamido group-containing, fluorochemical endgroups derived or derivable from the reaction of (i) the dicarboxylic acid (or derivative) and at least one fluorine-containing, sulfonamido group-containing monoalcohol or (ii) the polyol and at least one fluorine-containing, sulfonamido group-co
Jariwala Chetan P.
Klun Thomas P.
Linert Jeffrey G.
Stern Richard M.
3M Innovative Properties Company
Niland Patrick D.
Weiss Lucy C.
LandOfFree
Water- and oil-repellent composition does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Water- and oil-repellent composition, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Water- and oil-repellent composition will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3042134