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.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Dispersion Chemistry (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

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Citations (3)

• 1987
  • 1987-04-10 EP EP87303157A patent/EP0252576A3/de not_active Withdrawn

Patent Citations (3)

Non-Patent Citations (1)

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