US3466136A - Shrinkproofing of wool - Google Patents

Shrinkproofing of wool Download PDF

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US3466136A
US3466136A US352700A US3466136DA US3466136A US 3466136 A US3466136 A US 3466136A US 352700 A US352700 A US 352700A US 3466136D A US3466136D A US 3466136DA US 3466136 A US3466136 A US 3466136A
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solution
diamine
chloride
wool
water
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William L Wasley
Robert E Whitfield
Lowell A Miller
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US Department of Agriculture USDA
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507Polyesters
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59Polyamides; Polyimides

Definitions

  • This invention relates to and has among its objects the provision of novel methods for treating textile materials, particularly wool, to achieve shrinkproofing and other desirable effects. Further objects and advantages of the invention will be evident from the following description wherein parts and percentages are by weight, unless other wise specified.
  • a wool fabric is serially impregnatedwith two solutions--the first being a solution of a'diarnine in water, the second being a solution of a diacid chloride in a waterimmiscible, volatile, inert solvent.
  • the fibers are coated with superposed layers of the mutually ⁇ insoluble solutions: an inner layer of diamine in water and an outer layer of diacid chloride in water-immiscible solvent.
  • the diamine and diacid chloride react almost instantaneously at the interface between the phases, producing in situ on the fibers a highmolecular weight, resinous polyamide which coats the fibers and renders the fabric shrinkproof without detriment to the hand, porosity, and other valuable properties of, the fabric.
  • the polyamide is chemically .hdnded to the wool so that the shrinkproofing effect is highly durable, i.e., the polyamide deposit is not removed by repeated washing of the treated fabric in conventional soap and water or detergent and water laundering formulations, or in conventional dry-cleaning formulations. From a procedural standpoint, the process has the advantage of simplicity and rapidity in that the basic operation is simply a serial impregnation of the fabric in the two solutions.
  • a preferred class of reducing agents comprises the inorganic salts which provide sulphide ions in aqueous: solution. Typical of this class are the alkali metal, alkaline earth metal, ammonium, etc. sulphides and hydrosulphides.
  • Another very useful class of reducing agents comprises the 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 glyt cerol; .dithio-glycerol; butyl mercaptan; thiornalic acid or its, salts; .thio-lactic acid or its salts; thiophenol; thiocresol;
  • Formamidine sulphinic acid also known as iminoaminomethane sulphinic acid betaine.
  • Formaldehyde sulphoxylates generally used in the form of their alkali metal, zinc, or ammonium salts.
  • the reducing agents used in accordance with the invention may be defined as sulphur-containing, reductive, disulphidesplitting agents because of the fact that they all contain sulphur in their structures and because they have the ability to open the disulphide (cystine) 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 efficacy 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 over the known techniques.
  • the reducing agent is used in an amount from quire any heat curing of the treated fabric as is commonly necessary in most resin shrinkproofing procedures.
  • One phase of the invention involves the addition of a reducing agent to one of the complementary treating solutions, preferably to the diamine solution.
  • a primary advantage obtained thereby is that when the Product is subsequently subjected to a conventional setting treatment (heating while constrained in a predetermined shape), it acquires a permanent set. Accordingly, when the fabric or garments made therefrom are subjected to such stresses as crushing, folding, or use in the rain or other humid conditions, they remain essentially free from wrinkles or creases. Moreover, this set is maintained even when the material is subjected to repeated washing or dry cleaning. Another advantage is that such desirable setting effect is about 0.1 to 5 parts per part of diamine in the treating solution.
  • the maximum concentration of the reducing agent is generally preferred to limit the maximum concentration of the reducing agent to less than 0.5 molar, preferably not more than about 0.2 molar.
  • the reducing agents in. conjunction with an alkaline agent to raise the pH of the solution of reducing agent plus diamine to a level of about 12 to 13.
  • additional alkaline material will not usually be necessary because of the strongly basic character of the sulphides.
  • alkaline material such as an alkali metal hydroxide, carbonate, or, more preferably, an alkali metal metasilicate or dithiocarbamate.
  • Patent 3,078,138 is employed with, of course, the change that the reducing agent is added.
  • the textilein the form of garments, fabris, yarn, roving, top, etc.- is entered into an aqueous solution containing a diamine plus the reducing agent.
  • the textile After the textile has been impregnated with this solution it is pressed to remove excess liquid.
  • the second solution for example, a solution of a diacid chloride in a volatile, inert, Water-immiscible solvent.
  • the textile After another pressing to remove excess liquid, the textile is washed in warm water containing a small proportion of a soap or synthetic detergent and rinsed in order to remove unreacted materials and particles of resinous reaction product which are not firmly attached to the textile fibers. Following this, the textile is dried and then treated to establish the permanent set. This is done in conventional manner and simply involves arranging the material in a desired pattern and applying heat while constraining it in such pattern. For example, if a fiat set is desired (as in the case with ordinary yardage) the product is subjected to a standard semi-decating procedure. This involves winding the fabric, sandwiched between smooth cotton cloth, onto the hollow, perforated shaft of the semi-decater device.
  • the basic principles of the aforesaid Miller et al. process (3,078,138) are applied in conjunction with certain additives-a silicate or a dithiocarbamate-whereby to achieve advantageous results over and above those obtained by the patented procedures.
  • certain additives-a silicate or a dithiocarbamate-whereby to achieve advantageous results over and above those obtained by the patented procedures.
  • silicate sodium metasilicate is preferred.
  • alkali metal silicates may be used, for example, alkali metal metasilicates, ortho silicates, or any of the molecularlydehydrated silicates, or polysilicates as they may be termed, such as Na Si O Na Si O Na Si O etc.
  • dithiocarbamate we prefer to use ethylene bis-(sodium dithiocarbamate) which has the formula s s NaSi 1N H-CHz-CHz-NH-iL-S-N a
  • dithiocarbamates are prepared by reacting a primary or secondary amine with carbon bisulphide in the presence of a base such as sodium hydroxide whereby a hydrogen atom attached to nitrogen is replaced by the radical
  • a base such as sodium hydroxide
  • M is a metal such as an alkali metal
  • Typical of the compounds which may be used are propylene bis- (sodium dithiocarbamate), tetramethylene bis-(sodium dithiocarbamate), paraphenylene bis-(sodium dithiocarbamate), piperazine bis-(sodium dithiocarbamate), sodium ethyl dithiocarbamate, sodium phenyl dithiocarbamate, sodium piperidyl dithiocarbamate, etc.
  • the amount of the agent is not critical and may be varied depending on such circumstances as the efiicacy of the agent selected, the character of the fibers being treated, the degree of improvement in shrinkproofing desired, etc. Even small amounts of the agents will provide some degree of improvement over the known techniques.
  • the agents in question are strongly alkaline and are usually used in such amount as to raise the pH of the diamine solution to above 12. At this point it may be mentioned that Miller et al.
  • addition of sodium carbonate in amount adequate for HCl-acceptance does not yield the results obtained as described herein when, for example, sodium metasllicate or ethylene bis-(sodium dithiocarbamate) is added to the diamine solutionnote Examples 2 and 3, below.
  • the alkali metal hydroxides suggested by Miller et al. are useful as HCl-acceptors, they exert such a corrosive action that the wool fibers being treated are damaged-they develop a harsh hand totally unlike the smooth hand attained When wool fabrics are treated in accordance with the present invention, using silicates or dithiocarbamates as the additive.
  • alkali metal hydroxides are useful additives for HCl-acceptance, they cannot provide the combination of desirable results-improved shrinkage control plus retention of the hand of the textileobtained with the additives used in accordance with the present invention.
  • silicates and dithiocarbamates are believed to involve the following mechanism: In the known practice, there is a likelihood that the diamine in the treating solution will react with CO from the atmosphere, yielding reaction products such as carbamates and carbonates which interfere with proper amine-diacid chloride condensation. However, it is postulated that the added silicate (or dithiocarbamate) prevents or minimizes this diamine-CO reaction with the net result that the diamine is utilized fully in the desired condensation with the diacid chloride. Another point is that it is believed that the silicate (or dithiocarbamate) has the effect of opening up reactive sites on the wool molecules.
  • Patent 3,078,138 is employed with, of course, the change that the silicate or dithiocarbamate is added.
  • the textile material-in the form of garments, fabrics, yarn, roving, top, etc. is entered into an aqueous solution containing a diamine plus the added silicate or dithiocarbamate.
  • the textile After the textile has been impregnated with this solution, it is pressed to remove excess liquid.
  • the second solution for example, a solution of a diacid chloride in a volatile, inert, water-immiscible solvent.
  • the textile After another pressing to remove excess liquid, the textile is wased in Warm water containing a small proportion of a soap or synthetic detergent and rinsed, thus to remove unreacted materials, particles of resin not firmly bonded to the fibers, ect. Following this, the textile is dried.
  • Other conventional treatments such as dyeing, shearing, pressing, semi-decating, etc. may be applied as desired.
  • the invention encompases the utilization of any of the reaction systems -disclosed in Patents 3,078,138, 3,084,0l8, 3,084,019 and 3,093,441-where one of the reactants is a diamine and the other is a bifunctional compound capable of forming polymers with the diamine.
  • Typical of these bifunctional compounds are diacid, chlorides, bischloroformates, diisocyanates, and mixtures thereof.
  • the polymer formed is a polyamide; where a bischloroformate is used, the polymer is a polyurethane; where a disocyanate is used, the polymer is a polyurea.
  • a diacid chloride is used
  • the polymer formed is a polyamide; where a bischloroformate is used, the polymer is a polyurethane; where a disocyanate is used, the polymer is a polyurea.
  • interpolymers may be produced. Typical of the last is the use of a diamine in conjunction with a mixture of a diacid chloride and a bischloroformate to produce a type of interpolynter which may be termed a copoly amide-urethane.
  • the invention encompasses application of the critical factors described above in connection with any system for shrinkproofin'g which involves serial impregnation of a wool textile with (1) an aqueous diamine solution and then with (2) a solution of a bifunction-al compound capable of forming a polymer with the diamine, said second solution having as its solvent an inert, essentially 'waterdmmiscible solvent.
  • a bifunction-al compound capable of forming a polymer with the diamine
  • the second solution having as its solvent an inert, essentially 'waterdmmiscible solvent.
  • typical of the bifunctional compounds which can be employed in the second solution are acid chlorides, bischloroformates, diisocyanates, and mixtures thereof.
  • diamine one may employ any of the aromatic,
  • dliamines may be substituted if desired with various non-interferring (nonfunctional) substituents such as ether radicals, thioether radicals, tertiary amino groups, sulphone groups, fluorine atoms, etc.
  • Typical compounds in this category are listed below merely by way of illustration and not by way of limitation: ethylene diamine; trimethylene diamine; tetramethylene diamine; hexamethylene diamine; octamethylene diamine; decamethylene diamine; N, N'-dimethyl-l, 3-propanediamine; l,2-diamino2-methylpropane; 2,7-diamino 2,6 dimethyloctane; N,N-dirnethyl-l,6-hexanediamine; 1,4-diamino cyclohexane; 1,4-bis-(a)
  • aliphatic alpha, omega diamines particularly of the type wherein n has a value of 2 to 12, preferably 6 to 10. Particularly preferred in hexamethylene diamine, i.e., the compound of the above formula wherein 11:6.
  • diacid chloride one may employ any of the aliphatic, aromatic, or heterocyclic compounds containing two carbonylchloride (-COCl) groups, preferably separated by at least two carbon atoms.
  • the diacid chlorides may be substituted if desired with non-interfering (non-functional) substituents such as ether groups, thioether groups, sulphone groups, etc.
  • Typical examples of compounds in this category are listed below merely by way of illustration and not limitation: oxalyl chloride, maleyl chloride, fumaryl chloride, malonyl chloride, succiny chloride, glutaryl chloride, adipyl chloride, pirneyl chloride, suberyl chloride, azelayl chloride, sebacyl chloride, cyclohexane-1,4-biscarbonyl chloride, phtha'lyl chloride, isophthalyl chloride, terephthalyl chloride, 4,4'-biphenyl-dicarbonyl chloride, ,B-hydromucony'l chloride,
  • diacid chloride it is generally preferred to use the aliphatic compounds containing two carbonylchloride groups in alpha, omega positions, particularly those of the type:
  • n has a value from 2 to 12.
  • Another preferred category includes the compounds of the formula ClCOA-COC1 '(Where A is the benzene or cyclohexane radical), especially para-substituted compounds such as terephthalyl and hexahydroterephthalyl chlorides.
  • the bischloroformate one may use any of the aliphatic, aromatic, or heterocyclic compounds containing two chloroformate groups preferably separated by at least two carbon atoms.
  • the bischlorofor-mates may be substituted if desired with non-interfering (non-functional) substituents such as sulphone groups, ether groups, thioether groups, etc.
  • Typical examples of compounds in this category are listed below merely by way of illustration and not limitation: ethylene glycol bischloroformate, diethylene glycol bischloroformate, 2,2-dimethyl propane 1,3-diol bischloroformate, propane-1,3-diol bischloroformate, butane-1,4-diol bischloroformate, hexane 1,6 diol bisch'loroformate, octane-1,8-diol bischloroformate, decane 1,10-di0l bischloroformate, butane-1,2-dio1 bischloroformate, hexane-1,2-di0l bischloroformate, Z-methoxyglycerol-1,3-bischloroformate, glycerol 1,2 bischloroformate, glycerol-1,3-bischloroformate, diglycerol bischloroformate, hexa
  • aliphatic bischloroformates for example, those of the type:
  • CICO' (CHZ)L1 OPJCI wherein n has a value from 2 to 12.
  • Another preferred category of compounds are the bis-chloroformates derived from polyethylene glycols, e.g.
  • a useful category of aromatic bischloroformates are the bisphenol chloroformates, that is, compounds of the type:
  • RC-R represents an aliphatic hydrocarbon group containing 1 to 12 carbon atoms and R is hydrogen or a low alkyl radical.
  • the sulphur analogues of the bischloroformates may be used and such are included within the spirit of the invention.
  • the compounds containing two group one may use any of the compounds containing the sulphur analoges of these groups, for example, the compounds containing two groups of the formula it XCCl wherein one X is sulphur and the other is oxygen or wherein both Xs are sulphur.
  • the bischloroformates are preferred because they are reactive and relatively inexpensive, it is not essential that they contain chlorine and one may use the corresponding bisbromoformates or bisiodoformates.
  • the diisocyanate one may employ any of the aliphatic, aromatic, or heterocyclic compounds containing two isocyanate (-NCO) groups, prefer-ably separated by at least two carbon atoms.
  • the diisocyanates may be substituted if desired with non-interfering (nonfunctional) substituents such as ether groups, thioether groups, sulphone groups, etc, Typical examples of compounds in this category are listed below merely by way of illustration and not limitation: ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, haxamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, cyclohexylene diisocyanate, bis(2-isocyanatoethyl) ether, bis(2-isocyanatoethyl) ether of ethylene glycol, o-phenylene
  • diphenyl ether-4,4'-diisocyanate i.e.
  • biphenylene diisocyanate 3,3 dimethoxy-biphenylene- 4,4-diisocyanate, naphthalene diisocyanates, polymethyl polyphenyl isocyanates, etc.
  • the sulphur analogues of these compounds may be used and such are included within the spirit of the invention.
  • the compounds containing two NCO groups one may use their analogues containing either two NCS groups or one -NCO group and one NCS group.
  • Another point to be made is that it is within the spirit of the invention to utilize the derivatives which yield the same products with compounds containing active hydrogen as do the isocyanates.
  • the biscarbamyl chlorides which may be used in place of the diisocyanates,
  • the preferred compounds are the aliphatic diisocyanates, for example, those of the type OCH( CH -NCO wherein n has a value from 2 to 12.
  • Other preferred compounds are the tolune diisocyanates, xylyene diisocyanates, and diphenylmethane-4,4'-diisocyanate which may also be termed methylene-bis(p-phenylisocyanate).
  • the process of the invention makes use of an interfacial polymerization (formation of a polymer at the interface between mutually-immiscible phases of the individual rectants), it is evident that the polymer-forming agents need be applied in solutions wherein the solvents are substantially mutually immiscible.
  • the diamine reactant is applied in aqueous solution while the complementary reactant (diacid chloride, bischloroformate, or
  • diisocyanate is applied as a solution in an inert, essentially water-immiscible solvent, preferably one which is volatile, for example, benzene, carbon tetrachloride, toluene, xylene, ethylene dichloride, chloroform, hexane, octane, petroleum ether, or other volatile petroleum hydrocarbon mixture.
  • an inert essentially water-immiscible solvent
  • the solution of the complementary reactant be dilute; that is, it should contain about /2 to preferably /2 to 2%, of the reactant.
  • the conditions of treatment such as the rate of traversal of the fabric, concentration of the reactants, degree of pressing, etc., are so correlated that the product contains about 0.25 to 3% of polymer.
  • reaction promoters are required in the reactive solutions.
  • agents such agents as tertiary amines to the aqueous diamine solution.
  • Other typesof agents which may be added to the diamine solution or to the solution of the complementary reactant are tributyl tin chloride, stannous tartrate, ferric chloride, titanium tetrachloride, boron trifluoride-diethyl ether complex, or tin salts of fat acids such as tin laurate, myristate, etc.
  • a surface-active agent for this purpose one may use such agents as sodium alkyl (C -C sulphates, the sodium alkane (C C sulphonates, the sodium alkyl (C C benzene sulphonates, esters or sulphosuccinic acid such as sodium dioctylsulphosuccinate, and soaps, typically sodium salts of fat acids.
  • Surface-active agents of the non-ionic type may also be used and they have the desirable property of being non-substantive; that is, they are not preferentially absorbed by the wool.
  • nonionic agents are the reaction products of ethylene oxide with fatty acids, with polyhydric alcohols, with partial esters of fatty acids and polyhydric alcohols or with alkyl phenols, etc.
  • Typical of such agents are a polyoxyethylene stearate containing about oxyethylene groups per mole, a polyoxyethylene ether of sorbit-an monolaurate containing about 16 oxyethylene groups per mole, a distearate of polyoxyethylene ether of sorbitol containing about 40 oxyethylene groups per mole, iso-octyl phenyl ether of polyethylene glycol, etc.
  • a useful class of non-ionic agents are the nonylphenoxy polyethyleneoxy ethanols, containing 9 to 12 moles of ethylene oxide per mole of nonylphenol, as these compounds are readily soluble in the diamine solution even in the presence of relatively high concentrations of sodium carbonate. Generally, only a small proportion of surfaceactive agents is used, on the order of 0.05 to 0.5%, based on the weight of the solution.
  • a supplementary solvent may be added to the primary solvent (water) in quantity suflicient to disperse the active reactant.
  • the primary solvent water
  • one may employ acetone, or other iner-t, volatile solvent, particularly one that is at least partially miscible with water.
  • Wool is by no means the only substrate which can be treated.
  • the invention can be utilized in the treatment of any fibrous material. Typical examples of such materials are animal hides; leather; animal hair; cotton; hemp; jute; ramie; linen; wood; paper; synthetic cellulosic fibers such as viscose, cellulose acetate, cellulose acetatebutyrate; casein fibers; polyvinyl alcohol-protein fibers; alginic fibers; glass fibers; asbestos; and organic noncellulosic fibers such as Poly (ethylene glycol terephthalate), polyacrylonitrile, polyethylene, polyvinyl chloride, polyvinylidene chloride, etc.
  • Such applications of the teachings of the invention may be for the purpose of obtaining functional or decorative effects such as sizing, finishing, increasing gloss or transparency, increasing water-repellency, increasing adhesionor bonding-characteristics of the substrates with rubber, polyester resins, etc.
  • the process of the invention is of special advantage as applied to hydrogen-donor textiles, for example, protein and cellulosic fibers, because these are especially adapted for chemical bonding of the resin to the fiber molecules.
  • Standard wash procedure for shrinkage test The tests for shrinkage referred to below were conducted in the following manner: The wool samples were washed in a reversing agitator-type household washing machine, using a three-pound load, a water temperature of 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. In most cases this washing program was repeated several times. The damp material was then tumble-dried in a householdtype clothes dryer. The samples were then measured to determine their length and width and the shrinkage calculated from the original dimensions.
  • Solution B -3% sebacoyl chloride in a petroleum distillate (Stoddard solvent).
  • EXAMPLE 2 Comparison of sodium metasilicate and sodium carbonate Solution A.--Aqueous solution containing 2% hexamethylene diamine and 2% sodium metasilicate. Solution A .-Aqueous solution containing 2% hexaunethylene diamine and 2% sodium carbonate. Solution B.3% Sebacoyl chloride in a petroleum distillate (Stoddard solvent).
  • An all-wool worsted fabric was treated, in continuous operation, in the following manner: Immersion in solution A or A for 5 seconds, pressing to remove excess liquid, immersion in solution B for 5 seconds, pressing to remove excess liquid, washing in warm water containing a small amount of a detergent, rinsing in plain water, and drying in air.
  • EXAMPLE 3 6. The process of claim 3 wherein said sulphur-contain- Solution A.An aqueous solution containing 0.2 molar ing, reductive, disulphide-splitting agent is ,B-mercaptohcxamethylene diamine plus one of the following ad- 75 ethanol.

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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)
  • Chemical Or Physical Treatment Of Fibers (AREA)
US352700A 1964-03-17 1964-03-17 Shrinkproofing of wool Expired - Lifetime US3466136A (en)

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DE (1) DE1469421A1 (ko)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4102642A (en) * 1976-04-30 1978-07-25 Banks John B Treatment of fabric comprising cotton or keratinous fibers for shrink resistance
US4835803A (en) * 1986-07-24 1989-06-06 Shigesaburo Mizushima Process for producing a shape-memorizing wool and animal hair

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2508713A (en) * 1946-10-07 1950-05-23 Harris Res Lab Treatment of keratinous material
US2935016A (en) * 1952-09-05 1960-05-03 Hughes Aircraft Co High-speed printer
US3049445A (en) * 1961-03-23 1962-08-14 Lundgren Harold Palmer Shrinkproofing wool-containing textiles with polyepoxides and polyamides in the pressence of a reducing agent
US3051544A (en) * 1959-02-12 1962-08-28 Stevens & Co Inc J P Lustered wool product and method of making the same
US3078138A (en) * 1960-04-15 1963-02-19 Lowell A Miller Shrinkproofing wool with polyamides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2508713A (en) * 1946-10-07 1950-05-23 Harris Res Lab Treatment of keratinous material
US2935016A (en) * 1952-09-05 1960-05-03 Hughes Aircraft Co High-speed printer
US3051544A (en) * 1959-02-12 1962-08-28 Stevens & Co Inc J P Lustered wool product and method of making the same
US3078138A (en) * 1960-04-15 1963-02-19 Lowell A Miller Shrinkproofing wool with polyamides
US3049445A (en) * 1961-03-23 1962-08-14 Lundgren Harold Palmer Shrinkproofing wool-containing textiles with polyepoxides and polyamides in the pressence of a reducing agent

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4102642A (en) * 1976-04-30 1978-07-25 Banks John B Treatment of fabric comprising cotton or keratinous fibers for shrink resistance
US4835803A (en) * 1986-07-24 1989-06-06 Shigesaburo Mizushima Process for producing a shape-memorizing wool and animal hair

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AT252864B (de) 1967-03-10
NL6503375A (ko) 1965-09-20
DE1469421A1 (de) 1969-07-24
BE661152A (ko) 1965-07-01

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