US3646153A - Synthetic fibers having improved soil and stain repellency - Google Patents

Synthetic fibers having improved soil and stain repellency Download PDF

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US3646153A
US3646153A US867368A US3646153DA US3646153A US 3646153 A US3646153 A US 3646153A US 867368 A US867368 A US 867368A US 3646153D A US3646153D A US 3646153DA US 3646153 A US3646153 A US 3646153A
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additive
fiber
formula
prepared
fibers
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Bryce C Oxenrider
Cyril Woolf
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Honeywell International Inc
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Allied Chemical Corp
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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
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/712—Monoisocyanates or monoisothiocyanates containing halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • This invention relates to synthetic fibers having improved soil and stain repellency.
  • the present method used to impart soil and stain repellency to fabrics involves coating the fabric with an oil and water repellent compound.
  • the coating is applied using common textile finishing techniques, such as treating the fabric with a padding bath of a solution or aqueous dispersion of the compound or spraying the surface of the fabric with the compound.
  • the operation represents a separate step which must be performed upon a fabric after it has been dyed or printed.
  • a subsequent curing step is normally required to set the coating.
  • the coating is present on the fabric as a distinct phase which is subject to removal. Soil which penetrates the coating is not easily removed by laundering or dry celaning because the soild becomes trapped beneath the coating.
  • Another drawback of the present method is the difficulty inherent therein of applying a uniform coating to the fabric.
  • the coating tends to be distributed unevenly on the fabric and to form globules thereon.
  • a principal advantage of this invention is that oil and stain repellency can be 3,646,153 Patented Feb. 29, 1972 readiy imparted directly to the fiber by the fiber manufacturer, thereby eliminating the need for the manufacturer of the ultimate textile product to apply a repellent coating to the fabric.
  • the additive is added to the resin in an amount ranging from about 0.1 to about 2%, preferably about 0.5 to 1.5%, based on the weight of the resin.
  • This small amount of additive causes a substantial lowering of the surface energy of the fiber, which is a direct measure of the ability of the fiber to repel oil and water borne soil and stain.
  • a fiber of unmodified nylon-6 normally has a surface energy of about 46 dynes/cm.
  • a fiber of nylon-6 containing 1% of an additive of this invention has a surface energy which is only slightly more than that of the additive itself (the additives have surface energies ranging from about 10 to 20 dynes/cm.).
  • the additive migrates to the surface of the fiber as the fiber is extruded to form a boundary layer between the rest of the fiber system and that which contacts the fiber.
  • This boundary layer is not permanently removed by scouring, laundering, dry cleaning or dyeing, which indicates that it is stable to use conditions.
  • the fiber can be dyed just like the unmodified fiber, which is surprising in view of the repellent nature of the layer.
  • the fiuorocompound additives of this invention are characterized in their molecular structure in having from one to four fiuoroalkyl groups, which provide the repellency, pendent from an organic radical which serves to make the additive dispersible in the resin.
  • the additive is amphipathic in that one segment of the molecule has an aflinity for the resin substrate while the remainder of the molecule, containing the perfiuoroalkyl groups, is essentially repellent in nature.
  • the terms dispersed and dispersible are used herein to indicate that the additive and the resin together form a macroscopically homogeneous single phase which behaves substantially like the resin alone in processing and in forming filaments.
  • the additive can be present in the resin as 1) a solution of the additive in the resin, (2) a random distribution of additive particles throughout the resin, or (3) a concentration of additive particles near the surface of the resin.
  • the fiuoroalkyl group is the more critical portion of the molecule and has the formula:
  • Y is selected from the group consisting of F C and radicals having the formula wherein R and R are fluorine or perfiuoroalkyl groups having from one to two carbon atoms, provided that not more than three of the R and R groups are perfluoroalkyl groups. R and R are preferably fluorine. Preferred results are obtained when the total number of perfluorinated carbon atoms in each fluoroalkyl group is from 5 to and the total number of fluoroalkyl groups is at least two.
  • the 'fiuoroalkyl group is sometimes referred to hereinafter as R;.
  • the fluoroalkyl groups are pendent from an organic radirml which makes the additive dispersible in the resin.
  • the resin is normally basically a hydrocarbon containing functional groups, such as amide and ester linkages
  • dispersibility in the resin is achieved by having the organic radical portion of the additive molecule be of such structure as to effect chemical association, such as hydrogen bonding, between the resin and the organic radical portion.
  • the organic radical can contain other atoms, such as oxygen forming an ether linkage, which do not interfere with the dispersibility desired to be effected.
  • the additive must also possess certain physical properties.
  • the additive must be substantially thermally stable at the temperature at which the filament is extruded. This temperature normally is within the range of 200 to 350 C.
  • An additive is thermally stable if it survives the extrusion process without forming undesirable decomposition products and without decomposing to such an extent as to lose an appreciable amount of effectiveness in imparting soil and stain repellency to the filament.
  • the additive In addition to being thermally stable, the additive must also be nonfugitive, i.e., not appreciably volatile, at the temperature of extrusion, otherwise it would escape from the filament.
  • the additive must itself have a low surface energy in order to impart a low surface energy to the filament. To be suitable, the additive must have a surface energy of less than 20 dynes/ cm.
  • R is hydrogen, trichloromethyl, or a phenyl radical
  • aralk'yl or aralkylene diradical of 6 to 13 carbon atoms
  • esters derived from acids having the formula R COOH wherein the Y group of the R; component is F C are well known materials and can be made Maximum Surface use temperenergy, Class B: R ature, C. dynes/em.
  • the cyclic anhydride reactants are well known materials.
  • the triaza reactants are readily prepared by reacting a lower alkyl ester of an acid having the formula R;COOI-I with an amine having the formula z 2) z 2) z z from the acids, which are generally available commercially.
  • Acids wherein Y has the formula can be prepared from a telomer halide having the formula wherein R and R have the afore-stated meanings, w and x are integers indicating the respective degrees of telomerization, and E is bromine or iodine.
  • the telomer halides are prepared by reacting telogens of the formula 1 FRg FOCFgCF- E with telomerizable unsaturated compounds, i.e., tetrafiuoroethylene and ethylene, the reaction being initiated by heat or free radical catalyst.
  • the telogens are prepared by reacting the corresponding perfluorinated ketone with an ionizable fluoride salt, e.g. CsF, to form the corresponding organic salt, and then reacting the organic salt with tetrafluoroethylene and either bromine or iodine. Preparation of the telogens is described in greater detail in US. Pat. No. 3,453,333.
  • Acids having the formula wherein n is can be prepared by reacting the corresponding telomer halide with ICN or (CN) at pressures above atmospheres and at temperatures above 300 C. to form the nitrile, followed by hydrolysis of the nitrile in accordance with conventional methods to form the acid.
  • Acids wherein n is greater than zero can be prepared by reacting the corresponding telomer halide with an alkali metal cyanide in the presence of dimethyl sulfoxide at temperatures between 60 and 100 C. to form the nitrile, from which the acid can be prepared in accordance with conventional methods.
  • the acid can also be prepared (-regardless of whether 11 is O or greater) by reacting the telomer halide with sulfur trioxide, followed by hydrolysis of the reaction product to obtain the acid.
  • the acid contains one less carbon atom than the telomer halide from which it was prepared.
  • the acid thus formed can be converted to the corresponding telomer iodide for further telomerization by reaction with alkali-free silver oxide to form the silver salt, followed by reaction of the silver salt with powdered iodine to form the telomer iodide.
  • acids having either an odd or even number of hydrocarbyl or fluorocarbyl groups can be prepared.
  • the additives of Class B are prepared by reacting the triaza compound referred to above with a diacid chloride having the formula ClOCRCOCl, where R has the meaning previously given for the additives of Class B, with the exception that R is not a dicarboxy phenyl radical.
  • R has the meaning previously given for the additives of Class B, with the exception that R is not a dicarboxy phenyl radical.
  • R is a dicarboxy phenyl radical having the formula pyromellitic anhydride is used as the reactant in place of a diacid chloride.
  • the reaction is carried out in an inert solvent, such as acetone, at temperatures ranging from room temperature up to the reflux temperature of the reaction mixture.
  • the additives of Class B, as novel compositions of matter, are the subject of copending application S.N. 867,373, filed concurrently herewith, the pertinent subject matter of which is incorporated herein by referonce.
  • the additives of Class C are prepared by reacting a compound of the formula R CN with trioxane in the presence of a catalytic amount, about 1% by weight, of a strong acid, such as H 80
  • a catalytic amount about 1% by weight
  • H 80 a strong acid
  • Nitrile reactants having the formula CF (CF (CH CN) are known compounds and can be prepared from commercially available materials in accordance with known methods.
  • Nitrile reactants having the formula can be prepared from telomer halides in accordance with the methods described in the penultimate paragraph above, which methods are described in greater detail in Canadian Patents 823,673 and 823,674, corresponding to US. S.N. 721,115 and 721,l17, respectively, both US. applications having been filed on Apr. 12, 1968, the pertinent subject matter of which is incorporated herein by reference.
  • 'lhe additives of Class D are prepared by reacting a nitrile of the formula R CN with an aldehyde of the formula RCHO, wherein R has the meaning previously given for the additives of Class D, in the presence of an acid catalyst.
  • Additives having the formula RfCONHCHZNHCORf are obtained as lay-products in the preparation of the additives of Class C.
  • the additives of Class D, as novel compositions of matter, are the subject of copending application S.N. 867,372, filed concurrently herewith, the pertinent subject matter of which is incorporated herein by reference.
  • the additives of Class E are prepared by reacting tris(2- carboxyethyl)isocyanurate with an alcohol of the formula R OH under anhydrous conditions, using as a solvent a perfiuorocarboxylic acid having up to 8 carbon atoms.
  • the reaction product contains a mixture of mono, diand triesters.
  • the additives of Class F are prepared by reacting tri- (2-hydroxyethyl)isocyanurate with an acid having the formula R,COOH under anhydrous conditions using an inert solvent.
  • the reaction product contains a mixture of mono, diand triesters.
  • the substituted urea additives of Classes G, H, and I are readily prepared by refluxing the triaza compound previously referred to with the appropriate isocyanate or diisocyanate in a solvent such as acetone.
  • a solvent such as acetone.
  • the appropriate isocyanate or diisocyanate compounds are well known in the art.
  • the additives of Class I are prepared in accordance with the method used to prepare the additives of Class B using oxalyl chloride as the diacid chloride reactant.
  • the filaments of the invention are prepared by forming an intimate blend of the additive and the resin and then extruding the blend into filaments in accordance with methods known to the art.
  • the method of forming the blend is not critical.
  • the blend can be formed by treating the resin in powder form with a solution of the additive and then extruding and pelletizing the treated resin after it has been allowed to dry.
  • Another method of forming the blend comprises dry blending the additive with the resin in powder form and then working the mixture on a rubber mill or similar device.
  • the incorporation of the additive into the resin does not interfere with the formation of the filament or fibers drawn therefrom.
  • the fiuoroalkyl groups of the additive tend to render the additive incompatible with the resin, the additive does not disturb the normal macroscopic homogeneity of the polymer phase. This is surprising in view of the critical rheological conditions involved in the extrusion of filaments and the drawing of fibers.
  • the additive can be present in the filament in any of the following ways: (a) as finely dispersed, randomly distributed particles in the resin matrix, (b) as finely dispersed particles concentrated at the fiber surface, (c) as an invisible solution in the resin matrix. But regardless of how the additive is present, it effectively imparts antisoiling and antistaining properties to the filament.
  • the surface energy of the filament can be lowered even further by annealing the filament after it has been extruded.
  • Annealing increases the mobility of the additive and allows it to migrate to the surface of the filament.
  • Annealing is preferably carried out at the highest practical temperature, which is normally just below the temperature at which degradation of the fiber occurs, and for an optimum period which can readily be determined for each particular fiber by simple experiment. For fibers prepared from nylon-6, the preferred period is two to four hours. Annealing is normally performed in an inert atmosphere, such as nitrogen, to prevent oxidative degradation of the fiber.
  • This invention is generally applicable to filaments prepared from any fiber-forrning thermoplastic resin, such as polypropylene, polyamide, polyester, polyacrylonitrile and blends thereof. Particularly good results are obtained with polyarnide and polyester resins (including blends thereof), especially with polyamide resins.
  • thermoplastic resin such as polypropylene, polyamide, polyester, polyacrylonitrile and blends thereof.
  • nylon-6 or nylon-66 is the resin
  • especially preferred results are obtained using the additive l,7-bis(4- perfluoroisopropoxybutyryl) -1,4,7-triazaheptane monoglutaramide.
  • Example 1 Preparation of additive.-60.4 grams of 1,7 bis(4-perfluoroisopropoxybutyryl) 1,4,7 triazaheptane were dissolved in 250 ml. of acetone. To this solution was added a solution of 8.35 grams of glutaric anhydride in 100 ml. of acetone. The reaction mixture was stirred at 50 C. for one hour, then cooled and diluted with water.
  • the product layer was dissolved in ether, washed with water, treated with charcoal and finally dried over MgSO
  • the product obtained after evaporation of the ether solution was 1,7 bis(4-perfluorois0propoxybutyryl) 1,4,7 triazaheptane monoglutaramide, a waxy solid having a melting point of 80 C., and was obtained at a yield of about 100%.
  • the surface energy of unmodified nylon-6 fiber is about 46 dynes/cm.
  • the surface energy of a fiber directly reflects its ability to repel oil and water borne soil and stain.
  • the lower surface energy of the 60 denier fiber is presumably due to the more favorable surface to volume ratio of the fiber, which allows a greater concentration of the additive at the surface.
  • Photomicrographs of the fibers revealed no visible additive particles, indicating that the additive was either dissolved or very finely dispersed in the resin matrix.
  • Annealing at l20l50 C. for two to four hours in an inert atmosphere caused a lowering of the surface energy of the undrawn 16 and 8 denier fibers to 18-22 dynes/cm. and 25-27 dynes/cm. respectively. This indicates that the additive is capable of migrating through the resin matrix to the surface.
  • the fibers were dyed according to standard procedures using various commercially available dyes, such as Necelan Blue FFRD, C. I. Disperse Blue 3 and Kiton Fast Blue CB. It was found that the fibers containing the additive were as receptive to the dye as unmodified fibers and that the dye was just as colorfast when the fibers were subjected to laundering and drycleaning. Furthermore, dyeing had no adverse effect on the surface energy on the fibers containing the additive.
  • various commercially available dyes such as Necelan Blue FFRD, C. I. Disperse Blue 3 and Kiton Fast Blue CB.
  • a test cloth was prepared using the 15 denier fiber and the ability of the cloth to resist common household stains, including catsup, French dressing, spinach, chocolate and hot coffee, was compared with that of a control cloth prepared from unmodified nylon-6 fiber.
  • the cloth prepared from the modified fiber had better stain resistance and also exhibited better stain release during subsequent laundermg.
  • Example 2 Preparation of additive-To 202 grams perfluorooctanoyl chloride were added 45 ml. anhydrous methanol. The temperature rose to about 65 C. as HCl was evolved. An additional liter of methanol was added over a period of about one hour. The mixture was then heated at about 65 C. for about minutes. The reaction product was separated from the layer of unreacted methanol, washed with water, dried overnight over Na SO crystals, filtered and distilled. 164 grams of methyl perfiuorooctanoate were recovered.
  • Preparation of fibers-Fibers were prepared using 1.0% of the additive prepared above.
  • An undrawn filament having a diameter of 16 mils (about 1300 denier) had a surface energy of less than 18 dynes/cm.
  • the resulting fiber had a surface energy of 22 dynes/cm.
  • Photomicrographs of the fibers revealed that the additive is present as a distinct band under the skin of the fiber. This is in contrast to Example 1, where the additive was not visible at all.
  • Example 3 Preparation of additive.--985 grams of 1,7 bis (perfluorooctanoyl)-1,4,7-triazal1eptane and 143 grams of triethyl amine were dissolved in 5 liters of acetone. To this solution was added dropwise a solution of 112 grams of isophthalylchloride in one liter of acetone. The reaction mixture was stirred at 50 C. for 4 hours, then cooled to room temperature. The resulting precipitate was recovered, washed with acetone and was recrystallized from hot ethanol.
  • the product was 1,7 bis(perfiuorooctanoyl)- 1,4,7-triazaheptane isophthalamide, a white solid having a melting point of 178 C., and was obtained at a yield of 85% Preparation of fibers.-Fibers were prepared using 0.1, 0.25, 0.50, and 1.0% of the additive prepared above. The surface energy of the fibers is tabulated below:
  • Example 4 Preparation of additive.l,7-bis(perfluorooctanoyl)- 1,4,7-triazaheptane adipamide was prepared following the general method of Example 3, except adipyl chloride was substituted for isophthalylchloride. The product was a white solid having a melting point of 190-195 C.
  • Fibers were prepared using 1% of the additive prepared above.
  • An undrawn filament of 60 denier had a surface energy of less than 18 dynes/cm.
  • the filament was drawn 4: 1, the resulting fiber had a surface energy of 25 dynes/ cm.
  • Photomicrographs of the fibers revealed that the additive was present as a random distribution of particles throughout the resin matrix.
  • Example 5 Preparation of additive.A mixture f 258 grams of 12,l2,l3,13,14,l4,l5,l-octafiuoro-l5 heptafluoroisopropoxypentadecanoic acid and 410 grams of thionyl chloride was heated to reflux over a period of 40 minutes and then maintained at reflux for 3 hours. The reaction mixture was cooled to room temperature and excess thionyl chloride was evaporated off under vacuum to give 267 grams of crude acid chloride.
  • the compound l2,12,13,13,14,14,15,15-octafluoro-l5- heptafluoroisopropoxypentadecanoic acid is a known compound, better described in Canadian Pats. 823,673 and 823,674, corresponding to U.S. Ser. Nos. 721,115 and 721,117, respectively, both U.S. applications having been filed on Apr. 2, 1968.
  • Example 6 Preparation of additivegrams of C F O(CF CH CH CN and 0.7 gram concentrated sulfuric acid in 100 ml. of carbon tetrachloride were warmed to reflux. A solution of 4. 6 grams of trioxane in 150 ml. of carbon tetrachloride was added dropwise over a period of two hours. The reaction was continued at reflux for an additional two hours. The product precipitated upon cooling, was washed with water, dried, recrystallized from carbon tetrachloride and identified as 61.0 grams of white product, melting point 81-83 C., were obtained at a yield of 89%. From the motor liquor were recovered 7.0 grams of the bisamide E H oaryo omnomomdrrn CHZNHC onlonnornlo 03F:
  • Example 7 Preparation of additive-8.7 grams of tris(2-carboxyethyl) isocyanurate were dissolved in 20 grams of trifluoroacetic anhydride at C. to the clear solution was added dropwise 14 grams of hexafluoroisopropanol. The mixture was reacted at C. for 3 hours. The solvent (CF COOH) was then removed by distillation and the residue was dissolved in chloroform. The product was washed with water, dried and recovered as a white solid, melting point 60 C., yield The product was identified as Preparation of fibers. The additive prepared above is used in accordance with this invention to produce fibers having improved soil and stain repellency.
  • Example 8 Preparation of additive-89 grams (0.01 mol) of 1,7- bis(perfluorooctanoyl)-1,4,7-triazaheptane and 1.20 grams (0.01 mol) of phenylisocyanate were reacated in 50 ml. of acetone for minutes at refiux temperature. The reaction mixture was left standing at room temperature overnight. The mixture was diluted with an excess of water, which caused the product to separate as an oily layer which gradually solidified. The product was filtered ofl, air dried, and recrystallized from ethanol-water.
  • the product a white solid having a melting point of 115- 118 C., was obtained at a 95% yield and was identified as N,N-bis(perfluorooctanamidoethyl)-N-phenyl urea.
  • Example 9 The additive having the formula C F O (CF (CH NI-ICO (CHOH) CH OH was prepared in 98% yeild by reacting The additive is suitable for use in this invention.
  • Example 10 The additive DL- (perfluorooctanoamido)caprolactam, melting point 159 C., was prepared in 64% yield by reacting methyl perfluorooctanoate with ot-amino caprolactam.
  • the additive is suitable for use in this invention to impart soil and stain repellency to extruded synthetic fibers.
  • Example 11 Fibers were prepared from a blend of 30% polyethylene terephthalate and 70% nylon-6 containing 0.5% of the additive of Example 3.
  • An undrawn filament having a diameter of 16 mils had a surface energy of less than 18 dynes/cm.
  • the resulting fiber had a surface energy of 22 dynes/ cm.
  • Example 12 Fibers were prepared from polypropylene containing 1% by Weight of 1,7 bis(perfluorooctanoyl)-4-stearoyl- 1,4,7-triazaheptane.
  • An undrawn filament of 60 denier had a surface energy of less than 18 dynes/cm.
  • a control fiber containing no additive had a surface energy of 22 dynes/cm.
  • Example 13 Fibers were prepared from polyethylene terephthalate containing 1% of the additive of Example 3.
  • An undrawn filament of 60 denier had a surface energy of 27 dynes/ cm. When the filament was drawn 4:1, the resulting fiber had the same surface energy, 27 dynes/cm.
  • a control fiber of polyethylene terephthalate containing no additive had a surface energy of 42 dynes/cm.
  • the additive is selected from the group consisting of (a) monoamides of the formula wherein R is an alkyl diradical of 1 to 8 carbon atoms, an alkylene diradical of 2 to 8 carbon atoms, or a phenyl diradical;
  • diarnides of the formula O (I) CHgCHzNH iii-R1 wherein R is an alkyl diradical of 1 to 8 carbon atoms, an alkylene diradical of 2 to 8 carbon atoms, a phenyl diradical, or a dicarboxy phenyl diradical having the formula (c) hexahydrotriazines of the formula (d) bisamides of the formula 0 R 0 Rg NHgNH Rg wherein R is hydrogen, trichloromethyl or a phenyl radical;

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
US867368A 1969-10-17 1969-10-17 Synthetic fibers having improved soil and stain repellency Expired - Lifetime US3646153A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US86737069A 1969-10-17 1969-10-17
US86736869A 1969-10-17 1969-10-17
US86737269A 1969-10-17 1969-10-17
US86737369A 1969-10-17 1969-10-17
US86737169A 1969-10-17 1969-10-17

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US867368A Expired - Lifetime US3646153A (en) 1969-10-17 1969-10-17 Synthetic fibers having improved soil and stain repellency
US867373A Expired - Lifetime US3697562A (en) 1969-10-17 1969-10-17 Novel fluorocarbon diamides
US00867372A Expired - Lifetime US3786093A (en) 1969-10-17 1969-10-17 Novel bisamides containing fluorine
US867370A Expired - Lifetime US3657235A (en) 1969-10-17 1969-10-17 Hexahydro-1 3 5-trisubstituted-s-triazines containing fluorine
US00867371A Expired - Lifetime US3754026A (en) 1969-10-17 1969-10-17 Fluorocarbon amides

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US867373A Expired - Lifetime US3697562A (en) 1969-10-17 1969-10-17 Novel fluorocarbon diamides
US00867372A Expired - Lifetime US3786093A (en) 1969-10-17 1969-10-17 Novel bisamides containing fluorine
US867370A Expired - Lifetime US3657235A (en) 1969-10-17 1969-10-17 Hexahydro-1 3 5-trisubstituted-s-triazines containing fluorine
US00867371A Expired - Lifetime US3754026A (en) 1969-10-17 1969-10-17 Fluorocarbon amides

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JP (1) JPS502653B1 (https=)
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FR (1) FR2065912A5 (https=)
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US3876617A (en) * 1972-04-26 1975-04-08 Montedison Spa Fluorine-containing elastomeric polyamides and copolyamides and process for their preparation
US4195105A (en) * 1975-06-30 1980-03-25 Allied Chemical Corporation Fluorinated polyalkylene polyamides as stain repellents
US4209610A (en) * 1975-06-30 1980-06-24 Frank Mares Partially fluorinated esters or amide/esters of benzene polycarboxylic acids, and dyeable pet and nylon fibers incorporating the same and process of making such fibers
US4219625A (en) * 1977-12-16 1980-08-26 Allied Chemical Corporation Fluorinated polyol esters
US4500438A (en) * 1983-06-24 1985-02-19 American Hoechst Corporation Multi-ring fluorinated carbamates with textile soil repellent activity
US4534770A (en) * 1983-06-24 1985-08-13 American Hoechst Corporation Multi-ring fluorinated carbamates with textiles soil repellent activity
US20050058779A1 (en) * 2003-09-12 2005-03-17 Goldbaum Richard H. Suppression of repellency in polyolefins
US20080227724A1 (en) * 2003-12-01 2008-09-18 Cambridge University Technical Services Limited Anti-Inflammatory Agents
US20080312119A1 (en) * 2007-06-14 2008-12-18 Jaynes Bingham S Hard surface cleaning compositions comprising certain perfluroalkyl substituted compounds
US20100113691A1 (en) * 2008-11-06 2010-05-06 E. I. Du Pont De Nemours And Company Fluoro olefin polymerization

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US3852313A (en) * 1969-10-17 1974-12-03 Allied Chem Novel fluorocarbon acids
US3855261A (en) * 1972-03-27 1974-12-17 Goodrich Co B F (hydrocarbonthio)oxamide vulcanization retarders
US4043923A (en) * 1974-02-26 1977-08-23 Minnesota Mining And Manufacturing Company Textile treatment composition
DE2628047A1 (de) * 1975-06-30 1977-01-27 Allied Chem Schmutzabstossende mittel und verfahren zu deren herstellung
USRE30337E (en) * 1978-11-27 1980-07-15 Minnesota Mining And Manufacturing Company Textile treatment composition
EP0287695A1 (en) * 1987-04-22 1988-10-26 Janus Label Corporation A method and apparatus for manufacturing discrete elements, the discrete elements and a method and apparatus for applying the discrete elements
WO1992018569A1 (en) * 1991-04-11 1992-10-29 Peach State Labs, Inc. Soil resistant fibers
AU2001295603A1 (en) 2000-10-16 2002-04-29 Chemguard Incorporated Mono- and polyamides of perfluoroalkyl-substituted unsaturated acids
ATE482184T1 (de) * 2003-10-27 2010-10-15 Huntsman Textile Effects Ger Perfluoralkylsubstituierte acrylatmonomere und polymere davon
US8048953B2 (en) * 2006-11-13 2011-11-01 E. I. Du Pont De Nemours And Company Fluororpolymer compositions and treated substrates
US20080202384A1 (en) * 2007-02-28 2008-08-28 Sheng Peng Fluoropolymer compositions and method of use

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US3141758A (en) * 1961-07-07 1964-07-21 Monsanto Co Method of inhibiting the germination of grass seeds
US3555056A (en) * 1968-10-14 1971-01-12 Allied Chem Novel amide and a novel diacyl derivative of a triaza alkane

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3876617A (en) * 1972-04-26 1975-04-08 Montedison Spa Fluorine-containing elastomeric polyamides and copolyamides and process for their preparation
US4195105A (en) * 1975-06-30 1980-03-25 Allied Chemical Corporation Fluorinated polyalkylene polyamides as stain repellents
US4209610A (en) * 1975-06-30 1980-06-24 Frank Mares Partially fluorinated esters or amide/esters of benzene polycarboxylic acids, and dyeable pet and nylon fibers incorporating the same and process of making such fibers
US4219625A (en) * 1977-12-16 1980-08-26 Allied Chemical Corporation Fluorinated polyol esters
US4500438A (en) * 1983-06-24 1985-02-19 American Hoechst Corporation Multi-ring fluorinated carbamates with textile soil repellent activity
US4534770A (en) * 1983-06-24 1985-08-13 American Hoechst Corporation Multi-ring fluorinated carbamates with textiles soil repellent activity
US20050058779A1 (en) * 2003-09-12 2005-03-17 Goldbaum Richard H. Suppression of repellency in polyolefins
US20080227724A1 (en) * 2003-12-01 2008-09-18 Cambridge University Technical Services Limited Anti-Inflammatory Agents
US20080312119A1 (en) * 2007-06-14 2008-12-18 Jaynes Bingham S Hard surface cleaning compositions comprising certain perfluroalkyl substituted compounds
US20100113691A1 (en) * 2008-11-06 2010-05-06 E. I. Du Pont De Nemours And Company Fluoro olefin polymerization

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US3754026A (en) 1973-08-21
US3786093A (en) 1974-01-15
US3697562A (en) 1972-10-10
US3657235A (en) 1972-04-18
FR2065912A5 (https=) 1971-08-06
GB1296426A (https=) 1972-11-15
JPS502653B1 (https=) 1975-01-28
DE2049642A1 (de) 1971-04-29

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