Compositions – Leather or fur treating
Reexamination Certificate
1999-09-17
2002-08-27
Green, Anthony (Department: 1755)
Compositions
Leather or fur treating
C252S008610, C252S008620, C427S389000, C427S389900, C428S473000, C526S242000, C526S248000, C528S396000, C528S401000
Reexamination Certificate
active
06440321
ABSTRACT:
1. FIELD OF THE INVENTION
The present invention relates to a fluorochemical composition to impart water and/or oil repellency to a substrate, in particular to a fibrous material such as textile or leather. In particular, the present invention relates to fluorochemical compositions that are based on fluoroaliphatic and hydrocarbon radical containing condensates of an amino resin. The present invention also relates to a method of making these condensates and to a method of treatment of a substrate therewith.
2. BACKGROUND OF THE INVENTION
Organofluorine compounds (i.e., fluorochemicals) are substances containing portions that are fluorocarbon in nature (e.g., hydrophobic, oleophobic, and chemically inert) and portions that are organic or hydrocarbon in nature (e.g., chemically reactive in organic reactions). Some fluorochemicals are familiar to the general public, such as SCOTCHGARD™ carpet protector, which imparts oil and water repellency and stain and soil resistance to carpet. Other such substances have various industrial uses, such as reducing the surface tension of liquids, reducing evaporation and inflammability of volatile organic liquids, and improving the leveling of organic polymer coatings.
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
.
Fluorochemical based water and/or oil repellent compositions for treating substrates, in particular textiles and leather are of substantial commercial importance. Amongst water and/or oil repellent compositions known in the art to treat substrates are those based on amino resins and in particular condensates of formaldehyde and melamine. For example, an aqueous emulsion of fluorochemical containing melamines (FC-melamine) is commercially used as an oil and water repellent. However, due to the poor solubility of the FC-melamines in common organic solvents, it is generally required to first dissolve the FC-melamine in a fluorinated solvent or a chlorofluorinated solvent and then disperse that solution in water in the presence of an emulsifier using high energy emulsifying equipment. The solvent can subsequently be recovered via distillation. Such procedure is cumbersome, expensive and moreover requires the use of environmentally unacceptable solvents.
DE 3133303 describes FC-melamines that are obtained by condensation of highly etherified hexamethylolmelamine and a perfluorinated thiol. These compounds can be used in the form of an aqueous emulsion to treat textiles and leather in order to provide water and oil repellency thereto. While good results can be obtained on textiles, the results of such FC-melamines on leather leaves a desire for further improvement. Moreover, as set out above, these compounds are generally only soluble in fluorinated solvents.
U.S. Pat. No. 3,510,455 teaches the production of thermosettable fluorinated prepolymers by reacting an aldehyde, a nitrogen compound, e.g. urea or melamine, and a fluorinated aliphatic compound which contains a perfluorinated alkyl chain as well as at least one functional group with an active hydrogen atom. These prepolymers are soluble in usual solvents and cure on polar surfaces to continuous, adherent films. The prepolymers prepared according to this patent are not believed to be suitable for the treatment of textile materials.
U.S. Pat. No. 3,362,782 teaches the application of condensation products of optionally etherified methylolated compounds of heterocyclic nitrogen compounds with 1,1-dihydroperfluoroalkyl alcohols or perfluorocarboxylic acid amides, e.g. with perfluoroheptyloxymethylpenta-(methoxymethyl)-melamine for the anti-soiling finishing of cellulose textile material. For the application an organic solvent is used. However, the oil-and water-repellent effects achieved with these condensation products do not meet the present requirements. Moreover, unproportionally large quantities of these condensation products have to be used.
Fatty acid derivatives of melamine are disclosed in U.S. Pat. No. 3,506,661 to treat textiles and in particular for water repellent impregnation. These melamine derivatives are said to be soluble in chlorated hydrocarbons, in aromatic hydrocarbons such as benzene, benzol and toluol. However, these compounds are unsuitable as oil repellents and also do not provide the presently desired water repellency on textiles.
U.S. Pat. No. 3,480,579 discloses the use of condensates of hexaalkyloxymethyl melamines and long chain aliphatic acids in a composition to impart water repellency to a textile. According to this disclosure, the composition preferably also contains a fluorinated oil and water repellent compound in particular a polymeric, fluorine containing aliphatic compound.
U.S. Pat. No. 5,292,796 discloses fluorochemical compositions comprising fluorinated compounds, wherein the fluorinated compound comprises a fluorochemical oligomeric portion bonded through —O—, —S—, —NH— or CO
2
— to a moiety comprising a group derived from an amino resin. Particularly disclosed amino resins include methylolated melamines, benzoguanamines and acetylguanamines and methylated derivatives thereof The compositions can be used to impart durable abrasion-resistant oil and water repellent properties. Further, according to the teaching of this patent, the amino resin may contain a long chain aliphatic group, and, if desired to increase the hydrophobic character of a substrate to be treated, it is possible to include compounds such as fatty acid condensates with melamine or urea derivatives. According to the examples in this patent, the fluorochemical is dissolved in hexafluoroxylene and the resultant solution is emulsified in water with the aid of a surfactant.
3. SUMMARY OF THE INVENTION
The present invention provides a fluorochemical composition that is readily soluble in non-fluorinated organic solvents and that can provide good and/or improved water and/or oil repellency on substrates, particularly textile or leather substrates.
The fluorochemical composition comprises one or more condensates of (i) a methylolated amide or an alkoxylated derivative thereof, (ii) a hydrocarbon compound selected from an alcohol, a thiol, an amide or an acid having a hydrocarbon group of at least 6 carbon atoms and which hydrocarbon group is optionally substituted with up to 3 substituents and (iii) a fluorinated compound corresponding to formula (I):
R
f
—(X
l
)
n
—Z
l
(I)
wherein:
R
f
represents a fluorinated aliphatic group;
X
l
represents an organic divalent linking group;
Z
l
represents hydroxy, thiol, an amide group or an acid group and n is 0 or 1.
The present invention also provides the use of the fluorochemical composition to impart water repellency and/or oil repellency to a substrate.
The present invention further provides a method of treatment of a substrate with the fluorochemical composition and substrates comprising the fluorochemical composition on their surface.
Also provided is a method of making the fluorochemical composition.
4. DETAILED DESCRIPTION OF THE PRESENT INVENTION
The fluorochemical composition can be prepared by reacting, in the presence of an acid catalyst, (i) a methylolated amine or an alkoxylated derivative thereof, (ii) a hydrocarbon compound selected from an alcohol, a thiol, an amide or an acid having a hydrocarbon group with at least 6 carbon atoms and which hydrocarbon group is optionally substituted with up to 3 substituents and (iii) a fluorinated compound corresponding to formula (I):
R
f
—(X
1
)
n
—Z
1
(I)
wherein:
R
f
Audenaert Frans A.
Coppens Dirk M.
Dams Rudolf J.
3M Innovative Properties Company
Green Anthony
Jordan Robert H.
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