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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/22—Esters containing halogen
  • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/911—Emulsifying agents
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2164—Coating or impregnation specified as water repellent
  • Y10T442/2172—Also specified as oil repellent
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2164—Coating or impregnation specified as water repellent
  • Y10T442/2189—Fluorocarbon containing

Definitions

• fluorinated polymers which provide repellency to oils and water (liquids) do not by necessity have any repellency for dry-soils, i.e., particulate matter.
• particulate matter usually soils a fabric by being rubbed or ground into the fabric, for example, between and among the individual threads. Removal of such dry-soil requires the laundering medium to suspend the particle and float it away from the fibers of the fabric. If the fabric repels water, of course, it is more diflicult to remove the particulate matter.
• Novel fluorinated aqueous emulsion polymers have now been discovered which, when used in treating textile fabrics, display the desired properties and quantities such as imparting oil repellency prior to curing and also imparting to the treated textile fabric a resistance to dry soiling, thus overcoming some of the outstanding problems in the area of oil and water repellency and dry soil resistance which exist for garment manufacturers and the like.
• the perfluoroalkyl group R is preferably a mixture of straight chain groups CF CF (CF where n is 4, 6, 8, 10 and 12 in the approximate weight ratio 35/30/18/8/3, the monomer having an average molecular weight of 522. These are preferred since mixtures of these groups are commercially available, financially practical and give the best results. Branched or other straight chain perfluoroalkyl groups may, however, also be utilized.
• the second essential monomer in the present polymers is methyl acrylate or ethyl acrylate with methyl acrylate being preferred. From about 30 to 5 parts of units derived from such monomers must be present in the polymer.
• the sum of the units derived from the first and second essential monomers present in the polymer is 100 parts.
• the monomers which are used and are commercially available are N- methylol acrylamide, N-methylol methacrylamide, 2-hydroxyethyl acrylate, Z-hydroxyethyl methacrylate, and of these, N-methylol acrylamide and Z-hydroxyethyl methacrylate are preferred.
• About 0 to 1 part of units derived from these optional monomers may be present per 100 parts of units derived from the two essential monomers.
• the polymers of this invention are aqueous emulsion polymers, that is; prepared by an aqueous emulsion polymerization technique.
• the molecular weight of the polymer In preparing the polymers of this invention according to the usual emulsion polymerization techniques, it is preferable to control the molecular weight of the polymer by addition of small amounts of a chain transfer such as dodecylmercaptan. In general, from about 0.04% to 1.0%, based on total weight of monomers, is used.
• the polymers having lower molecular weight, i.e., those resulting when the amount of dodecylmercaptan is nearer 1.0% generally have somewhat better soil resistance than the polymers of higher molecular weight, i.e., those resulting when the amount of dodecylmercaptan is nearer 0.04% or is entirely absent.
• the emulsion polymerization is otherwise quite standard.
• the monomers are preemulsified in water using a suitable emulsifying agent, the initiator is added, polymerization is initiated by heating and heating is continued until polymerization is complete.
• Any emulsifying agent which does not interfere with polymerization may be used.
• cationic agents such as either the quaternary salts [R'N(CH +X- or the acid salts [RN(CH -HX are used. In both cases R is a longer chain alkyl group, of from about 12 to 20 carbons, and X is a water solubilizing cation such as halide ion, acetate ion, etc.
• Any water soluble initiator may be used; the water soluble azo compounds such as azobis(isobutyramidine)dihydrochloride are preferred.
• the polymers of this invention are generally applied to textiles as aqueous emulsions by spraying, dipping, padding or other well-known methods. After excess liquid has been removed, for example, by squeeze rolls, the treated fabric is dried, then cured by heating, e.g., at 275 to 380 F. for at least 40 seconds. As will be seen in Example 3, it is not necessary to cure the treated fabrics to obtain oil repellency as such develops on merely drying. The curing does, however, increase durability and hence is desirable.
• the polymers of this invention can be coapplied with other adjuvants such as textile resins, water-repellents and other additives often added to textiles if so desired.
• other adjuvants such as textile resins, water-repellents and other additives often added to textiles if so desired.
• Such other additives which detract from dry soil resistance, however, should be avoided when maximum soil resistance is desired.
• Dry soil resistance is particularly important on textiles coming in contact with dirt and rubbing action such as upholstery of all kinds.
• a particularly important use for the polymers of this invention is on automobile upholstery, particularly the nylon tricot variety.
• the fiuorinated monomer in all cases had the structure ⁇ Vhel'ein n is 4, 6, 8, 10 and 12 in the weight ratio 35/30/18/8/3, average molecular weight 522, prepared by following the procedure of Example II of Fasick and Raynolds, U.S. Patent 3,282,905, using the alcohols CF CF(CF- CH CH H These alcohols were prepared by utilizing the procedure of Parsons, U.S. Patent 3,234,294 to prepare CF CF CF ),,I
• esters may be prepared from the iodides CF CF (CF ,CH CH I using the procedure of Fasick, U.S. Patent 3,239,557.
• Example l Several polymers were prepared using the procedure below and having the compositions shown in Table'I. The procedure is as follows:
• the resulting emulsion of monomers was purged with nitrogen for one hour, then added to 200 parts air-free deionized water along with 66 parts of water rinse. Then 0.503 part commercial Z-hydroxyethyl methacrylate, 0.840 part of a by weight aqueous solution of N-methylol acrylamide and dodecylmercaptan as indicated in Table I were added. After the resulting mixture was heated at C. for 0.5 hour, a mixture of 0.08 part azobis(isobutyramidine)dihydrochloride in 0.25 part water was added to initiate the polymerization. The temperature was allowed to adjust to C. and the reaction mass was maintained for 4 hours with agitation. The mass was then cooled to ambient temperature, giving an emulsion containing about 25% by weight polymer. The monomer ratio in the polymers was the same as the ratio of monomers used.
• Example 2 Each of the above-prepared emulsions were diluted with water to contain sufiicient polymer to provide 6.21%
• CF3CF2 CH CH O CC CH2 in polymerized form in the emulsion, i.e., all emulsions then had equal fluorine content.
• Each emulsion was padded on nylon tricot automobile upholstery at 1.5% on weight of fabric of the emulsion, i.e., 0.093% polymerized 0n of fabric.
• Each pad bath also contained 0.06% Mykon NRW3, a non-rewetting thermally unstable nitrogen compound, Sun Chemical Corp., and 3.0% isopropyl alcohol on weight of bath. The treated nylon samples were then dried and cured at 380 F. for 100 seconds.
• Scotchgard FC-214 a product of Minnesota Mining and Manufacturing Co., at 0.45% on weight of fabric of each of the two components parts A and B of said Scotchgard product, the Mykon NRW 3 and isopropyl alcohol being the same as above.
• the treated nylon was cured in the same manner as above.
• Water repellencies of the treated fabrics were determined using Test Method 22l964 of the American Association of Texile Chemists and Colorists. A rating of 100 denotes no water penetration or surface adhesion, a
• Oil repellency was determined by Test Method 118- 1966T of the A.A.T.C.C., this test comprises placing a drop of test solution carefull on the textile on a flat horizontal surface. After thirty seconds, any penetration or wicking into the fabric is noted visually.
• the nature of the test solutions is shown below; Nujol, of course, is a purified petroleum oil. Anything with a rating of five or greater is good or excellent, anything with a rating of one or over can be used for certain purposes. As an example, if a treated fabric repels the Nos. 1-6 solutions but not the number 7 solution, its rating is 6.
• a sample, 5 x 5 inches, of each treated fabric is prepared.
• a light reflectance reading is taken using the Colormaster Differential Colorimeter, Meeco Instrument Manufacturing and Engineering Equipment Corp., Warrington, Pa., using the filter which gives the highest reflectance reading.
• a 5 x 5 inch card stock template having a 1 x 1 inch square hole in the center is then placed on the sample and 0.1 g. of synthetic soil is applied through a 40 mesh sieve.
• the sample, template and covering 96 x 100 thread white cotton cloth are then clamped to a 4 x 6 x 4 inch urethane foam block and placed in a pilling tester (Custom Scientific Instruments, Inc., Arlington, N.J., catalog No. CS-53041).
• a 2 x 2 x inch urethane foam block covered with the same cotton cloth is placed in the floating rack.
• the floating block is passed back and forth over the covered test sample for two minutes.
• the pilling tester machine requires modification to take the urethane foam blocks.
• Loose soil is then removed from the sample by holding a 50 psi. air nozzle on the fabric and moving it back and forth over the fabric once each in the warp and filling directions. A reflectance reading is then taken in the soil area.
• the percent soiling is then determined by the equation percent soiling: R
• R is reflectance before soiling and R after soiling.
• the synthetic soil was the so-called Cyanamide Soil" and had the following composition:
• Formulations 1 and 2 were padded on nylon auto fabric at the indicated concentrations.
• Formulation 3-6 were padded on Thermosol dyed 65/35 polyester/ cotton poplin and undyed, mercerized cotton poplin.
• the treated fabric samples were placed in a curing oven heated at 275 F. for varying periods of time.
• the samples of fabric were then air dried at room temperature to constant weight and tested for oil and water repellency by the methods described earlier. The results are shown in Table III below:
• polymer 1- which is within the scope of this invention, rapidly develops oil repellency on all three fabrics whereas polymer 1-K, based on methyl methacrylate and without the scope of this invention, does not.
• polymer 1-K based on methyl methacrylate and without the scope of this invention, does not.
• the nylon fabric takes about 20 seconds to dry in the oven, the polyester/cotton about 40 seconds to dry and the cotton poplin even longer.
• the fabric temperature will not exceed 212 F., the boiling point of water, until the fabric is dry.
• oil repellency develop merely by drying since it provides the treated textile with protection prior to cure hence prevent damage due to accidental contact with oils during handling. It is entirely unexpected that changing from a methyl acrylate monomer to methyl methacrylate monomer should have such marked effect.
• An oiland Water-repellent and dry soil resistant aqueous emulsion polymer consisting essentially of (a) from about 70 to 95 parts of units derived from monomers having the structure R CH CH O CC CH3 CH2 where R; is a perfluoroalkyl group of 4 to 14 carbon atoms;
• R is H or CH said polymer having been prepared in the presence of from 8 about 0.04% to 1.0% of a chain transfer agent based on the total weight of the monomers.
• An aqueous emulsion polymer according to claim 1 consisting essentially of (a) about parts of units derived from R CH CH O CC ZCHZ (b) about 15 parts of units derived from methyl acrylate, and r (c) a mixture of about 0.25 part of units derived from N-methylol acrylamide and 0.25 part of units derived from 2-hydroxyethyl methacrylate.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic 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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Cited By (33)

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• 1970
  • 1970-01-29 US US3645990D patent/US3645990A/en not_active Expired - Lifetime
• 1971
  • 1971-01-13 CA CA102,705A patent/CA959595A/en not_active Expired
  • 1971-01-19 GB GB254071A patent/GB1327744A/en not_active Expired
  • 1971-01-27 BE BE762088A patent/BE762088A/xx unknown
  • 1971-01-28 FR FR7102880A patent/FR2077395B1/fr not_active Expired
  • 1971-01-29 NL NL7101232A patent/NL7101232A/xx unknown
  • 1971-01-29 DE DE2104267A patent/DE2104267C3/de not_active Expired
  • 1971-01-29 CH CH134571A patent/CH547831A/xx not_active IP Right Cessation

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