US3416880A - Modification of cellulosic textiles with methylolated hydroxyalkyl carbamates - Google Patents

Modification of cellulosic textiles with methylolated hydroxyalkyl carbamates Download PDF

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Publication number
US3416880A
US3416880A US63478567A US3416880A US 3416880 A US3416880 A US 3416880A US 63478567 A US63478567 A US 63478567A US 3416880 A US3416880 A US 3416880A
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United States
Prior art keywords
fabric
formaldehyde
carbamate
condensate
treated
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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English (en)
Inventor
Russell M H Kullman
Jr John G Frick
Robert M Reinhard
John D Reid
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US Department of Agriculture USDA
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Agriculture Usa
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Filing date
Publication date
Priority to GB3482565A priority Critical patent/GB1071284A/en
Priority to CH1221565A priority patent/CH435201A/de
Priority to CH1221465A priority patent/CH451909A/de
Priority to FR34023A priority patent/FR1457758A/fr
Priority to FR34593A priority patent/FR1457768A/fr
Application filed by Agriculture Usa filed Critical Agriculture Usa
Priority to US63478567 priority patent/US3416880A/en
Application granted granted Critical
Publication of US3416880A publication Critical patent/US3416880A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING 
    • B63B19/00—Arrangements or adaptations of ports, doors, windows, port-holes, or other openings or covers
    • B63B19/12—Hatches; Hatchways
    • B63B19/24—Hatch fastenings, e.g. cleats
    • 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

  • Methylol derivatives of hydroxaylkyl carbamates produced by reacting a hydroxyalkyl carbaniate with at least two molar equivalents of formaldehyde in aqueous alkaline solution, may be used as new finishing agents for cotton to produce wrinkle-resistant and wash-wear fabric. These agents have little or no adverse effect on colorfastness-to-light of dyed fabric. Hydroxyethyl carbamate is a typical example of a useful compound for making this type of agent. These finishes are very durable and cellulosic materials treated therewith may be held for substantial periods of time during which the fabrics may be converted into garments prior to the heat-setting operation.
  • This invention relates to new finishing agents, to treating baths containing these finishing agents, and to the application of these treating baths to cellulosic fibrous ma terials. More specifically, it relates to wash-wear cellulosic fabrics which are not only resistant to wrinkling but are also resistant to chlorine damage and which exhibit outstanding durability to removal of these properties by laundering. Most important, dyed fabrics when treated with these novel finishing agents and then exposed to actinic light are characterized by their superior resistance to fading.
  • Textiles composed of cellulosic fibers such as cotton and rayon are commonly finished by a wrinkle-resistant or wash-wear treatment. Such treatments improve the appearance of the textile by preventing the formation of wrinkles or mussiness while the textile is in use.
  • the treatments also, can give the textiles the ability to dry smoothly after washing and thereby reduce, or eliminate, the need for pressing.
  • an agent called a crosslinking agent or resin-former is applied to the textile under conditions that promote reaction of the agent with cellulose, or with itself.
  • the agents used for this purpose are most commonly monomeric, or lowmolecular weight condensates, or addition products of formaldehyde and an organic amide, such as dimethylol urea, dimethylol ethyleneurea, and trimethylol melamine. Less commonly used are other classes of agents, such as acetals and diepoxides. Preference for the formaldehydeamide condensates is due to their economy, their effectiveness, and their ease of application.
  • cellulosic material includes fibrous cellulosic material in which the major component is natural or synthetic.
  • the hydroxyethyl carbamate-formaldehyde condensates used in this invention are prepared by treating a hydroxyethyl carbamate containing two to six carbon atoms with at least two molar equivalents of formaldehyde in an aqueous alkaline solution.
  • An excess 0 formaldehyde over the two molar equivalents theoretically require is ordinarily preferred to help complete the reaction.
  • Best results are obtained when the reaction is allowed to proceed under alkaline conditions, preferably at pH 9l1, at a temperature from about 20 to C. for a period of time. The time required will depend upon the temperature selected with longer times required at the lower temperatures. The time required may vary from about 20 minutes at 80 C. to 20 hours at ambient room temperature.
  • the essential requirement is to continue the reaction until at least an average of about 1.5 moles formaldehyde has combined with the carbamate. This may be determined by titrating the uncombined formaldehyde and sub tracting this quantity from the total formaldehyde added initially. After the reaction period, the solution is neutralized and is ready for the preparation of the treating bath.
  • the reaction solution is diluted to contain about 5 to 20 weight percent of the condensate, after which an acidic salt catalyst is added to make 0.5 to about 6.0 weight percent of the solution. It is also within the scope of our invention to use organic acids such as maleic acid or maleic anhydride. Concentration of the condensate in the treating solution will be determined by the type fabric to be treated, the equipment to be used, and the degree of wrinkle-resistance or 'wash-wear property desired. Concentration of the acidic catalyst will depend on the type catalyst to be used and the concentration of condensate selected. Preferred catalysts are metallic, ammonium, or amine salts of strong mineral acids.
  • the treating solution or treating bath may contain auxiliary agents commonly used in textile finishing. These include wetting agents to assist impregnation of the fabric, softening agents to modify the hand and feel of the fabric, and fluorescent agents to give the fabric a bright appearance.
  • the carbamate-formaldehyde condensate is applied to the fabric by the usual finishing procedures.
  • the fabric is soaked with the treating bath and padded (passed between padder rolls) or centrifuged so that it weighs one and a half to twice its dry weight.
  • the fabric is then dried at relatively low temperatures and heated 1 to 5 minutes at 130 to 200 C. to effect reaction of the hydroxyalkyl carbamate-formaldehyde condensate.
  • the fabric may then be washed, if desired.
  • the treatment of the cellulosic material by the process of our invention may be carried out as a continuous series of steps; or the treatment may be carried out as a series of intermittent steps.
  • the various steps in the finishing process may be carried out continuously, that is, wetting the cellulosic material with the treating bath, maintaining a period of dwell to enable the aqueous treating bath to penetrate into and through the cellulosic material, removing the excess treating bath, drying the wet cellulosic material preferably at relatively low temperatures and subsequently subjecting the dried material to a heat treatment to complete the treatment.
  • the temperature for the heat treatment (cure) may range from about 130 C. to about 200 C. for 1 to 5 minutes, the longer time being required for the lower temperatures.
  • the cellulosic material may be wet out and squeezed in a commercial padder to remove the excess treating bath after which the wet material may be transported to another part of the finishing plant to be dried.
  • the dried material may then be held for a period of time prior to receiving the high-temperature heat treatment during which interval it may be passed through a button-breaker to soften the fabric, or passed through a friction calender or an embossing calender to impart physical properties to the fabric which will then be retained after the heat treatment.
  • It is an advantage of the treating agents of our invention that cellulosic materials treated therewith may be held for substantial periods of time prior to heat-setting during which time the fabrics may be converted into garments prior to the heat-setting operation.
  • EXAMPLE 1 A condensate was prepared by mixing one mole of hydroxyethyl carbamate, 2.2 moles of formeldehyde, and sufficient water to make a 33% solution of the condensate on the basis of reaction with only 2.0 moles of formaldehyde. The solution was adjusted to pH -10 with sodium hydroxide and allowed to stand overnight, 16 hours, at 23 C. The solution was then adjusted to pH 6.5-7.0 with hydrochloric acid. The above solution was diluted with water and sufficient zinc nitrate hexahydrate added to give a treating bath containing 10% condensate and 0.6% zinc nitrate hexahydrate.
  • Cotton printcloth was held in this treating bath until saturated, the excess removed by passing the wet fabric between squeeze-rolls and the process repeated. The wet fabric was then dried at 60 C. for seven minutes after which it was heated at C. for three minutes. The heattreated fabric was then washed in a detergent solution, thoroughly rinsed, and dried. It was then tested using an untreated sample of the same fabric as a control. The results follow:
  • Untreated Treated fabric fabric Crease recovery angle (warp plus fill value) 186 252 Percent strength loss in test for chlorine resistance 21 22 Gray scale rating of fabric dyed with Untreated Treated fabric fabric Direct Blue 78 5 5 Direct Red 26 2 3 Test results show that the fabric treated with the hydroxyethyl carbamate-formaldehyde condensate had noticeably greater wrinkle resistance, essentially no greater susceptibility to damage by chlorine, and the treatment did not promote degradation by actinic light.
  • EXAMPLE 2 A condensate was prepared by mixing one mole of hydroxyethyl carbamate, 2.5 moles of formaldehyde, and suflicient water to make a 50% solution of the condensate on the basis of reaction with only 2.0 moles of formaldehyde. The solution was adjusted to and maintained at pH 10 with sodium hydroxide and allowed to stand overnight, 16 hours at 23 C. The solution was then adjusted to pH 6.57.0 with hydrochloric acid. The above solution was diluted with water and zinc nitrate hexahydrate added to give a treating bath containing 10% hydroxyethyl carbamate-formaldehyde condensate and 0.6% zinc nitrate hexahydrate.
  • Cotton printcloth was then passed into and through the treating bath, squeezed, and the process repeated.
  • the wet fabric was dried at 60 C. for seven minutes, and then heat treated at 160 C. for three minutes.
  • the treated fabric was washed in a detergent solution, preferably nonionic, thoroughly rinsed, and dried. It was then tested with an untreated sample of the fabric with the following results:
  • EXAMPLE 4 A condensate was prepared by mixing 0.1 mole of dihydroxypropyl carbamate, 0.25 mole of formaldehyde, and sufficient water to make a 50% solution of the condensate, on the basis of reaction with only 0.2 mole of formaldehyde. Another condensate was prepared by mix- These results show that dyed fabrics treated with dihydroxypropyl carbamate-formaldehyde and hydroxypropyl carbamate-formaldehyde condensates are superior to dyed fabric treated with the ethyleneurea-formaldehyde condensate. They are also comparable to the hydroxyethyl carbamate-formaldehyde condensate finish and to the untreated dyed control in fading of dyes due to actinic light.
  • a process for imparting a wrinkle-resistance and wash-wear finish to a cellulosic fibrous material comprising- (a) passing the cellulosic fibrous material into and through a treating bath containing about 5 to about 20 weight percent of the monomeric condensation product produced by the reaction at a pH of from about 8.5 to 11 and at temperatures of less than about C. of a hydroxyalkyl carbamate and formaldehyde and from about 0.5 to 6.0 weight percent of an acidic salt catalyst,
  • a process according to claim 2 wherein the hydroxyalkyl carbamate is Z-hydroxyethyl carbamate and the acidic salt catalyst is zinc nitrate hexahydrate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • Ocean & Marine Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US63478567 1964-10-13 1967-02-10 Modification of cellulosic textiles with methylolated hydroxyalkyl carbamates Expired - Lifetime US3416880A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
GB3482565A GB1071284A (en) 1964-10-13 1965-08-13 Formaldehyde/carbamate condensation products and their use in treatment of textiles
CH1221565A CH435201A (de) 1964-10-13 1965-08-31 Verfahren zur Erzielung einer Knitterfest- und Wash- and Wear-Ausrüstung
CH1221465A CH451909A (de) 1964-10-13 1965-08-31 Verfahren zur Herstellung von haltbaren wässrigen Lösungen, enthaltend N,N-Dimethyloloxyalkylcarbamate, N-Monomethyloloxyalkylcarbamate und freien Formaldehyd
FR34023A FR1457758A (fr) 1964-10-13 1965-10-07 Fermeture d'écoutille
FR34593A FR1457768A (fr) 1964-10-13 1965-10-12 Traitement de matières cellulosiques teintes pour l'obtention de tissus résistants au plissage et permettant le lavage sans avoir à repasser
US63478567 US3416880A (en) 1964-10-13 1967-02-10 Modification of cellulosic textiles with methylolated hydroxyalkyl carbamates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US40366864A 1964-10-13 1964-10-13
US63478567 US3416880A (en) 1964-10-13 1967-02-10 Modification of cellulosic textiles with methylolated hydroxyalkyl carbamates

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US3416880A true US3416880A (en) 1968-12-17

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CH (2) CH435201A (de)
GB (1) GB1071284A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3503701A (en) * 1965-11-15 1970-03-31 Stevens & Co Inc J P Textile treating agents and methods of preparing same
US3512920A (en) * 1967-05-01 1970-05-19 Celanese Corp Wrinkle resistant fabric
US3548427A (en) * 1966-11-21 1970-12-22 Millmaster Onyx Corp Alkyl carbamate/isopropyl carbamate formaldehyde resin compositions and the modification of fabrics therewith

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2627524A (en) * 1949-11-17 1953-02-03 Jefferson Chem Co Inc Hydroxy carbamates and process of producing same
US2774746A (en) * 1954-06-16 1956-12-18 Rohm & Haas Comp Diethylene glycol bis-carbamateformaldehyde condensates
US2850407A (en) * 1956-05-28 1958-09-02 Dow Chemical Co Textile finishing compositions containing adduct of beta-amino lower alkyl carbamateand formaldehyde, method of applying same, and the treated textile
US2928812A (en) * 1953-10-02 1960-03-15 Erust Robert Hydroxyalkyl carbamate-formaldehyde condensation products
US3144299A (en) * 1961-06-06 1964-08-11 Jr John G Frick Wrinkle resistance finish for cellulosic textiles
US3160469A (en) * 1962-07-19 1964-12-08 Sidney L Vail Biscarbamate-formaldehyde adducts for wrinkle resistance finishes
US3230030A (en) * 1962-09-27 1966-01-18 Clifford M Moran Process of producing wrinkle resistant cellulose fabrics of relatively high moistureregain

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2627524A (en) * 1949-11-17 1953-02-03 Jefferson Chem Co Inc Hydroxy carbamates and process of producing same
US2928812A (en) * 1953-10-02 1960-03-15 Erust Robert Hydroxyalkyl carbamate-formaldehyde condensation products
US2774746A (en) * 1954-06-16 1956-12-18 Rohm & Haas Comp Diethylene glycol bis-carbamateformaldehyde condensates
US2850407A (en) * 1956-05-28 1958-09-02 Dow Chemical Co Textile finishing compositions containing adduct of beta-amino lower alkyl carbamateand formaldehyde, method of applying same, and the treated textile
US3144299A (en) * 1961-06-06 1964-08-11 Jr John G Frick Wrinkle resistance finish for cellulosic textiles
US3160469A (en) * 1962-07-19 1964-12-08 Sidney L Vail Biscarbamate-formaldehyde adducts for wrinkle resistance finishes
US3230030A (en) * 1962-09-27 1966-01-18 Clifford M Moran Process of producing wrinkle resistant cellulose fabrics of relatively high moistureregain

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3503701A (en) * 1965-11-15 1970-03-31 Stevens & Co Inc J P Textile treating agents and methods of preparing same
US3548427A (en) * 1966-11-21 1970-12-22 Millmaster Onyx Corp Alkyl carbamate/isopropyl carbamate formaldehyde resin compositions and the modification of fabrics therewith
US3512920A (en) * 1967-05-01 1970-05-19 Celanese Corp Wrinkle resistant fabric

Also Published As

Publication number Publication date
CH1221565A4 (de) 1967-01-31
GB1071284A (en) 1967-06-07
CH435201A (de) 1967-10-31
CH451909A (de) 1968-05-15

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