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
  • D06M15/507—Polyesters
  • D06M15/5075—Polyesters containing sulfonic groups
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
  • D06M15/568—Reaction products of isocyanates with polyethers

Definitions

• ABSTRACT The invention relates to treatment of cellulosic textile fabrics with methylolated alkoxyalkyl carbamate fin-' 4 Claims, No Drawings TREATMENT OF CELLULOSIC TEXTILE FABRICS WITH METI-IYLOLATED ALKOXYALKYL CARBAMATES
• This invention relates to the preparation of textile fabrics having improved wrinkle and shrink resistance and other improved properties. More specifically, this invention relates to a process for treating cellulosic textile fabrics with methylolated alkoxyalkyl carbamates and to the treated fabrics produced thereby.
• finishing agents prepared by reacting aliphatic monocarbamates with formaldehyde. These products have been found to be very effective in imparting wrinkle resistance and washwear properties to the fabric, while displaying the important advantages, as compared with conventional nitrogenous finishing agents, of enhanced resistance to chlorine damage and durability under conditions promoting acid hydolysis.
• finishing agents of this type have been prepared from alkyl carbamates, such as methyl, ethyl, propyl or butyl carbamate, or from hydroxyalkyl carbamates, such as hydroxyethyl carbamate, and have been observed from certain deficiencies, for example, with regard to abrasion resistance, tear strength and fabric hand, which have hindered their optimum commercial development.
• these finishing agents though greatly superior to conventional nitrogenous finishing agents such as dimethylol ethyleneurea or methylated methylolmelamine with respect to resistance to chlorine damage and durability to acid hydrolysis, are, in certain instances, still somewhat deficient in this regard. It is toward the objectives of overcoming these deficiencies and of providing treated textile fabrics of improved properties that the present invention is directed.
• This invention is based on the discovery that finishing agents for treating cellulosic textile fabrics which are prepared by reaction of formaldehyde with an alkoxyalkly carbamate, as hereinafter define, permit the preparation of fabrics with superior properties as compared to the finishes derived from alkyl or hydroxyalkyl carbamates in accordance with the teachings of the prior art. It was unexpected and surprising to find that the methylolated alkoxyalkyl carbamates described herein are superior finishing agents to both the methylolated alkyl carbamates and methylolated hydroxylakyl carbamates.
• alkoxyalkyl carbamates employed in preparing the textile treating agents of this invention are compounds of the general formula:
• a value of from I to ID and preferably of from l to 3. They may be prepared by any of several methods known to the art. A particularly convenient method of preparation involves the reaction of urea with a glycol ether of the formula:
• glycol ethers within the scope of this definition are the methyl, ethy, butyl, isobutyl, hexyl and 2- ethylhexyl ethers of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, and mixed polyethylene-polypropylene glycol.
• alkoxyalkyl carbamates described above are reacted with formaldehyde to produce the methylolated alkoxyalkyl carbamates having utility as textile finishing agents in accordance with this invention.
• the exact structure of the reaction product of formaldehyde with the alkoxyalkyl carbamate has not been established, but it is believed that a mixture of monomethylol and dimethylol derivatives results, viz., a mixture of an N- methylol alkoxyalkyl carbamate of the formula:
• the formaldehyde is believed to be present as free formaldehyde and some as combined formaldehyde which is present in a form which has not yet been established.
• reaction conditions are not narrowly critical.
• a suitable procedure is to dissolve the alkoxyalkyl carbamate in water, add the formaldehyde to the aqueous solution, adjust the pH to the desired level, and then heat the mixture for the period necessary to effect methylolation. Upon cooling, neutralization, dilution with water, and filtration, the product is recovered as a clear, colorless solution of the methylolated alkoxyalkyl carbamate.
• the reaction of formaldehyde and the alkoxyalkyl carbamate may be effected at temperatures from about 20C., preferably about 50C., to the reflux temperature of the reaction mixture, i.e., slightly above I00C. Reaction times of from about If) minutes to about 24 hours, and preferably from about I to 5 hours, may be employed.
• the initial pH of the reaction mixture should be from about 4 to about 10, and preferably from about 8 to about 10.
• the most important factor in determining the performance of the finishing agents is the ratio of formaldehyde to alkoxyalkyl carbamate employed.
• the reaction products of particular utility for the purposes of this invention are those prepared by reacting the formaldehyde with the alkoxyalkly carbamate in a molar ratio of from about 1.5 to about 3 moles of formaldehyde per mole of alkoxyalkyl carbamate, and preferably in a molar ratio of from about 2 to about 2.5.
• Textile fabrics which are amenable to treatment with the finishing agents of this invention are the cellulosic textile fabrics.
• the term cellulosic textile fabric is intended to include fabrics, whether woven or knitted, and garments or other articles made from such fabrics, and is also intended to include both cellulose fabrics, including regenerated cellulose, and cellulosecontaining fabrics.
• the cellulosic textile fabrics comprehended thus include cotton fabrics, linen fabrics, rayon fabrics, fabrics consisting of blends of cotton, linen or rayon fibers, and fabrics consisting of blends of cellulose fibers and non-cellulosic fibers.
• the finish may be applied to the cellulosic textile fabric in any suitable manner known to the art, for example, by dipping or padding.
• the finishing agent which term is employed herein to mean the reaction product of formaldehyde and the alkoxyalkyl carbamate, is applied to the fabric from aqueous solution.
• aqueous treating solution may, if desired, contain, in addition to the finishing agent, other materials employed in textile finishing such as plasticizers, softening agents, hand builders, and the like.
• the amount of finishing agent to be applied to the fabric varies widely depending upon the type of fabric and its intended application, and, accordingly, the present invention comprehends the use of any effective amount.
• Amounts of from about l to about 30 per cent by weight of the finishing agent, based on the weight of the textile fabric, are ordinarily employed, i.e., an addon of about 1 to about 30 per cent. It is preferred to employ an amount of at least about 4 per cent.
• the add-on will depend upon the concentration of the finishing agent in the treating solution and the weight of solution which the textile fabric will retain, i.e., the wet pick-up.
• a wet pick-up of from about 50 to about 120 per cent may be readily effected by conventional techniques, while the treating solution applied to the textile fabric in practicing this invention may contain from as little as about 2 per cent, or less, to as much as about 25 per cent, or more, of the finishing agent. Accordingly, no difficulty is encountered in achieving the desired add-on.
• methylolated alkoxyalkyl carbamates of this invention require curing following application to the textile fabric to promote reaction with the fibers of the fabric and thereby impart the desired properties, such as wrinkle resistance and wash-wear characteristics.
• Suitable catalysts for the curing reaction are metal salts of strong mineral acids, particularly zinz fluoborate and the hydrates of magnesium chloride and zinc nitrate.
• the catalyst is ordinarly added to the aqueous treating solution and should be employed in a concentration sufficient to give a retention of catalyst of about 0.5 to about weight per cent, based on the weight of the fabric. Larger amounts of catalyst, within the range specified, are preferably employed at the higher add-on levels of the finishing agent.
• the optimum amount of catalyst varies depending on the particular catalyst employed. For example, with magnesium chloride it is preferred to utilize a ratio of catalyst to finishing agent by weight, as retained on the fabric, of from about 0.2 to about 0.6, while with zinc nitrate or zinc fluoborate the preferred ratio is from about 0.05 to about 0.2.
• the fabric is subjected to heating to remove the water and then curing is effected by the application of further heat. It is preferred to dry the fabric at temperatures lower than those employed in the curing. Thus, drying is usually carried out at temperatures of up to about C., while temperatures from 150C. to about 200C. are ordinarily employed in the curing step. The time required to effect the curing will vary from as little as about 1 minute, or less, to as much as about 5 minutes, or more. Normal curing, i.e., curing immediately after drying, or deferred curing,,i.e., after the fabric has been made into a garment, may be employed as desired.
• the methylolated alkoxyalkyl carbamates have been found to be, in general, equivalent in durability to acid hydrolysis to the methylolated hydroxyalkyl carbamates, but superior in resistance to chlorine damage particularly in that they exhibit excellent resistance to chlorine damage even when the fabric treating and curing conditions are varied widely whereas the methylolated hydroxyalkly carbamates exhibit undesired criticality as regards the fabric treating and curing conditions necessary.
• the methylolated alkoxyalkyl carbamate finishing agents described herein provide improved abrasion resistance and, in certain instances, a more desirable hand, as compared with the methylolated alkyl and hydroxyalkly carbamates. Moreover, they are more efficient on a molar basis and equally as efficient on a weight basis as the prior art finishing agents.
• Wash-Wear Rating determined by AATCC Tentative Test Method 88A-1964T.
• the rating which is indicative of the smoothness of appearance of the fabric, ranges from 1 to 5 with intermediate ratings indicated by and symbols.
• EXAMPLE 1 Samples of desized, scoured, bleached and'mercerized white cotton printcloth having a thread count of X 80 were padded with a treating batch containing the methylolated methoxyethyl carbamate using a Butterworth Laboratory Padder.
• the treating bath was composed of methylolated methoxyethyl carbamate, MgCl2. 6H O, Fabritone PE (a commercial softner composed of emulsitied polyethylene was of 30% solids content) and TERGITOL TMN (trade-mark for a nonionic surfactant characterized as a trimethyl nonyl ether of polyethylene glycol) with the balance being water.
• Fabritone PE a commercial softner composed of emulsitied polyethylene was of 30% solids content
• TERGITOL TMN trade-mark for a nonionic surfactant characterized as a trimethyl nonyl ether of polyethylene glycol
• the treated fabric with a more pleasing hand than the fabric catalyst employed was MgC1 6H O and the treating treated with methylolated ethyl carbamate. bath contained 0.1 per cent by weight TERGlTOL TMN. After treatment, the wet fabric was placed on a EXAMPLE 2 pin tenter frame, dried at 150C. for 1.5 minutes, and I5 cured at 175C. for 1.25 minutes. The add-on levels Several methylolated alkoxyalkyl carbamates were and the properties of the treated fabric are summarized prepared and evaluated as finishing agents for cotton in Table 111 below.
• the strength loss due to retained chlorine was amount of 2 moles of p-formaldehyde per mole of al- 74% with the methylolated hydroxyethyl carbamate as koxalkyl carbamate, heating to about 80C. to dissolve compared with a maximum of 13% for the four methylthe p-formaldehyde, and then permitting the mixture to olated alkoxyalkyl carbamates evaluated.
• the strength loss due to retained chlorine was amount of 2 moles of p-formaldehyde per mole of al- 74% with the methylolated hydroxyethyl carbamate as koxalkyl carbamate, heating to about 80C. to dissolve compared with a maximum of 13% for the four methylthe p-formaldehyde, and then permitting the mixture to olated alkoxyalkyl carbamates evaluated.
• the methylolated hydroxyethyl carbamate was prepared by reacting p-formaldehyde with hydroxyethyl carbamate,
• the data indicate that the methylolated alkoxyalkyl carbamates provide, in general, at least comparable performance to the methylolated hydroxyethyl carbamate as regards crease recovery, wash-wearcharacteristics, and fabric strength.
• EXAMPLE 3 tions under which the methylolation of the methoxyethyl carbamate was carried out and the properties of the fabric samples treated with the finishingagents produced under the differing conditions are sum- This example demonstrates the effect of methylolai d i Tables 1V, V and V1 for test series one, tion conditions on the performance of methylolated d three respectively.
• the fabric employed was a cotton printcloth having a thread count of 80 X 80, a dry crease recovery of 158, a tear strenght (warp filling) of 1,180 grams, and a tensile strength (filling) of 37 lbs;
• the catalyst was MgCl .6H O;
• the add-on was 4% of methylolaed methoxyethyl carbamate and 1.2% of catalyst; and the treated fabric was dried for 1.5 minutes at C. and cured for 1.25 minutes at 175C.
• the same cotton printcloth was employed; the catalyst was Zn(NO 6H O; the add-on was 4% of methylolated methoxyetyl carbamate and 0.2% of catalyst; and the treated fabric was dried for 1.5 minutes at 150C. and cured for 1.25 minutes at C.
• the fabric was a cotton broadcloth having a thread count of 136 X 64, a dry crease recovery of 155, a tear srength (warp filling) of 1,520 grams, and a tensile strength (filling) of 61 lbs;
• the catalyst was MgCl .6H O;
• the add-on was 4% of methylolated methoxyethyl carbamate and 1.6% of catalyst; and the treated fabric was dried for 1.5 minutes at 150C. and cured for 1.25 minutes at C.
• the reaction condi- As evidenced by the data Tables 1V, V and V1, the
• methylolated alkoxyalkyl carbamate finishing agents of the present invention can be prepared over a relatively broad range of methylolation conditions and still perform effectively.
• the molar ratio of formaldehyde to alkoxyalkyl carbamate is the most significant variable, with crease recovery increasing and both tear strength and tensile strength decreasing with increasing formaldehyde to alkoxyalkyl cabamate ratios.
• EXAMPLE 4 80 X 80 and in each instance it was padded with a Butterworth Laboratory Padder at a wet pick-up of 80% and then dried on a pin tenter frame at 150C. for 1.5 minutes.
• methylolated hydroxyethyl carbamate will provide good resistance to chlorine damage only if a very high formaldehyde to carbamate ratio is employed in effecting the methylolation, with the resulting disadvantage of a very strong formaldehyde odor in the fabric.
• changes in the pH of the treating bath or the curing conditions strongly influence the resistance to chlorine damage for fabric treated with methylolated hydroxyethyl carbamate, but have little effect on the resistance to chlorine damage of fabric treated with methylolated methoxyethyl carbamate. Accordingly, much less stringent control of fabric treating conditions is permissible with the methylolated methoxyethyl carbamate. This is an important distinction between the methylolated alkoxyalkyl carbamate finishing agents of this invention and the methylolated hydroxyalkyl carbamate finishing agents of the prior art.
• R is an alkyl group of l to 8 carbon atoms
• R is an alkylene radical of 2 carbon atoms
• n is an integer having a'value of 1, said reaction being conducted at from about 20C. to about the reflux temperature of the reaction mixture for a period of time from about minutes to about 24 hours at an initial pH of from about four to about ten in a ratio of about 1.5 to about three moles of formaldehyde per mole of alkoxyalkyl carbamate.
• R is an alkyl group of l to 4 carbon atoms.
• the improvement for obtaining improved chlorine resistance which comprises employing as the cross-linking agent a product obtained by the reaction of formaldehydc in an aqueous alkaline solution with a glycol ether carbamate having the formula:
• Colutm 1 lines 24-25 should read: I "such as hydroxyethyl or hydrox ropyl VP carbamate, and have been observed to suffer Q from certain deficiencies, for example, with re-".

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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)

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Cited By (7)

Citations (3)

• 1966
  • 1966-02-16 US US527772A patent/US3871822A/en not_active Expired - Lifetime
• 1967
  • 1967-01-31 IL IL27370A patent/IL27370A/xx unknown
  • 1967-02-09 DE DE19671619185 patent/DE1619185A1/de active Pending
  • 1967-02-13 BE BE694000D patent/BE694000A/xx unknown
  • 1967-02-13 FR FR94680A patent/FR1511299A/fr not_active Expired
  • 1967-02-14 SE SE2061/67A patent/SE320647B/xx unknown
  • 1967-02-15 GB GB7216/67A patent/GB1105250A/en not_active Expired
  • 1967-02-16 NL NL6702351A patent/NL6702351A/xx unknown

Patent Citations (3)

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