WO2007011593A1 - Fluorochemical urethane composition for treatment of fibrous substrates - Google Patents
Fluorochemical urethane composition for treatment of fibrous substrates Download PDFInfo
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- WO2007011593A1 WO2007011593A1 PCT/US2006/026984 US2006026984W WO2007011593A1 WO 2007011593 A1 WO2007011593 A1 WO 2007011593A1 US 2006026984 W US2006026984 W US 2006026984W WO 2007011593 A1 WO2007011593 A1 WO 2007011593A1
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
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- C09D131/04—Homopolymers or copolymers of vinyl acetate
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
Definitions
- This invention relates to chemical compositions comprising one or more fluorochemical urethane compounds, and one or more auxiliary compounds for treatment of a fibrous substrate.
- the invention further relates to fluorochemical coating compositions comprising at least one solvent and the chemical compositions of the present invention.
- the coating compositions are capable of improving one or more of the oil- repellency, stain- and/or soil repellency and stain and/or soil release properties, with improved durability, of the fibrous substrate treated with the composition.
- This invention also relates to articles comprising a fibrous substrate bearing a cured coating derived from the coating compositions of the present invention. The cured coating resists being worn- off due to wear, abrasion and cleaning.
- this invention relates to a process for imparting stain-release characteristics to substrates.
- Fluorochemical compositions that have been disclosed 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.
- the present invention provides novel fluorochemical compositions that can impart one or more of the following uniform, durable properties: oil- repellency and/or soil- and stain-resistance and/or soil- and stain-repellency.
- These fluorochemical compositions may be water and/or organic solvent soluble.
- this invention relates to chemical compositions comprising one or more fluorochemical urethane compounds, and one or more auxiliary compounds capable of further improving the soil- and/or stain release and oil- repellency of a fibrous substrate.
- urethane compounds comprise the reaction product of: (a) one or more polyfunctional isocyanate compounds; (b) one or more hydrophilic polyoxyalkylene compounds; (c) one or more fluorochemical monofunctional compounds and may further optionally comprise (d) one or more isocyanate-reactive silanes; and /or (e) a moiety having an isocyanate blocking group such as methyl ethyl ketone oxime, etc.
- the chemical compositions of the present invention comprising one or more urethane compounds, impart one or more of release, repellency and resistance characteristics to oil, stains and soils, and exhibit durability (i.e., they resist being worn-off) when exposed to wear and abrasion from use, cleaning, and the elements. Therefore, these compositions can be applied as coatings to a wide variety of substrates, for example, by topical application, to impart durable release/repellency/resistant properties to the substrates. When applied as a coating, the chemical compositions of the present invention can provide uniform properties to a fibrous substrate and do not change the appearance of the substrate to which they are applied. Even though the urethane compounds are of relatively low fluorochemical content, the chemical compositions of the present invention provide durable stain-release properties comparable to or better than those of the prior art
- compositions of the present invention include those compositions comprising terminal fluorochemical groups having from two to twelve carbons, preferably from three to six carbons, and more preferably four carbons. Even with Rf groups that are relatively short (i.e., six or fewer carbons), these chemical compositions, surprisingly, exhibit excellent release/resistance/repellency. Although compositions comprising lower fluorine content are less expensive, those of skill in the art have typically overlooked R f groups shorter than eight carbons because they have been known to impart inferior oil- and water-repellency and stain resistance.
- Another embodiment of the present invention relates to a composition for treatment of fibrous substrates comprising a mixture of the chemical composition of the present invention and a solvent.
- this treatment composition provides a uniform distribution of the chemical composition on the substrate without altering the appearance of the substrate.
- a high temperature cure is not required to provide this coating; the treatment composition can be cured (i.e., dried) at ambient temperatures.
- a high temperature cure e.g., temperatures in above about 125 0 F or 49 0 C
- This invention also relates to an article comprising a fibrous substrate having a cured coating derived from at least one solvent and a chemical composition of the present invention. After application and curing of the chemical composition, the substrate displays durable release/resistance/repellency properties.
- This invention further relates to a method for imparting stain-release characteristics to a fibrous substrate, having 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 and (b) allowing the coating composition to cure (i.e., dry).
- Acyloxy means a radical -OC(O)R where R is, alkyl, alkenyl, and cycloalkyl, e.g., acetoxy, 3,3,3-trifluoroacetoxy, propionyloxy, and the like.
- Alkoxy means a radical -OR where R is an alkyl group as defined below, e.g., methoxy, ethoxy, propoxy, butoxy, and the like.
- Alkyl means a linear saturated monovalent hydrocarbon radical having from one to about twelve carbon atoms or a branched saturated monovalent hydrocarbon radical having from three to about twelve carbon atoms, e.g., methyl, ethyl, 1 -propyl, 2-propyl, pentyl, and the like.
- Alkylene means a linear saturated divalent hydrocarbon radical having from one to about twelve carbon atoms or a branched saturated divalent hydrocarbon radical having from three to about twelve carbon atoms, e.g., methylene, ethylene, propylene, 2- methylpropylene, pentylene, hexylene, and the like.
- Aryl aliphatic means an alkylene radical defined above with an aromatic group attached to the alkylene radical, e.g., benzyl, pyridylmethyl, 1-naphthylethyl, and the like.
- “Cured chemical composition” means that the chemical composition is dried or solvent has evaporated from the chemical composition at ambient temperature (15 to 35°C) for up to approximately 24 hours or at elevated temperature until dryness.
- Fibrous substrate means materials comprised of synthetic fibers such as wovens, knits, nonwovens, carpets, and other textiles; and materials comprised of natural fibers such as cotton, paper, and leather.
- Fluorocarbon monofunctional compound means a compound having one isocyanate-reactive functional group and a perfluoroalkyl or a perfluoroheteoralkyl group, e.g., C 4 F 9 SO 2 N(CH 3 )CH 2 CH 2 OH, C 4 F 9 SO 2 N(CH 3 )CH 2 CH 2 NH 2 , C 4 F 9 CH 2 CH 2 OH, C 4 F 9 CH 2 CH 2 SH, C 2 F 5 O(C 2 F 4 O) 3 CF 2 CONHC 2 H 4 OH,
- Fluorochemical urethane compound means a compound derived or derivable from the reaction of at least one polyfunctional isocyanate compound at least one hydrophilic polyoxyalkylene compound, and at least one fluorinated monofunctional compound
- Heteroacyloxy has essentially the meaning given above for acyloxy except that one or more heteroatoms (i.e. oxygen, sulfur, and/or nitrogen) may be present in the R group and the total number of carbon atoms present may be up to 50, e.g., CH 3 CH 2 OCH 2 CH 2 C(O)O-. C 4 H 9 OCH 2 CH 2 OCH 2 CH 2 C(O)O-, CH 3 O(CH 2 CH 2 O) 1 CH 2 CH 2 C(O)O-, and the like.
- Heteroalkoxy has essentially the meaning given above for alkoxy except that one or more heteroatoms (i.e.
- oxygen, sulfur, and/or nitrogen may be present in the alkyl chain and the total number of carbon atoms present may be up to 50, e.g., CH 3 CH 2 OCH 2 CH 2 O-, C 4 H 9 OCH 2 CH 2 OCH 2 CH 2 O-, CH 3 O(CH 2 CH 2 O) n H, and the like.
- Heteroalkyl has essentially the meaning given above for alkyl except that one or more catenated (that is - in chain) heteroatoms (i.e., oxygen, sulfur, and/or nitrogen) may be present in the alkyl chain, these heteroatoms being separated from each other by at least one carbon, e.g., CH 3 CH 2 OCH 2 CH 2 -, CH 3 CH 2 OCH 2 CH 2 OCH(CH 3 )CH 2 -, C 4 F 9 CH 2 CH 2 SCH 2 CH 2 -, and the like.
- Heteroalkylene has essentially the meaning given above for alkylene except that one or more catenated heteroatoms (i.e., oxygen, sulfur, and/or nitrogen) may be present in the alkylene chain, these heteroatoms being separated from each other by at least one carbon, e.g., -CH 2 OCH 2 O-, -CH 2 CH 2 OCH 2 CH 2 -, -CH 2 CH 2 N(CH 3 )CH 2 CH 2 -, - CH 2 CH 2 SCH 2 CH 2 -, and the like.
- one or more catenated heteroatoms i.e., oxygen, sulfur, and/or nitrogen
- Heteroaryl aliphatic means an aryl aliphatic radical defined above except that catenated oxygen, sulfur, and/or nitrogen atoms may be present, e.g., phenyleneoxymethyl, phenyleneoxyethyl, benzyleneoxymethyl, and the like.
- Halo means fluoro, chloro, bromo, or iodo, preferably fluoro and chloro.
- Isocyanate blocking group means a group capable of reacting with an isocyanate group providing abeyant reactivity.
- abeyant chemical reactivity means the reactive character is existing in a temporarily inactive form or state, i.e., the reactivity is temporarily set aside and is capable is being regenerated at some future time.
- Isocyanate-reactive functional group means a functional group that is capable of reacting with an isocyanate group, such as hydroxyl, amino, thiol, etc.
- Perfluoroalkyl has essentially the meaning given above for “alkyl” except that all or essentially all of the hydrogen atoms of the alkyl radical are replaced by fluorine atoms and the number of carbon atoms is from 2 to about 12, e.g., perfluoropropyl, perfluorobutyl, perfluorooctyl, and the like.
- Perfluoroalkylene has essentially the meaning given above for “alkylene” except that all or essentially all of the hydrogen atoms of the alkylene radical are replaced by fluorine atoms, e.g., perfluoropropylene, perfluorobutylene, perfluorooctylene, and the like.
- Perfluoroheteroalkyl has essentially the meaning given above for “heteroalkyl” except that all or essentially all of the hydrogen atoms of the heteroalkyl radical are replaced by fluorine atoms and the number of carbon atoms is from 3 to about 100, e.g.
- Perfluoroheteroalkylene has essentially the meaning given above for “heteroalkyl ene” except that all or essentially all of the hydrogen atoms of the heteroalkylene radical are replaced by fluorine atoms, and the number of carbon atoms is from 3 to about 100, e.g., -CF 2 OCF 2 -, -CF 2 O(CF 2 O) n (CF 2 CF 2 O) 1n CF 2 -, C 3 F 7 O(CF(CF 3 )CF 2 O) P CF(CF 3 )- and the like wherein n and m are the same or different and p is equal to or greater than 3.
- Perfluorinated group means an organic group wherein all or essentially all of the carbon bonded hydrogen atoms are replaced with fluorine atoms, e.g., perfluoroalkyl, perfluoroheteroalkyl, and the like.
- Polyisocyanate compound means a compound containing two or more isocyanate radicals, -NCO, attached to a multivalent organic group, e.g. hexamethylene diisocyanate, the biuret and isocyanurate of hexamethylene diisocyanate, and the like.
- Reactive polyoxyalkylene means a polymer having oxyalkylene repeat units with an average of 1 or more isocyanate-reactive functional groups per molecule.
- Silane group means a group comprising silicon to which at least one hydrolyzable group is bonded, e.g., -Si(OCH 3 ) 3 , -Si(OOCCH 3 ) 2 CH 3 , -Si(Cl) 3 , and the like.
- Repellency is a measure of a treated substrate's resistance to wetting by oil and/or water and or adhesion of particulate soil. Repellency may be measured by the test methods described herein. "Resistance” is the context or soiling or staining is a measure of the treated substrate's ability to avoid staining and/or soiling when contacted by stain or soil respectively.
- Release is a measure of the treated substrate's ability to have soil and/or stain removed by cleaning or laundering.
- “Release/resistance/repellency” means the composition demonstrates at least one of oil repellency, water repellency, stain release, stain repellency, soil release and soil repellency.
- the chemical compositions of the present invention comprise one or more fluorochemical urethane compounds and one or more hydrophobic auxiliary agents capable of further improving the resistance/release/repellency of a fibrous substrate treated with the fluorochemical urethane compounds. It has been surprisingly found that the oil resistance imparted by coating compositions comprising fluorochemical urethane compounds as described herein can be improved by incorporating, i.e., blending, into the composition certain hydrophobic hydrocarbon auxiliary agents as discussed herein.
- the fluorochemical urethane compound(s) used in compositions of the invention comprise the reaction product of (a) one or more polyfunctional isocyanate compounds; (b) one or more hydrophilic polyoxyalkylene compounds; and (c) one or more fluorochemical monofunctional compounds; and (d) optionally, one or more silane compounds; and/or (e) optionally, an isocyanate blocking group such a oxime, etc.
- the fluorochemical urethane compounds can be described as:
- x is an integer from 2 to 20
- a is from 1 to x
- b is from 1 to 0.3 x
- c is from 0 to 0.3 x
- d is from 0 to 0.25 x
- e is from 0 to 0.6 x with the proviso that b + c is at least 0.0005 x
- Q, X ' , R 2 , Z 3 R f , R 3 , R 4 , R 1 , Y, and W are as defined below.
- Each fluorochemical urethane compound comprises a urethane group that is derived or derivable from the reaction of at least one polyfunctional isocyanate compound and at least one hydrophilic polyoxyalkylene compound.
- the fluorochemical urethane compound is terminated, on average, with (i) one or more perfluoroalkyl groups, one or more perfluoroheteroalkyl groups; and (ii) optionally, one or more silane groups; and/or (iii) optionally, one or more isocyanate blocking groups.
- the reaction product will provide a mixture of compounds, some percentage of which will comprise compounds as described, but may further comprise urethane compounds having different substitution patterns and degree of substitution.
- the composition of the present invention comprises 1) a mixture of urethane molecules arising from the reaction of (a) one or more polyfunctional isocyanate compounds, (b) one or more hydrophilic polyoxyalkylene compounds, (c) one or more fluorochemical monofunctional compounds, and (d) optionally, one or more silane compounds, and/or (e) optionally one or more isocyanate blocking groups and 2) one or more auxiliary compounds as described below.
- the amount of said hydrophilic polyoxyalkylene compound is sufficient to react with between about 0.05 and 30 percent of available isocyanate groups, the amount of said silanes when used is sufficient to react with between about 0.1 and 25 percent of available isocyanate groups, the amount of said isocyanate blocking group when used is sufficient to react with between about 0.1 and 60 percent of available isocyanate groups and the amount of said fluorochemical monofunctional compounds is sufficient to react with between about 40 and 90 percent of available isocyanate groups.
- the amount of said hydrophilic polyoxyalkylene(s) is sufficient to react with between about 3 and 30 percent of available isocyanate groups, the amount of said silanes is sufficient to react with between 0.1 and 15 percent of available isocyanate groups, the amount of said isocyanate blocking group when used is sufficient to react with between 10 and 50 percent of available isocyanate groups and the amount of said fluorochemical monofunctional compounds is sufficient to react with between 50 and 90 percent of available isocyanate groups.
- RfZR 2 - is a residue of at least one of the fluorochemical monofunctional compounds
- Rf is a perfluoroalkyl group having 2 to about 12 carbon atoms, or a perfluoroheteroalkyl group having 3 to about 50 carbon atoms;
- Z is a covalent bond, sulfonamido (-SO 2 NR-), or carboxamido (-CONR-) where R is hydrogen or alkyl, a carboxyl group, or a sulfonyl group;
- R is an alkylene, heteroalkylene, aryl alkylene, or heteroaryl aliphatic group
- R is a divalent straight or branched chain alkylene, cycloalkylene, or heteroalkylene group of 1 to 14 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and most preferably two carbon atoms, and preferably R is alkylene or heteroalkylene of 1 to 14 carbon atoms;
- Q is a multi-valent organic group that is a residue of the polyfunctional isocyanate compound
- R 3 is a polyvalent, preferably divalent, organic group which is a residue of the hydrophilic polyoxyalkylene
- R is monovalent organic group which is a residue of the hydrophilic polyoxyalkylene
- X' is -O-, -S-, or -N(R)-, wherein R is hydrogen or C 1 -C 4 alkyl; each Y is independently a hydroxy; a hydrolyzable moiety selected from the group consisting of alkoxy, acyloxy, heteroalkoxy, heteroacyloxy, halo, and oxime; or a non- hydrolyzable moiety selected from the group consisting of phenyl, alicyclic, straight-chain aliphatic, and branched-chain aliphatic, wherein at least one Y is a hydrolyzable moiety.
- W is the residue of a moiety capable of reacting with an isocyanate group and possesses abeyant chemical reactivity such as oxime, lactam, phenol, and the like.
- A is selected from the group consisting of R f ZR 2 -OCONH-, (Y) 3 SiR 1 XCONH-, and (Y) 3 SiR 1 NHCOOR 3 OCONH-.
- 1 is an integer from 1 to (m+n-1).
- m is an integer from 0 to 2; and
- n is an integer from 1 to 10.
- reaction product will contain a mixture of compounds in which the substitution patterns of the isocyanate groups will vary.
- Polyfunctional isocyanate compounds useful in the present invention comprise isocyanate groups attached to the multivalent organic group, Q, which can comprise a multivalent aliphatic, alicyclic, or aromatic moiety; or a multivalent aliphatic, alicyclic or aromatic moiety attached to a blocked isocyanate, a biuret, an isocyanurate, or a uretdione, or mixtures thereof.
- Preferred polyfunctional isocyanate compounds contain at least two and preferably three or more -NCO groups.
- Compounds containing two -NCO groups are comprised of divalent aliphatic, alicyclic, arylaliphatic, or aromatic moieties to which the -NCO radicals are attached.
- Preferred compounds containing three -NCO radicals are comprised of isocyanatoaliphatic, isocyanatoalicyclic, or isocyanatoaromatic, monovalent moieties, which are attached to a biuret or an isocyanurate.
- suitable polyfunctional isocyanate compounds include isocyanate functional derivatives of the polyfunctional isocyanate compounds as defined herein.
- derivatives include, but are not limited to, those selected from the group consisting of ureas, biurets, allophanates, dimers and trimers (such as uretdiones and isocyanurates) of isocyanate compounds, and mixtures thereof.
- Any suitable organic polyisocyanate such as an aliphatic, alicyclic, aryl aliphatic, or aromatic polyisocyanate, may be used either singly or in mixtures of two or more.
- the aliphatic polyfunctional isocyanate compounds generally provide better light stability than the aromatic compounds, and are preferred for treatment of fibrous substrates.
- Aromatic polyfunctional isocyanate compounds are generally more economical and reactive toward hydrophilic polyoxyalkylene compounds and other isocyanate-reactive compounds than are aliphatic polyfunctional isocyanate compounds.
- Suitable aromatic polyfunctional isocyanate compounds include, but are not limited to, those selected from the group consisting of 2,4-toluene diisocyanate (TDI), 2,6- toluene diisocyanate, an adduct of TDI with trimethylolpropane (available as DesmodurTM CB from Bayer Corporation, Pittsburgh, PA), the isocyanurate trimer of TDI (available as DesmodurTM IL from Bayer Corporation, Pittsburgh, PA), diphenylmethane 4,4'-diisocyanate (MDI), diphenylmethane 2,4'-diisocyanate, 1,5-diisocyanato-naphthalene, 1,4-phenylene diisocyanate, 1, 3 -phenylene diisocyanate, 1- methyloxy-2,4-phenylene diisocyanate, 1 -chlorophenyl-2,4-diisocyanate, and mixtures thereof.
- TDI 2,4-tol
- useful alicyclic polyfunctional isocyanate compounds include, but are not limited to, those selected from the group consisting of dicyclohexylmethane diisocyanate (Hi 2 MDI, commercially available as DesmodurTMW, available from Bayer Corporation, Pittsburgh, PA), 4,4'-isopropyl-bis(cyclohexylisocyanate), isophorone diisocyanate (IPDI), cyclobutane- 1,3 -diisocyanate, cyclohexane 1,3 -diisocyanate, cyclohexane 1,4-diisocyanate (CHDI), l,4-cyclohexanebis(methylene isocyanate) (BDI), 1 ,3-bis(isocyanatomethyl)cyclohexane (H 6 XDI), 3-isocyanatomethyl-3,5,5- trimethylcyclohexyl isocyanate, and mixtures thereof.
- Hi 2 MDI commercially available
- useful aliphatic polyfunctional isocyanate compounds include, but are not limited to, those selected from the group consisting of 1,4-tetramethylene diisocyanate, hexamethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), 1,12-dodecane diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate (TMDI), 2,4,4-trimethyl-hexamethylene diisocyanate (TMDI), 2-methyl-l,5-pentamethylene diisocyanate, dimer diisocyanate, the urea of hexamethylene diisocyanate, the biuret of hexamethylene 1,6-diisocyanate (HDI) (available as DesmodurTMN-100 andN-3200 from Bayer Corporation, Pittsburgh, PA), the isocyanurate of HDI (available as DemodurTM N- 3300 and DesmodurTM N-3600 from Bayer Corporation, Pittsburgh, PA),
- aryl aliphatic polyisocyanates include, but are not limited to, those selected from the group consisting of m-tetramethyl xylylene diisocyanate (m- TMXDI), p-tetramethyl xylylene diisocyanate (p-TMXDI), 1,4-xylylene diisocyanate (XDI), 1,3-xylylene diisocyanate, p-(l-isocyanatoethyl)-phenyl isocyanate, m-(3- isocyanatobutyl)-phenyl isocyanate, 4-(2-isocyanatocyclohexyl-methyl)-phenyl isocyanate, and mixtures thereof.
- m- TMXDI m-tetramethyl xylylene diisocyanate
- p-TMXDI p-tetramethyl xylylene diisocyanate
- XDI 1,4-xyly
- Preferred polyisocyanates include those selected from the group consisting of hexamethylene 1,6-diisocyanate (HDI), 1,12-dodecane diisocyanate isophorone diisocyanate, toluene diisocyanate, dicyclohexylmethane 4,4'-diisocyanate, MDI, derivatives of all the aforementioned, including DesmodurTM N-100, N-3200, N- 3300, N-3400, N-3600, and mixtures thereof.
- HDI hexamethylene 1,6-diisocyanate
- 1,12-dodecane diisocyanate isophorone diisocyanate 1,12-dodecane diisocyanate isophorone diisocyanate
- toluene diisocyanate dicyclohexylmethane 4,4'-diisocyanate
- MDI dicyclohexylmethane 4,4'-diisocyanate
- Suitable commercially available polyfunctional isocyanates are exemplified by DesmodurTM N-3200, DesmodurTM N-3300, DesmodurTM N-3400, Desmodur TM N-3600, DesmodurTM H (HDI), DesmodurTM W (bis[4-isocyanatocyclohexyl]methane), MondurTM M (4,4'-diisocyanatodiphenylmethane), MondurTM TDS (98% toluene 2,4-diisocyanate), MondurTM TD-80 (a mixture of 80% 2,4 and 20% 2,6-toluene diisocyanate isomers), and DesmodurTM N-IOO, each available from Bayer Corporation, Pittsburgh, PA.
- DesmodurTM N-3200 DesmodurTM N-3300, DesmodurTM N-3400, Desmodur TM N-3600, DesmodurTM H (HDI), DesmodurTM W (bis[4-isocyanatocyclohexyl]methan
- triisocyanates are those obtained by reacting three moles of a diisocyanate with one mole of a triol.
- a diisocyanate For example, toluene diisocyanate, 3- isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate, or m-tetramethylxylene diisocyanate can be reacted with 1,1,1 -tris(hydroxymethyl)propane to form triisocyanates.
- the product from the reaction with m-tetramethylxylene diisocyanate is commercially available as CYTHANE 3160 (American Cyanamid, Stamford, Conn.).
- Hydrophilic polyoxyalkylene compounds suitable for use in preparing the first component fluorochemical urethane compounds of the present invention include those polyoxyalkylene compounds that have an average functionality of 1 or greater (preferably, about 1 to 5; more preferably, about 1 to 3; most preferably, about 1 to T).
- the isocyanate-reactive groups can be primary or secondary, with primary groups being preferred for their greater reactivity. Mixtures of compounds having different functionalities, for examples mixtures of polyoxyalkylene compounds having one, two and three isocyanate-reactive groups, may be used provided the average is equal to or greater than 1.
- the polyoxyalkylene groups include those having 1 to 3 carbon atoms such as polyoxyethylene, polyoxypropylene, and copolymers thereof such as polymers having both oxy ethylene and oxypropylene units.
- polyoxyalkylene containing compounds include alkyl ethers of polyglycols such as,- e.g., methyl or ethyl ether of polyethylene glycol, hydroxy terminated methyl or ethyl ether of a random or block copolymer of ethylene oxide and propylene oxide, amino terminated methyl or ethyl ether of polyethylene oxide, polyethylene glycol, polypropylene glycol, a hydroxy terminated copolymer (including a block copolymer) of ethylene oxide and propylene oxide, a mono- or diamino- terminated poly(alkylene oxide) such as JeffamineTM ED, JeffamineTM EDR- 148 and poly(oxyalkylene) thiols.
- alkyl ethers of polyglycols such as,- e.g., methyl or ethyl ether of polyethylene glycol, hydroxy terminated methyl or ethyl ether of a random or block copolymer
- aliphatic polyisocyanates include BaygardTM VP SP 23012, RucoguardTM EPF 1421 and TubicoatTM Fix ICB.
- Useful commercially available hydrophilic polyoxyalkylene compounds for the first component include CarbowaxTM poly(ethylene glycol) materials in the number average molecular weight (M n ) range of from about 200 to about 2000 (available from Union Carbide Corp.); poly(propylene glycol) materials such as PPG-425 (available from Lyondell Chemicals); block copolymers of poly(ethylene glycol) and poly(propylene glycol) such as PluronicTM L31 (available from BASF Corporation); the "PeP” series (available from Wyandotte Chemicals Corporation) of polyoxyalkylene tetrols having secondary hydroxyl groups, for example, "PeP" 450, 550, and 650.
- Fluorochemical monofunctional compounds suitable for use in preparing the chemical compositions of the present invention include those that comprise at least one R f group.
- the R f groups can contain straight chain, branched chain, or cyclic fluorinated alkylene groups or any combination thereof.
- the R f groups can optionally contain one or more heteroatoms (i.e., oxygen, sulfur, and/or nitrogen) in the carbon-carbon chain so as to form a carbon-heteroatom-carbon chain (i.e., a heteroalkylene group).
- Fully- fluorinated groups are generally preferred, but hydrogen or chlorine atoms can also be present as substituents, provided that no more than one atom of either is present for every two carbon atoms.
- any R f group contain at least about 40% fluorine by weight, more preferably at least about 50% fluorine by weight.
- the terminal portion of the group is generally fully-fluorinated, preferably containing at least three fluorine atoms, e.g., CF 3 O-, CF 3 CF 2 -, CF 3 CF 2 CF 2 -, (CF 3 ) 2 N-, (CF 3 ) 2 CF-, SF 5 CF 2 -.
- Useful fluorochemical monofunctional compounds include compounds of the following formula:
- R f , Z, and R 2 are each as defined above;
- X is an isocyanate-reactive functional groups, for example -NH 2 ; -SH; -OH; - COOH; or -NRH where R is H or a C 1 to C 4 alkyl.
- Representative examples of useful fluorochemical monofunctional compounds include the following:
- Silane compounds suitable for use in the chemical compositions of the present invention are those of the following formula:
- these silane compounds contain one, two, or three hydrolysable groups (Y) on the silicon and one organic group including an isocyanate-reactive or an active hydrogen reactive radical (X — R 1 ).
- Any of the conventional hydrolysable groups such as those selected from the group consisting of alkoxy, acyloxy, heteroalkoxy, heteroacyloxy, halo, oxime, and the like, can be used as the hydrolyzable group (Y).
- the hydrolysable group (Y) is preferably alkoxy or acyloxy and more preferably alkoxy.
- Y When Y is halo, the hydrogen halide liberated from the halogen-containing silane can cause polymer degradation when cellulose substrates are used.
- Representative divalent bridging radicals (R 1 ) include, but are not limited to, those selected from the group consisting Of-CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 OCH 2 CH 2 -, -CH 2 CH 2 C 6 H 4 CH 2 CH 2 -, and -CH 2 CH 2 O(C 2 H 4 O) 2 CH 2 CH 2 N(CH 3 )CH 2 CH 2 CH 2 -.
- silane compounds are those which contain one or two hydrolyzable groups, such as those having the structures R 2 OSi(R 7 ) 2 R'XH and (R 8 O) 2 Si(R ⁇ R 1 XH, wherein R 1 is as previously defined, and R 7 and R 8 are selected from the group consisting of a phenyl group, an alicycylic group, or a straight or branched aliphatic group having from about 1 to about 12 carbon atoms.
- R and R are a lower alkyl group comprising 1 to 4 carbon atoms.
- Bonds thus formed are water resistant and can provide enhanced durability of the stain-release properties imparted by the chemical compositions of the present invention.
- silane compounds are well known in the art and many are commercially available or are readily prepared.
- Representative isocyanate-reactive silane compounds include, but are not limited to, those selected from the group consisting of:
- Isocyanate blocking agents are compounds that upon reaction with an isocyanate group yield a group that is unreactive at room temperature with compounds that at room temperature normally react with an isocyanate but which group at elevated temperature reacts with isocyanate reactive compounds. Generally, at elevated temperature the blocking group will be released from the blocked polyisocyanate group thereby generating the isocyanate group again which can then react with an isocyanate reactive group, such as may be found on the surface of a fibrous substrate. Blocking agents and their mechanisms have been described in detail in "Blocked isocyanates III.: Part. A, Mechanisms and chemistry" by Douglas Wicks and Zeno W. Wicks Jr., Progress in Organic Coatings, 36 (1999), pp. 14-172.
- Preferred blocking agents include aryl alcohols such as phenols, lactams such as ⁇ - caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, oximes such as formaldoxime, acetaldoxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, 2-butanone oxime or diethyl glyoxime.
- aryl alcohols such as phenols
- lactams such as ⁇ - caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam
- oximes such as formaldoxime, acetaldoxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, 2-butanone oxime or diethyl glyoxime.
- Blocking groups are generally capable of improving durability of the repellency properties or soil/stain release properties include non-fluorinated organic compounds that have one or more groups (or a precursor thereof) capable of reacting with the surface of the fibrous substrate. Examples thereof include compounds that have isocyanate groups or blocked isocyanates as described herein.
- the chemical compositions of the present invention may be made according to the following step- wise synthesis. As one skilled in the art would understand, the order of the steps is non-limiting and can be modified so as to produce a desired chemical composition.
- the polyfunctional isocyanate compound and the monofunctional fluorochemical compound are dissolved together under dry conditions, preferably in a solvent, and then heating the resulting solution at approximately 40 to 8O 0 C, preferably approximately 60 to 70°C, with mixing in the presence of a catalyst for one-half to two hours, preferably one hour.
- a catalyst level of up to about 0.5 percent by weight of the polyfunctional isocyanate/polyoxyalkylene mixture may be used, but typically about 0.00005 to about 0.5 percent by weight is required, with 0.02 to 0.1 percent by weight being preferred.
- Suitable catalysts include, but are not limited to, tertiary amine and tin compounds.
- useful tin compounds include tin II and tin IV salts such as stannous octanoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin di-2-ethylhexanoate, and dibutyltinoxide.
- tertiary amine compounds examples include triethylamine, tributylamine, triethylenediamine, tripropylamine, bis(dimethylaminoethyl) ether, morpholine compounds such as ethyl morpholine, and 2,2'-dimorpholinodiethyl ether, 1,4- diazabicyclo[2.2.2]octane (DABCO, Aldrich Chemical Co., Milwaukee, Wis.), and 1,8- diazabicyclo[5.4.0]undec-7-ene (DBU, Aldrich Chemical Co., Milwaukee, Wis.). Tin compounds are preferred.
- the resulting fluorochemical functional urethane compounds are then further optionally reacted with one or more of the silane compounds and/or one or more of the isocyanate blocking groups described above.
- the silane compound or isocyanate blocking group when used is added to the above reaction mixture, and reacts with a substantial portion of the remaining NCO groups. Terminal silane-containing groups are thereby bonded to the isocyanate functional urethane compounds.
- Aminosilanes are preferred, because of the rapid and complete reaction that occurs between the remaining NCO groups and the silane compound's amino groups.
- Isocyanato functional silane compounds may be used and are preferred when the ratio of polyfunctional isocyanate compound to the hydrophilic difunctional polyoxyalkylene and fluorochemical monofunctional compound is such that the resulting compound has a terminal hydroxyl group.
- polyoxyalkylene compounds having an average functionality of 1 or greater, described above by reacting any of the remaining NCO groups in the resulting mixture with one or more of the reactive polyoxyalkylene compounds described above.
- the polyoxyalkylene compound(s) is (are) added to the reaction mixture, using the same conditions as with the previous additions.
- the polyoxyalkylene compound(s) may be added at the same time as the fluorochemical compound, and prior to the optional silane or isocyanate blocking group.
- the coating composition of the invention further comprises an auxiliary compound that is capable of improving the repellency/resistant/release properties.
- the auxiliary component improves the oil repellency and stain release in general and the durability of the stain release.
- the auxiliary compounds are generally non-fluorinated organic compounds and are also called auxiliary compounds hereinafter.
- Suitable auxiliary compounds capable of improving the oil- repellency properties include for example hydrophobic homopolymers of alkyl esters of acrylic monomers.
- Auxiliary compounds that are capable of enhancing the soil/stain release properties are generally non-fluorinated organic compounds such as for example hydrophobic homopolymers of alkyl esters of acrylic monomers.
- a class of compound that can be advantageously used as the auxiliary component in a fluorochemical urethane treatment composition of this invention include hydrophobic polymers derived from vinyl monomers including polymers of acrylic and/or methacrylic monomers, vinyl acetate and the like. Particular examples of such polymers include homo- and copolymers of alkyl esters of acrylic and methacrylic acid such as, for example, C 1 to C 20, preferred Ci to Cn, alkyl esters of acrylic acid.
- alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isooctyl (meth)acrylate, dodecyl (meth)acrylate, and octodecyl (meth)acrylate.
- suitable polymers include a homopolymer of methyl aery late, a homopolymer of butyl methacrylate, a homopolymer of lauryl methacrylate, a homopolymer of isooctyl acrylate, a homopolymer of methyl methacrylate and a copolymer of methyl acrylate and decyl acrylate.
- the weight ratio of the first component fluorochemical urethane compound(s) to the second component auxiliary compound may be from about 99: 1 to 40:60 and is typically from about 85: 15 to 50:50. It will be understood that it may be possible to use compositions that are outside this range subject to impairment of resultant oil repellency and/or stain resistance.
- the treatment composition for fibrous substrates comprises a mixture of the chemical compositions of the present invention and at least one solvent.
- the treatment compositions When applied to fibrous substrates, the treatment compositions impart stain-release characteristics and exhibit durability (i.e., they resist being worn-off) when exposed to wear and abrasion from use, cleaning, and the elements.
- the chemical compositions of the present invention can be dissolved, dispersed, or emulsified in a variety of solvents to form coating compositions suitable for use in coating the chemical compositions of the present invention onto a substrate.
- Fibrous substrate treatment compositions may contain from about 0.1 to about 50 weight percent chemical composition.
- the chemical composition is used in the coating composition at about 0.1 to about 10 weight percent, most preferably from about 2 to about 4 weight percent.
- Suitable solvents include water, alcohols, esters, glycol ethers, amides, ketones, chlorohydrocarbons, chlorocarbons, and mixtures thereof.
- water is the preferred solvent because it does not raise any environmental concerns and is accepted as safe and non-toxic.
- the treatment compositions of the present invention can be applied to a wide variety of fibrous substrates resulting in an article that displays durable stain-release properties.
- the article of the present invention comprises a fibrous substrate having a treatment derived from at least one solvent and a chemical composition of the present invention. After application and curing of the coating composition, the substrate displays durable stain-release properties.
- the treatment composition may also be applied to other substrates including glass, ceramic, stone, metal, semi-porous materials such as grout, cement and concrete, wood, paint, plastics, rubber.
- the treatment compositions of the present invention can be applied to a wide variety of fibrous substrates including woven, knit, and nonwoven fabrics, textiles, carpets, leather, and paper.
- Substrates having nucleophilic groups, such as cotton are preferred because they can bond to the silane groups and/or blocked isocyanate groups when present in the chemical compositions of the present invention, thereby increasing durability of the fiber treatment.
- Any application method known to one skilled in the art can be used including spraying, dipping, immersion, foaming, atomizing, aerosolizing, misting, flood-coating, and the like.
- the coating composition .of the present invention is applied to the substrate and is allowed to cure (i.e., dry), at ambient or elevated temperature.
- the fibrous substrate is contacted with the fluorochemical coating composition of the invention.
- the substrate can be immersed in the fluorochemical treating composition.
- the treated substrate can then be run through a padder/roller to remove excess fluorochemical composition and dried or cured.
- the treated substrate may be dried at room temperature by leaving it in air or may alternatively or additionally be subjected to a heat treatment, for example, in an oven.
- a heat treatment is typically carried out at temperatures between about 5O 0 C and about 190 0 C depending on the particular system or application method used.
- a temperature of about 12O 0 C to 170 0 C, in particular of about 150 0 C to about 17O 0 C for a period of about 20 seconds to 10 minutes, preferably 3 to 5 minutes, is suitable.
- the chemical composition can be applied by spraying the composition on the fibrous substrate.
- An ambient cure preferably takes place at approximately 15 to 35 0 C (i.e., ambient temperature) until dryness is achieved, up to approximately 24 hours.
- the chemical composition can also form chemical bonds with the substrate and between molecules of the chemical composition.
- the choice of either heat-treatment or ambient cure often depends on the desired end-use. For consumer applications, where the composition may be applied to household laundry or carpeting, an ambient cure is typically desired.
- an elevated temperature cure or heat-treatment may be desirable.
- the amount of the treating composition applied to the fibrous substrate is chosen so that a sufficiently high level of the desired properties are imparted to the substrate surface without substantially affecting the look and feel of the treated substrate. Such amount is usually such that the resulting amount of the fluorochemical urethane composition on the treated fibrous substrate will be between 0.05% and 5% by weight based on the weight of the fibrous substrate, known as solids on fabric or SOF.
- the amount that is sufficient to impart desired properties can be determined empirically and can be increased as necessary or desired.
- Fibrous substrates that can be treated with the fluorochemical composition include in particular, textiles.
- the fibrous substrate may be based on synthetic fibers, e.g., polyester, polyamide and polyacrylate fibers or natural fibers, e.g., cellulose fibers as well as mixtures thereof.
- the fibrous substrate may be a woven as well as a non- woven substrate.
- Preferred substrates are cellulosic materials such as cotton, rayon, TENCELTM and blends of cellulosic materials.
- the resulting treated substrates derived from at least one solvent and a chemical composition of the present invention have been found to be resist soils and/or stains and/or to release soils and/or stains with simple washing methods.
- the fabric tested was 100% cotton woven twill fabric (Style: Super HippogatorTM; Color: Khaki) from Avondale Mills, Graniteville, SC.
- a 100% cotton twill fabric was sent through a horizontal padder that contained a bath of the diluted polymer, and was then immediately sent through a set of nip rollers.
- the concentration of the bath was adjusted to produce a fabric that when dry had a fluorochemical coating of 0.3, 0.6 and 1.0 percent solids based on the fabric total weight
- the bath also contained a glyoxal-type resin, Freerez® PFK (from Noveon,
- This test measures the resistance of the treated fabric to oil-based insults.
- a drop of one standard surface tension fluid (of a series of 8, with decreasing surface tensions) is dropped on a treated fabric. If after thirty seconds there is no wetting, the next highest standard number fluid (next lowest surface tension) is tested. When the lowest number fluid soaks into the fabric, the next lower number is the rating. For example, the fabric will receive a three rating, if the number four fluid wets the fabric.
- 3 M Protective Material and Consumer Specialties Division's "Oil Repellency Test I" method Document # 98-0212-0719-0). Performance Test - Stain Release
- This test evaluates the release of forced-in oil-based stains from the treated fabric surface during simulated home laundering. As indicated below, three stains were applied - Stain K (mineral oil), Stain E (corn oil), Stain C (dirty motor oil). These stains (five drops of each stain) were applied to the same area of the fabric with a dropper from a short distance above, covered with glassine paper and weighted with 1/4 Ib weights for one minute. The weights and glassine paper were removed from the fabric. The fabric was then blotted and allowed to hang for one hour before laundering.
- the Stain Release Test was run on treated fabric after initial treatment and after 5 consecutive launderings followed by 45 minute tumble-drying. Details to the laundering procedure are found in the 3M Protective Materials "Laboratory Laundering Procedures" for home laundering simulation (Document #98-0212-0703-4).
- Emulsification DI water (944 grams; at 14O 0 F (6O 0 C)) was slowly added to this vigorously stirred organic mixture. This pre-emulsion mixture was then sonicated for 2 minutes. A rotary evaporator connected to an aspirator was used to strip the MIBK from the mixture. The resulting emulsion was 20 to 30 percent solids.
- MeFBSE/N3300/MPEG 750 Fluorochemical urethane MeFBSE/N3300/MPEG 750
- MeFBSE 50.08 grams
- MPEG 750 18.57 grams
- ethyl acetate 150 grams
- the solution was heated to reflux to remove residual water by azeotropic distillation of ethyl acetate. 50 mL of ethyl acetate were removed.
- the reaction was complete when the isocyanate had been consumed and the -NCO peak at 2270 cm '1 was no longer visible in the FTIR.
- the approximately 50 weight percent solids solution of the fluorochemical urethane in ethyl acetate was then cooled to room temperature.
- a premixed solution of 2.0 grams EthoquadTM 18/25 and 300 grams DI water was prepared in a 500 ml flask. This solution was added in one portion to the ethyl acetate solution of the urethane at room temperature with sufficient agitation to thoroughly mix both phases.
- the combined material was homogenized using a Cole-Parmer Instruments ultrasonic processor model CPX600 for five minutes at 100% power.
- the reaction mixture was heated to 105 0 F under a nitrogen atmosphere and a solution of 12 grams DBTDL catalyst and 5 mL of ethyl acetate was added in one portion. After an exothermic reaction subsided, the reaction was held at 165 0 F (74 0 C) for two hours.
- the batch was cooled to 100 0 F and 22.4 pounds PEG 1450 was added to the reaction mixture.
- a premixed solution of 25 grams APTMS and 5 grams ethyl acetate was then added.
- the temperature was raised to 165°F (74 0 C) and held there for two hours. Water (65 grams) was then added to the reactor. The temperature was reduced to 14O 0 F (6O 0 C) and held there for thirty minutes.
- the solution of the fluorochemical urethane in ethyl acetate was then cooled to room temperature. This urethane was emulsified in the same manner as described for Fluorochemical Urethane Dispersion A.
- the poly(methyl acrylate) homopolymer dispersion was prepared by making a premixed solution of methyl acrylate monomer (80 grams) and TDDM (0.4 grams). The premix was purged with nitrogen by three vacuum-nitrogen cycles and kept under nitrogen. A one liter three-necked round bottom flask was charged with) DI water (231.3 grams, EthoquadTM 18/25 surfactant (3 grams), methyl acrylate (20 grams) and TDDM (0.1 grams). The aqueous mixture was purged with nitrogen by three vacuum-nitrogen cycles. The reactor was kept under a nitrogen cap. The temperature of the reactor was raised to 14O 0 F (60 0 C).
- the poly(butyl methacrylate) homopolymer dispersion was prepared in a 500 mL, 3- necked round bottom flask fitted with a water cooled condenser, overhead mechanical stirrer, thermocouple, temperature controller, nitrogen inlet and heating mantle. 50 grams of butyl methacrylate monomer (from Aldrich) was placed in the flask with 200 grams DI water and 3.33 grams EthoquadTM 18/25 (30 percent by weight solution in water). The mixture was purged with nitrogen by three vacuum-nitrogen cycles and kept under nitrogen. The flask was then charged with 0.25 grams V-50 and 0.25 grams tert-dodecyl mercaptan.
- the temperature of the reaction mixture was raised to 14O 0 F (60°C) in 41 0 F (5 0 C) increments, letting the exotherm subside at each increment before proceeding. Once the reaction reached 14O 0 F (6O 0 C), the reaction was allowed to continue overnight. The next day, there was some coagulum around the stir shaft. The fluid portion of the reaction mixture was a blue translucent emulsion. The emulsion was decanted from the flask. The percent solids were 12.3 weight percent in water.
- the poly(isooctyl acrylate) homopolymer dispersion was prepared in a 250 mL, 3- necked round bottom flask fitted with a water cooled condenser, overhead mechanical stirrer, thermocouple, temperature controller, nitrogen inlet, and heating mantle. 2 grams of isooctyl acrylate monomer were placed in the flask with 150 grams DI water and 1 gram DTAB. The mixture was purged with nitrogen and kept under nitrogen. After the temperature of the reactor was raised to 100 0 F (4O 0 C), the flask was then charged with a premix of 0.04 grams V-50 and 10 grams DI water.
- Blends of the fluorochemical urethanes (such as Fluorochemical Urethane Dispersion A, Fluorochemical Urethane Dispersion B, or Fluorochemical Urethane Dispersion C) and hydrophobic auxiliary compounds (such as poly(methyl acrylate)) were prepared by weighing the desired ratio of the compounds into a container and mixing well.
- fluorochemical urethanes such as Fluorochemical Urethane Dispersion A, Fluorochemical Urethane Dispersion B, or Fluorochemical Urethane Dispersion C
- hydrophobic auxiliary compounds such as poly(methyl acrylate
- Examples 1-6 were blends of Fluorochemical Urethane Dispersion A, Fluorochemical Urethane Dispersion B, or Fluorochemical Urethane Dispersion C with poly(methyl acrylate). The weight ratios of the blends are given in Table 2.
- Blends of Fluorochemical Urethane A with other acrylic polymers were prepared as described above. The blend compositions and weight ratios are summarized in Table 6. W 2
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX2008000455A MX2008000455A (en) | 2005-07-15 | 2006-07-12 | Fluorochemical urethane composition for treatment of fibrous substrates. |
BRPI0615548-0A BRPI0615548A2 (en) | 2005-07-15 | 2006-07-12 | chemical composition, treatment composition, article and method for imparting stain removal characteristics to a substrate |
CA002614950A CA2614950A1 (en) | 2005-07-15 | 2006-07-12 | Fluorochemical urethane composition for treatment of fibrous substrates |
EP06786962A EP1915410A1 (en) | 2005-07-15 | 2006-07-12 | Fluorochemical urethane composition for treatment of fibrous substrates |
JP2008521550A JP2009501272A (en) | 2005-07-15 | 2006-07-12 | Fluorochemical urethane composition for treating fibrous substrates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US11/183,004 | 2005-07-15 | ||
US11/183,004 US20070014927A1 (en) | 2005-07-15 | 2005-07-15 | Fluorochemical urethane composition for treatment of fibrous substrates |
Publications (1)
Publication Number | Publication Date |
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WO2007011593A1 true WO2007011593A1 (en) | 2007-01-25 |
Family
ID=37106290
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US2006/026984 WO2007011593A1 (en) | 2005-07-15 | 2006-07-12 | Fluorochemical urethane composition for treatment of fibrous substrates |
Country Status (9)
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US (1) | US20070014927A1 (en) |
EP (1) | EP1915410A1 (en) |
JP (1) | JP2009501272A (en) |
KR (1) | KR20080032184A (en) |
CN (1) | CN101223204A (en) |
BR (1) | BRPI0615548A2 (en) |
CA (1) | CA2614950A1 (en) |
MX (1) | MX2008000455A (en) |
WO (1) | WO2007011593A1 (en) |
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JP2010526926A (en) * | 2007-05-16 | 2010-08-05 | ソルヴェイ・ソレクシス・エッセ・ピ・ア | Fluorinated polyurethane composition |
US10227780B2 (en) | 2009-12-31 | 2019-03-12 | Firestone Building Products Co., LLC | Asphaltic membrane with mullite-containing granules |
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US7199090B2 (en) * | 2003-09-29 | 2007-04-03 | Ethena Healthcare Inc. | High alcohol content gel-like and foaming compositions comprising an alcohol and fluorosurfactant |
US7754092B2 (en) * | 2007-10-31 | 2010-07-13 | E.I. Du Pont De Nemours And Company | Soil resist additive |
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EP4110504A2 (en) | 2020-04-17 | 2023-01-04 | Kraton Polymers LLC | Antimicrobial spray composition |
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- 2006-07-12 BR BRPI0615548-0A patent/BRPI0615548A2/en not_active Application Discontinuation
- 2006-07-12 EP EP06786962A patent/EP1915410A1/en not_active Withdrawn
- 2006-07-12 MX MX2008000455A patent/MX2008000455A/en unknown
- 2006-07-12 WO PCT/US2006/026984 patent/WO2007011593A1/en active Application Filing
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JP2010526926A (en) * | 2007-05-16 | 2010-08-05 | ソルヴェイ・ソレクシス・エッセ・ピ・ア | Fluorinated polyurethane composition |
US10227780B2 (en) | 2009-12-31 | 2019-03-12 | Firestone Building Products Co., LLC | Asphaltic membrane with mullite-containing granules |
US10626615B2 (en) | 2009-12-31 | 2020-04-21 | Firestone Building Products Co., LLC | Asphaltic membrane with mullite-containing granules |
Also Published As
Publication number | Publication date |
---|---|
JP2009501272A (en) | 2009-01-15 |
US20070014927A1 (en) | 2007-01-18 |
BRPI0615548A2 (en) | 2011-05-24 |
CN101223204A (en) | 2008-07-16 |
EP1915410A1 (en) | 2008-04-30 |
MX2008000455A (en) | 2008-03-10 |
CA2614950A1 (en) | 2007-01-25 |
KR20080032184A (en) | 2008-04-14 |
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