US3645989A - Fluorinated oil- and water-repellent and dry soil resistant polymers - Google Patents

Fluorinated oil- and water-repellent and dry soil resistant polymers Download PDF

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Publication number
US3645989A
US3645989A US3645989DA US3645989A US 3645989 A US3645989 A US 3645989A US 3645989D A US3645989D A US 3645989DA US 3645989 A US3645989 A US 3645989A
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water
polymer
polymers
dry
monomers
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Thomas King Tandy Jr
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EIDP Inc
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EI Du Pont de Nemours and Co
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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
    • 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

  • a second problem is that many of these fiuorinated polymer-treated textiles lose their oil and water repellency after laundering when the textile is dried in air at ambient temperatures.
  • the repellency can in large part be restored by heating as, for example, during pressing or during drying in a heated drier.
  • This lack of repellency after the so-called home wash-air dry laundering has greatly affected usefulness of the fluorinated oiland water-repellents in the permanent press garment market, for example, where the entire purpose of the permanent press treatment is to obviate the necessity for pressing or heated drying.
  • a second facet of this problem is, of course, that the laundered fabrics lack any protection provided by oil repellency in particular bet-ween laundering and the pressing or heated drying which otherwise restores repellency.
  • the polymers of this invention continue to impart oil and water repellency to textiles after laundering and air drying.
  • 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 difiicult to remove the particulate matter.
  • Novel fluorinated polymers have now been discovered which, when used in treating textile fabrics, display the desired properties and qualities such as imparting oil repellency prior to curing maintaining this repellency even after laundering or washing 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.
  • R is H or CH
  • the amount of units derived from these monomers which will be used may vary from 0 to 1 part per 100 parts of the other two monomers.
  • These polymers preferably have an inherent viscosity as a 0.5% solution in trichlorotriiluoroethane at 30 C. of from 0.2 to 3.
  • the periluoroalkyl 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 508 moles wt. These are preferred since mixtures of these groups are commercially available, financially practical and give the best results. Branched or other straight chain perfiuoroalkyl 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 40 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.
  • N-hydroxyalkyl acrylamides of structure CH CRCONHCH OH, hydroxyalkyl acrylic esters of structure CH CRCO CH CH OH and mixtures thereof, wherein R is H or CH
  • the monomers which are used and are commercially available are N-methylol acrylamide, N-methylol methacrylarnide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and of these, N-methylol acrylamide and 2-hydroxyethyl methacrylate are preferred.
  • About 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 must be emulsion polymers, that is, prepared by an emulsion polymerization technique.
  • Emulsion polymerization means that the monomers are emulsified in water with a suitable emulsifying agent and are caused to polymerize with a water soluble initiator.
  • the molecular weight of the polymer is controlled by addition of small amounts of a chain transfer such as dodecylmercaptan.
  • a chain transfer such as dodecylmercaptan.
  • 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 emulsfying agent which does not interfere with polymerization may be used.
  • cationic agents such as either the quaternary salts [RN(CH ]+X- or the acid salts [RN(CH -HX are used.
  • R is a longer chain alkyl group, of from about 12 to carbons
  • 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 inherent viscosities of the polymers of this invention be from 0.2 to 3, when measured at C. as 0.5% solutions in trichlorotrifluoroethane.
  • Inherent viscosity is determined by the formula 1 V V; 6 1D where V, is the inherent viscosity, C is the polymer concentration in grams per 100 ml. of solution, V is the viscosity of the solution, V is the viscosity of the solvent and In is the natural logarithm.
  • the polymer emulsions obtained by the above procedures are usually used directly in the pad bath without isolation of the polymer.
  • the dry fabric is oil and water repellent without further heating but such further heating may increase the degree of repellency somewhat.
  • the textile material will retain repellency even after many launderings or drycleanings.
  • Suitable substrates for application of the polymers of this invention are fibers, yarns, fabrics and articles made of filaments, fibers or yarns derived from natural, modified natural or synthetic polymeric materials or from blends of these.
  • Examples are cotton, silk, regenerated cellulose, nylon and like synthetic polyamides, fiber-forming linear polyesters, fiber-forming polyacrylonitrile and modified acrylonitrile polymers, cellulose nitrate, cellulose acetate, fiberglass and the like.
  • These may be in many forms of knit and woven fabrics including sateen, poplin, broadcloth, jean cloth gabardine, upholstery materials as well as nonwoven fabrics and the like used to fabricate rainwear, work clothing, suiting, female apparel, renting, autobody tops, furniture upholstery, draperies and a variety of others.
  • a 60% by weight monomer emulsion in water containing by weight C1248 alkyl trimethylammonium chloride was prepared by combining R CH CH O CCH CH2 methyl acrylate and water with high speed agitation. The mixture was then further agitated for ten minutes and diluted with water to 50% monomer concentration. The 50% emulsion was purged with nitrogen for one hour, then the desired amounts of N-methylolacrylamide (as a 60% aqueous solution) and 2-hydroxyethyl methacrylate were added along with a small amount of dodecylmercaptan (0.075 to 0.20%). The resulting emulsion was then further diluted to 25% concentration, heated to 65 C.
  • percent OWF percent bathx percent wet pickup/ 100.
  • Water repellencies of the treated fabrics were determined using Test Method 22-1952 of the American Association of Textile Chemists and Colorists. A rating of 100 denotes no water penetration or surface adhesion, a rating of 90 denotes slight random sticking or wetting and so on.
  • Oil repellency test comprises placing a drop of test solution carefully on the textile on a fiat horizontal surface. After three minutes, any penetration or wicking into the fabric is noted visually. To aid in the observation, the test solutions in some cases contained a small amount of oil-soluble blue dye to increase visibility.
  • Nujol of course, is a purified petroleum oil. Anything with a rating or 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 No. 1-6 solutions but not the number 7 solution, its rating is 6.
  • A hexadecy1trimethyl ammonium chloride
  • B oetadecyldimethylamine acetate
  • C octadecyltrimetl1yi ammonium chloride.
  • the dry-cleaning test consists of agitating the sample for 120 minutes in tetrachloroethylene containing 1.5% (weight/volume) of a commercial dry-cleaning detergent (R. R. Street Co., 886 Detergent), extraction with tetrachloroethylene, drying for three minutes at 66 C. in a drum and followed by a 15 second pressing at 149 C. on each side of the fabric.
  • a commercial dry-cleaning detergent R. R. Street Co., 886 Detergent
  • a sample, x 5 inches, of each tested 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 rfilter which gives the highest refiectance reading.
  • a 5 x 5 inch card stock template having 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 inch urethane foam block and placed in a pilling tester (Custom Scientific Instruments, Inc., Arlington, N.J., catalog No. (TS-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 file directions.
  • a reflectance reading is then taken in the soil area.
  • the synthetic soil was the so-called Cyanamide Soil and had the following composition:
  • EXAMPLE 2 A formulation was prepared as described above having the following composition: a
  • Permanent press Component Percent OWF Permanent press resin 12.0. Catalyst 2.3. Stabilizer d 0.04. Polymer emulsion As indicated.
  • EXAMPLE 3 Formulation B.--Crease resistant finish
  • EXAMPLE 5 The formulations of Examples 2-4 were used to pad various materials which were then tested for dry-soiling resistance. The results are shown in Table V below. It
  • Percent OWF should :be noted that for purposes of comparision two a polymers were utilized in these formulations, I-15 wh1ch Crease resistant resin 2.0. catalystb 02 is within the scope of the invention and I-20 WhiCh 1s Isopropanol c 3.0. Acetic acid 5 TABLE V Stabilizer c 0.04.
  • Formulation C Plain finish Component percent OWF Isopropanol a 3.0. Polymer dispersion As indicated.
  • An oiland water-repellent and dry soil resistant polymer consisting essentially of (a) from about 60 to 95 parts of units derived from monomers having the structure RfCHgCHg where R is a perfiuoroalkyl group of 4 to 14 carbon atoms;
  • a polymer according to claim 1 wherein R, in the units defined in part (a) of claim 1 has the formula CF CF (CF wherein n has the numerical values 4, 6, 8, and 12 present in the approximate weight ratio 35/30/18/8/3.
  • a polymer according to claim 1 consisting essentially of (a) about -90 parts of units derived from References Cited UNITED STATES PATENTS 4/1968 Fasick et al. 260-890 8/1969 Raynolds et al ll7161 JOSEPH L. SCHOFER, Primary Examiner S. M. LEVIN, Assistant Examiner US. Cl. X.R.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US3645989D 1970-01-29 1970-01-29 Fluorinated oil- and water-repellent and dry soil resistant polymers Expired - Lifetime US3645989A (en)

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BE (1) BE747062A (enExample)
DE (1) DE2011339A1 (enExample)
FR (1) FR2074828A5 (enExample)
GB (1) GB1261152A (enExample)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3753716A (en) * 1972-02-04 1973-08-21 Konishiroku Photo Ind Method for antistatic treatment of plastic films
US3879490A (en) * 1973-05-03 1975-04-22 Thiokol Corp Inherently mold-releasable mold or casting composition
US3880949A (en) * 1973-05-03 1975-04-29 Thiokol Chemical Corp Inherently mold-releasable mold or casting composition
US3916053A (en) * 1971-09-12 1975-10-28 Minnesota Mining & Mfg Carpet treating and treated carpet
US3940359A (en) * 1974-05-08 1976-02-24 E. I. Du Pont De Nemours And Company Soil-repellent coating compositions
US3943112A (en) * 1971-08-31 1976-03-09 E. I. Du Pont De Nemours And Company Copolymers of polyhalogenated isocyanates
US4007305A (en) * 1974-12-23 1977-02-08 Basf Wyandotte Corporation Method of imparting nondurable soil release and soil repellency properties to textile materials
US4059688A (en) * 1976-06-29 1977-11-22 Clairol Incorporated Hair fixing compositions containing fluoroterpolymers and method
US4100340A (en) * 1976-03-08 1978-07-11 Hoechst Aktiengesellschaft Copolymers containing perfluoroalkyl groups
US4296224A (en) * 1978-09-28 1981-10-20 Daikin Kogyo Co., Ltd. Perfluoroalkyl-acr[methacr]ylate, hydroxy-chloropropyl-acrylate polymer
US4424325A (en) 1980-05-27 1984-01-03 Daikin Kogyo Co., Ltd. Photosensitive material
US4504642A (en) * 1981-09-10 1985-03-12 Daikin Kogyo Co., Ltd. Acrylic type self-adhesive
US4925906A (en) * 1989-01-03 1990-05-15 Allied-Signal Inc. Stain-resistant polymers derived from the itaconic acid useful as coatings for fibers
US5006408A (en) * 1989-01-03 1991-04-09 Allied-Signal Inc. Stain-resistant polymers derived from itaconic acid useful as coatings for fibers
US5149754A (en) * 1989-01-03 1992-09-22 Allied-Signal Inc Stain-resistant polymers derived from itaconic acid useful as coatings for fibers
US5153046A (en) * 1990-05-24 1992-10-06 E. I. Du Pont De Nemours And Company Fluorochemical composition for imparting antisoiling protection and lubricity to textile fibers
US20030008585A1 (en) * 1995-03-21 2003-01-09 Hi-Tex, Inc. Treated textile fabric
US6541138B2 (en) 1996-08-07 2003-04-01 Hi-Tex, Inc. Treated textile fabric
US20070021019A1 (en) * 2005-07-21 2007-01-25 Hi-Tex, Inc. Treated textile fabric
US20070149075A1 (en) * 2004-12-22 2007-06-28 O'rear Edgar A Method for making an article hydrophobic and oleophobic as well as articles made therefrom and their use
WO2007080055A3 (en) * 2006-01-10 2007-09-07 Clariant Int Ltd Fluorous telomeric compounds and polymers containing same
US20100224817A1 (en) * 2007-10-11 2010-09-09 Unimatec Co., Ltd. Water-and oil-repellent

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000144119A (ja) 1998-08-31 2000-05-26 Asahi Glass Co Ltd 水系防汚加工剤組成物とその製造方法およびそれで処理された被処理物

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3943112A (en) * 1971-08-31 1976-03-09 E. I. Du Pont De Nemours And Company Copolymers of polyhalogenated isocyanates
US3916053A (en) * 1971-09-12 1975-10-28 Minnesota Mining & Mfg Carpet treating and treated carpet
US3753716A (en) * 1972-02-04 1973-08-21 Konishiroku Photo Ind Method for antistatic treatment of plastic films
US3879490A (en) * 1973-05-03 1975-04-22 Thiokol Corp Inherently mold-releasable mold or casting composition
US3880949A (en) * 1973-05-03 1975-04-29 Thiokol Chemical Corp Inherently mold-releasable mold or casting composition
US3940359A (en) * 1974-05-08 1976-02-24 E. I. Du Pont De Nemours And Company Soil-repellent coating compositions
US4007305A (en) * 1974-12-23 1977-02-08 Basf Wyandotte Corporation Method of imparting nondurable soil release and soil repellency properties to textile materials
US4100340A (en) * 1976-03-08 1978-07-11 Hoechst Aktiengesellschaft Copolymers containing perfluoroalkyl groups
US4059688A (en) * 1976-06-29 1977-11-22 Clairol Incorporated Hair fixing compositions containing fluoroterpolymers and method
FR2356412A1 (fr) * 1976-06-29 1978-01-27 Bristol Myers Co Composition fixant la chevelure contenant des fluoroterpolymeres et procede pour les utiliser
US4296224A (en) * 1978-09-28 1981-10-20 Daikin Kogyo Co., Ltd. Perfluoroalkyl-acr[methacr]ylate, hydroxy-chloropropyl-acrylate polymer
US4424325A (en) 1980-05-27 1984-01-03 Daikin Kogyo Co., Ltd. Photosensitive material
US4504642A (en) * 1981-09-10 1985-03-12 Daikin Kogyo Co., Ltd. Acrylic type self-adhesive
US5006408A (en) * 1989-01-03 1991-04-09 Allied-Signal Inc. Stain-resistant polymers derived from itaconic acid useful as coatings for fibers
US4925906A (en) * 1989-01-03 1990-05-15 Allied-Signal Inc. Stain-resistant polymers derived from the itaconic acid useful as coatings for fibers
US5149754A (en) * 1989-01-03 1992-09-22 Allied-Signal Inc Stain-resistant polymers derived from itaconic acid useful as coatings for fibers
US5153046A (en) * 1990-05-24 1992-10-06 E. I. Du Pont De Nemours And Company Fluorochemical composition for imparting antisoiling protection and lubricity to textile fibers
US6884491B2 (en) 1995-03-21 2005-04-26 Hi-Tex, Inc. Treated textile fabric
US20030008585A1 (en) * 1995-03-21 2003-01-09 Hi-Tex, Inc. Treated textile fabric
US6541138B2 (en) 1996-08-07 2003-04-01 Hi-Tex, Inc. Treated textile fabric
US20040018787A1 (en) * 1996-08-07 2004-01-29 Hi-Tex, Inc. Treated textile fabric
US20070149075A1 (en) * 2004-12-22 2007-06-28 O'rear Edgar A Method for making an article hydrophobic and oleophobic as well as articles made therefrom and their use
US7906177B2 (en) * 2004-12-22 2011-03-15 The Board Of Regents Of The University Of Oklahoma Method for making an article hydrophobic and oleophobic as well as articles made therefrom and their use
US20070021019A1 (en) * 2005-07-21 2007-01-25 Hi-Tex, Inc. Treated textile fabric
US7531219B2 (en) 2005-07-21 2009-05-12 Hi-Tex, Inc. Treated textile fabric
WO2007080055A3 (en) * 2006-01-10 2007-09-07 Clariant Int Ltd Fluorous telomeric compounds and polymers containing same
US20100224817A1 (en) * 2007-10-11 2010-09-09 Unimatec Co., Ltd. Water-and oil-repellent
US8680223B2 (en) * 2007-10-11 2014-03-25 Unimatec Co., Ltd. Water-and oil-repellent

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DE2011339A1 (de) 1971-08-05
BE747062A (fr) 1970-08-17
GB1261152A (en) 1972-01-26
FR2074828A5 (enExample) 1971-10-08

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