US3450559A - Fibers and fabrics finished with a dicarboxylic reagent modified polyolefin wax - Google Patents

Fibers and fabrics finished with a dicarboxylic reagent modified polyolefin wax Download PDF

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US3450559A
US3450559A US506119A US3450559DA US3450559A US 3450559 A US3450559 A US 3450559A US 506119 A US506119 A US 506119A US 3450559D A US3450559D A US 3450559DA US 3450559 A US3450559 A US 3450559A
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wax
fibers
fabric
modified
modified polyolefin
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US506119A
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Gretchen S Schaufelberger
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Union Carbide Corp
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Union Carbide Corp
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Assigned to MORGAN GUARANTY TRUST COMPANY OF NEW YORK, AND MORGAN BANK ( DELAWARE ) AS COLLATERAL ( AGENTS ) SEE RECORD FOR THE REMAINING ASSIGNEES. reassignment MORGAN GUARANTY TRUST COMPANY OF NEW YORK, AND MORGAN BANK ( DELAWARE ) AS COLLATERAL ( AGENTS ) SEE RECORD FOR THE REMAINING ASSIGNEES. MORTGAGE (SEE DOCUMENT FOR DETAILS). Assignors: STP CORPORATION, A CORP. OF DE.,, UNION CARBIDE AGRICULTURAL PRODUCTS CO., INC., A CORP. OF PA.,, UNION CARBIDE CORPORATION, A CORP.,, UNION CARBIDE EUROPE S.A., A SWISS CORP.
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Assigned to UNION CARBIDE CORPORATION, reassignment UNION CARBIDE CORPORATION, RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: MORGAN BANK (DELAWARE) AS COLLATERAL AGENT
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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
    • 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
    • Y10T442/2221—Coating or impregnation is specified as water proof
    • Y10T442/2254—Natural oil or wax containing
    • 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
    • Y10T442/2311—Coating or impregnation is a lubricant or a surface friction reducing agent other than specified as improving the "hand" of the fabric or increasing the softness thereof
    • Y10T442/2336—Natural oil or wax containing
    • 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
    • Y10T442/2344—Coating or impregnation is anti-slip or friction-increasing other than specified as an abrasive
    • 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
    • Y10T442/2352—Coating or impregnation functions to soften the feel of or improve the "hand" of the fabric
    • 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
    • Y10T442/2369—Coating or impregnation improves elasticity, bendability, resiliency, flexibility, or shape retention of the fabric
    • 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
    • Y10T442/2369—Coating or impregnation improves elasticity, bendability, resiliency, flexibility, or shape retention of the fabric
    • Y10T442/2385—Improves shrink resistance
    • 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
    • Y10T442/2525—Coating or impregnation functions biologically [e.g., insect repellent, antiseptic, insecticide, bactericide, etc.]
    • Y10T442/2541—Insect repellent

Definitions

  • This invention relates to the finishing of fiber and articles made from fibers such as textiles. More particularly, the invention relates to novel finishing agents for fibers and textiles.
  • Fibers useful herein can be classified as natural, semisynthetic, synthetic or glass fibers and include natural organic fibers comprising essentially cellulosic fibers (from vegetable sources) such as cotton, hemp, flax (linen), ramie, sisal, jute and the like; polymeric natural organic fibers e.g.
  • proteinaceous fibers from animal sources
  • silk produced from the moth of the Bombyx species
  • wool and the like polymeric semi-synthetic organic fibers comprising rayons or cellulose derivatives made from wood pulp or cotton linters such as regenerated cellulose rayons such as viscose rayon and cuprammonium rayon, cellulose esters such as acetate rayon and cellulose ethers such as ethyl cellulose
  • polymeric synthetic organic fibers e.g.
  • nylons polyamides
  • polyesters reaction product of polybasic acids and glycols
  • polyethylene polypropylene
  • vinyl chloride/vinyl acetate copolymer vinyl chloride/acrylonitrile copolymer polyacrylonitrile
  • vinyl chloride/vinylidene chloride copolymer polyurethanes and the like
  • glass fibers such as Fiberglas.
  • Finishing herein refers to treatment of fibers either per se or as a textile or fabric to impart new characteristics and properties such as handle, appearance, drape, touch (surface lubricity, flexibility, compressibility and elastic recovery), softness, sheen, durability, shrink resistance, proofing against crushing, slip, water and moths.
  • Cationic salts of simple primary amines such as hexadecyl amine hydroacetate, salts of simple tertiary amines such as hexadecyl dimethylamine hydroacetate, quaternary ammonium salts such as hexadecyl dimethyl benzyl ammonium chloride, salts of amino acids such as monostearoyl diethylene triamine dihydroacetaate, quarternary ammonium salts of amino amides such as ,B-diethylaminoethylstearamide ethosulfate, salts of imidazolines such as ,u-heptadecyl, N-aminoethyl imidazoline dihydroacetatae, quarternary derivatives of imidazolines, salts of amino esters such as B-dihydroxyethyl amine stearatehydroacetate and quaternary ammonium salts of amino esters have heretofore been used as finishing agents. Practical
  • a fiber finishing agent comprising an unsaturated dicarboxylic reagent modified polyolefin wax.
  • Textiles and fabrics having improved tear strength, edge-wear resistance, needle burn resistance and flex abrasion resistance are obtained by treating the textile with an unsaturated dicarboxylic reagent modified polyolefin wax.
  • polyolefin is used in the present specification and claims to denote normally solid homopolymers of monoolefinically unsaturated hydrocarbons as well as normally solid copolymers thereof, with one or more other organic compounds copolymerizable therewith which contain polymer producing unsaturation, such as is present for example in carbon monoxide and formaldehyde and in compounds containing the ethylene linkage e.g.
  • Preferred polyolefins in this invention contain at least 50 percent by weight of a combined alpha-mono-olefinically unsaturated hydrocarbon having from 2 to 4 carbon atoms inclusive, i.e. butene-l, propylene and especially ethylene.
  • a combined alpha-mono-olefinically unsaturated hydrocarbon having from 2 to 4 carbon atoms inclusive, i.e. butene-l, propylene and especially ethylene.
  • the wax to be modified is polyethylene the density of the polyolefin is critical and must be above 0.940.
  • modified polyolefin wax refers to low molecular weight waxes e.g. molecular Weights from about 1000 to about 5000 of polyolefins as that term is defined above which have been reacted with an unsaturated dicarboxylic reagent as defined below.
  • the particular method of preparation of the unsaturated dicarboxylic reagent modified polyolefin Waxes used in the present invention is not critical.
  • these waxes can be prepared, in general, by reaction of an unsaturated dicarboxylic reagent with a low molecular weight polymer polymerized directly to that weight, or a low molecular weight polymer for modification can be obtained by the pyrolysis or thermal degradation of a high molecular weight polyolefin e.g. a polyethylene having a density of 3 from 0.94 to 0.98 and higher.
  • the pyrolysis is conveniently carried out in a heated pyrolysis tube at about 450-600 C. but can be effected in any known manner.
  • the resulting waxes range in molecular weight from about 1000 to about 5000, and preferably from 1500 to 5000.
  • a polyethylene wax having a density above about 0.94 and a molecular weight of from about 1500 to 5000 is blended in the liquid phase, i.e., in the melt or in solution with from 1 to 25 percent by weight of an unsaturated dicarboxylic reagent e.g. maleic anhydride and reacted by being agitated therewith at temperatures of from about 130 C. to about 250 C. and preferably above 180 C. With lower density polyethylenes reaction temperatures of 80 C. and above are suitable. What is required is that the reaction mixture be agitatable.
  • the blending and agitation can be carried out in any manner which insures intimate commingling of the reactants and good heat transfer throughout the reaction mass during the reaction time.
  • the polyethylene wax can be dissolved in an inert liquid organic solvent for the wax and carboxylic reagent such as toluene, xylene, cyclohexane, methylcyclohexane, isooctane and chlorinated hydrocarbon solvents such as orthodichlorobenzene, 1,1,2-trichloroethane and a-chloronaphthalene.
  • the dissolving of the polyethylene wax is most conveniently accomplished at temperatures above 110 C. in aromatic solvents for higher density polyethylenes.
  • reaction in the melt in the absense of an organic solvent by heating a high density polyethylene wax to its melting point (ca. 130 C.) and above, e.g. to 180 C. and stirring in from 5 to percent, based on the wax, of an unsaturated dicarboxylic reagent e.g. maleic anhydride and continuing heating for 60-90 minutes.
  • an unsaturated dicarboxylic reagent e.g. maleic anhydride
  • the modification reaction can be effected under pressure to prevent undue volatilization of the unsaturated dicarboxylic reagent or loss of solvent.
  • the viscosity of the melted polyethylene waxes e.g., 250-1000 centipoises at 200 C. is such that rapid stirring of the unsaturated dicarboxylic reagent is easily accomplished.
  • the exact manner or of addition of the reactants is not critical. Any excess unsaturated dicarboxylic reagent is removed after the reaction as by vacuum distillation or like technique.
  • unsaturated dicarboxylic reagent as used in the present specification and claims is meant an organic compound containing two carboxyl groups (COOH) and having from 4 to 10 carbon atoms and at least one double bond, e.g. maleic acid, tetrahydrophthalic acid, fumaric acid, glutaconic acid, itaconic acid, and the like and anhydrides of the unsaturated dicarboxylic acids e.g. maleic anhydride. All of these unsaturated dicarboxylic reagents are capable of undergoing an addition reaction to one or more olefinic linkages occurring in polyethylene waxes.
  • modified wax to fibers or textiles can be readily accomplished by use of a hot melt or solution of the wax and roller coating, dip coating, spray coating or otherwise.
  • an anionic, cationic or non-ionic emulsion of the modified wax as the coating mixture.
  • water emulsions are prepared by melting together the carboxylic reagent modified polyolefin wax and a fatty acid such as, for example, formic, acetic, propionic, butyric, valeric, caproic, enanthylic, caprylic, pelargonic, capric, undecylic, lauric, trideoic, myristic, pentadecanoic, palmitic, megaric, stearic, nondecylic, arachidic, behenic, carnaubic, hyenic, carborceric, cerotic, laccroic, melissic, montanic, psyllic, acrylic crotonic, isocrotonic, vinylacetic, methylacrylic, tiglic, angelic, senecioic
  • An amine soap is then added such as monoand triethanolamine, mono-isopropanolamine, diisopropanolamine, triisopropanol'amine, morpholine, N,N-dimethylethanolamine and N,N-diethylethanolamine.
  • the mixture is stirred until thoroughly mixed or until it becomes clear.
  • Other emulsifying aids such as polymeric glycols and ethoxylated soybean oils can also be used depending on whether an anionic, cationic or non-ionic emulsion system is desired. Water which has been heated to about C. is added and the mass stirred under pressure.
  • the mixture is then vigorously agitated in a suitable device, e.g., a bladed mixer colloid mill or other shear producing apparatus to form the emulsion.
  • a suitable device e.g., a bladed mixer colloid mill or other shear producing apparatus.
  • An unsaturated dicarboxylic reagent modified polyolefin wax solids content of from 0.1 to 25 percent is preferred in emulsions to be used as finishing agents.
  • the water emulsion of the modified wax is easily coated onto the fiber substrate by any of the conventional techniques including brushing, dipping, spraying, roller coating and the like.
  • the water of the emulsion is evaporated either by allowing the coated-on emulsion to stand at room temperature or preferably by force drying as by air movement around and/or application of heat to the emulsion coating. Upon drying there remains a non-tacky and non-blocking coating which imparts improved handle, lubricity and abrasion resistance to fibers.
  • modified wax based on the fabric weight is coated onto the fabric.
  • Preferred amounts are between 0.1 and 10% by weight on the "same basis.
  • the coated substrate After application of the unsaturated dicarboxylic reagent modified polyolefin wax to the fiber substrate it is preferred to subject the coated substrate to a post-heating step, particularly by heating to a temperature above the melting point of the wax provided the fiber is not degraded thereby.
  • a post-heating step particularly by heating to a temperature above the melting point of the wax provided the fiber is not degraded thereby.
  • N-octadecyl-N- ethylene urea alkyl isocyanates, thiocyanates, organo-silicon compounds, aluminum oxides and soaps, copper soaps, chromium soaps, zirconium soaps and oxide, organo-halosilanes, rare earth metal soaps, petroleum and vegetable waxes, methylol stearamide, pyridium chlorides.
  • Flameproofing agents can also be combined with modified polyolefin wax prior to application to the textile fibers such as boric acid/borax mixtures, ferric hydroxide, antimony oxychloride, stannic oxide hydrated, titanic hydroxide, bismuth trioxide hydrated, zinc stannate, aluminum bo rate, lead peroxide, cerium hydroxide, aluminum hydroxide, chromic hydroxide, silica hydrated, aluminum silicate, magnesium silicate and magnesium ammonium phosphate and with these pentachlorodiphenyl, neoprene, chlorinated paraffin, vinyl chloride resins and aniline hydrochloride.
  • modified polyolefin wax prior to application to the textile fibers
  • modified polyolefin wax such as boric acid/borax mixtures, ferric hydroxide, antimony oxychloride, stannic oxide hydrated, titanic hydroxide, bismuth trioxide hydrated, zinc stannate, aluminum bo rate, lead peroxide
  • flameproofing agents include volatile phosphates and sulfamates. Mothproofing agents and mildewcides too can be applied with the finishing agent such as inorganic fluorides, dichlorobenzene-sulfon-methylamide, p-aminobenzenesulfonamide, dichlorodiphenyl trichloroethane (DDT), pentachlorophenol and the sodium salt of pentachlorodihydroxy triphenylmethan-sulfonic acid.
  • finishing agent such as inorganic fluorides, dichlorobenzene-sulfon-methylamide, p-aminobenzenesulfonamide, dichlorodiphenyl trichloroethane (DDT), pentachlorophenol and the sodium salt of pentachlorodihydroxy triphenylmethan-sulfonic acid.
  • rot-proofing agents such as copper salts of rosin and tall oil, terpinol hydrate as well as alkalies, formaldehyde, dyes, pigments, sequestrants, dispersants, starch, dextrin, glue, gums, china clay, Epsom salts, glycerol, soaps, soluble oils, antichlors, antifoaming and antistatic agents, batching oils, enzymes, lubricants, rust preventatives, spotting and weighting aids.
  • EXAMPLE 1 A maleic anhydride modified polyethylene wax was prepared by extruding a 0.96 density resin from a screw extruder through a hot tube 48 inches in length, having a diameter of three inches and fitted with an axially positioned 2 and A5 inch diameter torpedo, at a rate of 32 pounds per hour. The torpedo was heated to 425 C.
  • the modified wax contained 2.7% carboxyl (calculated as succinic acid) and had a viscosity of 530 centipoises at 140 C.
  • One hundred grams of the modified wax was mixed with grams of morpholine, 20 grams of oleic acid and 800 grams of water. The mixture was charged to a pressure reaction vessel and heated to 150 C. with agitation and immediately cooled. There was obtained a white emulsion having a solids content of 14.7%.
  • the above emulsion was diluted to 10 percent by weight polyethylene wax.
  • a piece of rayon triacetate fabric was immersed in the emulsion.
  • One section of the fabric was air dried and then heated for one minute at 350 F.
  • a second section was only air dried. Both sections were well coated with an adherent covering of the modified wax.
  • the heat-treated fabric was smoother and had better handle. Puncture of the post-treated fabric with a needle did not break the threads. Both sections of fabric were waterproof.
  • EXAMPLE 2 Several solutions of the modified wax prepared in Example 1 were prepared by diluting the emulsion to 2.5, 5 and 10% solids. Squares of cotton fabric were immersed in each of these solutions. One-half of each square was air dried for two hours at room temperature. The other half of each square was oven dried at 130 C. for 45 minutes. The post-treated fabric was water resistant, with applied water balling up.”
  • post-heat treatment of coated fabric at 160l75 C. for 1 to 60 minutes provides a superior product in terms of tear strength, edgewear resistance, needle burn resistance and flex abrasion resistance. Heat-treated fabrics retain these properties, including water-proofness, after laundering.
  • Example 2 was duplicated using a 0.3% solids emulsion prepared as above but using a cationic emulsifier, an ethoxylated soybean oil derivative mixed with acetic acid. Samples of cotton fabric (Example 3) and viscose rayon (Example 4) were immersed until the weight pickup of emulsion was 100%. Samples were dried at 175 F. for 3 minutes. Flex abrasion was measured according to ASTM D-1175-55T.
  • EXAMPLE 5 Strips of fiber glass cloth, (No. 181 weave, type 2967 finish), 4" x 2", were immersed in emulsions of maleic anhydride modified high density polyethylene wax as described in Example 1. Emulsion solids content and immersion conditions were adjusted such that the cloth picked up 0.5, 1.0, 2.5, 5.0 and 10.0 wt. percent solids.
  • the cloth samples were squeezed partly dry, then air dried at room temperature. The samples of dried cloth were then heat treated at C. for 10 minutes in an air oven to fuse the polyethylene wax coating.
  • the fiber glass cloth sample treated with 0.5 wt. percent solids from a cationic or anionic emulsion was significantly improved in softness, hand, or drape properties as shown in the following table:
  • the modified polyethylene wax coating functions as a lubricant and permits slippage at fiber interfaces.
  • the results show that the 0.5% emulsion solids level gave the softest fabric, and the fabric became stiffer at higher levels.
  • cellulosic fibers such as cotton and rayon improved in the present invention but proteinaceous substrate such as wool are also improved.
  • proteinaceous substrate such as wool
  • the application of a 2% by weight emulsion as prepared in Example 1 onto a woolen cloth imparts needle burn resistance and improved handle.
  • Synthetic fibers can also be improved particularly in handle by application of the modified wax in accordance with the present invention.
  • polypropylene, nylon, and polyester fabrics can be improved in edgewear resistance, needle burn resistance and durability by the application of modified wax coatings.
  • Fabric comprising textile fibers thereon of from about 0.01 to about 25 percent by weight, based on the weight of said fabric, of a finishing agent consisting essentially of a polyethylene wax having a density of at least 0.940 and a molecular weight between 1000 and 5000 which has been modified by reaction with from 1 to 25 percent by weight of an unsaturated dicarboxylic reagent having from 4 to 10 carbon atoms.
  • a finishing agent consisting essentially of a polyethylene wax having a density of at least 0.940 and a molecular weight between 1000 and 5000 which has been modified by reaction with from 1 to 25 percent by weight of an unsaturated dicarboxylic reagent having from 4 to 10 carbon atoms.
  • said polyolefin having a coating wax is polyethylene wax and said reagent is maleic anhydride.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Description

United States Patent 3 450,559 FIBERS AND FABRICS FINISHED WITH A DICAR- lvlvolgzYLlC REAGENT MODIFIED POLYOLEFIN A Gretchen S. Schaufelberger, Basking Ridge, NJ., assignor t; Iliniou Carbide Corporation, a corporation of New or No Drawing. Continuation-in-part of application Ser. No. 330,248, Dec. 13, 1963. This application Nov. 2, 1965, Ser. No. 506,119
Int. Cl. C03c 25/00; C0811 19/02, B44d 1/22 U.S. Cl. 117-126 4 Claims ABSTRACT OF THE DISCLOSURE Textile fibers and fabrics finished with a dicarboxylic acid modified polyolefin wax to impart characteristics such as handle, appearance, drape, touch, softness, sheen, durability, shrink resistance, and the like.
This application is a continuation-in-part of copending application Ser. No. 330,248, filed Dec. 13, 1963 which in turn is a continuation-in-part of application Ser. No. 203,440 filed June 19, 1962, both now abandoned, which in turn is a continuation-in-part of application Ser. No. 158,581 filed Dec. 11, 1961, also now abandoned.
This invention relates to the finishing of fiber and articles made from fibers such as textiles. More particularly, the invention relates to novel finishing agents for fibers and textiles.
As disclosed in application Ser. No. 158,581 a wide variety of substances can be coated with modified polyethylene wax. Substrates such as those cellulosic and polymeric in nature were there disclosed to have been coated with this wax. The particular form of the substrate is of course not critical. The present application relates to a specific form of substrate namely textile fiber. The basic nature of the fiber as a cellulosic or polymeric substrate is not changed.
Fibers useful herein can be classified as natural, semisynthetic, synthetic or glass fibers and include natural organic fibers comprising essentially cellulosic fibers (from vegetable sources) such as cotton, hemp, flax (linen), ramie, sisal, jute and the like; polymeric natural organic fibers e.g. proteinaceous fibers (from animal sources) such as silk (produced from the moth of the Bombyx species), wool and the like; polymeric semi-synthetic organic fibers comprising rayons or cellulose derivatives made from wood pulp or cotton linters such as regenerated cellulose rayons such as viscose rayon and cuprammonium rayon, cellulose esters such as acetate rayon and cellulose ethers such as ethyl cellulose; polymeric synthetic organic fibers e.g. nylons (polyamides), polyesters (reaction product of polybasic acids and glycols) polyethylene, polypropylene, vinyl chloride/vinyl acetate copolymer, vinyl chloride/acrylonitrile copolymer polyacrylonitrile, vinyl chloride/vinylidene chloride copolymer, polyurethanes and the like; and glass fibers such as Fiberglas.
Finishing herein refers to treatment of fibers either per se or as a textile or fabric to impart new characteristics and properties such as handle, appearance, drape, touch (surface lubricity, flexibility, compressibility and elastic recovery), softness, sheen, durability, shrink resistance, proofing against crushing, slip, water and moths.
Cationic salts of simple primary amines such as hexadecyl amine hydroacetate, salts of simple tertiary amines such as hexadecyl dimethylamine hydroacetate, quaternary ammonium salts such as hexadecyl dimethyl benzyl ammonium chloride, salts of amino acids such as monostearoyl diethylene triamine dihydroacetaate, quarternary ammonium salts of amino amides such as ,B-diethylaminoethylstearamide ethosulfate, salts of imidazolines such as ,u-heptadecyl, N-aminoethyl imidazoline dihydroacetatae, quarternary derivatives of imidazolines, salts of amino esters such as B-dihydroxyethyl amine stearatehydroacetate and quaternary ammonium salts of amino esters have heretofore been used as finishing agents. Practically all materials that are in commercial use are derived from stearic acid. Hydrocarbon chains of greater length have been sought but high cost and poor availability have barred their general use despite promising experimental results.
It is an object, therefore, of the present invention to provide finishing agents of relatively very great molecular weight for improving the tear strength, edgewear resistance, needle burn resistance and flex abrasion resistance of fibers.
It is another object to provide textiles and fabrics having improved handle.
It is another object to increase the water repellancy of textiles and fabrics, especially of proteinaceous and cellulosic fiber textiles.
A fiber finishing agent has now been discovered comprising an unsaturated dicarboxylic reagent modified polyolefin wax. Textiles and fabrics having improved tear strength, edge-wear resistance, needle burn resistance and flex abrasion resistance are obtained by treating the textile with an unsaturated dicarboxylic reagent modified polyolefin wax.
The term polyolefin is used in the present specification and claims to denote normally solid homopolymers of monoolefinically unsaturated hydrocarbons as well as normally solid copolymers thereof, with one or more other organic compounds copolymerizable therewith which contain polymer producing unsaturation, such as is present for example in carbon monoxide and formaldehyde and in compounds containing the ethylene linkage e.g. styrene, vinyl stearate, butene, vinyl acetate, vinyl formate, methacrylatc, monobutyl maleate, 2-ethyl hexyl acrylate, N-methyl-N-vinyl acetamide, methacrylic acid, ethyl acrylate, acrylic acid, isoprene, butadiene, acrylamide, vinyl triethoxysilane, bicycloheptene, bicycloheptadiene, divinyl phosphonate and the like. Many other copolymerizable monomers which can be used in addition to these illustrative compounds are well known in the art. Preferred polyolefins in this invention contain at least 50 percent by weight of a combined alpha-mono-olefinically unsaturated hydrocarbon having from 2 to 4 carbon atoms inclusive, i.e. butene-l, propylene and especially ethylene. Where the wax to be modified is polyethylene the density of the polyolefin is critical and must be above 0.940.
The term modified polyolefin wax refers to low molecular weight waxes e.g. molecular Weights from about 1000 to about 5000 of polyolefins as that term is defined above which have been reacted with an unsaturated dicarboxylic reagent as defined below. The particular method of preparation of the unsaturated dicarboxylic reagent modified polyolefin Waxes used in the present invention is not critical. For example, these waxes can be prepared, in general, by reaction of an unsaturated dicarboxylic reagent with a low molecular weight polymer polymerized directly to that weight, or a low molecular weight polymer for modification can be obtained by the pyrolysis or thermal degradation of a high molecular weight polyolefin e.g. a polyethylene having a density of 3 from 0.94 to 0.98 and higher. The pyrolysis is conveniently carried out in a heated pyrolysis tube at about 450-600 C. but can be effected in any known manner. The resulting waxes range in molecular weight from about 1000 to about 5000, and preferably from 1500 to 5000.
In a preferred method of preparing the preferred modified polyethylene waxes, a polyethylene wax having a density above about 0.94 and a molecular weight of from about 1500 to 5000 is blended in the liquid phase, i.e., in the melt or in solution with from 1 to 25 percent by weight of an unsaturated dicarboxylic reagent e.g. maleic anhydride and reacted by being agitated therewith at temperatures of from about 130 C. to about 250 C. and preferably above 180 C. With lower density polyethylenes reaction temperatures of 80 C. and above are suitable. What is required is that the reaction mixture be agitatable. The blending and agitation can be carried out in any manner which insures intimate commingling of the reactants and good heat transfer throughout the reaction mass during the reaction time. For example, the polyethylene wax can be dissolved in an inert liquid organic solvent for the wax and carboxylic reagent such as toluene, xylene, cyclohexane, methylcyclohexane, isooctane and chlorinated hydrocarbon solvents such as orthodichlorobenzene, 1,1,2-trichloroethane and a-chloronaphthalene. The dissolving of the polyethylene wax is most conveniently accomplished at temperatures above 110 C. in aromatic solvents for higher density polyethylenes.
It is preferred to effect reaction in the melt in the absense of an organic solvent by heating a high density polyethylene wax to its melting point (ca. 130 C.) and above, e.g. to 180 C. and stirring in from 5 to percent, based on the wax, of an unsaturated dicarboxylic reagent e.g. maleic anhydride and continuing heating for 60-90 minutes. Temperatures of reaction either in solution or in the melt above about 250 C. confer no added benefit in speed of reaction or quality of modified wax obtained and, hence, will not be ordinarily used. The modification reaction can be effected under pressure to prevent undue volatilization of the unsaturated dicarboxylic reagent or loss of solvent. The viscosity of the melted polyethylene waxes, e.g., 250-1000 centipoises at 200 C. is such that rapid stirring of the unsaturated dicarboxylic reagent is easily accomplished. The exact manner or of addition of the reactants is not critical. Any excess unsaturated dicarboxylic reagent is removed after the reaction as by vacuum distillation or like technique.
By the term unsaturated dicarboxylic reagent as used in the present specification and claims is meant an organic compound containing two carboxyl groups (COOH) and having from 4 to 10 carbon atoms and at least one double bond, e.g. maleic acid, tetrahydrophthalic acid, fumaric acid, glutaconic acid, itaconic acid, and the like and anhydrides of the unsaturated dicarboxylic acids e.g. maleic anhydride. All of these unsaturated dicarboxylic reagents are capable of undergoing an addition reaction to one or more olefinic linkages occurring in polyethylene waxes.
The application of the modified wax to fibers or textiles can be readily accomplished by use of a hot melt or solution of the wax and roller coating, dip coating, spray coating or otherwise.
Alternatively and advantageously the limitations of hot melt or solution application or incorporation can be avoided by use of an anionic, cationic or non-ionic emulsion of the modified wax as the coating mixture. Typically water emulsions are prepared by melting together the carboxylic reagent modified polyolefin wax and a fatty acid such as, for example, formic, acetic, propionic, butyric, valeric, caproic, enanthylic, caprylic, pelargonic, capric, undecylic, lauric, trideoic, myristic, pentadecanoic, palmitic, megaric, stearic, nondecylic, arachidic, behenic, carnaubic, hyenic, carborceric, cerotic, laccroic, melissic, montanic, psyllic, acrylic crotonic, isocrotonic, vinylacetic, methylacrylic, tiglic, angelic, senecioic, hexenic, teracrylic,
4 hypogeic, oleic, elaidic, eurcic, brassidic, propiolic, propynoic, tetrolic, 2-butynoic, pentinoic, 2-pentiuoic, amylpropiolic, palmitotic, stearolic, behenolic, sorbic, linoleic and linolinic acids. These acides have the general formula wherein n is an integer from 0 to 32 and x is an odd number from 5 to +1 with the proviso that when 11 :0, x=+1. An amine soap is then added such as monoand triethanolamine, mono-isopropanolamine, diisopropanolamine, triisopropanol'amine, morpholine, N,N-dimethylethanolamine and N,N-diethylethanolamine. The mixture is stirred until thoroughly mixed or until it becomes clear. Other emulsifying aids such as polymeric glycols and ethoxylated soybean oils can also be used depending on whether an anionic, cationic or non-ionic emulsion system is desired. Water which has been heated to about C. is added and the mass stirred under pressure. The mixture is then vigorously agitated in a suitable device, e.g., a bladed mixer colloid mill or other shear producing apparatus to form the emulsion. An unsaturated dicarboxylic reagent modified polyolefin wax solids content of from 0.1 to 25 percent is preferred in emulsions to be used as finishing agents.
The water emulsion of the modified wax is easily coated onto the fiber substrate by any of the conventional techniques including brushing, dipping, spraying, roller coating and the like. The water of the emulsion is evaporated either by allowing the coated-on emulsion to stand at room temperature or preferably by force drying as by air movement around and/or application of heat to the emulsion coating. Upon drying there remains a non-tacky and non-blocking coating which imparts improved handle, lubricity and abrasion resistance to fibers.
Generally from about 0.01 to about 25% by weight of modified wax based on the fabric weight is coated onto the fabric. Preferred amounts are between 0.1 and 10% by weight on the "same basis.
After application of the unsaturated dicarboxylic reagent modified polyolefin wax to the fiber substrate it is preferred to subject the coated substrate to a post-heating step, particularly by heating to a temperature above the melting point of the wax provided the fiber is not degraded thereby. This enables a greater degree of flow of the wax into the interstices of the fabric and facilitates reaction of the reactive groups of the wax with the reactive groups of the fibers e.g. acid or anhydride groups on the wax with hydroxyl groups or acetate groups on cellulosic fibers such as cotton or rayon.
As mentioned above, the finishing of textile fibers improves the water repellency characteristics. Other aids can be simultaneously employed including N-octadecyl-N- ethylene urea, alkyl isocyanates, thiocyanates, organo-silicon compounds, aluminum oxides and soaps, copper soaps, chromium soaps, zirconium soaps and oxide, organo-halosilanes, rare earth metal soaps, petroleum and vegetable waxes, methylol stearamide, pyridium chlorides. Flameproofing agents can also be combined with modified polyolefin wax prior to application to the textile fibers such as boric acid/borax mixtures, ferric hydroxide, antimony oxychloride, stannic oxide hydrated, titanic hydroxide, bismuth trioxide hydrated, zinc stannate, aluminum bo rate, lead peroxide, cerium hydroxide, aluminum hydroxide, chromic hydroxide, silica hydrated, aluminum silicate, magnesium silicate and magnesium ammonium phosphate and with these pentachlorodiphenyl, neoprene, chlorinated paraffin, vinyl chloride resins and aniline hydrochloride.
Other flameproofing agents include volatile phosphates and sulfamates. Mothproofing agents and mildewcides too can be applied with the finishing agent such as inorganic fluorides, dichlorobenzene-sulfon-methylamide, p-aminobenzenesulfonamide, dichlorodiphenyl trichloroethane (DDT), pentachlorophenol and the sodium salt of pentachlorodihydroxy triphenylmethan-sulfonic acid. Also rot-proofing agents such as copper salts of rosin and tall oil, terpinol hydrate as well as alkalies, formaldehyde, dyes, pigments, sequestrants, dispersants, starch, dextrin, glue, gums, china clay, Epsom salts, glycerol, soaps, soluble oils, antichlors, antifoaming and antistatic agents, batching oils, enzymes, lubricants, rust preventatives, spotting and weighting aids.
The present invention is illustrated by the following examples. Alyl parts and percentages are by weight unless otherwise stated.
EXAMPLE 1 A maleic anhydride modified polyethylene wax was prepared by extruding a 0.96 density resin from a screw extruder through a hot tube 48 inches in length, having a diameter of three inches and fitted with an axially positioned 2 and A5 inch diameter torpedo, at a rate of 32 pounds per hour. The torpedo was heated to 425 C.
Sixty pounds of the resulting wax was reacted with 6 pounds of maleic anhydride for 90 minutes at 220 C. in a gallon autoclave equipped with a Dowtherm jacket, and a 6 inch turbine agitator. The reaction product was recovered by stripping the excess maleic anhydride under 5 mm. Hg pressure and removing the reaction product. The modified wax contained 2.7% carboxyl (calculated as succinic acid) and had a viscosity of 530 centipoises at 140 C.
One hundred grams of the modified wax was mixed with grams of morpholine, 20 grams of oleic acid and 800 grams of water. The mixture was charged to a pressure reaction vessel and heated to 150 C. with agitation and immediately cooled. There was obtained a white emulsion having a solids content of 14.7%.
The above emulsion was diluted to 10 percent by weight polyethylene wax. A piece of rayon triacetate fabric was immersed in the emulsion. One section of the fabric was air dried and then heated for one minute at 350 F. A second section was only air dried. Both sections were well coated with an adherent covering of the modified wax. The heat-treated fabric was smoother and had better handle. Puncture of the post-treated fabric with a needle did not break the threads. Both sections of fabric were waterproof.
EXAMPLE 2 Several solutions of the modified wax prepared in Example 1 were prepared by diluting the emulsion to 2.5, 5 and 10% solids. Squares of cotton fabric were immersed in each of these solutions. One-half of each square was air dried for two hours at room temperature. The other half of each square was oven dried at 130 C. for 45 minutes. The post-treated fabric was water resistant, with applied water balling up."
While not necessary, post-heat treatment of coated fabric at 160l75 C. for 1 to 60 minutes provides a superior product in terms of tear strength, edgewear resistance, needle burn resistance and flex abrasion resistance. Heat-treated fabrics retain these properties, including water-proofness, after laundering.
EXAMPLES 34 Example 2 was duplicated using a 0.3% solids emulsion prepared as above but using a cationic emulsifier, an ethoxylated soybean oil derivative mixed with acetic acid. Samples of cotton fabric (Example 3) and viscose rayon (Example 4) were immersed until the weight pickup of emulsion was 100%. Samples were dried at 175 F. for 3 minutes. Flex abrasion was measured according to ASTM D-1175-55T.
EXAMPLE 5 Strips of fiber glass cloth, (No. 181 weave, type 2967 finish), 4" x 2", were immersed in emulsions of maleic anhydride modified high density polyethylene wax as described in Example 1. Emulsion solids content and immersion conditions were adjusted such that the cloth picked up 0.5, 1.0, 2.5, 5.0 and 10.0 wt. percent solids.
The cloth samples were squeezed partly dry, then air dried at room temperature. The samples of dried cloth were then heat treated at C. for 10 minutes in an air oven to fuse the polyethylene wax coating.
After treatment the samples were examined visually and by feel to qualitatively rate the softness. The fabric stiffness was quantitatively rated also by the blending length test for fabrics (ASTM-1488-55T).
The fiber glass cloth sample treated with 0.5 wt. percent solids from a cationic or anionic emulsion was significantly improved in softness, hand, or drape properties as shown in the following table:
Bending length, cm.
Percent solids Percent solids (ASTM (emulsion) (on fabric) Hand or "feel 148855T) 0 Med. soft 4. 1
-0. 5 Soft 3. 2
l. 0 Med. soft 4. 2
2. 5 Increasing stiffness 5. 5
5. 0 From med. soft 6.0
The modified polyethylene wax coating functions as a lubricant and permits slippage at fiber interfaces. The results show that the 0.5% emulsion solids level gave the softest fabric, and the fabric became stiffer at higher levels.
Control I & II
Samples of cotton (I) and rayon (II) fabric without any finishing agent were tested for flex abrasion resistance.
Control III & IV
Samples of cotton (III) and rayon (IV) fabric were immersed in an emulsion polymerized (high pressure) low density polyethylene. Results were as follows:
Flex abraision Resistance (cycles Example Solids on fabric to failure) 3 0. 3 1, 550 4 0. 3 2, 527 0 656 0. 3 864 0 395 0. 3 763 Other polyolefin waxes such as polypropylene wax modified with unsaturated dicarboxylic reagents such as maleic acid provide similar results.
As indicated above not only are cellulosic fibers such as cotton and rayon improved in the present invention but proteinaceous substrate such as wool are also improved. As an illustration, the application of a 2% by weight emulsion as prepared in Example 1 onto a woolen cloth imparts needle burn resistance and improved handle.
Synthetic fibers can also be improved particularly in handle by application of the modified wax in accordance with the present invention. Thus, polypropylene, nylon, and polyester fabrics can be improved in edgewear resistance, needle burn resistance and durability by the application of modified wax coatings.
What is claimed is:
1. Fabric comprising textile fibers thereon of from about 0.01 to about 25 percent by weight, based on the weight of said fabric, of a finishing agent consisting essentially of a polyethylene wax having a density of at least 0.940 and a molecular weight between 1000 and 5000 which has been modified by reaction with from 1 to 25 percent by weight of an unsaturated dicarboxylic reagent having from 4 to 10 carbon atoms.
2. Fabric claimed in claim 1 wherein said fabric comprises organic fibers.
3. Fabric claimed in claim 1 wherein said fabric comprises glass fibers.
4. Fabric claimed in claim 1 wherein said polyolefin having a coating wax is polyethylene wax and said reagent is maleic anhydride.
References Cited UNITED STATES PATENTS Huijser et a1 26082 Laner 117-126 X Mattinson et a1. 117168 X Bohrer 117-139.5 X Jefferson et a1 117-139.5 Wilder 106-270 X Johnson 117-139.5
8 Wolinsky 26028.5 Ross 117-139.5 Patterson et a1. 117138.8 Shippe et a1. 106270 WILLIAM D. MARTIN, Primary Examiner.
THEODORE G. DAVIS, Assistant Examiner.
US. Cl. X.R.
US506119A 1965-11-02 1965-11-02 Fibers and fabrics finished with a dicarboxylic reagent modified polyolefin wax Expired - Lifetime US3450559A (en)

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