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
2000-11-08
2003-02-25
Cain, Edward J. (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...
C524S544000, C524S560000, C525S199000, C525S200000, C525S276000
Reexamination Certificate
active
06525127
ABSTRACT:
This invention relates to fluorochemical compositions for use in providing repellent properties to a fibrous substrate material. In another aspect, this invention relates to fluorochemical compounds that contain pendent fluoroaliphatic groups proximal to one another. In yet another aspect, it relates to fluorochemical compounds that are at least in part oligomeric in nature.
The utility of organofluorine compounds as surface-active agents (i.e., surfactants) 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). Generally, the organofluorine substances described above are those which have carbon-bonded fluorine in the form of a monovalent fluoroaliphatic radical such as a perfluoroalkyl group, typically —C
n
F
2n+1
, where n is at least 3, the terminal part of which group is trifluoromethyl, —CF
3
.
U.S. Pat. No. 3,758,447 (Falk et al.) describes polymers that result from free radical polymerization of a monomer in the presence of perfluoroalkyl mercaptans, which act as chain-transfer agents. Mercaptans that contain pairs or triplets of closely-packed perfluoroalkyl groups are said to produce polymers with higher oil repellency levels compared with analogous polymers derived from a mercaptan with just one perfluoroalkyl group or perfluoroalkyl groups that are not closely packed.
U.S. Pat. No. 5,453,540 (Dams et al.) describes fluorochemical compositions for the treatment of textiles comprising: (i) a fluorochemical oligomeric portion comprising an aliphatic backbone with a plurality of fluoroaliphatic groups attached thereto, each fluoroaliphatic group having a fully fluorinated terminal group and each independently linked to a carbon atom of the aliphatic backbone through an organic linking group;(ii) an organic moiety (which can be functional or non-functional, and which is different from the fluorochemical oligomeric portion); (iii) a non-polymeric isocyanate-derived linking group which links the fluorochemical oligomeric portion to the organic moiety; and (iv) a group bonded thereto, which can impart soft hand, stain release, water repellency, or a durable property when the compound is applied to a fibrous substrate.
J. Polymer Science, Part A 1988, 26, 2991 (Chujo et al.) describes a di-carboxyl terminated macromonomer prepared by the free radical co-polymerization of a perfluoroalkylethyl acrylate and methyl methacrylate in the presence of thiomalic acid. Also described is the reaction of such macromonomers with organic dicarboxylic acids and organic diamines in the presence of an appropriate catalyst to afford a copolymer wherein the macromonomer is grafted onto a polyamide chain.
The treatment of hides and skins to form leather involves a number of interdependent chemical and mechanical operations. These operations may be divided into a sequence of “wet end” steps followed by a sequence of “dry” steps. A description of each of these operations is provided in Fundamentals of Leather Manufacturing, Prof Dr Heidemann (Eduard Roether KG, 1993). The primary tanning operation involves the treatment of the hide to preserve it and form useful leather. Chrome tanning salts are well known and widely used for this purpose. Chrome-tanned hides or skins are known in the art as “wet blue leather”. In order to produce a uniform piece of leather with the required physical and aesthetic properties, a second tanning step, known as “retanning” is employed. Retanning can be accomplished using a variety of naturally derived materials including extracts from vegetables or plants, and synthetic tanning agents known as “syntans”, or combinations thereof. After or during retanning, the leather can be colored and fatliquored.
A number of publications have proposed various copolymers for treating leather during tanning and retanning, addressing the problem of making treated leather more water resistant or completely waterproof.
EP-A-372 746 discloses a method and process for treating leather utilizing selected amphiphilic copolymers for improving the strength, temper and water resistance of the leather. The amphiphilic copolymers are formed from a predominant amount of at least one hydrophobic monomer and a minor amount of at least one copolymerizable hydrophilic monomer. The application states that the process may be particularly useful as a one step substitute for conventional retanning and fatliquoring treatment steps.
EP-A-682 044 discloses copolymers comprising ethylenically unsaturated dicarboxylic acid anhydrides, long chain olefins and fluorolefins. Leathers treated with these polymers are shown to yield good waterproofness results according to the Bally-Penotrometer test.
U.S. Pat. No. 5,124,181 discloses copolymers which contain a) from 50 to 90% by weight of C
8
-C
40
-alkyl methacrylates, vinyl esters of C
8
-C
40
-carboxylic acids or mixtures thereof and b) from 10 to 50% by weight of monoethylenically unsaturated C
3
-C
12
-carboxylic acids, monoethylenically unsaturated dicarboxylic anhydrides, monoesters or monoamides of monoethylenically unsaturated C
4
-C
12
-dicarboxylic acids, amides of C
3
-C
12
-monocarboxylic acids or mixtures thereof as copolymerized units and which have molecular weights of from 500 to 30,000. The copolymers are used in at least partially neutralized form in aqueous solution or dispersion for making leather and furs water repellent.
WO 94/01587 discloses water-dispersible and/or water-emulsifiable co-oligomers containing (a) fatty crotonates; (b) radically copolymerizable, hydrophilic, ethylenically unsaturated acids and/or their anhydrides, and possibly (c) minor amounts of other copolymerizable comonomers. These co-oligomers are used as amphiphilic agents for greasing leather and pelts.
Despite the various publications there continues to be a need for further fluorochemical compositions for the treatment of leather to impart desired properties thereto such as water repellency, water proofness, oil repellency and stain resistance. It is further desired that such fluorochemical compositions be readily produced in a cost effective way, have sufficient storage stability and are efficient even if applied in low quantities to the substrate. Highly desired fluorochemical compositions are those that can impart both good water repellency as well as oil repellency to leather substrates. In one aspect, the present invention relates to the wet end operations which take place after primary tanning, namely retanning and fatliquoring.
SUMMARY OF THE INVENTION
This invention provides a method of treating fibrous substrates comprising contacting the fibrous substrate with a composition comprising alkylated fluorochemical oligomeric compounds comprising:
(i) a fluorochemical oligomeric portion comprising an aliphatic backbone with a plurality of pendant fluoroaliphatic groups, each fluoroaliphatic group having a fully fluorinated terminal group and each independently linked to a carbon atom of the aliphatic backbone through an organic linking group;
(ii) an aliphatic moiety having at least 12 carbon atoms; and
(iii) a linking group which links the fluorochemical oligomeric portion to the aliphatic moiety.
In another aspect, the invention provides a method of treating fibrous substrates comprising contacting the fibrous substrate with a composition comprising alkylated fluorochemical oligomeric compounds comprising:
(i) an oligomeric portion having both fluoroaliphatic and fluorine-free aliphatic pendent groups;
(ii) an aliphatic moiety having at least 12 carbon atoms; and
(iii) a linking group which links the oligomeric portion to the aliphatic moiety;
In another aspect, the present invention provides a fluorochemical leather treatment composition comprising at least one fluorochemical compound described herein. In another aspect, the present invention provides a treated substrate comprising a coating of the treatment composition on at least a portion
Dams Rudolf J.
Eggleston James D.
Jariwala Chetan P.
Yandrasits Michael A.
Cain Edward J.
Kokko Kent S.
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