US3542505A - Treatment of textiles with aziridine-modified polyurethanes - Google Patents

Treatment of textiles with aziridine-modified polyurethanes Download PDF

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US3542505A
US3542505A US3542505DA US3542505A US 3542505 A US3542505 A US 3542505A US 3542505D A US3542505D A US 3542505DA US 3542505 A US3542505 A US 3542505A
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aziridine
acid
fabric
wool
textile
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Allen G Pittman
William L Wasley
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US Department of Agriculture USDA
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US Department of Agriculture USDA
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    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/48—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing the ethylene imine ring
    • 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
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/45—Shrinking resistance, anti-felting properties
    • 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
    • Y10T442/2393—Coating or impregnation provides crease-resistance or wash and wear characteristics

Definitions

  • a polyether polyurethane containing free NCO groups is reacted with ethylene imine to yield an aziridine-modified polymer which is formed into an emulsion and applied to a textile material.
  • the treated textile may be directly cured or the curing operation may be delayed until the fabric is manufactured into a finished garment, the latter system being preferred to attain permanent creases.
  • This invention relates to and has among its objects the provision of novel processes for treating textile materials and the products of such processes.
  • a special object of the invention is the provision of such treatments involving the use of aziridine-modified polyurethanes whereby to provide such benefits as improved shrinkage resistance and permanent press qualities. Further objects and advantages of the invention will be evident from the following description wherein parts and percentages are by weight unless. otherwise specified.
  • the aziridines of the invention are particularly useful in applications involving delayed curing, that is, where the aziridine is applied to the fabric, the treated fabric is manufactured into a garment provided with appropriate creases in selected areas, and the garment is then subjected to a curing treatment so that the completed garment is not only shrink resistant but also press-free, i.e., it can be subjected to repeated washings without requiring pressing to maintain the creases.
  • the particular ad vantages of the present invention which make them especially adapted to such use are:
  • Our aziridines do not undergo spontaneous curing; they remain in the uncured state even after long storage of the treated fabric.
  • the aziridines remain in the uncured state even if subjected to moisture at ordinary temperatures.
  • the treated fabrics may be subjected to moist conditions as may be required in certain garment fabrication steps without premature curing and without decomposition of the applied aziridine.
  • A is the residue of a polyether polyol or polyester polyol having a valence of n
  • R is a hydrocarbon radical containing at least two can bon atoms
  • R is hydrogen, halogen, lower alkoxy, or a radical of the structure R" is hydrogen or a lower alkyl radical, n is an integer from 2 to 10, and x is an integer from 1 to 2.
  • the aziridine derivatives of the invention are prepared by reacting an alkylene imine, such as ethylene, propylene, or butylene imine, with a polyether (or polyester) polyurethane containing free isocyanate groups. This simple reaction establishes the desired aziridine-modfiication for padding and insulation applications, and in the proof the starting polymer. A typical, but by no means least two free NCO groups per polymer molecule.
  • ferred are the polymer intermediates having a molecular ([JH; (EH3 f H Isoeyanate-terminated ooN NH-iI-OTCHzCHzCHzOH2O7CNH NCO Wyeth Wlyurethane 2CH2-CH2 Ethylene imine ([3113 (3H3 CE; H (l) /CH2 l N- NH NH( 1-O CH2CHzCHa- CHrO ⁇ -CNH NHC-N C a m Hz Azlrldine-modified polyether polyurethane (In the above formulas, m represents the number of Weight of at least 500, more preferably those having a tetramethyleneether repeating units.
  • This may range, for 25 molecular weight of at least 1000. Also, it is generally example, about from 5 to 50.) preferred to use the polyether-based polymers, for ex-
  • the reaction is carried out at about to 40 C., ample,-the NCO-containing polyurethane derived from and under essentially anhydrous conditions to avoid hypolyalkylene ether glycols such as polyethylene ether drolysis of the isocyanate groups.
  • the alkylene imine glycols,-polytrimethylene ether glycols, polytetramethylene is supplied in excess to ensure conversion of all isocyanate ether glycols, polypropyleneether glycols and the like.
  • the intermediate m-phenylene diisocyanate may be any polyether polyurethane which contains at 3,3'-diphenyl-4,4-biphenylene diisocyanate 4,4-biphenylene diisocyanate 3,3'-dichloro-4,4-biphenylene diisocyanate 1,6-hexamethylenediisocyanate 1,4-tetramethylene-diisocyanate l,10-decamethylenediisocyanate 1,S-naphthalenediisocyanate cumene-2,4-diisocyanate 4-methoxyl ,3 -phenylenediisocyanate 4-chloro-1,3-phenylenediisocyanate 4-bromo-l,3-phenylenediisocyanate 4-ethoxy-l,3-phenylenediisocyanate 2!,4-diis
  • R and R in Formula I the values of R and R in Formula I.
  • R will be a hydrocarbon radical and R will represent a hydrogen atom forming part of said hydrocarbon radical.
  • the reactant contains a substituent such as chlorine or methoxy-as would be the case with, for example, 4-chloro-l,3-phenylene diisocyanate or 4- methoxy-l,3-phenylene diisocyanate-R will be the hydrocarbon residue of the reactant and R will be the substituentchlorine or methoxy in the given examples.
  • polyether polyols and polyester polyols, and representative examples of these polyols are described below:
  • polyether polyols which may be so used are those prepared by reaction of an alkylene oxide with an initiator containing active hydrogen groups, a typical example of the initiator being a polyhydric alcohol such as ethylene glycol.
  • the reaction is usually carried out in the presence of either an acidic or basic catalyst.
  • alkylene oxides which may be employed in the synthesis include ethylene oxide, propylene oxide, any of the isomeric butylene oxides, and mixtures of two or more diiferent alkylene oxides such as mixtures of ethylene and propylene oxides.
  • the resulting polymers contain a polyether backbone and are terminated by hydroxyl groups. The number of hydroxyl groups per polymer molecule is determined by the functionality of the active hydrogen initiator.
  • a difunctional alcohol such as ethylene glycol (as the active hydrogen initiator) leads to polyether chains in which there are two hydroxyl groups per polymer molecule.
  • the resulting polyether molecules contain an average of three hydroxyl groups per molecule.
  • Even higher functionalitymore hydroxyl groups is obtained when the oxide is polymerized in the presence of such polyols as pentaerythritol, sorbitol, dipentaerythritol, and the like.
  • polyhydric alcohols which may be reacted with alkylene oxides to produce useful polyether polyols include:
  • propylene glycol trimethylene glycol 1,2-butylene glycol 1,3-butanediol 1,4-butanediol 1,5-pentanediol 1,2-hexylene glycol 1, l0-decanediol 1,2-cyclohexanediol 2-butene-1,4diol 3-cyclohexene-1,l-dimethanol 4-methyl-3-cyclohexene-1,l-dimethanol B-methylene-1,5-pentanediol diethylene glycol (Z-hydroxyethoxy -1-propanol 4- (Z-hydroxyethoxy) -1-butanol 5- Z-hydroxypropoxy) l-pentanol 1- (2-hydr0xymethoxy) -2-hexanol I-(Z-hydroxypropoxy)-2-octanol 3-a1lyloxy-1,5-pentanedio1 2-allyloxymethyl-Z-methyl-1,3-propane
  • polyether polyols are the polytetramethylene glycols. They are prepared by the ring-opening polymerization of tetrahydrofuran, and contain the repeating unit.
  • Termination of the polymer chains is by hydroxyl groups.
  • polyester polyols which may be employed as precursors for the aziridines of the invention, are most readily prepared by condensation polymerization of a polyol with a polybasic acid.
  • the polyol and acid reactants are used in such proportion that essentially all the acid groups are esterified and the resulting chain of ester units is terminated by hydroxyl groups.
  • polybasic acids for producing these polymers are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, thapsic acid, maleic acid, fumaric acid, glutaconic acid, a-hydromuconic acid, fi-hydromuconic acid, a-butyl-u-ethylglutaric acid, a,p-diethylsuccinic acid, 0- phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, mellophanicacid, prehnitic acid, pyromellitic acid, citric acid, benzenepentacarboxylc acid, l,4-cyclohexanedicarboxylic acid, diglycollic acid, thiodiglycollic acid, dim
  • polyols for forming these polymers includes ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, butene-l,4-diol, 1,5-pentane diol, 1,4-pentane diol, 1,3-pentane diol, 1,6-hexane diol, hexene-1,6-diol, 1,7-heptane diol, diethylene glycol, glycerine, trimethylol propane, 1,3,6-hexanetriol, triethanolamine, pentaerythrtiol, sorbitol, and any of the other polyols listed hereinabove in connection with the preparation of polyether polyols.
  • polyester polyols are those which include polyether units so that they may be considered as polyester polyols or as polyether polyols, depending on whether the ester or the ether groups are in majority.
  • the compounds may be produced by the condensation polymerization of any of the above-mentioned polybasic carboxylic acids with a polyalkyleneether glycoltypically, a polyethyleneether glycol having a molecular weight of about 200 to 2000-using the glycol in the require proportion to assure termination by hydroxyl.
  • Esters of the hydroxyl-co'ntaining acid, ricinoleic acid form another category of useful polyester polyols.
  • esters of ricinoleic acid with ethylene glycol, propylene glycol, glycerol, pentaerythritol, diglycerol, dipentaerythritol, polyalkyleneether glycols, and the like.
  • Representative of this category of polyester polyols is castor oil which is composed mainly of the tri-glyceride of ricinoleic acid.
  • the aziridines of the invention may be applied to the textile in various ways.
  • One technique involves applying the aziridine as such to the textile, using warming if necessary to make the aziridine flow, and distributing it with calender rolls or the like.
  • a preferred technique involves dissolving the aziridine in an inert, volatile solvent and applying the resulting solution to the textile material.
  • Typical of the solvents which may be used are benzene, toluene, xylene, dioxane, diisopropyl ether, dibutyl ether, butyl acetate, chlorinated hydrocarbons such as chloroform, carbon tetrachloride, ethylene dichloride, trichloroethylene, 1,3-dichlorobenzene, fiuorohydrocarbons such as benzotrifiuoride, 1,3 bis-(trifiuoromethyl)benzene, etc., petroleum distillates such as petroleum naphthas, etc.
  • chlorinated hydrocarbons such as chloroform, carbon tetrachloride, ethylene dichloride, trichloroethylene, 1,3-dichlorobenzene, fiuorohydrocarbons such as benzotrifiuoride, 1,3 bis-(trifiuoromethyl)benzene, etc.
  • petroleum distillates such as petroleum naphthas, etc
  • emusifying agent such as an alkylphenoxypoly-(ethyleneoxy)ethanol, polyoxyethylene sorbitan monopalmitate, polyoxyethylene lauryl ether, polyoxyethylene-polyoxypropylene stearate, sorbitan monopalmitate, I
  • the concentration of the aziridine in the dispersion this last term being herein employed in a generic sense to include solutions and emulsins-is not critical and may be varied depending on such circumstances as the solubility characteristics of aziridine, the amount of aziridine to be deposited on the fibers, the viscosity of the dispersion, etc. In general, a practical range of concentration would be from about 1% to about
  • the dispersion may be distributed on the textile material by any of the usual methods, for example, by spraying, brushing, padding, dipping, etc. A preferred technique involves immersing the textile in the dispersion and then passing it through squeeze rolls to remove the excess of liquid.
  • Such techniques as blowing air through the treated textile may be employed to reduce the amount of liquid which exists in interstices between fibrous elements.
  • the conditions of application are so adjusted that the textile material contains the proportion of aziridine desired.
  • the amount of aziridine is about from 0.5 to 20%, based on the weight of the textile ma- 8 terial but it is obvious that higher proportions may be used for special purposes.
  • the amount of aziridine is usually limited to a range of about 0.5 to 10% to attain the desired end such as shrink resistance without interference with the hand of the textile.
  • the treated textile is cured (heated) to effect an insolubilization ofthe applled aziridine and to promote bonding of the azirine to the textile.
  • bonding is known to occur and it is believed to involve chemical combination of the aziridlne w th active radicals present in the textile substrate, these act ve radicals including carboxyl, hydroxyl, amino, and th ol groups.
  • Such groups are, of course, present in many textile materials including wool, animal hair, leather, and other proteinaceous materials; cotton, rayon, linen, and other cellulosic fibers, nylon, polyurethanes, and many other syntheic fibers.
  • the solvent or other volatile dispersing medium is preferably evaporated prior to the curing operation.
  • Such prior evaporation is not a critical step and the evaporation may be simply effected as part of the curing step.
  • the temperature applied in the curing step is not critical and usually is within the range from about 50 C. to about 150 It is obvious that the time required for the curing will vary with such factors as the reactivity of the selected aziridine, the type of textile material, and particularly the temperature so that a lower curing temperature Wlli require a longer curing time and vice versa.
  • the temperature of curing should not be so high as to cause degradation of the textile or the azlridme.
  • an adequate cure is elTected by heatlng the treated textile in an oven at about C. for about 5 to 60 minutes.
  • the present invention is of particular advantage in its application to wool, this is by no means the only type of fiber which comes into the ambit of the invention.
  • the invention is applicable to the treatment of any textile material and this material may be in any physical form, e.g., bulk fibers, filaments, yarns, threads, slivers, roving, top, webbing, cord, tapes, woven or knitted fabrics, felts or other non-woven fabrics, garments or garment parts.
  • textile materials to which the invention may be applied are: Polysaccharide-containing textiles, for instance, those formed of or containing cellulose or regenerated celluloses, e.g., cotton, linen, hemp, jute, ramie, sisal, cellulose acetate rayons, cellulose acetate-butyrate rayons, saponified acetate rayons, viscose rayons, cuprammonium rayons, ethyl cellulose, fibers prepared from amylose, algins, or pectins; mixtures of two or more of such polysaccharide-containing textiles.
  • cellulose or regenerated celluloses e.g., cotton, linen, hemp, jute, ramie, sisal, cellulose acetate rayons, cellulose acetate-butyrate rayons, saponified acetate rayons, viscose rayons, cuprammonium rayons, ethyl cellulose, fibers prepared from amylose, algins, or pect
  • Protein-containing textiles for instance, those formed of or containing wool, silk, animal hair, mohair, leather, fur, regenerated protein fibers such as those prepared from casein, soybeans, peanut protein, zein, gluten, egg albumin, collagen, or keratins, such as feathers, animal hoof or horn. Mixtures of any two of more protein-containing textiles. Mixtures of polysaccharide-containing textiles and protein-containing textiles, e.g., blends of wool and cotton; wool and viscose, etc.
  • Textiles formed of or containing synthetic resins e.g., alkyd resins, polyvinyl alcohol, partially esterified or partially etheri-fied polyvinyl alcohol, nylon, polyurethanes, polyethylene glycol terephthalate, polyacrylonitrile, polyethylene, polypropylene, polyvinyl chloride, and polyvinylidene iodine chloride.
  • Inorganic fibers such as asbestos and glass fibers.
  • the applications of the teachings of the invention may be for the purposes of obtaining functional or decorative effects such as shrinkproofing, developing permanent crease qualities, sizing, finishing, increasing abrasion resistance, increasing gloss or transparency, increasing water-, oil-, and soil-repellency, increasing adhesion or bonding characteristics of the substrates with rubber, polyetser resins, etc.
  • a particular embodiment of this invention is concerned with the production of wool products which exhibit not only shrink resistance but also permanent press qualities.
  • Existing wool shrinkproofing treatments do lead to dimensionally-stable fabrics; however, when the fabrics are washed or drycleaned they have a mussy appearance and must be pressed.
  • Creases have been set in woolen garments by, for example, treatment with reducing agents such as ammonium thioglycollate or sodium bisulphite. The creases, however, do not withstand aqueous laundering nor generally more than 1 or 2 dry-cleanings. Of course, no shrinkproofing is attained with these creasing procedures.
  • This embodiment of the invention is most profitably practiced in a system which incorporates a delayed cure, that is, the aziridine is applied to the fabric but curing is delayed until the fabric has been made up into the desired product which may be, for example, a completed garment. The curing then not only bonds the aziridine to the fabric, but also renders permanent the creases or pleats which have been imparted to the fabric.
  • a delayed cure that is, the aziridine is applied to the fabric but curing is delayed until the fabric has been made up into the desired product which may be, for example, a completed garment.
  • the curing then not only bonds the aziridine to the fabric, but also renders permanent the creases or pleats which have been imparted to the fabric.
  • the aziridine is applied to the fabric using a solution or emulsion of the aziridine, as described hereinabove.
  • the conditions of application may be adjusted to vary the amount of aziridine deposited on the fabric. Usually, it is preferred to deposit about 0.2 to 20% of the aziridine, based on the weight of the fabric.
  • a reducing agent such as sodium bisulphite, is incorporated in the liquid preparation of the aziridine. However, as hereinafter explained the reducing agent may be applied at a later stage in the process.
  • the treated fabric is then dried to remove the solvent or other carrier in which the aziridine was dispersed for the application step.
  • the drying may be in air at ordinary (room) temperature, or, warm air may be applied to increase the rate of evaporation.
  • room ordinary
  • warm air may be applied to increase the rate of evaporation.
  • the temperature of the treated fabric should be kept below about 50 C. However, since curing does not occur immediately, short exposures to higher temperatures are permissible.
  • the fabric containing the aziridine in its uncured state is then made up into the desired product.
  • This may be, for example, a garment, in which case the fabric would be subjected to the usual garment-making operations of cutting, sewing, and pressing. Included in these operations would be formation of creases or pleats in selected areas by the usual pressing methods employed by the tailor.
  • a reducing agent may be applied to the textile during the moistening step which commonly forms a part of the pressing operation.
  • an aqueous solution of the reducing agent may be sprayed on the textile, particularly in those areas where it is intended to form creases or pleats.
  • the aziridines of the invention are particularly characterized by their stability, i.e. their ability to remain in an uncured state for long periods of time. Moreover, their stability is not affected by moisture. If moisture is applied (as necessary in certain garment fabricating steps) there is no danger of premature curing.
  • the garment or other textile article is then subjected to a curing operation to insolubilize the aziridine and bond it to the wool fibers.
  • the curing is accomplished by placing the garments in an oven where they are maintained at a temperature and for a time sufiicient to cause the desired curing of the applied aziridine.
  • temperatures of at least 50 C., preferably about -150 C. are applied for period of about 5-60 minutes.
  • the product after removal from the oven is now ready for use or for sale and, as previously noted, exhibits not only resistance to shrinkage when washed but also retains its pleats, creases, or other conformations imparted to the garment.
  • the products retain a neat appearance free from wrinkling or mussiness so that they are truly press-free, i.e., no pressing is needed even after repeated washings.
  • a reducing agent is preferably applied to the textile, concomitantly with application of the aziridine or in a later step but prior to curing.
  • reducing agents include: Inorganic sulphides such as alkali metal, alkaline earth metal, ammonuim, etc. sulphides and hydrosulphides.
  • Organic compounds containing a thiol group as, for example, thioglycollic acid, or its salts such as the alkali metal or ammonium salts; beta-mercapto ethanol; monthio glycerol; dithio-glycerol; butyl mercaptan; thiomalic acid or its salts; thio-lactic acid or its salts; thiophenol; thiocresol; etc.
  • Formamidine sulphinic acid also known as iminoaminomethane sulphinic acid betaine.
  • Formaldehyde sulphoxylates generally used in the form of their alkali metalwzinc, or ammonium salts.
  • the reducing agents used in accordance with the invention may be defined as sulphur-containing, reductive, disulphide-splitting agents because of the fact that they all contain sulphur in their structures and because they have the ability to open the disulphide (cysine) linkage in the wool molecule, generally converting a single disulphide (--SS) bond into two thiol (-SH) groups.
  • the amount of reducing agent is not critical and may be varied depending on such circumstances as the eflicacy of the agent selected, the durability of set desired in the product, the character of the fibers being treated, etc. Even minute amounts of the reducing agent will provide some degree of improvement.
  • the reducing agent is used in an amount from about (1L1 to about 2%, based on the weight of the textile substrate being treated. It is, of course, obvious that the reducing agent should not be applied in such a high proporion as would degrade the textile substrate.
  • the use of a reducing agent in conjunction with our aziridines is primarily of advantage in treat- 1 1 ments where the substrate is to be provided with durable creases or other configurations, it is within the broad ambit to employ the reducing agent in other procedures, e.g., ones wherein creasing is not involved.
  • the advantage of the reducing agent is that it enhances bonding of the aziridine to the textile substrate.
  • the invention includes in is broad compass any textile-treating procedure wherein the reducing agent is used in conjuncton with our aziridines, and is appled to the textile concomitantly with the aziridine or at any earlier or later stage, prior ot the curing step.
  • Washing procedure for shrinkage tests The samples were washed in a reversing agitator-type household washing machine, using a three-pound load, a water temperature of 105 F, and a low-sudsing detergent in a concentration of 0.1% in the wash liquor. The wash cycle itself was for 75 minutes, followed by the usual rinses and spin-drying. The damp material from the washer was then tumble-dried in a household-type clothes dryer. The dried samples were measured to determine their length nad width and the shrinkage calculated from the original dimensions.
  • Example 2 Application of aziridine-modified polytetramethyleneether polyurethane
  • the emulsion prepared as described above in Example 1 was diluted with water (to levels indicated below) and applied to swatches of wool. In some instances, measured amounts of NaHSO were added to the emulsions.
  • the treatments in each case were as follows: Wool swatches were immersed in the emulsion bath until completely wet-out, then the swatches were run through a squeeze roll to attain a wet-pick-up of 80100%, based on the weight of the fabric. The damp fabrics were dried in air at room temperature.
  • each swatch was moistened by spraying with water, folded, and then subjected to steaming and pressing on a tailors hot-head press.
  • the fabrics were steamed for 10-20 seconds, then pressure (-80 p.s.i.) and heat (ca. 140l50 C.) applied for 20 seconds.
  • the creased swatches were then cured in a forced draft oven at 300 F. for 20 minutes.
  • the cured swatches were then given three 75-minute washes (as described above) and tumble-dried after each wash. The swatches were measured for shrinkage and examined for crease retention and over-all appearance after each tumble drying (following each wash).
  • Excellent (E) sharp crease, fabric flat and in no need of ironing.
  • Good (G) sharp crease, fabric fiat but could use slight touching up with the iron.
  • Fair (F) crease still visible but not sharp, some wrinkling, needs definite ironing;
  • A represents the residue of a polytetramethyleneether glycol containing about twenty-five units.
  • Example 3 Examination of treated fabrics at intervals for delayed-cure features
  • the emulsion prepared as described in Example 1 was diluted to an aziridine concentration of 2%. In one of the runs, the diluted emulsion per se was used; in a second run spectrum of the solution revealed no residual NCO groups. 2% of NaHSO was added.
  • Wool fabric was treated as follows: Swatches of the wool were wet-out in the emulsion bath, pressed to 80- 100% wet pick-u and air-dried at room temperature. The dried fabrics were then stored at room temperature, and after certain times of storage (3, 8, 1.5, and 30 days) were creased and cured as described in Example 2. The swatches were then subjected to four 75-minute washes with tumble-drying after each wash. The results are tabulated below:
  • Example 4 The starting material for this synthesis was a com* flashal liquid polyether polyurethane having a molecular weight of about 850 and an isocyanate (-NCO) content of about 9.5%. It is believed to have the structure wherein A represents the residue of polytetramethyleneether glycol containing about seven One hundred grams (0.12 mole) of the liquid poly urethane was dissolved in 300 ml. of dry benzene. While stirring, 13 ml. (0.26 mole) of ethylene imine was added at a rate slow enough that the reaction temperature did not rise above 40 C.
  • An emulsion containing 3% of the aziridine-modified polyurethane was prepared as follows: To 47 grams of the solution of the aziridine polymer, prepared as described above, was added 1 gram of a commercial emulsifier, tris(polyoxyethylene)sorbitan monopalmitate, and 450 ml. of water and applying rapid agitation in a blender. More dilute emulsions were prepared by incorporating water in this stock emulsion.
  • Samples of wool flannel were treated with the emulsions by padding with the emulsion, squeezing through rollers to remove excess liquid, and then curing in an oven for 20 minutes at 300 F.
  • the treated samples were then tested for shrink resist ance, using the Accelerotor method.
  • the fabric samples are milled at 1700 r.p.m. for 2 minutes at 40-42 C. in an Accelerotor with aqueous sodium oleate (0.5%) solution, using a liquor-to-Wool ratio of 50 to 1.
  • the samples were measured to determine their area and the shrinkage calculated from the original area. This is a very severe test which applied to untreated wool samples gives an area shrinkage of 40-50%.
  • the Accelerotor is described in American Dyestufl Reporter, vol. 45, p. 685, Sept. 10, 1956.
  • the starting material for the synthesis was a commercial liquid polyether polyurethane having a molecular weight of about 1300 and an isocyanate (NCO) content of 6.5%. It is believed to have the structure O LNH NCO ea. 13
  • Emulsions were prepared of the aziridine-modified polyurethane, and these were applied to wool flannel, and tested for shrinkage, all as described above in Example 4. The results are tabulated below.
  • Example 7 A series of experiments were carried out to compare the effectiveness of the aziridine derivatives of the invention with that of various commercial products recommended for shrinkproofing applications.
  • the various products tested were:
  • the main component of the polymer is a soft acrylate, polybutyl acrylate. It is sold under the name HA-8 by Rohm and Haas Co. for wool shrinkproofing and other uses. It was used with an acid catalyst, ZnNO in accordance with the manufacturers recommendation. It was applied in the form of a 4% emulsion, to which was added sodium bisulphite (1% (D) A urea-formaldehyde condensation product, consisting basically of dihydroxyethylene dimethylol urea:
  • Samples of a wool fabric were treated with the various agents described above, using the following technique in each case.
  • the fabric was wet-out in the aqueous solution or emulsion of the agent, put through squeeze rolls to 80-100% wet pick-up, and dried in air overnight.
  • the next day the samples were moistened by spraying with water and were creased by folding and application of steam and pressure. The creased samples were then cured in an oven3l0 F. for minutes.
  • Example 8 Experiments were carried out to compare the effectiveness of the process of the invention with one wherein a commercially-employed shrinkproofing treatment was followed by treatment with sodium bisulphite.
  • a sample of undyed worsted (wool) fabric was given a shrinkproofing treatment by application of polyhexamethylene sebacamide through interfacial polymerization, as disclosed in Pat. 3,078,138.
  • the fabric was first immersed in an aqueous solution of hexamethylene diamine (1.5%) and sodium carbonate (1.5%), run through squeeze rolls, then immersed in a solution of sebacoyl chloride (2.0%) in a volatile petroleum hydrocarbon solvent, run through squeeze rolls, and washed in water to remove unreacted materials, and dried.
  • the fabric was then wet-out with an aqueous 2% solution of sodium bisulphite and creased by folding and application of steam and pressure, as described in Example 2.
  • Example 9 A hydroxy-terminated polyethylene adipate of molecular weight approximately 6500 was end-capped by reaction with an excess of toluene diisocyanate to produce a polyether polyurethane with terminal NCO groups. One mole of this polymer was then reacted with two moles of ethylene imine to produce an aziridine-terminated polyether polyurethane. A 2% emulsion of this aziridine-modified polymer was prepared as in Example 1, part (B), and wool fabric was treated with the emulsion as described in Example 2. After four 75-minute washes the treated fabric showed 3% shrinkage in the warp and 2% shrinkage in the fill directions, while the control (untreated wool fabric) had shrunk 30% in the warp and 24% in the fill under the same washing conditions.
  • a process of treating textile material to improve its properties which comprises depositing on the textile material an aziridine-modified polyurethane of the structure I CHR" wherein:
  • A is the residue of a polyether polyol or polyester polyol having a valence of n
  • R is a hydrocarbon radical containing at least two carbon atoms
  • R" is hydrogen or a lower alkyl radical
  • n is an integer from 2 to 10
  • x is an integer from 1 to 2.
  • R is hydrogen, halogen, lower alkoxy, or a radical of the structure CHR R is hydrogen or a lower alkyl radical,
  • n is an integer from 2 to 10
  • x is an integer from 1 to 2.
  • DONALD LEVY Primary Examiner C. E. VAN HORN, Assistant Examiner US. Cl. X.R.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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US67606767A 1967-10-18 1967-10-18
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Cited By (6)

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Publication number Priority date Publication date Assignee Title
US3925581A (en) * 1972-09-01 1975-12-09 Bayer Ag Process for finishing textiles made of fibers which contain keratin
US4263188A (en) * 1979-05-23 1981-04-21 Verbatim Corporation Aqueous coating composition and method
US4404253A (en) * 1979-04-11 1983-09-13 Agfa-Gevaert Aktiengesellschaft Magnetic recording medium
DE3435619A1 (de) * 1984-09-28 1986-04-03 Chemische Fabrik Pfersee Gmbh, 8900 Augsburg Verfahren zum schrumpf- und filzfestmachen von keratinfasern enthaltendem textilgut
US6056788A (en) * 1997-03-04 2000-05-02 Ciba Specialty Chemicals Corporation Processes for creasing moist wool fabrics
CN114940739A (zh) * 2022-06-08 2022-08-26 万华化学集团股份有限公司 一种高耐热易溶解tpu及其制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3920881A (en) * 1973-07-02 1975-11-18 American Cyanamid Co Textile finish using a combination of an aminoplast resin and monomethyloldicyandiamide
JPS55132777A (en) * 1979-04-02 1980-10-15 Sumitomo Chemical Co Resin processing of knitted fabric
US4306872A (en) * 1980-01-17 1981-12-22 American Cyanamid Company Imidazolidinones in a durable press process

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US2327760A (en) * 1940-07-19 1943-08-24 Bestian Herbert Fibrous materials
US2881046A (en) * 1959-04-07 Process for reacting protein fibers with
US2891877A (en) * 1956-06-05 1959-06-23 Leon H Chance Flame resistant organic textiles and method of production
US3279882A (en) * 1964-07-07 1966-10-18 Stevens & Co Inc J P Process of stabilizing proteinaceous materials through treatment with a polyethyleneimine and a polyaziridine
US3285798A (en) * 1962-06-06 1966-11-15 Stevens & Co Inc J P Chemical composition, process using same and resulting product
US3300274A (en) * 1963-10-22 1967-01-24 Allen G Pittman Process of treating textiles with perfluoroacyl bis-(1-aziridine) compounds and resulting textile products
US3454671A (en) * 1964-11-02 1969-07-08 Bayer Ag Polyurethanes having improved dyeability,light fastness and fastness to waste gases and method of preparing the same

Patent Citations (7)

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Publication number Priority date Publication date Assignee Title
US2881046A (en) * 1959-04-07 Process for reacting protein fibers with
US2327760A (en) * 1940-07-19 1943-08-24 Bestian Herbert Fibrous materials
US2891877A (en) * 1956-06-05 1959-06-23 Leon H Chance Flame resistant organic textiles and method of production
US3285798A (en) * 1962-06-06 1966-11-15 Stevens & Co Inc J P Chemical composition, process using same and resulting product
US3300274A (en) * 1963-10-22 1967-01-24 Allen G Pittman Process of treating textiles with perfluoroacyl bis-(1-aziridine) compounds and resulting textile products
US3279882A (en) * 1964-07-07 1966-10-18 Stevens & Co Inc J P Process of stabilizing proteinaceous materials through treatment with a polyethyleneimine and a polyaziridine
US3454671A (en) * 1964-11-02 1969-07-08 Bayer Ag Polyurethanes having improved dyeability,light fastness and fastness to waste gases and method of preparing the same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925581A (en) * 1972-09-01 1975-12-09 Bayer Ag Process for finishing textiles made of fibers which contain keratin
US4404253A (en) * 1979-04-11 1983-09-13 Agfa-Gevaert Aktiengesellschaft Magnetic recording medium
US4263188A (en) * 1979-05-23 1981-04-21 Verbatim Corporation Aqueous coating composition and method
DE3435619A1 (de) * 1984-09-28 1986-04-03 Chemische Fabrik Pfersee Gmbh, 8900 Augsburg Verfahren zum schrumpf- und filzfestmachen von keratinfasern enthaltendem textilgut
US6056788A (en) * 1997-03-04 2000-05-02 Ciba Specialty Chemicals Corporation Processes for creasing moist wool fabrics
CN114940739A (zh) * 2022-06-08 2022-08-26 万华化学集团股份有限公司 一种高耐热易溶解tpu及其制备方法
CN114940739B (zh) * 2022-06-08 2023-07-11 万华化学集团股份有限公司 一种高耐热易溶解tpu及其制备方法

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GB1250332A (de) 1971-10-20
DE1802808A1 (de) 1970-01-08
US3627556A (en) 1971-12-14
CH1524468D (de) 1900-01-01
NL6814683A (de) 1969-04-15

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