EP0252576A2 - Zusammensetzung zur Behandlung in Textilien auf der Basis eines Lösungsmittels - Google Patents
Zusammensetzung zur Behandlung in Textilien auf der Basis eines Lösungsmittels Download PDFInfo
- Publication number
- EP0252576A2 EP0252576A2 EP87303157A EP87303157A EP0252576A2 EP 0252576 A2 EP0252576 A2 EP 0252576A2 EP 87303157 A EP87303157 A EP 87303157A EP 87303157 A EP87303157 A EP 87303157A EP 0252576 A2 EP0252576 A2 EP 0252576A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- meth
- acrylate
- units derived
- polymer chain
- fluoropolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 239000004744 fabric Substances 0.000 title claims description 28
- 239000002904 solvent Substances 0.000 title claims description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 20
- 239000004753 textile Substances 0.000 claims abstract description 16
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 claims abstract description 11
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- JTMTVBCMZZJAKI-UHFFFAOYSA-N (2-chloro-3-hydroxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(Cl)CO JTMTVBCMZZJAKI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920002313 fluoropolymer Polymers 0.000 claims description 37
- 239000004811 fluoropolymer Substances 0.000 claims description 37
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 7
- 239000000443 aerosol Substances 0.000 claims description 7
- 238000009472 formulation Methods 0.000 claims description 7
- 239000003380 propellant Substances 0.000 claims description 7
- -1 2-ethylhexyl Chemical group 0.000 claims description 5
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 claims description 4
- 229940099364 dichlorofluoromethane Drugs 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims description 3
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical group CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004338 Dichlorodifluoromethane Substances 0.000 claims description 3
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 3
- 235000019404 dichlorodifluoromethane Nutrition 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000935 solvent evaporation Methods 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- IUNVCWLKOOCPIT-UHFFFAOYSA-N 6-methylheptylsulfanyl 2-hydroxyacetate Chemical compound CC(C)CCCCCSOC(=O)CO IUNVCWLKOOCPIT-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011953 free-radical catalyst Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011850 water-based material Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
- D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/06—Processes in which the treating agent is dispersed in a gas, e.g. aerosols
Definitions
- the present invention relates to fluoropolymer compositions for imparting oil- and water- repellency to textiles by solvent application.
- the patent literature discloses numerous fluoropolymer compositions having utility as textile treating agents. These fluoropolymers generally contain pendent perfluoroalkyl groups of three or more carbon atoms, which provide oil- and water-repellency when the compositions are applied to fabric surfaces. Methods for producing such polymers, either in aqueous emulsion or in solvent systems, are well known.
- oil- and water-repellent fluoropolymers are applied to textiles as a latex emulsion in an aqueous bath.
- fluorochemical textile finishes can be used on particular fabrics, e.g., expensive upholstery, where unique or delicate fabric characteristics preclude use of water-based materials.
- Solvent finishes are also ideally suited for use by commercial dry-cleaners, who employ conventional dry cleaning equipment and solvents for both cleaning and refurbishing of rainwear.
- solvent finishes can be applied to textiles from aerosols, which are convenient for the home consumer.
- the customary means of preparing a textile finish for solvent application is to dissolve the active ingredient in a suitable organic solvent.
- a suitable organic solvent In the case of many fluorochemical textile finishes, however, this presents a problem because these compounds generally have inherent insolvency in most non-polar solvents.
- difficulties are encountered in achieving uniform application, or spreading, of the fluoropolymer on the textile surface prior to evaporation of solvent. Too-rapid solvent evaporation results in "frosting", particularly on dark fabrics.
- the present invention provides solvent-based fabric treatment compositions for imparting oil- and water- repellency to textiles, comprising by weight:
- the present invention provides textile treatment compositions containing polymers of perfluoroalkyl (meth)acrylate and other monomers such as 2-chlorohydroxypropyl methacrylate and other alkyl (meth)acrylates; propylene glycol monomethyl ether; and trichlorotrifluoroethane.
- These compositions are suitable for solvent application, by spraying or otherwise, to impart water and oil repellency to fabrics.
- the polymers employed in the compositions of the invention are obtained by polymerizing perfluoroalkyl (meth)acrylate and other monomers by conventional solvent polymerization techniques.
- Any of the conventional neutral solvents such as ethyl acetate, acetone, methyl isobutyl ketone, 1,1,1-trichloroethane, 1,2-dichlorotetrafluoroethane, l,l,2-trichloro-l,2,2-trifluoroethane, ethanol, isopropanol, and mixtures thereof can be used.
- the resulting polymer solutions can be diluted, if desired, with additional polymerization solvent.
- the polymers can be isolated by removal of solvent.
- a suitable catalyst can be any of the commonly known agents for initiating the polymerization of an ethylenically unsaturated compound.
- Such commonly employed initiators include 2,2'-azodiisobutyramidine dihydrochloride, 2,2'-azodiisobutyronitrile, and 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile).
- Catalyst concentration can be about 0.1 to 12 percent based on the weight of total monomers.
- chain transfer agents such as dodecyl mercaptan and isooctyl thioglycolate
- cross-linking agents such as ethylene dimethacrylate
- solutions containing either of the foregoing polymers exclusively, or mixtures of the two, can be formulated. Preferably, however, mixtures are employed.
- the most preferred compositions of the invention comprise (by weight of fluoropolymer) 60-80% fluoropolymer class A, and 20-40% fluoropolymer class B .
- Perfluoroalkyl monomers of the formula CF3CF2(CF2)kC2H40C(O)CR CH2, where R is -H or -CH 3 and k is an even integer from 2 to 12, are conventional and commercially available. They can be prepared by esterification of an appropriate perfluoroalcohol CF3CF2(CF2)kC2H40H with (meth)acrylic acid, for example, as described in U. S. Patent 3,282,905.
- the perfluoroalkyl group is linear, although compositions containing branched-chain perfluoroalkyl groups are suitable.
- perfluoroalkyl monomers are supplied as a mixture of monomers of varying perfluoroalkyl chain length, typically from 4-14 carbons.
- a representative material contains monomers of the foregoing formula having k equal to 2, 4, 6, 8, 10 and 12 in an approximate weight ratio of 2:35:30:18:8:3.
- the second monomer constituent is selected from the group consisting of alkyl (meth)acrylates having alkyl chain lengths of 2 to 18 carbons.
- alkyl refers to both linear and branched-chain alkyl groups.
- Examples of such monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, and stearyl (meth)acrylate.
- 2-ethylhexyl methacrylate is preferred.
- one or more specialized monomers can be incorporated into the fluoropolymers of class B in lesser amounts, e.g., 0.1-1 percent by weight, to impart improved cross-linking and substantivity.
- These monomer include N-methylol (meth)acrylamide and hydroxyethyl (meth)acrylate.
- compositions of the invention include propylene glycol monomethyl ether (PGME), in the range of 0.1-10% by weight.
- PGME propylene glycol monomethyl ether
- the solvent base of the compositions of the present invention consists essentially of at least 80% by weight trichlorotrifluoroethane. Minor amounts of other miscible solvents, such as methyl isobutyl ketone or 1,1,1-trichloroethane, which may remain as residues from solvent polymerization steps, will not adversely affect composition performance.
- compositions disclosed herein are useful to impart oil, water, and soil repellency to a wide range of substrates. Due to their organic solubility and repellency properties, the copolymers are easy to apply and require little if any curing; thus, they are particularly suitable for treating substrates such as apparel, upholstered furniture, delicate fabrics, and leather, where mild drying conditions are desirable.
- the compositions of this invention are adapted to be marketed commercially in the form of stable concentrates that can be diluted readily using additional trichlorotrifluoroethane solvent, or formulated into into aerosol sprays using suitable propellants.
- Suitable propellants include dichlorofluoromethane, carbon dioxide, mixtures of propane and isobutane, dichlorodifluoromethane, 1,1,1-chlorodifluoroethane, and 1,1-difluoroethane. Of the foregoing, dichlorofluoromethane is preferred.
- Example illustrates the invention. Unless otherwise indicated, all parts and percentages are by weight. The percent by weight of monomer units in polymers is based on the weights of monomers charged.
- 75 parts perfluoroalkyl monomer of the formula CF 3 CF 2 (CF 2 ) k C 2 H 4 OC(O)C(CH 3 ) CH 2 , having k is equal to 2 , 4, 6, 8, 10 and 12 in an approximate weight ratio of 2:35:30:18:8:3, 25 parts 2-chlorohydroxypropyl methacrylate, and 100 parts methyl isobutyl ketone were charged in a closed vessel. While purging with nitrogen, the resulting solution was heated to 70°C for one hour, and then one part 2,2'-azodiisobutyronitrile initiator in three parts methyl isobutyl ketone was added. The resulting solution was held at 80°C for 12 hours.
- Polymer conversion was 98% was determined by measurement of nonvolatile solids.
- the polymer solution was then diluted with trichlorotrifluoroethane to provide a solution containing 1% nonvolatile solids, and applied to fabric samples at the rate of 25 parts polymer solution to 100 parts fabric.
- Treated fabric samples were tested for oil repellency by a modification of AATCC Standard Test Method No. 118, conducted as follows.
- a series of organic liquids, identified below, were applied dropwise to fabric samples on a flat horizontal surface. Beginning with the lowest numbered test liquid, (Rating No. 1) one drop (approximately 5 mm in diameter or 0.05 mL volume) was placed on each of three locations at least 5 mm apart. The drops were observed for 30 seconds. If, at the end of this period, two of the three drops were still spherical to hemispherical in shape with no wicking around the drops, three drops of the next numbered liquid were placed on adjacent sites and similarly observed for 30 seconds. The procedure was continued until one of the test liquids resulted in two of the three drops failing to remain spherical to hemispherical, or wetting or wicking occurred.
- the oil repellency rating of a tested fabric is the highest numbered test liquid for which two of three drops remained spherical to hemispherical with no wicking for 30 seconds.
- treated textiles with a rating of 5 or greater are good or excellent; textiles having a rating of one or greater can be used for certain applications.
- the following test liquids were employed:
- Nujol is a trademark of Plough, Inc., for a mineral oil having a Saybolt viscosity of 3606390 at 38° and a specific gravity of 0.880/0.900 at 15 C.
- Water repellency of treated fabrics was similarly determined by carefully placing a drop of seven aqueous test solutions on each of three locations at least two inches apart.
- the test solutions used in water repellency testing were as follows:
- the water repellency rating corresponded to the highest numbered test solution for which two of the three drops remained spherical or hemispherical and did not wick into the fabric for at least two minutes.
- the higher the water repellency rating the better the resistance to staining by water-based substances.
- treated fabrics with a rating of five or greater are excellent; three or four are good; and anything with a rating of one or greater can be used for certain purposes.
- Spray water repellency was determined for treated fabric samples using standard Test Method No. 22 of the American Association of Textile Chemists and Colorists. In this test, 250 mL of water at 27°C is poured in a narrow stream onto a fabric sample stretched on a 6-inch (15.2 cm) diameter metal hoop. The water is discharged from a funnel suspended six inches (15.2 cm) above the fabric sample. After removal of excess water, the fabric is visually scored by reference to published standards. A rating of 100 denotes no water penetration or surface adhesion; a rating of 90 denotes slight random sticking or wetting; lower values indicate greater wetting. In the following tables, results of repellency testing of various composition/propellant formulations of different fabric samples are reported. Each formulation contained two fluoropolymers.
- the first fluoropolymer present at 0.6% by weight, corresponded to class "A", above, and was prepared as just described.
- the second fluoropolymer corresponding to class "B" above, was present at 0.3% by weight.
- This material was prepared substantially as described above, but consisted of 69% polymer units derived from perfluoroalkyl methacrylate monomer, 30% polymer units derived from 2-ethylhexyl methacrylate, 0.1% polymer units derived from N-methylol methacrylamide and 0.1% polymer units derived from hydroxyethyl methacrylate.
- the compositions contained 1.5% PGME and trichlorotrifluoroethane to make 100%.
- Table 1 The various formulations are described in Table 1, below:
- Tables 2-7 indicate the results of oil, water, and water-spray repellency testing on various fabric types.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US85344186A | 1986-04-16 | 1986-04-16 | |
| US853441 | 1986-04-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0252576A2 true EP0252576A2 (de) | 1988-01-13 |
| EP0252576A3 EP0252576A3 (de) | 1990-08-08 |
Family
ID=25316043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87303157A Withdrawn EP0252576A3 (de) | 1986-04-16 | 1987-04-10 | Zusammensetzung zur Behandlung in Textilien auf der Basis eines Lösungsmittels |
Country Status (1)
| Country | Link |
|---|---|
| EP (1) | EP0252576A3 (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0594154A1 (de) * | 1992-10-21 | 1994-04-27 | Minnesota Mining And Manufacturing Company | Auftragung von Fluorchemikalien auf Textilsubstraten |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3282905A (en) * | 1961-05-03 | 1966-11-01 | Du Pont | Fluorine containing esters and polymers thereof |
| EP0124236A1 (de) * | 1983-03-28 | 1984-11-07 | E.I. Du Pont De Nemours And Company | Fluor enthaltende Copolymere |
| EP0157138A1 (de) * | 1984-02-29 | 1985-10-09 | Bayer Ag | Verfahren zur Herstellung von Hydrophobier- und Oleophobiermittel |
-
1987
- 1987-04-10 EP EP87303157A patent/EP0252576A3/de not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3282905A (en) * | 1961-05-03 | 1966-11-01 | Du Pont | Fluorine containing esters and polymers thereof |
| EP0124236A1 (de) * | 1983-03-28 | 1984-11-07 | E.I. Du Pont De Nemours And Company | Fluor enthaltende Copolymere |
| EP0157138A1 (de) * | 1984-02-29 | 1985-10-09 | Bayer Ag | Verfahren zur Herstellung von Hydrophobier- und Oleophobiermittel |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 100, 1984 Columbus, Ohio, USA "Waterproofing of fabrics with improved fastness" ref. no. 122725 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0594154A1 (de) * | 1992-10-21 | 1994-04-27 | Minnesota Mining And Manufacturing Company | Auftragung von Fluorchemikalien auf Textilsubstraten |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0252576A3 (de) | 1990-08-08 |
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