US3738981A - Textile treating compositions,process of treating textiles and textile articles - Google Patents

Textile treating compositions,process of treating textiles and textile articles Download PDF

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US3738981A
US3738981A US00883347A US3738981DA US3738981A US 3738981 A US3738981 A US 3738981A US 00883347 A US00883347 A US 00883347A US 3738981D A US3738981D A US 3738981DA US 3738981 A US3738981 A US 3738981A
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textile
parts
gms
toluene
carbamic acid
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K Graff
A Sherman
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Zeneca Inc
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ICI Americas Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • 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

Definitions

  • textile treating compositions comprising a novel class of carbamic acid esters containing at least one thermally labile carbamic acid ester group and containing at least one thermally stable carbamic acid ester group derived from a polyoxyethylene ether.
  • the textile treating compositions may be applied to textile materials to improve the physical characteristics thereof; for example, anti-soiling and/0r soil release characteristics.
  • This invention relates to textile treating compositions, to methods of treating textiles, and to textiles having improved physical properties. More particularly, this invention relates to novel carbamic acid esters which are useful for treating textile materials to impart anti-soiling and/ or soil release characteristics thereto.
  • the cross-linking treatment has an adverse effect on the tear strength, hand, soiling, and abrasion resistance properties of the textile material.
  • the cross-linked textile material although exhibiting the beneficial characteristics of durable press behavior, has poor abrasion resistance, poor hand, poor texture, and poor soiling properties. It is known that some of the aforementioned properties can be improved by using polyester fibers, alone or in blends with cotton.
  • Polyester fibers have a propensity to accept and retain oily grime and dirt. Accordingly, when the garment is being worn, soil and/or oily materials accumulate on the garment and settle on the fabric. Once the garment becomes soiled, it is then subjected to a cleaning process for removal of the dirt and/or oily deposits, and only a drycleaning process will successfully clean the garment.
  • the cleaning process normally employed is washing in a conventional home washing machine by the housewife.
  • a wash cycle it is virtually impossible to remove the soil and/or oily stains from the garment and secondly, assuming that the undesirable materials are removed from the garment or a fairly clean garment is being washed, soil remaining in the wash water is redeposited onto the garment prior to the end of the wash cycle.
  • soil remaining in the wash water is redeposited onto the garment prior to the end of the wash cycle.
  • Such a condition, heretofore unavoidable is quite disadvantageous in that the garment after being worn never again assumes a truly clean appearance, but instead tends to gray and/or yellow due Patented June 12, 1973 to the soil and/or oily materials deposited and remaining thereon. Further use and washing of the garment increases the intensity of the gray to the point that ultimately the garment is not acceptable for further wear due to its discoloration.
  • an object of this invention to provide novel textile treating compositions for application to textile materials to impart thereto anti-soiling and/or soil release characteristics to the textile materials and which will adhere to the textile materials through numerous laundering.
  • novel carbamic acid esters of the present invention may be prepared by reacting, simultaneously or consecutively in any order, aromatic polyisocyanate, polyoxyethylene ether, and a thermally reversible blocking agent, such as phenol, methyl phenol, dimethyl phenol, trimethyl phenol, ethyl phenol, caprolactam, and mixtures thereof.
  • a thermally reversible blocking agent such as phenol, methyl phenol, dimethyl phenol, trimethyl phenol, ethyl phenol, caprolactam, and mixtures thereof.
  • the polyisocyanate may be reacted with the blocking agent in such proportions that l-NCO groups remains and may subsequently be reacted with the polyoxyethylene ether.
  • the amounts of polyoxyethylene ether compound, polyisocyanate, and blocking agent used are selected to assure that the resultant carbamate contains at least one thermally stable carbamate group derived from the polyby reacting the polyisocyanate, blocking agent, and polyoxyethylene ether in such proportions that the ratio of mols of blocking agent to NCO groups is less than one and the number of NCO groups is equal to or less than the sum of the hydroxyl groups and mols of blocking agent.
  • one mol of a polyoxyethylene ether containing two hydroxyl groups and two mols of a diisocyanate may be reacted with two mols of blocking agent whereas one mol of the polyoxyethylene ether and two mols of a triisocyanate may be reacted with four mols of a blocking agent.
  • the reaction is carried out under conditions which exclude moisture and preferably in the substantial absence of oxygen to minimize discoloration of the resulting carbamic acid ester. Temperatures up to 200 C. may be used. Preferably, the reaction is carried out at 35 C. to 100 C. when caprolactam is used as the blocl ing agent and at 50 C. to 160 C. when a phenol is used as the blocking agent.
  • the reaction may be conducted in the absence of a solvent or in the presence of a solvent which is inert to isocyanate groups.
  • solvents include cellosolve acetate,, acetone, methylethyl ketone, cyclohexanone, chloroform, benzene, perchloroethylene, chlorobenzene, and trifluoroethane.
  • catalyst such as aliphatic tertiary amines, alkali or alkaline earth metal oxides, carbonates, alcoholates, and phenates, and metal salts of carboxylic acids may be used to facilitate the reaction. If catalyst is used, it should be neutralized after completion of the reaction.
  • the polyisocyanates which may be used to prepare the carbamic acid ester of this invention are aromatic polyisocyanates; that is, isocyanates containing at least two NCO groups directly attached to carbon atoms of an aromatic ring.
  • aromatic polyisocyanates which may be used to prepare the carbamic acid esters of this invention include 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; phenylene diisocyanate; methoxyphenylene 2,4-diisocyanate; diphenylmethane 4,4'-diisocyanate; 3-methyl-diphenylrnethane 4,,4'-diisocyanate; diphenylether 2,4,4'-triisocyanate; and mixtures thereof.
  • the preferred isocyanate is 2,4-toluene diisocyanate.
  • the polyoxyethylene ethers which may be used to prepare the carbamic acid esters of this invention are the water-soluble or readily dispersible polyoxyethylene ethers having a molecular Weight of at least 6,000, and preferably at least 10,000, and containing at least one aliphatic hydroxyl group, and preferably at least two aliphatic hy droxyl groups, and at least 90% by Weight of oxyethylene groups present as polyoxyethylene chains containing at least 60 oxyethylene groups.
  • a preferred class of these polyoxyethylene ethers have a molecular weight of not more than about 100,000 and have two aliphatic primary hydroxyl groups, each of said aliphatic primary hydroxyl groups being directly attached to a polyoxyethylene chain containing at least 6 oxyethylene groups.
  • polyoxyethylene ethers are well-known compounds and many are commercially available.
  • a particularly preferred class of polyoxyethylene ethers comprises polyoxyethylene glycols having a molecular weight of at least 6,000 and the reaction products of a molar excess of a polyoxyethylene glycol having a molecular weight of at least 3,000 with a compound selected from the group consisting of organic diisocyanates, dicarboxylic acids or anhydrides, and organic diepoxy compounds having two oxirane epoxy groups in which the oxirane oxygen is bonded to adjacent carbon atoms, and preferably to adjacent carbon atoms of a cycloaliphatic ring.
  • the reaction of the polyoxyethylene glycol with organic diisocyanate may be carried out under reaction conditions conventional in the art for reacting a diisocyanate with a glycol.
  • the reaction may be conducted by heating a mixture of the reactants to a temperature of from 100 C. to 200 C. in the presence or absence of an amine catalyst.
  • the organic diisocyanate may be an aromatic diisocyanate or an aliphatic diisocyante.
  • diisocyanates include hexamcthylene diisocyanate tluene diisocyanates, phenylene diisocyanate, diphenylmethane diisocyanates, and methoxyphenylene diisocyanates.
  • the reaction of the polyoxyethylene glycol with the dicarboxylic acid or anhydride may be carried out under esterification conditions conventional in the art. For example, a mixture of three mols of the glycol and two mols of the acid or anhydride may be heated to a temperature of 150 C. to 200 C. until esterification is essentially complete.
  • the reaction may be conducted in the absence or presence of an acid catalyst, such as toluene-sulfonic acid, or a basic catalyst, such as sodium hydroxide.
  • an acid catalyst such as toluene-sulfonic acid
  • a basic catalyst such as sodium hydroxide.
  • dicarboxylic acids and anhydrides includes succinic acid, maleic acid, terephthalic acid, diglycolic acid, adipic acid, and anhydrides thereof.
  • polyoxyethylene ethers prepared by reacting a polyoxyethylene glycol with an organic diepoxy compound are disclosed in United States Pat. Nos. 2,990,396 and 3,182,099. The complete disclosures of these two patents are specifically incorporated into the present application by reference.
  • EXAMPLE 1 188 gms. of phenol is dissolved in about 350 ml. of distilled toluene from which any water has been azeotroped. To this solution are added 348 gms. of 2,4-toluene dissocyanate which is washed into the flask with about 114 ml. of toluene. The mixture is then stirred and refluxed (100-110 C.) under nitrogen for two hours to yield a monophenol-blocked 2,4-toluene diisocyanate solution in toluene. 250 gms. of toluene are added to 374 gms.
  • Carbowax 6000 polyoxyethylene glycol of about 6000 molecular weight and sold by Union Carbide
  • the mixture is refluxed for about 2 hours to azeotrope about 1 ml. of water.
  • To 50 gms. (0.1 mol reactant) of the above toluene solution of phenol-blocked 2,4-toluene diisocyanate and 100 gms. of dried toluene are added 1.0 gms. of hydrogenated tallow dimethylamine in 5 gms. of toluene.
  • the mixture is then heated to about C., and the above-described Carbowax and toluene solution is added over about a 10-minute period through a steam heated funnel.
  • the stirred mixture is heated at about 8082 C. for 2 hours. The heat is then removed and the mixture neutralized with 3 gms. of glacial acetic acid Washed in with 4.5 gms. toluene, and the toluene vacuum distilled to yield 397 gms. of a viscous, cloudy liquid 1:2:2 Carbowax 600-2,4-toluene diisocyanate-phenol carbamic acid ester product, which hardened to a waxy solid when cold. The product is dispersible in water and soluble in dioxane.
  • EXAMPLE 2 374 gms. of Carbowax 6000 are added to 250 gms. of toluene and the mixture refluxed 1.5 hours to azeotrope 0.5 ml. water to give a hazy viscous product. To this product are added gradually a heated solution (about 80 C.) of 17.5 gms. of 2,4-toluene diisocyanate in gms. of dried toluene. The mixture is heated at 100 C. for 2 hours, and 11.3 gms. of caprolactam in 100 gms. of dried toluene are added to the mixture.
  • EXAMPLE 3 225 gms. of Carbowax 20M (a polyoxyethylene ether having a molecular weight of 15,00020,000 and synthesized by reacting about 3 mols of Carbowax 6000 with about 2 mols of diepoxide.
  • the product is sold by Union Carbide).
  • 17.5 gms. of 2,4toluene diisocyanate, and 11.3 gms. of caprolactam are reacted in accordance with the process described in Example 2 to give a 1:2:2 addition product of the three reactants.
  • the addition of water to a dioxane solution of the product gives a cloudy solution.
  • a sample of the product is toluene solution diluted with dioxane gave a pale yellow, hazy solution containing 10.5% solids, 12.2% toluene, and 77.3% dioxane.
  • EXAMPLE 4 250 gms. of toluene are added to 748 gms. of Carbowax 6000, and the mixture refluxed to about 120 C. for 2 hours to azeotrope 1.0 ml. of water. This solution is then added slowly to 26.2 gms. of 2,4-toluene diisocyanate in 100 gms. of dried toluene over a -minute period with stirring. The temperature increases from 58 C. to 81 C. 1.0 gms. of hydrogenated tallow dimethylamine in 5 ml. of toluene is added, and the mixture is heated for about 2 hours at about 80 C. (under a nitrogen blanket). 9.4 gms.
  • EXAMPLE 5 225 gms. of Carbowax 20M are added to 100 of toluene and the water present (about 0.5 ml.) azeotroped off over 1 hour. The toluene is then stripped 01f under vacuum. 200 ml. ethyl acetate are slowly added at 50 C. of 0.5 gm. of dimethyloctadecylamine and 8.93 gms. of 1:1 2,4-toluene diisocyanatephenol condensation product (prepared by reacting phenol with toluene diisocyanate for 2 hours at 150 C.) are then added. The mixture is heated at 45 C. with stirring for about 2.5 hours, the catalyst is then neutralized with acetic acid. The solid product is dissolved in warm water to give a slight viscous, milky off-white 10% solution of 1:2:2 condensation product of Carbowax 20M-toluene diisocyanate-phenol.
  • Example 5 is repeated except that 3 times the amount of 1:1 toluene diisocyanate-phenol condensation product is employed.
  • the reaction product is the 1:6:6 condensation product of Carbowax 20M-toluene diisocyanatephenol.
  • EXAMPLE 7 A mixture of 200 ml. of toluene and 225 gms. of Carbowax 20M is azeotroped to remove about 5.0 ml. of water and the toluene distilled under vacuum. 200 ml. ethyl acetate, 17.5 gms. of 2,4-toluene diisocyanate, and 0.5 gm. of dimethyloctadecylamine are added and the mixture heated at about 75C. with stirring for about 2 hours. 11.3 gms. of caprolactam are added and the temperature is raised to 75 C. and maintained at that temperature with stirring for 12 hours.
  • the product is then cooled, neutralized with glacial acetic acid, and divided into three portions which are respectively dissolved in dioxane, isopropanol, and water.
  • the product is a 1:6:6 condensation product of Carbowax 20M, toluene diisocyanate, and caprolactam.
  • EXAMPLE 8 A 1:6:6 condensation product of Carbowax 20M, toluene diisocyanate, and caprolactam is prepared in accordance with the process of Example 7. The product is divided into three equal portions which are respectively dissolved in Carbitol acetate, propylene glycol, and Ansul 141 for use on textiles.
  • EXAMPLE 9 A 1:6:6 condensation product of Carbowax 20M, 2,4- toluene diisocyanate, and caprolactam are prepared in accordance with the process of Example 7 except that Cellosolve acetate is used as a reaction solvent in place of ethyl acetate. The product is separated into three portions which are dissolved in Carbitol acetate, dimethylformamide, and propylene glycol.
  • EXAMPLE 10 225 gms. of Carbowax 20M and 50 ml. 1,1,2-trichloroethane are azeotroped to remove any water present and the trichloroethane is distilled off. 185 ml. urethane-grade Cellosolve acetate and 10.4 gms. of caprolactam are added. The mixture is cooled to 45 C., 16.1 gms. of 2,4-toluene diisocyanate is added and the mixture heated at 4548 C. with stirring for one hour. The condensation product of Carbowax 20M, toluene diisocyanate, and caprolactam is then cooled, divided into three separate portions, and dissolved in Cellosolve acetate, dioxane, and propylene glycol.
  • EXAMPLE 11 1125 gms. of Carbowax 20M, 914.8 gms. of urethanegrade Cellosolve acetate, and 230 ml. of 1,1,1-trichloroethane are azeotroped for 45 minutes with collection of 250 ml. of distillate to give an anhydrous product solution. Then, in a separate reaction vessel, 226 gms. of caprolactam, 52.2 gms. of 2,4-toluene diisocyanate, and 74.8 gms. of Cellosolve acetate are heated for 4 hours at about 70 C. and the solution cooled. 360.7 gms. of the above Carbowax 20M solution and 24.3 gms.
  • Example 12 The process of Example 11 is modified by heating the final reaction solution only 1 hour at 70 C., then raising the temperature to 90 C. for a further 2 hours reaction and by using about 50% more toluene diisocyanatecaprolactam 1:1 reaction product to give a Carbowax 20M-toluene diisocyanate-caprolactam carbamic acid ester.
  • the product contains 28% solids in a mixture of Cellosolve acetate, propylene glycol, and water.
  • EXAMPLE 13 To 600 gms. of a polyoxyethylene glycol having an average molecular weight of about 6000, there is added 600 gms. of anhydrous toluene and 2 gms. of boron trifiuoride-ether complex (47% boron trifluoride). The mixture is stirred under nitrogen and heated to about 60 C., and 20 gms. of 3,4-epoxy--methylcyclohexylmethyl- 3,4 epoxy-6-methylcyclohexanecarboxylate are added. Stirring is continued at about C. for three hours. Then 27 gms. of a 1:1 condensation product of 2,4- toluene diisocyanate and phenol is added and the mixture is stirred for an additional two hours at about 100 C.
  • EXAMPLE 14 600 gms. (0.15 mol) of a polyoxyethylene glycol of molecular weight about 4000 is refluxed with 600 ml.
  • toluene to azeotrope about 1 ml. of water.
  • To the anhydrous solution there is added 17.4 gms. (0.10 mol) toluene diisocyanate and 1.0 gm. dimethyl octadecylamine and the mixture is heated under nitrogen at about 100 C. for 2 hours with stirring. Then 27 gm. (0.10 mol) of a 1:1 condensation product of 2,4-toluene diisocyanate and phenol is added and the mixture is stirred an additional 2 hours at 100 C.
  • EXAMPLE 750 gms. (about 0.1 mol) Carbowax 6000 and 6.7 gms. (0.067 mol) succinic anhydride and 0.2 gm. antimony trioxide are stirred under nitrogen and gradually heated to about 200 C. Temperature is maintained at 200 C.2l0 C. until esterification is completed. (Acid number reduced to near zero.) The resulting polyester is cooled to 100 C. and diluted with 700 ml. Cellosolve acetate. Then 9.0 gms. (0.033 mol) of a 1:1 2,4-toluene diisocyanate-phenol condensation product is added and the mixture is stirred for two hours at about 100 C.
  • carbamic acid esters of the foregoing description may be used to treat textile materials to impart thereto improved physical characteristics such as anti-soiling properties. It has been found that, if the carbamic acid esters are applied to textile materials and then cured by heating the textile material to an elevated temperature, the carbamic acid esters become attached to the textile material so that the improved properties imparted to the textile material will not be removed by subsequent washing.
  • thermally labile carbamate group of the carbamic acid ester decomposes at elevated temperatures to form an aromatic NCO group and free phenol or free caprolactam and that the aromatic NCO group then reacts with the durable press agent, the textile material, and/ or other NCO groups to form thermally stable groups.
  • the carbamic acid esters of the present invention may be advantageously utilized for application to textile materials alone or in combination with a wide variety of chemical treating agents among which are included, for example, durable press compounds, softening compounds, anti-static compounds, emulsifying agents, wetting agents, and numerous other compounds that enhance the physical characteristics of the textile materials.
  • the textile material may be treated with the carbamic acid esters of this invention along with any of the wide variety of chemical treating agents listed above, either simultaneously or separately in any order.
  • a particularly preferred application of the carbamic esters of the present invention is the use of the esters along with a durable press compound. Accordingly, this invention also provides a textile treating composition comprising a durable press resin and a carbamic acid ester.
  • the amounts of durable press agent and carbamic acid ester present in the textile treating compositions of this invention may vary over a rather wide range and will depend, mainly, on the particular durable press agent and carbamic acid ester selected and on the particular textile material to be treated therewith.
  • the textile treating compositions of this invention may contain from about 50% to 95%, preferably from about 55% to 80%, by weight of the durable press agent and from about 50% to about 5%, preferably from about 45% to by weight of the carbamate, based on the total weight of durable press agent and carbamate.
  • Durable press agents useful in the preparation of textile treating compositions in accordance with the present invention include both monomer and polymers which when applied to a textile material and cured under conditions conventional in the art undergo reaction with the textile material and impart durable press and/ or Wrinkle resistant characteristics to the extile material.
  • Durable press agents that are preferred when practicing the present invention are the aminoplast resins. These nitrogen containing resins, when applied to textile materials and heated at temperatures at 130 C. to 200 C. in the presence of a catalyst, react with the textile material and become chemically attached thereto.
  • aminoplast resins that may be employed according to the present invention are the ethylene ureas, for example, dimethylol dihydroxy ethylene urea, dimethylol ethylene urea, ethylene urea formaldehyde, and hydroxyethylene urea formaldehyde; urea formaldehyde, for example, propylene urea formaldehyde and dimethylol urea formaldehyde; melamine formaldehyde, for example tetramethylol melamines, and pentamethylol melamines; carbamates, for example, alkyl carbamate formaldehydes; formaldehyde-acrolein condensation products; alkylol amides, for example, methylol formamide and methylol cetamide; acrylamides, for example, n-methylol acrylamide, n-methylol methylacrylamide, and n-methylol-nmethacrylamide; diureas, for example, dimethyl
  • aldehydes for example, formaldehyde and alpha adipaldehyde
  • epoxides for example, ethylene glycol diglycidyl ether and vinyl cyclohexene dioxide
  • the textile resins catalsyt for the durable press agent may be any of the acid or latent acid catalysts which are conventionally used in the art to facilitate reaction of durable press agents with textile material.
  • latent acid catalyst is meant a substance which develops acidity during the curing step.
  • catalysts include metal salts of strong acids, for example, magnesium chloride, magnesium sulfate, Zinc nitrate, and aluminum sulfate; ammonium salts, for example, ammonium chloride, ammonium dihydrogen phosphate, and ammonium thiocyanate; amine salts, for example, triethyl amine hydrochloride and triethanolarnine hydrochloride.
  • the amount of curing catalyst used for the durable press agent depends on the nature of the durable press agent, catalyst and on the curing temperature and curing time. In general, satisfactory results may be obtained by using from about 1% to about 50%, preferably from about 10% to about 35%, by weight of the catalyst based on the weight of durable press agent.
  • the amount of catalyst to be utilized is that conventionally used in activating the reaction between durable press resins and active hydrogen atoms present in the textile materials to be treated therewith.
  • the textile treating compositions of this invention may be applied to textile materials from an aqueous medium, an organic solvent, or an emulsion of water and organic solvent.
  • organic solvents which may be used include isopropanol, 1,1,1-trichloroethane, 1,1,2-trichloroethane, perchloroethylene, carbon tetrachloride, chloroform, pentachloroethane, and a dichlorobenzene.
  • Illustrative examples of surfactants which may be used to emulsify the carbamic acid ester in organic solvents include polyoxyethylene(25) castor oil, isopropylamine dodecylbenzene sulfonate, diethyl sulfate quaternary of polyoxyethylene(20)hydrogenated tallow amine and polyoxyethylene(10) nonyl phenol.
  • Textile materials may be treated with the bath containing a textile treating composition of this invention by any suitable means, such as by immersion therein or by spraying.
  • the textile material may either be run through a padding machine where the textile material is first dipped into the bath and then squeezed, or the textile materials may be dipped into the bath and the excess liquid extracted by centrifugation.
  • the textile materials are simply sprayed with the bath and dried by any suitable means.
  • the carbamic acid ester, durable press agent, and textile resin catalyst may be applied simultaneously or from separate baths.
  • the catalyst for the durable press agent may be applied with the durable press agent and/or carbamic acid ester or from a separate bath.
  • the amount of carbamic acid ester applied to the textile material may vary from about 0.1% to about 10%, preferably from about 0.5% to about 5%, by weight based on the dry weight of the textile material.
  • the textile material having the carbamic acid ester thereon It is necessary to subject the textile material having the carbamic acid ester thereon to an elevated temperature in order to initiate and curing reaction between the carbamic acid ester and the textile material.
  • the particular temperature used and the duration of the heating step depends on the nature of the textile material used and on the particular carbamic acid ester used. In each situation, however, the temperature and heating time is that necessary to sufficiently cause reaction of the carbamic acid ester with the textile material.
  • the heat cure may be elfected at temperatures from about F. to about 350 F. and in periods of time ranging from about 40 to about 60 minutes at the lower temperature to about 0.5 to 10 minutes at the higher temperature.
  • the preferred temperature is from about 300 to 350 F.
  • Textile materials which may be treated with the textile compositions of this invention include any textile material conventionally treated in the art with durable press and/or antisoiling agents; for example, textile material comprising cellulose or modified cellulose such as cotton, rayon, linen, and mixtures thereof; textile material containing non-cellulosics such as polyesters, nylon, acrylics, and mixtures thereof; and textile materials comprising a blend of cellulosic materials and non-cellulosic materials.
  • the textile materials may be in the form of filaments, fibers, threads and yarns or in the form of woven, nonwoven, knit, or otherwise formed fabrics, sheets, and cloths.
  • the preferred textile materials are polyester fabric and cotton/polyester blends.
  • Soil redeposition is determined versus untreated fabric.
  • About 16 ml. of a standard stock soiling mixture containing 38% peat moss, 17% Corsons Home-Crete (sand mix), 17% kaolin clay (Peerless clay #2), 17% silica (200 mesh), 1.75% Molacco furnace black, 0.5% red iron oxide N-1860, and 8.75% Nujol is diluted to one liter with hot tap water, 6 x 6-inch test swatches of the above treated fabrics are immersed in 200 ml. of the soil solution, the cloth agitated in the soil solution about 30 minutes at about F.
  • Soil release ratings of the treated textiles were determined by the Deering Milliken Research Corporation stain release procedure. Four drops of Gulf transmission fluid is allowed to fall on a glass surface, after 15 seconds a specimen of test cloth is placed on the oil, a sheet of polyethylene is placed over the test cloth, a standard 8-pound weight placed on the polyethylene over the oil spot, the weight, polyethylene, and cloth are removed after 30 seconds, the test cloth placed between two paper towels, the weight applied for 30 seconds, the test cloth washed once, and rated visually for soil release versus a photographic standard. Soil release ratings are from 5.0, no soil retained, to 1.0, no soil released.
  • the following laboratory laundering procedure is used for all washes.
  • the samples and at least 3 pounds of 8-oz. fabric in 36 x 36-inch pieces are loaded into a standard automatic washer, about 46 grams of Tide detergent added, about 120 F. water run in, and the samples Washed on a 12-minute wash cycle. After the required number of wash cycles, the samples and the cloth are dried about 45 minutes at about 160 F. and pressed with a hand iron. Pressing is omitted when a durable press finish has been applied to the samples in addition to the carbamate.
  • Example 3 1 9.53 parts of the product of Example 3 (1 part carbamatc), 5 parts of zinc nitrate hexahydrate, and 85.47 parts of water.
  • textile treating baths containing 20 parts of 45% aqueous solution of dihydroxy dimethylol ethylene urea, 1.5 parts of 65% aqueous solution of magnesium dichloride hexahydrate, the indicated amounts of carbarnate, and water to 100 parts are made up and applied to 65:35 polyester-cotton blend fabrics at 70% wet pickup on the Butterworth pad.
  • the treated fabrics are dried at 225 F. for 3 minutes and cured at 325 F. for 10 minutes.
  • Half of the treated fabrics are washed 5 times with detergent in hot water. All fabrics are conditioned overnight at 65% relative humidity and 72 F. prior to testing. Soil release ratings are made after immersing the fabrics in soiling solution prior to laundering and again after applying the soil after 5 launderings. Test results are given in Table III.
  • Example 36 and 37 textile treating baths containing 20 parts of 50% aqueous solution of dihydroxy dimethylol ethylene urea, 5 parts of a aqueous solution of magnesium chloride hexahydrate, 18 parts of the indicated carbamate solution, and 57 parts of water are applied to 65:35 polyester-cottorn blend fabrics at wet pickup on the Butterworth pad.
  • the treated fabrics are dried at 225 F. for 3 minutes and cured at 325 F. for 10 minutes.
  • Half of the treated fabrics are washed 10 times with detergent in hot water. All fabrics are conditioned overnight at 65 relative humidity and 72 F. prior to testing. Soil release ratings are made after immersing the fabrics in soiling solution prior to laundering and again after applying the soiling solution after 10 launderings. Test results are shown in Table V.
  • Example 38 a textile treating bath is prepared containing 1.45 parts of the carbamate of Example 10, 1.05 parts of Cellosolve acetate, 2.5 parts of propylene glycol and parts of water. The bath is padded onto polyester fabric at 80% wet pickup. The treated fabric samples are dried at 225 F. for 3 minutes and cured at 3 375 F. for 30 seconds. Half of the samples are washed 5 times with Tide in hot water. All samples are conditioned overnight prior to testing. The test results are shown in Table VI.
  • Example 39 a textile treating bath containing 9 parts of dihydroxy dimethylol ethylene urea, 3.2 parts of magnesium chloride hexahydrate, 5.8 parts of the carbamate of Example 10, 4.2 parts of Cellosolve acetate, 10 parts of propylene glycol, and 67.8 parts of water is applied to 65:35 polyester-cotton blend fabric at 75% wet pickup.
  • the treated fabrics are dried at 225 F. for 3 minutes and cured at 325 F. for 10 minutes.
  • Half of the treated fabrics are washed 5 times with detergent in hot Water. All treated fabrics are conditioned overnight at 65% relative humidity and 72 F. prior to testing. Soil release ratings are made after immersing the fabrics in soiling solution prior to laundering and again after ap plying the soiling solution after 5 launderings to test results as shown in Table VII.
  • textile treating baths containing 20 parts of a 45% aqueous solution of dihydroxy dimethylol ethylene urea, 3.3 parts of magnesium chloride hexahydrate, 2.0 parts of the indicated carbamate solution, and sufficient water to make 100 parts are padded on 50:50 polyester-cotton blend fabrics at 70% wet pickup.
  • the treated fabrics are dried at 225 F. for 3 minutes and cured at 325 F. for 10 minutes.
  • Half of the treated fabrics are washed 5 times with detergent and hot water. All fabrics are conditioned overnight at 65 relative humidity and 72 F. prior to testing. Soil release ratings are made after immersing the fabrics in soiling solution prior to laundering and again after applying the soiling solution after 5 launderings. Test results are given in Table VIII.
  • composition of matter which consists essentially of the reaction product of (a) an organic aromatic polyisocyanate containing at least 2 NCO groups directly attached to carbon atoms of an aromatic ring,
  • a thermally reversible blocking agent selected from the group consisting of caprolactam, phenol, lower alkyl substituted phenols containing from 1 to 2 alkyl groups, and mixtures thereof and (c) a polyoxyethylene ether having a molecular weight of at least 6,000, and containing at least two aliphatic hydroxyl groups and at least by weight of oxyethylene groups present as polyoxyethylene chains containing at least 60 oxyethylene groups, said reaction being carried out at a temperature from ambient temperature to 200 C.
  • organic aromatic polyisocyanate, thermally reversible blocking agent, and polyoxyethylene ether are selected to furnish a ratio of mols of blocking agent to NCO groups present in the aromatic polyisocyanate of less than 1 and a number of NCO groups of not more than the sum of the hydroxyl groups and mols of blocking agent.
  • thermally reversing blocking agent is selected from the group consisting of caprolactam, phenol, methylphenol, dimethylphenol, trimethylphenol, ethylphenol, and mixtures there- 0 3.
  • polyoxyethylene ether (c) is a polyoxyethylene glycol having a molecular weight of at least 6,000.
  • composition of claim 2 wherein the polyoxyethylene ether (c) comprises the reaction product of a diisocyanate with a molar excess of a polyoxyethylene glycol having a molecular weight of at least 3,000.
  • polyoxyethylene ether (0) comprises the reaction product of a dicarboxylic acid or anhydride with a molar excess of a polyethylene glycol having a molecular weight of at least 3,000.
  • polyoxyethylene ether (c) comprises the reaction product of an organic diepoxy compound having two oxirane epoxy groups in which the oxirane oxygen is bonded to adjacent carbon atoms with a molar excess of a polyethylene glycol having a molecular weight of at least 3,000.
  • organic aromatic polyisocyanate is selected from the group consisting of 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; phenylene diisocyanate; methoxyphenylene 2,4-diisocyanate; diphenylrnethane 4,4-diisocyanate; 3-methyl-diphenylmethane 4,4'-diisocyanate; diphenylether 2,4,4- triisocyanate; and mixtures thereof.
  • Patent No. 3 738 981 Inventor(s) Dated June 12, 1973 Kenneth W. Graff and Albert H. Sherman It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925462A (en) * 1972-12-29 1975-12-09 Ici America Inc Wash-durable antistatic agent
US3987033A (en) * 1974-12-12 1976-10-19 E. I. Du Pont De Nemours And Company Blocked isocyanates
US4152273A (en) * 1978-07-18 1979-05-01 Arkansas Co., Inc. Soil releasable hydrophilic surface finish for textile fabrics
US4280970A (en) * 1979-01-19 1981-07-28 Puropore Inc. Polyoxyethylene grafted membrane materials with grafting links derived from a diisocyanate

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2393101A1 (fr) * 1977-05-31 1978-12-29 Rhone Poulenc Textile Procede pour la mise en oeuvre de traitement antisalissure sur articles textiles a base de polyester
GB2193504A (en) * 1986-07-24 1988-02-10 Basf Corp Utilization of lactones and lactams in the preparation of polyurethane-polyurea microcellular foams
US4757095A (en) * 1986-07-24 1988-07-12 Basf Corporation Utilization of lactones and lactams in the preparation of polyurethane-polyurea products

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925462A (en) * 1972-12-29 1975-12-09 Ici America Inc Wash-durable antistatic agent
US3987033A (en) * 1974-12-12 1976-10-19 E. I. Du Pont De Nemours And Company Blocked isocyanates
US4152273A (en) * 1978-07-18 1979-05-01 Arkansas Co., Inc. Soil releasable hydrophilic surface finish for textile fabrics
US4280970A (en) * 1979-01-19 1981-07-28 Puropore Inc. Polyoxyethylene grafted membrane materials with grafting links derived from a diisocyanate

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CA930097A (en) 1973-07-10
JPS4828400B1 (enrdf_load_stackoverflow) 1973-08-31

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