US3519383A - Minimizing odor by adding methylol amides and methylol amines to reducing agent solutions used to treat wool - Google Patents

Minimizing odor by adding methylol amides and methylol amines to reducing agent solutions used to treat wool Download PDF

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US3519383A
US3519383A US764008*A US3519383DA US3519383A US 3519383 A US3519383 A US 3519383A US 3519383D A US3519383D A US 3519383DA US 3519383 A US3519383 A US 3519383A
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fabric
odor
reducing agent
formaldehyde
slight
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Earl Peters
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Deering Milliken Research Corp
Milliken Research Corp
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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
    • 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
    • D06M13/10—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 oxygen
    • D06M13/12—Aldehydes; Ketones
    • D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2412—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of unsaturated acyclic alcohols
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/01—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with hydrogen, water or heavy water; with hydrides of metals or complexes thereof; with boranes, diboranes, silanes, disilanes, phosphines, diphosphines, stibines, distibines, arsines, or diarsines or complexes thereof
    • D06M11/05—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with hydrogen, water or heavy water; with hydrides of metals or complexes thereof; with boranes, diboranes, silanes, disilanes, phosphines, diphosphines, stibines, distibines, arsines, or diarsines or complexes thereof with water, e.g. steam; with heavy water
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/54—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur dioxide; with sulfurous acid or its salts

Definitions

  • This invention relates to processes for eliminating the odor associated with keratin fibers which have been treated with reducing agents and to keratin fibers resulting from such processes.
  • Wool fabrics treated with reducing agents can, for example, be set in a creased configuration which is substantially durable to wetting.
  • This treatment has been utilized to improve fabrics containing wool fibers in many ways, e.g., to impart durable creases, pleats, and/or fiat configurations to wool fabrics, to impart to these fabrics a propensity for such setting operations, to elasticize wool fabrics and for many other purposes.
  • Fabrics treated with reducing agents have a characteristic, unpleasant odor.
  • the cause of the odor is unknown. It is not believed to be related to the sulfur content of many reducing agents utilized in the above processes since reducing agents which contain no sulfur atoms cause the same unpleasant odor. It is believed that the odor is merely characteristic of wool which has been treated with a reducing agent whereby disulfide linkages in the wool fiber are reduced to the sulfhydryl form.
  • These sulfhydryl groups are generally believed to be oxidized during subsequent setting operations, although the fact thereof and the mechanism of the oxidation reaction has given rise to a number of conflicting theories.
  • the end product invariably is characterized by an unpleasant odor.
  • a typical technique involves the use of masking agents on reduced wool fabrics. These agents mask the reduced wool odor, but often impart to the fabrics so-treated an odor which purchasers do not associate with normal wool. Consequently, the fabric containing the masking agent is nearly as objectionable in odor as the untreated reduced wool fabric. Furthermore, these masking agents often are not durable to conventional dry-cleaning techniques. It is particularly desirable that the reduced wool fabric be indistinguishable in odor from fabrics which have not been treated with reducing agents.
  • the odor problem associated with processes involving the use of reducing agents for modification of keratin fibers has been solved in accordance with this invention 3,519,383 Patented July 7, 1970 by contacting reduced keratin fibers, having the characteristic unpleasant odor, with an aldehyde compound.
  • the aldehyde may be applied as such or by way of an aldehyde-generating compound which, upon heating or chemical activation, generates the desired aldehyde.
  • Formaldehyde and formaldehyde generators are the most readily available aldehydes and are preferred for use in accordance with this invention.
  • the aldehyde When the aldehyde is applied to finished fabric, i.e., fabric which has undergone textile finishing operations, it is preferred that the aldehyde be derived from linear formaldehyde polymers, such as paraformaldehyde, which depolymerize upon heating to provide monomeric formaldehyde vapors.
  • the fabric is exposed to the vapors of the depolymerizing polymer in this embodiment of the invention. The vapors have little or deleterious effect on the fabric finish.
  • Typical aldehydes other than formaldehyde include saturated aliphatic aldehydes, such as acetaldehyde, propionaldehyde, butylaldehyde, isobutylaldehyde, valeraldehyde, isovaleraldehyde, caproaldehyde, enanthaldehyde, caprylaldehyde, pelargonaldehyde, capraldehyde, lauraldehyde, palmitic aldehyde, stearaldehyde and the like; unsaturated aliphatic aldehydes, such as acrolein, crotonaldehyde, tiglic aldehyde, citronellal, citral, propiolaldehyde and the like; alicyclic monofunctional aldehydes, such as formylcyclohexane and the like; aliphatic dialdehydes, such as glyoxal,
  • Typical aldehyde generating compounds include linear polymers, particularly those of the general formula HO (CH O) -H which depolymerize to monomeric formaldehyde gas upon vaporization.
  • this class of compounds there are included lower polyoxymethylene glycols, wherein n is from about 2 to about 8; paraformaldehyde, wherein n ranges from about 6 to about 100; alphapolyoxymethylenes, wherein n is greater than about 100; beta-polyoxymethylene wherein n is greater than about 100 and a trace of H is present, and the like.
  • Polyoxymethylene glycol derivatives may also be utilized, e.g., such as the polyoxymethylene diacetates, the lower polyoxymethylene dimethyl ethers, gamma-polyoxymethylenes (higher polyoxymethylene dimethyl ethers), delta-polyoxymethylenes, epsilon-polyoxymethylenes and the like.
  • higher temperatures e.g., up to about 200 C. are utilized to effect depolymerization of these derivatives.
  • depolymerization, with formaldehyde generation is most readily effected by treatment with dilute alkali or acid to produce the corresponding glycol which can then be hydrolyzed to formaldehyde solution.
  • Formaldehyde acetate may also be utilized.
  • Preferred formals are produced by reaction of formaldehyde with alcohols of the formula CH (OR) in the presence of an acid catalyst, wherein R is alkyl or aralkyl. These compounds hydrolyze to formaldehyde and the parent alcohol.
  • Preferred formals include methylol and 1,3-dioxolane. The latter compound hydrolyzes to formaldehyde and ethylene glycol and is particularly preferred among this class of compounds when used in presensitizing processes.
  • Additional suitable generating compounds include the various methylol compounds, for example, methylolalkanolamine sulfites, such as N-methylolethanolamine sulfite, N,N-dimethylolethanolamine sulfite, N,N-dimethylolisopropanolamine sulfite and the like; methylol amides, such as N-methylolformamide, N-methylolacetamide, N-methylolacrylamide and the like; amines, such as hexamethylene tetramine, trimethylolmelamine and the like; and compounds such as the alkali-metal formaldehyde bisulfites, including sodium and potassium formaldehyde bisulfites.
  • methylolalkanolamine sulfites such as N-methylolethanolamine sulfite, N,N-dimethylolethanolamine sulfite, N,N-dimethylolisopropanolamine sulfit
  • the above compounds may be utilized to eliminate the characteristic odor of keratin fibers which have been treated with any conventional reducing agents utilized for setting keratin fibers.
  • reducing agents include the metallic formaldehyde sulfoxylates, such as zinc formaldehyde sulfoxylate; alkali metal sulfoxylates, such as sodium formaldehyde sulfoxylate; alkali metal borohydrides, such as sodium borohydride and potassium borohydride; alkali metal sulfites, such as sodium or potassium bisulfite, sulfite, metabisulfite, or hydrosulfite; mercaptan acids, such as thioglycollic acid and its water-solu ble salts such as sodium, potassium, or ammonium thioglycollate; mercaptans, such as hydrogen sulfide and sodiurn or potassium hydrosulfide; alkyl mercaptans, such as butyl or butyl or ethyl mercaptans and mercaptan glycols, such as beta-mercaptoethanol; am
  • these reducing agents are applied to fabrics containing keratin fibers, after which the fabric is set in a durable configuration, e.g., creased, pleated and/or flat,
  • Fabrics may be treated with reducing agents at the mill level to impart thereto a propensity for subsequent durable setting.
  • These treatments have become known as presensitizing processes, whereby the fabric is presensitized for subsequent durable setting.
  • presensitizing processes There are presently two types of presensitizing processes, namely, the type which requires that water be sprayed onto the fabric prior to the setting operation and the type wherein water is not required.
  • the former type process is known as a wet crease presensitizing process, the latter being known as a dry crease process.
  • the fabric In a wet crease process, the fabric is impregnated with reducing agent at the mill level, after which it is dried and given a finish under mild conditions, generally involving low temperatures. The fabric is then shipped, cut into garments, sprayed with water to about 40% pickup, pressed on a Hoffman press and dried in the pressed configuration.
  • Dry crease processes have been provided by addition to the fabric at the mill level a low molecular weight polyhydroxy compound or a swelling agent as set forth in U.S. patent applications Ser. Nos. 167,420, now Pat. No. 3,423,166 and 111,447, now abandoned, respectively.
  • the additive is incorporated in the fabric along with the desired reducing agent.
  • the resulting fabric can be dried at higher temperatures without destroying the presensitization characteristics. More importantly, however, the resulting fabric can be set in a desired configuration without adding large amounts of water to the fabric. For that matter, no extraneous water whatsoever need be added beyond the regain level of the fabric to obtain excellent, durable configurations.
  • low molecular weight polyhydroxy compound a compound containing more than one hydroxy group and preferably having a molecular weight no greater than about 4000.
  • a particularly preferred group of glycols includes the polyfunctional glycols having terminal hydroxyl groups separated by 2 to 10 methylene groups, including, of course, the preferred ethylene glycol as well as trimethylene glycol, tetramethylene glycol, pentmethylene glycol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol, nonamethylene glycol, and decamethylene glycol, or such glycols as 1,2-propylene glycol, dipropylene glycol, 1,3-butylene glycol, diethylene glycol, polyethylene glycol or the like.
  • Polyfunctional compounds containing more than 2 hydroxyl groups include the polyfunctional alcohol glycerols such as glycerine, quintenyl glycerin, diethylglycerol and mesicerin, as Well as trimethylol ethane, trimethylol butane, tris(hydroxymethyl)aminomethane and others.
  • Glycol ethers such as the water-soluble or dispersi'ble polyethylene glycols or polypropylene glycols having molecular Weights no greater than about 4000 also provide satisfactory results when utilized in accordance with this invention.
  • Urea constitues the most readily available and desirable swelling agent, although any other material which will swell wool fibers in aqueous medium is suitable.
  • guanadine compounds such as the hydrochloride; formamide, N,N-dimethylformamide, acetamide, thiourea, phenol, lithium salts, such as the chloride, bromide and iodide and the like are similarly useful.
  • the swelling agent or low molecular weight polyhydroxy compound may be utilized in any desired amount depending on requirements for particular fabrics. For example, as little as about 0.5 to about 1% of the additives, based on the weight of the fabric, provides some improvement, although, in general, larger amounts, e.g., from about 3 to about 10% by weight provide noticeable improvement. Larger amounts of up to about 50% or higher may be utilized, of course, if the particular end use justifies the increased chemical cost in the use of these additives.
  • reducing agent precursor as utilized herein is meant a chemical compound which forms a reducing agent for keratin fibers upon reaction with another chemical compound. It is generally preferred that the precursor compound have a pH of about 7 or greater as a 1% solution in water.
  • Particularly suitable compounds include lower alkanolamines, such as monoethanolamine, diethanolamine, triethanolamine, N-methyl ethanolamine, N-
  • Additional suitable basic precursor compounds include alkalis, such as the alkali-earth metal and alkali-metal compounds, including the hydroxides, carbonates, borates, phosphates, e.g., sodium hydroxide, potassium hydroxide, lithium hydroxide, strontium hydroxide, barium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium borate, potassium borate, sodium perborate, disodium monohydrogen phosphate and the like.
  • alkalis such as the alkali-earth metal and alkali-metal compounds
  • hydroxides e.g., sodium hydroxide, potassium hydroxide, lithium hydroxide, strontium hydroxide, barium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium borate, potassium borate, sodium perborate, disodium monohydrogen phosphate and the like.
  • Additional reducing agent precursor chemicals include aldehydes, particularly formaldehyde and glyoxal, although other aldehydes are suitable, e.g., saturated aliphatic adlehydes containing up to about 18 carbon atoms, such as acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, enanthaldehyde, nonaldehyde, palmitic aldehyde and the like; unsaturated aliphatic aldehydes, such as acrolein, crotonaldehyde, tiglic aldehyde, citral, propiolaldehyde and the like; alicyclic monofunctional aldehydes, such as formylcyclohexane and the like; aliphatic dialdehydes, such as glyoxal, pyruvaldehyde, malonaldehyde, succinaldeh
  • ammonia per se can be utilized as a reducing agent precursor, e.g., in combination with S0 or N 0 activator gases.
  • Ammonia may be provided as a gas, preferably anyhydrous, or as ammonium hydroxide, methylammonium hydroxide, ethylammonium hydroxide and similar compounds. When applied as a gas, it may be applied before, after or during the desired finishing operation.
  • ammonia gas may be utilized in combination with other reducing agent precursors.
  • a wool fabric can be impregnated With an alkanolamine, finished, and then exposed to both ammonia and S0 gases. This technique provides particularly excellent presensitization in that better creases, or other configurations, of improved durability can be accomplished in this manner.
  • ammonia may be utilized as a reducing agent activator per se, particularly in combination with nitrites to form ammonium nitrites, ammonium complexes and the like.
  • the reducing agent precursor except for ammonia gas, is preferably applied to the fabric prior to finishing in that these compounds are most conveniently applied to the fabric in liquid media which would substantially destroy the finish on the fabric.
  • Most of the precursors are soluble in water and can be applied to the fabric as aqueous solutions, although dispersions, emulsions and other systems are suitable. Uniform impregnation of the fabric is readily accomplished by conventional techniques, such as padding, spraying and the like. It should be appreciated, however, that the precursor chemical may be applied in gaseous form before or after finishing if the practitioner prefers to volatilize the normally liquid precursor systems.
  • reducing agent activator as utilized herein is meant a chemical compound, preferably in a gaseous state, which can react with one of the above reducing agent precursors to form a different chemical compound which is a reducing agent for keratin fibers, i.e., is capable of rupturing the disulfide bonds of the keratin fiber molecular structure. It is not known with certitude if a reducing agent per se is formed in situ on the keratin fibers being treated, although the formation thereof is highly probable since both precursor and activator are consumed during the treatment and cannot be washed out of the fabric in their pre-treatment form.
  • Most of the preferred activator gases are reducing agents for keratin fibers and it is possible that the pretreatment of the fibers with one of the precursor chemicals may merely sensitize the fibers for more efficient reaction of the keratin fibers with the reducing agent gas, whereby presensitization of the fibers for subsequent durable setting is effected.
  • presensitization is effected by the process of this invention where treatment with a reducing agent per se is essentially ineffective for such purpose.
  • excellent presensitization of keratin fibers for subsequent durable setting in the absence of large amounts of water is effected by the process of this invention wherein the fabric is first impregnated with monoisopropanolamine, subjected to the desired finishing operation and then exposed to S0 possibly to produce monoisopropanolamine sulfite in situ on the fabric.
  • S0 is a highly preferred reducing agent activator gas.
  • suitable activator gases include, however, hydrogen sulfide; mercaptans, such as methyl mercaptan (B.P. 6 C.), ethyl mercaptan (B.P. 37 C.) and the like; mercaptan alcohols, such as Z-mercaptoethanol (B.P. 5052 C. at 10 mm. Hg) and the like; nitrogen oxides, such as N 0 and the like; phosphorus-containing gases, such as phosphine and the like; nitrosating agents, such as NOCl, NOBr and the like.
  • the amount of reducing agent precursor and activator gas can be readily determined by one skilled in the art depending on the fabric being treated and the extent of presensitization desired.
  • the preferred precursor chemicals are fairly strong bases. Keratin fibers tend to degrade considerably during prolonged storage under basic conditions. It is preferred, therefore, that a sulficient amount of the reducing agent activator gas, which generally is acidic, be utilized for substantially complete reaction with the precursor chemical or until substantially neutral fabric is produced. Obviously, the fabric may be shipped under slightly acidic or basic conditions, or even under highly acidic or basic conditions, but the optimum degree of physical properties in combination with the presensitized characteristic is obtained when the fabric is shipped essentially neutral.
  • the fabric treated in accordance with this invention has a higher degree of creasability after prolonged storage than fabrics treated by previous techniques.
  • the performance of the fabric after storage is generally superior to the performance immediately after gassing. Consequently, conventional storage time has become an asset rather than a liability in the present presensitizing technique.
  • Fabric containing the precursor chemical may be exposed to the gaseous activator in conventional equipment.
  • steam boxes, decating apparatus, beam and package dye machines, drying ovens and the like may be utilized.
  • the aldehyde compounds of the present invention may be applied to fabrics treated by any of the above processes, before, during or after such processes.
  • the amount of aldehyde compound utilized will be determined by the type fabric treated, the degree of reduction produced by reducing agent treatment and the stage of the various processes at which the aldehyde compound is applied. For example, if the fabric has been finally set in a desired configuration or presensitization toward subsequent setting is not desired, an amount of aldehyde compound should be applied to the fabric which eliminates the reduced keratin fiber odor. In this regard, an excess of aldehyde compound may be utilized if desired and the excess removed by heating and/or washing the fabric.
  • the fabric can be tested for odor after the odor removal treatment is given. If an odor remains, additional aldehyde compound is applied. If the reduced keratin fiber odor is eliminated, but an aldehydic odor remains, the fabric may be heated or washed to remove the residual aldehydic odor without reinstituting the reduced keratin fiber odor. This, of course, indicates that some reaction has taken place and that this reaction is substantially irreversible even under conditions of heat and pressure.
  • aldehyde compound may be added to the fabric along with the presensitizing chemicals. After completion of the process, swatches of the fabric may be tested for creasability and odor. The creasing test may be made with or without water depending on the type process being practiced. If better than the desired level of creasing is obtained and a moderate reduced keratin fiber odor remains, additional aldehyde compound may be applied to the fabric. Conversely, if the crease performance is not as high as desired, less aldehyde compound should be utilized. In
  • the fabric can be re-run through one of the presensitizing processes without deleterious effects.
  • an aldehyde or generator thereof may be applied to the fabric without re-running it through the process.
  • the aldehyde may be based on the theoretical number of moles of reducing agent which would be produced in situ from the amounts of reducing agent precursor and activator compounds which are utilized.
  • While the process of this invention is particularly adapted to fabrics composed essentially of keratin fibers, particularly those composed entirely of wool fibers, it is also applicable to fabrics wherein synthetic, natural, or other keratin fibers are blended with the wool component.
  • Other keratin fibers include mohair, alpaca, cashmere, vicuna, guanaco, camels hair, llama and the like.
  • Preferred synthetic fibers for blending with these fibers include polyamides, such as polyhexamethylene adipamide; polyesters, such as polyethylene terephthalate; and acrylic fibers, such as acrylonitrile homopolymers or copolymers containing at least about 85% combined acrylonitrile, such as acrylonitrile/methyl acrylate (85/15), and cellulosics, such as cellulose acetate and viscose rayon.
  • polyamides such as polyhexamethylene adipamide
  • polyesters such as polyethylene terephthalate
  • acrylic fibers such as acrylonitrile homopolymers or copolymers containing at least about 85% combined acrylonitrile, such as acrylonitrile/methyl acrylate (85/15), and cellulosics, such as cellulose acetate and viscose rayon.
  • cotton is preferred.
  • the fibers need not be in fabric form during treatment.
  • the process may be conducted on top, tow, roving, sliver, yarn and the like.
  • the process of this invention may be performed on woven, non-woven, or knitted fabrics of any type, dyed or undyed.
  • dry crease performance data are obtained from presensitized fabric samples having dimensions of 4 /2 inches in the filling direction by 6 inches in the warp direction. These samples are folded in half with the fold parallel to the warp yarns. The samples are then placed on a Hoifman press, the cover is closed and locked and the samples are pressed with 30 seconds top steam and 30 seconds baking, followed by 10 seconds vacuuming.
  • the creased samples are then opened and placed in a standing water bath which contains a wetting agent and is heated to F. After 30 minutes the samples are removed, folded along the original crease line and allowed to air dry. After drying, the creases remaining in the samples are rated subjectively by at least three observers, the crease ratings runing from 1 (no appreciable crease) to 5 (very sharp crease).
  • each sample is hung in a closed container over a 37% formaldehyde solution.
  • the solution is heated to 5060 C. and maintained at that temperature for two hours.
  • the samples are entirely devoid of the characteristic reduced wool odor.
  • the relaxation shrinkage of the fabric samples which are exposed to formaldehyde vapors is substantially less than before exposure to formaldehyde.
  • the fabric sample treated with solution A above, before pressing has a relaxation shrinkage of 3.9% in the warp direction and 2.6% in the filling direction. After exposure to formaldehyde vapors, the corresponding values are 0.2 and 0.3%, respectively.
  • the fabric treated by solution E after pressing and without formaldehyde exposure, has warp and filling relaxation shrinkage values of 4.0 and 3.8%, respectively. After formaldehyde exposure, these values are 1.9 and 2.0%, respectively.
  • trouser legs made from the fabric treated by solution B have warp and filling relaxation shrinkage values reduced to 0.8 and 0.2%, respectively, by exposure to formaldehyde vapor.
  • the fabrics are placed on hangers and then hung in the steam box.
  • a 37% formaldehyde solution is poured into the steam box and steam is admitted, whereupon the steam becomes laden with formaldehyde. After 20 minutes, the fabrics are removed from the steam box.
  • Each fabric sample is devoid of the reduced wool odor and, furthermore, is devoid of a formaldehyde odor.
  • Samples of the worsted fabric of Example I are padded to approximately wet pick-up with each of the resulting solutions, after which the samples are dried at 200 F. in a mechanical convection oven.
  • a lustrous finish is imparted to the samples by steaming on a Hoffman press for 2 seconds between standard decater leader fabrics, followed by vacuum pumping for 10 seconds.
  • the fabrics are evaluated for odor both before and after creasing without a water spray.
  • the control fabric is similarly treated except that no formaldehyde generating compound is utilized.
  • the odor evaluations are conducted in an aluminum lined room in which the relative humidity is held to 45% 15% at 82 Fri-3 F. with a room dehumidifier. Also, the air in the room is constantly passed through an electrostatic precipitator which includes an activated carbon filter.
  • the fabric samples are placed in 6 x 8 inch round battery jars at 20% moisture content. These jars have ground edges and are covered with 8 x 8 x inch plate glass covers. The samples are maintained under these conditions for 2 days and are then evaluated individually by an odor-sensing panel of 10 persons on a scale of no odor, a very slight odor, a slight odor, a moderate odor, a heavy odor, and a very heavy odor.
  • the odor of the fabric samples is evaluated as in Example IV both before and after pressing in a dry state on a Hoffman press. Only a very slight reduced wool odor remains, compared to the very heavy odor characterizing the control fabric which is similarly treated but without paraformaldehyde. No odor of formaldehyde can be detected in these fabric samples.
  • EXAMPLE VI The reduced control fabric of Example V is cut and sewn into skirts, pleated with conventional pleating papers and steamed in an autoclave for 20 minutes to set the pleats.
  • a moderately heavy reduced wool odor is readily detected in these skirts.
  • Paraformaldehyde crystals are placed at the base of the autoclave and heated, whereupon formaldehyde vapors permeate the skirts. After 60 minutes in this atmosphere, the skirts are removed. Neither a reduced Wool odor nor a formaldehyde odor can be detected in the skirts.
  • Example VII The fabric of Example I is padded to 70% pick-up of an aqueous solution containing 6.0% monoisopropanolamine, 0.12% paraformaldehyde and 0.1% Synowet HR. This solution is obtained by heating the system with stirring to 120 F. to dissolve the paraformaldehyde crystals. After semi-decating by steaming for 1% minutes and vacuum pumping for 3 minutes, the fabric is wound onto the spindle of a package dye machine and placed in the machine. The machine is then sealed and the pressure therein is reduced to 60 mm. Hg.
  • Dry crease ratings of 3.2 are obtained with no characteristic reduced wool odor.
  • a fabric similarly treated but without paraformaldehyde dissolved in the treating solution is characterized by a heavy reduced wool odor.
  • Example VIII The procedure of Example VII is repeated except that after S0 is introduced into the machine, the pressure is decreased to 60 mm. after which the resulting partial vacuum is broken with air. The machine is then held at 71 cm. partial vacuum for minutes and the fabric removed and tested as before. Dry crease ratings of 4.0 are obtained and, again, no characteristic reduced wool odor is noticed.
  • Example IIX The procedure of Example VII is repeated except that S0 is blown through the fabric at 2 liters per minute for 5 minutes without previous evacuation of the machine. The fabric is permitted to stand in the SO -laden machine for 5 minutes, after which air is blown through the fabric for 30 minutes. Dry crease ratings of 2.7 are obtained with no trace of odor in the fabric.
  • Example IX The procedure of Example IX is repeated except that 1.0% Synsoft-LS polyethylene softener is added to the pad solution. Dry crease ratings of 3.2, with no reduced wool odor detectable, are obtained.
  • Example I The fabric of Example I is treated with the pad solution of Example X, semi-decated as in Examp e VII and sealed into a package dye machine. At a rate of 2 liters/ minute, S0 gas is blown through the fabric for 5 minutes. Air is then blown through the fabric for 5 minutes, after which ammonia and air are blown through the fabric until air leaving the machine is neutral. Dry crease ratings of 3.7 are obtained in this manner, with only very slight reduced wool odor in the fabric. No S0 or NH; odor is detected.
  • a control fabric similary treated but without paraformaldehyde in the original solution is characterized by a moderate reduced wool odor.
  • EXAMPLE XII The bisulfite addition product of aqueous formaldehyde and sodium metabisulfite (sodium formaldehyde bisulfite), is added, where indicated, to various aqueous pad solutions as set forth in Table III. Samples of the fabric of Example I are padded to 100% pick-up with these solutions and dried at 200 F. unless otherwise specified.
  • EXAMPLE XIII Dimethylolethanolamine sulfite is prepared by reacting 60 grams of paraformaldehyde with 61 grams of ethanolamine at 50-70 C. After cooling and filtering through glass wool, the reaction mass is saturated with S0 gas while being maintained cool with an ice bath. The resulting product is added (2%) to an aqueous solution containing 5% monoisopropanolamine sulfite and 0.1% Syn- Fac 905. The fabric of Example I is padded to pick-up with this solution and dried at 200 F.
  • the fabric is then creased on a Hoffman press without prior water spraying. Excellent creases, which are durable to subsequent wetting, are produced in this manner and only a very slight reduced wool odor remains in the fabric.
  • dimethylolisopropanolamine sulfite which may be produced by substituting 75 grams of isopropanolamine for the ethanolamine in the above procedure.
  • N-methylolformamide is produced by reacting 30 grams of paraformaldehyde with 45 grams of formamide 13 at 120-150 C. After cooling, the resulting product is mixed in equal parts with monoisopropanolamine sulfite. Thirteen (13) grams of this mixture are blended with 30 grams of ethylene glycol, after which 67 grams of the glycol are added. After stirring to insure complete dissolution, the resulting solution is padded to 100% pick-up onto the fabric of Example I. Again, excellent dry creases are obtained with little or no noticeable reduced wool odor.
  • EXAMPLE XV The fabric of Example I is padded to 100% pick-up with an aqueous solution containing 4.5% monoisopropanolamine sulfite, 1.5% paraformaldehyde, 0.1% Syn- Fao 905 and 7.2% urea.
  • the fabric is dried at 200-225 F. and semi-decated on a Hoffman press at seconds steam followed by 60 seconds vacuum while contained between two pieces of decater fabric.
  • This fabric weighing 1482 grams, is then rolled onto the beam of a laboratory gas treating machine, placed in the machine and heated to 140 F.
  • Ammonia gas (2.6 grams) is added to the system and circulated for six minutes. The excess ammonia is vented to the outside.
  • Sulfur dioxide gas (51.4 grams) is then added to the system and, after complete addition, is circulated for six minutes. The excess sulfur dioxide gas is vented to the outside.
  • Additional ammonia (1.3 grams) is then added to the system and circulated for six minutes. A final venting and exhausting is conducted for 10 minutes. The fabric is removed from the machine and tested.
  • the initial dry crease rating is 3.5. This rating after ageing at room conditions for one (1) week, increased to 4.3.
  • the process of this invention may be utilized in any process involving the use of reducing agents to modify the characteristics of keratin fibers.
  • a most surprising area of utility is in the presensitizing field.
  • aldehydes particularly formaldehyde
  • inhibit presensitization Consequently, it is most surprising that configurations can be obtained which are as good as, or better than, configurations obtainable when aldehydes are not utilized.
  • This is particularly true when the reducing agent and formaldehyde are applied to the keratin fibers from a single solution, or at least are present in the fabric simultaneously during setting. This phenomenon may be explained by the fact that the aldehyde may not react with the keratin fiber until after setting has occurred.
  • the aldehyde may then react to eliminate any further propensity for durable setting.
  • This propensity has been known to manifest itself in a crease-removing manner. Since this propensity would no longer exist under this theory, the resulting crease performance would be enhanced. It is to be understood, however, that there is no apparent explanation for the phenomenon whereby the odor of reduced wool is substantially minimized by treatment with the compounds of this invention.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatment Of Fiber Materials (AREA)
US764008*A 1963-05-27 1968-08-27 Minimizing odor by adding methylol amides and methylol amines to reducing agent solutions used to treat wool Expired - Lifetime US3519383A (en)

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US28356563A 1963-05-27 1963-05-27
US76400868A 1968-08-27 1968-08-27

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US (1) US3519383A (enrdf_load_stackoverflow)
BE (1) BE648429A (enrdf_load_stackoverflow)
CH (1) CH476883A (enrdf_load_stackoverflow)
DE (1) DE1469317A1 (enrdf_load_stackoverflow)
FR (1) FR1398238A (enrdf_load_stackoverflow)
GB (1) GB1068475A (enrdf_load_stackoverflow)
LU (1) LU46131A1 (enrdf_load_stackoverflow)
NL (1) NL6405053A (enrdf_load_stackoverflow)
SE (1) SE327689B (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090211593A1 (en) * 2007-10-05 2009-08-27 Peter Coppola Reactive Keratin Protein Formulations and Methods of Using for Revitalizing Hair
US20110104097A1 (en) * 2008-07-01 2011-05-05 Jean-Luc Dubois Topical compositions for the preservation of a human or animal body
CN104624049A (zh) * 2014-12-12 2015-05-20 李可文 具有润滑作用的柴油机尾气还原剂、其应用及制备方法
US20150299925A1 (en) * 2014-04-19 2015-10-22 Unshrinkit, Inc. Compositions and methods for treating keratinous material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108056926B (zh) * 2018-01-29 2022-04-05 华南师范大学 长波黑斑效应紫外线隔离剂的制备方法及其应用

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Publication number Priority date Publication date Assignee Title
GB443359A (en) * 1934-06-20 1936-02-20 Ici Ltd Compositions for setting animal fibres such as wool or hair
US2351718A (en) * 1935-12-09 1944-06-20 Speakman John Bamber Treatment of fibers or fibrous materials containing keratin
US2508713A (en) * 1946-10-07 1950-05-23 Harris Res Lab Treatment of keratinous material
US2740727A (en) * 1953-04-30 1956-04-03 Albany Felt Co Compressive shrinking blanket and method for producing same
US2806762A (en) * 1951-10-24 1957-09-17 Armour & Co Method of chemically curling animal hair with sulfur dioxide in aqueous solution
US2870041A (en) * 1958-06-02 1959-01-20 West Point Mfg Co Process for preventing aldehyde odors
US2983569A (en) * 1957-05-20 1961-05-09 Oreal Deformation of keratinous fibers with sulfite-borohydride composition
US3051544A (en) * 1959-02-12 1962-08-28 Stevens & Co Inc J P Lustered wool product and method of making the same
US3151439A (en) * 1962-07-09 1964-10-06 Deering Milliken Res Corp Process for making elastic keratinous yarns

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB443359A (en) * 1934-06-20 1936-02-20 Ici Ltd Compositions for setting animal fibres such as wool or hair
US2351718A (en) * 1935-12-09 1944-06-20 Speakman John Bamber Treatment of fibers or fibrous materials containing keratin
US2508713A (en) * 1946-10-07 1950-05-23 Harris Res Lab Treatment of keratinous material
US2806762A (en) * 1951-10-24 1957-09-17 Armour & Co Method of chemically curling animal hair with sulfur dioxide in aqueous solution
US2740727A (en) * 1953-04-30 1956-04-03 Albany Felt Co Compressive shrinking blanket and method for producing same
US2983569A (en) * 1957-05-20 1961-05-09 Oreal Deformation of keratinous fibers with sulfite-borohydride composition
US2870041A (en) * 1958-06-02 1959-01-20 West Point Mfg Co Process for preventing aldehyde odors
US3051544A (en) * 1959-02-12 1962-08-28 Stevens & Co Inc J P Lustered wool product and method of making the same
US3151439A (en) * 1962-07-09 1964-10-06 Deering Milliken Res Corp Process for making elastic keratinous yarns

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090211593A1 (en) * 2007-10-05 2009-08-27 Peter Coppola Reactive Keratin Protein Formulations and Methods of Using for Revitalizing Hair
US8785370B2 (en) 2007-10-05 2014-07-22 Keratin Complex Holdings, Inc. Reactive keratin protein formulations and methods of using for revitalizing hair
US20110104097A1 (en) * 2008-07-01 2011-05-05 Jean-Luc Dubois Topical compositions for the preservation of a human or animal body
US20150299925A1 (en) * 2014-04-19 2015-10-22 Unshrinkit, Inc. Compositions and methods for treating keratinous material
US11230807B2 (en) 2014-04-19 2022-01-25 52 Launch Llc Compositions and methods for treating keratinous material
CN104624049A (zh) * 2014-12-12 2015-05-20 李可文 具有润滑作用的柴油机尾气还原剂、其应用及制备方法

Also Published As

Publication number Publication date
CH476883A (fr) 1969-09-30
BE648429A (enrdf_load_stackoverflow) 1964-09-16
SE327689B (enrdf_load_stackoverflow) 1970-08-31
FR1398238A (fr) 1965-05-07
NL6405053A (enrdf_load_stackoverflow) 1964-11-30
DE1469317A1 (de) 1969-08-07
CH689664A4 (enrdf_load_stackoverflow) 1969-03-31
LU46131A1 (enrdf_load_stackoverflow) 1972-01-01
GB1068475A (en) 1967-05-10

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