US3642428A - Vapor phase resin fixation process for cellulosic material permitting subsequent cure - Google Patents

Vapor phase resin fixation process for cellulosic material permitting subsequent cure Download PDF

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US3642428A
US3642428A US32370A US3642428DA US3642428A US 3642428 A US3642428 A US 3642428A US 32370 A US32370 A US 32370A US 3642428D A US3642428D A US 3642428DA US 3642428 A US3642428 A US 3642428A
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fabric
formaldehyde
vapor
percent
precondensate
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Nelson F Getchell
Julian Berch
Norman R S Hollies
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Cotton Inc
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Cotton Inc
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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
    • D06M15/39Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423Amino-aldehyde resins
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/04Polyester fibers
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/09Polyolefin
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/21Nylon

Definitions

  • ABSTRACT Improved crease resistance and smooth drying characteristics are imparted to cellulosic fiber-containing materials, such as cotton fabric, with a minimum sacrifice in physical properties by a process including (1) applying an aqueous solution comprising at least one water-soluble polymer-forming compound possessing reactive N-methylol groups and a latent curing catalyst to the cellulosic material, (2) exposing the material in a water swollen state in the presence of formaldehyde to a reactive vapor atmosphere containing a gaseous acidic catalyst such as sulfur dioxide, and (3) drying the material in preparation for the manufacture of a durable press article therefrom.
  • a process including (1) applying an aqueous solution comprising at least one water-soluble polymer-forming compound possessing reactive N-methylol groups and a latent curing catalyst to the cellulosic material, (2) exposing the material in a water swollen state in the presence of formaldehyde to a reactive vapor atmosphere containing a gaseous acidic catalyst such as sulfur dioxide,
  • the latent curing catalyst is conveniently applied to the material from the same bath as the polymer-forming compound, but as an alternative it may be applied to the material from a separate bath, e.g., after the reactive vapor treatment and prior to the final cure.
  • the durable press article may be made by first making the dry uncured material into an article such as a garment having hot pressed creases therein and then curing the article (delayed cure), or by first curing the material and then making the cured material into a final product (precure).
  • a particularly promising approach to the production of easy care, durable press garments has involved the wet fixation of resinor polymer-forming creaseproofing agents such as formaldehyde-melamine precondensates, as disclosed, for example, in US. Pat. No. 3,138,802 which is assigned to the assignee of the present invention.
  • resinor polymer-forming creaseproofing agents such as formaldehyde-melamine precondensates
  • US. Pat. No. 3,138,802 which is assigned to the assignee of the present invention.
  • a fiber system such as a cotton fabric is protected against excessive strength loss and presensitized for durable press processing by fixation of a suitable polymer-former and creaseproofing agent within the fibers while they are wet and swollen but without greatly altering the dry crease recovery angle or durable press properties of the fiber system.
  • the latter properties are only imparted in the desired degree during a subsequent dry cure.
  • Such a process accordingly permits ready creasing or other distinct shaping of the fiber system during apparel manufacture or the like subsequent to the wet fixation step and prior to the delayed dry cure.
  • wet fixation processes heretofore known have usually required neutralization and wash-off of the strongly acid wet fixation catalyst subsequent to the wet fixing step, to be followed by drying and then recatalyzation and redrying prior to the actual cure, thus requiring additional processing time and effort.
  • aprimary object of the present invention is to provide a process for improving the crease resistance and smooth drying characteristics of cellulosic fiber-containing materials, which process substantially prevents or alleviates the problems of the prior art discussed above.
  • Another object of the present invention is to provide a process for achieving a favorable balance between easy care and physical properties of cellulosic-fiber containing materials, which process allows both delayed cure and precure procedures to be used.
  • Yet another object of the present invention is to provide a process for improving the crease resistance of cellulosic fibercontaining materials, which process permits ease of processing while minimizing processing time.
  • this invention provides an improved process for imparting crease resistance, that is, wrinkle resistance or shape retention, and smooth drying characteristics to cellulosic fiber-containing materials such as cotton.
  • the process comprises (1) applying to the cellulosic material an aqueous solution comprising at least one water-soluble polymer-forming alkaline-reacting compound possessing reactive N-methylol groups and at least one water soluble solid salt which functions as a latent curing catalyst in the eventual dry cure, (2) exposing the material'in a water swollen state at an elevated temperature and in the presence of formaldehyde to a reactive atmosphere or vapor phase which contains a strongly acidic gaseous catalyst which later is driven off by heat to leave the material in a neutral or near neutral condition, e.g., vapor phase may contain sulfur dioxide, acetic acid, formic acid or hydrogen chloride; and (3) drying the material in preparation for the final dry cure,
  • the latent curing catalyst does not normally perform any essential function in the process prior to the final dry cure step, it need not be included in the initial solution but may be applied later from a separate pad bath, e.g., between the polymerization step (2) and the drying step (3).
  • the durable press article may be made by first making the dry uncured material into a garment having creases hot pressed therein and then curing the garment (delayed cure), or by first curing the material and then making the cured material into a garment (precure).
  • N methylol compounds can be insolubilized or polymerized within moist swollen cellulosic fibers, i.e., fixed in the material into water insoluble products or resins, by exposure to a reactive atmosphere comprising formaldehyde and a gaseous acidic catalyst, and thereby at the same time usefully control and limit the debilitating effect which otherwise results when a fabric such as cotton is dry cured, and provide a fabric which can ultimately be dry cured without requiring any further application of cross-linking agent or catalyst after the fixation step.
  • a reactive atmosphere comprising formaldehyde and a gaseous acidic catalyst
  • the gaseous acid thus introduced into the system promotes the fixation of the methylolated melamine or similar precondensate at the reactive sites in the cellulose fibers of the cotton which are inherently also capable of reacting with a cross-linker such as formaldehyde.
  • a cross-linker such as formaldehyde.
  • the cellulosic material is first padded with an aqueous solution containing one or more polymeriza-. ble N-methylol compounds and a water-soluble salt servingas a latent curing catalyst, and then the padded material containing the appropriate amount of moisture is heated and exposed to a reactive atmosphere of gaseous sulfur dioxide and formaldehyde vapor at a temperature of at least about 100 C., thereby causing the N-methylol compound to become fixed in the material and the formaldehyde to become attached thereto so as to be capable of causing the desired cross-linking during a final dry cure step.
  • the padded material is first exposed to one hot gaseous atmosphere at relatively high moisture conditions to heat the material and optimize distribution and/or fixation or polymerization of the N-methylol compound in the fiber system in the substantial absence of extraneous formaldehyde to effect heating and resin insolubilization in a single stage or in a sequence of stages and the heated and preconditioned material is then exposed to a different atmosphere at lower moisture conditions in a later stage to optimize fixation of formaldehyde in the system for the final cure.
  • the present invention is useful for treating various natural or artificial cellulosic fibers alone or as mixtures with each other in various proportions or as mixtures with other fibers.
  • They include natural cellulosic fibers such as cotton, linen and hemp, as well as regenerated or artificial cellulosic fibers such as viscose rayon and cuprammonium rayon.
  • Fibers which may be used in blends with one or more of the above mentioned cellulosic fibers are, for example, wool, silk, cellulose acetate, polyamides (e.g., nylon), polyesters (e.g., polyethylene terephthalate), acrylics, polyolefins (e.g., polypropylene), polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol fibers.
  • Such blends preferably include at least percent by weight, and most preferably at least 40 percent by weight, of cotton or other natural or regenerated cellulose.
  • the material may be a knit, woven, nonwoven, or otherwise constructed fabric or the invention may be applied to fibers or yarns before they are converted into more complex structures.
  • the material may be fiat, creased, pleated, hemmed, or formed into virtually any shape after contact with the formaldehyde-containing atmosphere. After complete processing, the formed creaseproofed fabric will maintain the desired configuration substantially for the life of the article, that is, a durable press fabric will be produced which will retain its desired shape through numerous wear-wash-dry cycles,
  • the practice of the present invention characteristically involves the use of at least one water-soluble polymer-forming compound possessing reactive N-methylol groups, formaldehyde as a cross-linker, and a latent solid curing catalyst.
  • a water-soluble polymer-forming compound possessing reactive N-methylol groups, formaldehyde as a cross-linker, and a latent solid curing catalyst.
  • the polymer-forming compound upon exposure to a hot humid acid vapor atmosphere the polymer-forming compound is polymerized inside the cotton fibers while the latter are wet and swollen, so that the polymeric material so formed is fixed within the fibers and protects them against excessive strength loss which normally results from conventional creaseproofing treatments; and, on the other hand, the fixed polymeric material and cross-linker subsequently take part in cross-linking the cellulose when cured in the dry state in the presence of the latent curing catalyst.
  • the preferred polymer-forming N-methylol compounds at this time include the melamine-formaldehyde andthe phenolformaldehyde precondensates, though other N-methylol containing, polymer-forming compounds such as urea-formaldehyde precondensates are also useful.
  • the polymer formers useful herein include particularly the easily hardenable precondensates which are substantially water soluble and are obtained by condensation of formaldehyde with a compound such as melamine or a lower alkyl substituted melamine, a urea, or a hydroxy benzene such as therein as described, for instance, in U.S. Pat. No. 3,138,802.
  • Triazines obtained by condensing a methyl or other lower alkyl substituted melamine and formaldehyde are further examples of such precondensates.
  • Aerotex 23 an alkylated melamine-formaldehyde precondensate
  • Aerotex M-3 a dimethoxymethylhydroxymethylmelamine
  • Aerotex P-225 a hexakis- (methoxymethyl) melamine
  • Aerotex 19 which is a less completely fractionated modification of Aerotex P-225.
  • the practice of the present invention also involves the use of a conventional latent curing catalyst.
  • a water-soluble salt of a strong acid with a weak base such as ammonium salts of hydrochloric, sulfuric, nitric, oxalic, lactic, or other inorganic or organic acid, various amine hydrochlorides, as well as acid acting salts of metals such as zinc or magnesium, e.g., zinc nitrate or magnesium chloride or a mixed catalyst such as MgCl /ZnCl MgCl /citric acid or Zn(NO tartaric acid.
  • Zinc nitrate, zinc chloride, magnesium chloride and ammonium chloride represent latent curing catalysts the use of which is particularly preferred in conjunction with the present invention.
  • N-methylol polymer-forming compound such as a methylolated melamine or a mixture of such compounds and a latent curing catalyst to the fabric initially from a common aqueous solution or pad bath.
  • the curing catalyst may be omitted from this initial stage and only applied at a later stage of the process, as its presence is only required in the final dry curing step.
  • the polymerizable N-methylol compound or precondensate may be dissolved in water to form a solution containing from about 3 to 25 percent,.and preferably from about 5 to 15 percent, of the N-methylol compound.
  • a curing catalyst may be included in this same solution, or in a separate solution, in an amount of between about 1 and 10 percent, and preferably between about 4 and 6 percent, based on the weight of the N-methylol compound. The optimum concentration depends somewhat on the particular catalyst and particular N-methylol compound used, and may be determined by routine preliminary tests.
  • the padding or impregnation is carried out in such a manner that the add-on of N-methylol compound deposited on the material is between about 3 and 12 percent, and preferably between about 6 and 8 percent, calculated as dry solid deposit based on the weight of dry fibrous material owf").
  • the padding is normally performed at ambient temperature, e.g., between about 10 and 30 C.
  • an essential feature of this part of the process is that the deposited N-methylol compound is fixed in the fibrous material together with a cross-linking component while the fibers are distended or swollen with water, so that the compound or precondensate becomes insolubilized in the fibrous cellulosic material without, however, converting the latter to a shape holding, crease resistant form at this stage, i.e., without altering the dry crease recovery angle of the fiber system to such an extent as to impede the creasing or other distinct shaping of such a fiber system during subsequent manufacture of garments or other products therefrom.
  • the aqueous padding bath may also contain other conventional fabric treating agents, for instance, wetting agents and fabric softeners, i.e., polymers capable of forming a soft film on the material or fabric.
  • fabric softeners include a latex or fine aqueous dispersion of polyethylene, various alkyl acrylate polymers, acrylonitrilebutadiene copolymers, deacetylated ethylene-vinyl acetate copolymers, polyurethanes, and the like.
  • Polymeric additives suitable for this general purpose are otherwise well known in the art and in most cases are commercially available in concentrated aqueous latex form.
  • such a dispersion is preferably diluted to provide about 0.1 to 4 percent of softener based on the weight of the fabric (owf).
  • the fabric is heated while its moisture content is between about and about 90 percent, preferably between and 70 percent (owf), in the presence of a gaseous acid catalyst, so that the N-methylol compound is fixed in the material.
  • Maintaining an appropriate amount of moisture in the fabric, within the limits indicated, is important as it undergoes exposure to the hot vapor atmosphere or atmospheres.
  • the final product in such a case tends to suffer from a high strength loss analogous to the loss suffered in the conventional pad-dry-cure process.
  • the squeezed padded fabric is then introduced into a first stage of a reaction chamber where it is heated to the desired reaction temperature, e.g., at least C., but preferably between about and C., in a steam atmosphere while the moisture in the fabric is maintained at or adjusted to the appropriate level.
  • the hot fabric is then passed over rollers to a second stage of the chamber where an acid gas, e.g., S0 or formic acid, is introduced such that it impinges upon the fabric while the latter remains at a predetermined temperature and moisture content.
  • an acid gas e.g., S0 or formic acid
  • the fabric is then passed to a third stage where formaldehyde is introduced such that it impinges upon the fabric while maintaining appropriate controlled conditions of temperature, moisture and acidity, which maybe the same as or different from the corresponding conditions maintained in the earlier stages.
  • formaldehyde is introduced such that it impinges upon the fabric while maintaining appropriate controlled conditions of temperature, moisture and acidity, which maybe the same as or different from the corresponding conditions maintained in the earlier stages.
  • it is permissible and maybe advantageous to maintain a substantially lower moisture content in the third stage than in the earlier stages.
  • Such lower moisture level in the third stage can have the effect of facilitating not only the further polymerization of the polymer-former in the fibers but also the fixation of formaldehyde in the system.
  • the several phases of the process can be performed by passing the fabric through a series of completely separate consecutive chambers, or the entire vapor treatment can be performed by passing the padded fabric straight through a single stage containing a mixed atmosphere of water vapor, gaseous acid catalyst and formaldehyde.
  • the entire vapor treatment can be performed by passing the padded fabric straight through a single stage containing a mixed atmosphere of water vapor, gaseous acid catalyst and formaldehyde.
  • the moisture content of the fabric being treated is important, the concentrations of water, acid and formaldehyde vapors present in the treating atmosphere or gas phase can be varied within wide limits and are not particularly important in and of themselves. To produce optimum results for any particular case, they can be readily coordinated with other factors such as kindand amount of polymer-former padded on, species of acid vapor employed, reaction temperature and fabric, exposure time on the basis of preliminary trial runs and fabric evaluations. Generally speaking, the amounts of acid vapor and formaldehyde present in the vapor phase or phases filling the treating chambers are well in excess of the small amounts of such chemicals which are actually required for accomplishing the .desired'chemical reactions in the fabric being treated.
  • Sulfur dioxide has been found to give particularly good results and is the most preferred gaseous acid catalyst in the present invention, because it is especially adapted to form a strong acid in the presence of formaldehyde, probably taking the form of a sulfonic acid, and yet is easy to remove from the fabric by drying subsequent to the vapor treatment.
  • formaldehyde probably taking the form of a sulfonic acid
  • other acids which have a boiling point below about 120 C. e.g., formic or acetic acid
  • S Hydrochloric acid is similarly useful, though it may cause greater tendering of the fabric if it is left in the fabric without any counteracting acid acceptor over an extended period prior to final cure and washing.
  • the wet cotton fabric is passed in a continuous manner through one or more zones containing the reactive acid and formaldehyde vapors and maintained at a temperature of at least 80 C., preferably from about 100 to 170 C.
  • the fabric is passed through such a chamber or plurality of chambers or reaction stages at such a rate as to provide a total exposure time of from about seconds to about minutes, preferably 30 seconds to 2 minutes.
  • a fabric exposure time of about 1 minute at 102 C. to an atmosphere of water vapor and $0 in the first stage or stages and from about another 30 seconds to 1 minute in a subsequent formaldehyde-containing stage at a like temperature should be considered representative of satisfactory operating conditions.
  • the optimum vapor phase reaction condition is one which is just long enough to effect the desired degree of fixation of N- methylol compound (e.g., 3 to 12 percent of polymer based on the fabric) and active formaldehyde cross-linker (e.g., 0.2 to 5.0 percent on the fabric), without overexposing the fabric to the reactive atmosphere.
  • the reactive vapor phase may also contain inert gases such as air, nitrogen, carbon dioxide, helium, and the like.
  • steam is present in the hot vapor phase at least as a result of evaporation of water from the passing padded fabric or may be deliberately introduced as such into the treating chamber as a means of heating the padded fabric to the desired temperature or as ameans of controlling the moisture content of the fabric at the desired level or levels while it is being treated.
  • other sources of heat such as infrared lamps may be used.
  • the formaldehyde may be obtained for the process in any convenient manner, such as by heating a suspension of paraformaldehyde in mineral oil to generate formaldehyde gas or by passing air through an aqueous formaldehyde solution and metering the resulting formaldehyde vapor or vapor mixture in a suitable proportion into the reaction zone.
  • a highly methylolated melamine is used as the polymer-former, such a compound of itself may also furnish some active formaldehyde cross-linker when subjected to a high temperature in the eventual dry curing step.
  • the cellulosic material After exposure to the reactive atmosphere, if the initial pad bath contained a latent curing catalyst, the cellulosic material is directly dried in preparation for the manufacture of a durable press article therefrom. No other intervening rinsing or other processing is required in such a case. Only if a latent catalyst was not included in the initial pad bath is it necessary to pass the fabric after the vapor treatment and before the drying step through a second pad bath containing an aqueous solution of a suitable latent curing catalyst, whereby the fabric becomes catalyzed for the eventual dry cure. Drying conditions are not especially critical but drying should be restricted so that the moisture content of the fabric does not fall below 6 to 10 percent and so that inadvertent precuring is avoided. For example, the treated cellulosic material may be dried at temperatures between about 20 and 60 C. for an appropriate time.
  • the durable press article may be made by first making the dry uncured material into a garment having creases hot pressed therein and then curing the garment (delayed cure), or by first curing the material in a flat state and then making a final product from the cured material (precure").
  • the curing or final setting or creaseproofing of the treated fabric may be effected by dry curing in a walkin air oven at temperatures between about C. and the charring temperature of the fabric, preferably at a temperature of about to 180 C., or in any other convenient heating equipment. Curing may, for example. also be accomplished in equipment such as a garment press which has been provided with adequate heating and dwell time control means. A residence or dwell time of about 5 minutes in an air oven at C. gives satisfactory cure in a typical case although curing times in the range from between about 2 to 10 minutes can commonly be used.
  • cellulosic materials of the present invention may be treated with other conventionaltextile treating agents such as water repellants, an-
  • each of these samples was then passed over three transport rollers through a treating chamber having a volume of about 2% cubic feet (about 18 inches wide, 12 inches long and 24 inches high), one of said rollers being disposed adjacent the fabric inlet slot at one side of the base of the chamber, the second roller being disposed near the top of the chamber on a line intermediate the two sidewalls of the chamber and the third roller being disposed adjacent the fabric outlet slot at the base of the chamber across from the inlet slot, wherebythe fabric is passed through the chamber along an inverted V-shaped path about 4 feet in length.
  • Formaldehyde was generated by heating a paraformaldehyde-mineral oil mixture in a stainless steel tank. The heated vapor wascarried by metered compressed air through heated tubes and one of several gas inlet manifolds into the reaction chamber. Sulfur dioxide was introduced from a tank and metered through the same or similar feed lines. In some tests both sulfur dioxide and formaldehyde gas were introduced into the chamber through'a manifold located near the fabric entrance, but in the preferred operation only the S0 was introduced near the fabric entrance at the bottom while the formaldehyde was introduced in the interior of the chamber near the top roller. Steam injection was also available and was used in a few runs, but generally was found unnecessary in this small scale equipment because an adequate moisture content was easy to maintain in the padded fabric without steam injection. However, in commercial scale equipment steam injection may offer improved moisture control for optimum resin fixation.
  • exposure times of fabric in the chamber were capable of variation from 30 seconds to 3 minutes, as desired.
  • the formaldehyde generator was loaded with 200 grams of paraformaldehyde. Airflow into the generator was generally 5 cubic feet/hour while sulfur dioxide was supplied at 4 cubic feet/hour, measured at about 22 C. and about 1 atmosphere.
  • the formaldehyde generator temperature ranged from 120 to 140 C. and the treating chamber was in most cases maintained either at about 102 C. or at about 1 18 C. depending on the desired reaction conditions.
  • the fabrics were dried in an air oven at 52 C. for about minutes and-after pressing, air cured at 160 C. for 5 minutes, laundered (AATCC 124- 1967 111 B), and the appearance and other properties evaluated after one cycle of laundering and tumble drying (l L+D).
  • the fabrics were also evaluated prior to curing, after the vapor treatment and drying.
  • some of the treated dried samples were laundered before curing and their properties measured.
  • a sample of the same cotton sample was also treated by a previously used steam wet fix'procedure, similar to that described in copending application, Ser. No. 764,950. More particularly, in this run the fabric was padded at 60 percent wet pickup in a bath containing 29 percent Aerotex l9 methylolated melamine (65 percent active compound), 38 percent Fixapret PCL modified methylolated propylene acid (50 percent active compound), 0.1 percent Triton X-100 wetting agent, the bath being adjusted to a pH of 2 by addition of an appropriate amount of sulfuric acid.
  • this sample was steamed in the steam chamber at 102 C. for seconds, neutralized in 0.5 percent sodium carbonate solution. rinsed, washed and dried. T hereafter it was catalyzed by pudding at 60 percent wet pickup in a solution containing 0.8 percent ZnNOy6H O and 2 percent polyethylene softeners. After drying, the sample was dried, pressed and air cured at 160 C. for 10 minutes, the same as all the other samples, and its appearance and other physical properties determined.
  • the samples were exposed to an atmosphere consisting of saturated steam, or an atmosphere comprising gaseous sulfur dioxide and saturated steam, at about 102 C. for either 1 or 3 minutes to deposit or fix the precondensate inside the fibers, as indicated in Table II.
  • the samples were exposed to an atmosphere comprising a mixture of formaldehyde vapor, air and gaseous sulfur dioxide at l02 C. for 3 minutes in runs 2/1, 2/2 and 2/3, and at 1 15 C. for 1 minute in run 2/4.
  • fabrics treated in accordance with this aspect of the present invention also have a useful level of easy care and physical properties. Generally speaking, however, they do not exhibit any significant advantage over the fabrics from Examples l5 which were treated by the more rapid and somewhat simpler procedure, without any added steam.
  • the vapor treatment of the present invention converts the aminoplast precondensate to an insoluble form which resists laundering and upon recatalyzing of the fabric can serve to impart durable press properties to the fabric when dry cured.
  • most of the-precondensate remains water soluble such that it is removed by laundering and a subsequent cure is then incapable of producing satisfactory durable press properties.
  • the difference in add-on determined on the invention in fixing the aminoplast in a substantially insoluble form in the fabric while in the absence of such vapor treatment only a small fraction of the, initially applied aminoplast remains on the fabric after laundering.
  • Example 3/ l-A in comparing the procedure of Example 3/ l-A with the procedure used in all earlier examples, a laundering step and a recatalyzating step were interposed between the vapor treating step and the dry curing step.
  • This procedure permits the evaluation of the effectiveness of the resin fixation achieved by the vapor treatment, but is not required for any practical reasons.
  • Table III the easy care properties of the fabric in Example 3/1-B are not developed because in the absence of the vapor treatment there is insufficient resin fixation.
  • a process for treating a cellulosic fiber-containing textile material so as to make it susceptible to improvement of its crease retention and smooth drying characteristics by a subsequent cure comprises a. applying to the material an aqueous solution comprising at least one water-soluble polymer-forming precondensate possessing reactive N-methylol groups; exposing the material while swollen by moisture at a temperature of at least C. to a reactive atmosphere comprising formaldehyde vapor and a gaseous acid whereby said polymer-forming precondensate becomes fixed in the material;
  • a latent acid curing catalyst either as a component of the aqueous solution of step (a) or in the form of a separate aqueous solution which is applied after fixation step (b) and prior to drying step (d);
  • gaseous acid is selected from the group consisting of sulfur dioxide, formic acid, acetic acid and hydrogen chloride.
  • the cellulosic fiber-containing material comprises at least 20 percent cellulosic fibers
  • the aqueous N-methylol precondensate solution the final cured samples further confirms the effectiveness of applied to the material comprises a hardenable methylolated melamine compound and precondensate is fixed inside the cellulosic fibers by heating the material at a temperature of at least about 80 C. in a vapor phase comprising a gaseous acid and formaldehyde while maintaining the moisture content of the material between about 15 and 90 percent based on the weight ofthe material.
  • a process for making a cotton-containing fabric suitable for having improved crease resistance and smooth drying characteristics imparted to it upon eventual curing comprises a. applying to the fabric an aqueous solution comprising (i) at least one water-soluble formaldehyde-melamine precondensate having reactive N methylo1 groups and (ii) a latent acid curing catalyst;
  • the latent curing catalyst is selected from the group consisting of zinc nitrate, zinc chloride, ammonium chloride, and magnesium chloride, and wherein the vapor treated and dried fabric is heated at a temperature between about 120 and 180 durable press properties thereto.
  • an aqueous solution comprising about 3 to 25 percent of a water-soluble, hardenable formaldehyde melamine precondensate having reactive N-methy1ol groups and a formaldehyde to melamine ratio of between about 2:1 and 6:1 and about 1 to 10 percent, based on the amount of formaldehyde-melamine precondensate, of a water-soluble curing catalyst selected from the group consisting of zinc nitrate, zinc chloride, ammonium chloride and magnesium chloride;

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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)
US32370A 1970-04-27 1970-04-27 Vapor phase resin fixation process for cellulosic material permitting subsequent cure Expired - Lifetime US3642428A (en)

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US (1) US3642428A (de)
BE (1) BE764137A (de)
BR (1) BR7101925D0 (de)
CA (1) CA947009A (de)
CH (2) CH373971A4 (de)
DE (1) DE2114396A1 (de)
ES (1) ES389313A1 (de)
FR (1) FR2086370B1 (de)
GB (1) GB1313978A (de)
NL (1) NL7104168A (de)
NO (1) NO137161C (de)
SE (1) SE381690B (de)

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US3841832A (en) * 1971-12-06 1974-10-15 Cotton Inc Process for treating cellulosic material with formaldehyde in liquid phase and sulfur dioxide
US3865545A (en) * 1971-09-13 1975-02-11 Mc Graw Edison Co Durable press method
USRE30860E (en) * 1971-12-06 1982-02-02 Cotton, Incorporated Process for treating cellulosic material with formaldehyde in liquid phase and sulfur dioxide
EP0860542A2 (de) * 1996-12-17 1998-08-26 Nisshinbo Industries, Inc. Verfahren zur Behandlung von Textilien aus Cellulosefasern mit Harzen
US6203577B1 (en) * 1996-05-23 2001-03-20 Nisshinbo Industries, Inc. Shrink-proof treatment of cellulosic fiber textile
US6638319B2 (en) 2001-04-04 2003-10-28 Healthtex Apparel Corp. Polymer for printed cotton
US6645255B2 (en) 2001-04-04 2003-11-11 Healthtex Apparel Corp. Polymer-grafted stretchable cotton
US6645256B2 (en) 2001-04-04 2003-11-11 Healthtex Apparel Corp. Polymer grafted cotton
US11098444B2 (en) 2016-01-07 2021-08-24 Tommie Copper Ip, Inc. Cotton performance products and methods of their manufacture

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3865545A (en) * 1971-09-13 1975-02-11 Mc Graw Edison Co Durable press method
US3841832A (en) * 1971-12-06 1974-10-15 Cotton Inc Process for treating cellulosic material with formaldehyde in liquid phase and sulfur dioxide
USRE30860E (en) * 1971-12-06 1982-02-02 Cotton, Incorporated Process for treating cellulosic material with formaldehyde in liquid phase and sulfur dioxide
US6203577B1 (en) * 1996-05-23 2001-03-20 Nisshinbo Industries, Inc. Shrink-proof treatment of cellulosic fiber textile
EP0860542A2 (de) * 1996-12-17 1998-08-26 Nisshinbo Industries, Inc. Verfahren zur Behandlung von Textilien aus Cellulosefasern mit Harzen
EP0860542A3 (de) * 1996-12-17 1999-04-28 Nisshinbo Industries, Inc. Verfahren zur Behandlung von Textilien aus Cellulosefasern mit Harzen
US6638319B2 (en) 2001-04-04 2003-10-28 Healthtex Apparel Corp. Polymer for printed cotton
US6645255B2 (en) 2001-04-04 2003-11-11 Healthtex Apparel Corp. Polymer-grafted stretchable cotton
US6645256B2 (en) 2001-04-04 2003-11-11 Healthtex Apparel Corp. Polymer grafted cotton
US20040072948A1 (en) * 2001-04-04 2004-04-15 Sanduja Mohan L. Polymer-grafted stretchable cotton
US6908976B2 (en) 2001-04-04 2005-06-21 Healthtex Apparel Corp. Polymer-grafted stretchable cotton
US11098444B2 (en) 2016-01-07 2021-08-24 Tommie Copper Ip, Inc. Cotton performance products and methods of their manufacture

Also Published As

Publication number Publication date
NO137161C (no) 1978-01-11
BR7101925D0 (pt) 1973-05-03
CH592195B5 (de) 1977-10-14
BE764137A (fr) 1971-08-02
SE381690B (sv) 1975-12-15
GB1313978A (en) 1973-04-18
DE2114396A1 (de) 1971-11-11
ES389313A1 (es) 1973-06-01
FR2086370A1 (de) 1971-12-31
CA947009A (en) 1974-05-14
NL7104168A (de) 1971-10-29
FR2086370B1 (de) 1974-10-11
NO137161B (no) 1977-10-03
CH373971A4 (de) 1977-01-31

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