Classifications

• • 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
  • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
  • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
  • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
  • C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
  • C08G12/12—Ureas; Thioureas
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2369—Coating or impregnation improves elasticity, bendability, resiliency, flexibility, or shape retention of the fabric
  • Y10T442/2393—Coating or impregnation provides crease-resistance or wash and wear characteristics

Definitions

• agents being based on urea and formaldehyde, from which they are obtained by condensation in two steps at specific pH values and in specific molar ratios.
• the agents have along shelf life.
• the invention relates to a process for the manufacof cyclic ureas and, in particular, methylol compounds of urea are employed.
• Monomethylolurea and dimethylolurea display the greatest reactivity amongst the currently known N-methylol compounds suitable for textile finishing. They are therefore preferred. Because of their high reactivity and their limited solubility, it is not possible to prepare solutions of monomethylolurea and dimethylolurea having the shelf life required in practice.
• Methylolureas are crosslinked to the textile substrate in the presence of metal salt catalysts, ammonium salts or acids. If methylolureas are employed, the stability of the liquor in the presence of such catalysts is very limited.
• This object is achieved by a process for the manufacture of liquid finishing agents for cellulosic textiles, the agents having a long shelf life, wherein the reaction mixture obtainable by reaction of urea or methylolated urea or water-soluble urea-formaldehyde polycondensation products with formaldehyde in an overall molar ratio of urea: formaldehyde of 1 :3 10 in aqueous solution at pH values between and 3 is adjusted to pH values between 6 and 10 and such amounts of urea are added, at temperatures between and 80C, that an overall molar ratio of urea to formaldehyde of 1:1.5 2.5 results.
• Cellulosic textiles are woven fabrics, knitted fab- .rics and also non-woven fabrics of which the fibers consist of natural or regenerated cellulose orwhich contain .such fibers mixed with other fibers.
• the'overall molar ratio of urea to formaldehyde is to be understood as the molar ratio of urea to the sum of free formaldehyde and formaldehyde already chemically bound to urea (in the form of methylol groups or of methyleneor dimethylene-ether bridges CH- OCH l
• the pH values are measured with a glass electrode.
• urea in acid solution, can be employed as, a solid or as a solution and formaldehyde be employed as a solution or in the form of its polymers such as, for example, paraformaldehyde, trioxane or tetroxane, or in the form of its acetals, urea being reacted with formaldehyde in the molar ratio of l:3 to 1:10, preferably in the molar ratio of 1:4 to 1:6, in the presence of a strong inorganic or organic acid, at pH values between 3 and 0, preferably between 1.5 and 2.5, to give precondensates containing urone.
• This condensation can advantageously be carried out at temperatures between 60 and 100C, especially at to C.
• urea it is possible to convert methylenediurea or polymethyleneurea or their methylol compounds, such as, for example, urea-formaldehyde polycondensates, into precondensates containing urone by means of formaldehyde. It is also possible to use, as starting materials for the manufacture of the precondensates containing urone, the mixtures which result from the methylolation of urea with formaldehyde and which contain, in addition to free formaldehyde, inter alia the methylol compounds of urea, that is to say monomethylolurea, dimethylolurea, trimethylolurea and/or tetramethylolurea.
• Suitable acid catalysts are inorganic acids, such as hydrochloric acid, sulfuric acid and phosphoric acid, and strong organic acids such as o-toluenesulfonic acid, oxalic acid and phthalic acid.
• the reaction of the first stage can be carried out by treating the mixture of the abovementioned starting substances and formaldehyde with an acid and then heating it to the desired condensation temperature. It is however also possible first to heat the mixture of the starting substances with formaldehyde or its derivatives to the condensation temperature and only then to add the acid. According to a preferred embodiment, formaldehyde is mixed with the acid and heated to the desired condensation temperature. Urea or the abovementioned starting products are then introduced into this solution. In all embodiments it is also possible to employ mixtures of the starting components.
• the reaction time depends on the temperature, amount and strength of acid, and molar ratio and concentration of the starting substances.
• the formation of the urones can be followed by means of Raman spectroscopy; they show a strong emission line in the Raman spectrum at 810 cm
• the urone content can be determined quantitatively by measuring the intensity of the line.
• a factor of great importance to the shelf life of the products claimed according to the invention is that the acid condensation of urea with formaldehyde to give products containing urone is carried out in such a way that certain limiting conditions are observed.
• molar ratios of about 1:3 to 4 in the 1st stage of the reaction it is necessary to ensure that the neutralized samples do not become turbid or precipitate after standing for a short time. Such turbidity can occurregardless of the amount of acid chosen.
• the intermediates containing urone and free formaldehyde can be converted by further reaction with urea into aqueous finishing agents which display high reactivity, high stability and, in contrast to the aqueous solutions of the methylolureas, excellent liquor stability.
• the precondensates obtained in the manner described are reacted with such amounts of urea as to give an overall molar ratio of urea to formaldehyde of 1:1.5 2.5, preferably of 1:1.7 -2.3.
• the urea can be added in the form of a solid or as a solution.
• the reaction takes place at a pH between 6 and 10, preferably between 6.4 and 9 and at temperatures between 20 and 80C, preferably at 30 to 60C.
• the reaction time depends on the temperature and on the pH and is between one and five hours.
• the reaction can be followed, for example, by continuous quantitative determination of the free formaldehyde in the solution.
• the reaction is complete when the concentration of free formaldehyde shows practically no further decrease.
• liquid textile finishes thus produced show an excellent shelf life. When stored at temperatures below 25C, they remain usable for at least 6 months. This was not foreseeable.
• the new finishing agents are employed in conventional manner, preferably in the form of an aqueous impregnating bath to which the catalysts generally required for the crosslinking reaction are added.
• Potentially acid catalysts which are generally known, and customary, for textile finishing purposes, are particularly suitable.
• catalysts of this type which can be used are ammonium salts of strong acids, magnesium chloride, zinc chloride and zinc nitrate. Mixtures of several catalysts can also be used.
• the concentration of finishing agent depends, in the usual way, on the desired effect andis generally between 50 and 200 g/l.
• the goods being treated are impregnated with the impregnating liquor in the usual way.
• a padder is used for this purpose.
• the impregnated goods are freed from excess impregnating liquid in a known manner, for example by squeezing out. It is possible to dry the impregnated fibrous goods to a greater or lesser extent and then heat them to a temperature of 100 to 210C, preferably 130 to 180C, in the presence of the acid or potentially acid catalysts. in general, fixing is complete after 1 to 6 minutes under these conditions. It is possible mechanically to shape the fibrous goods during or after drying before fixing, for example by compression, crimping, ironing, calendering, embossing or pleating. Cellulosic textiles are given a durable creaseresist and shrink-resist finish in this way and the embossed effects and pleats are relatively resistant to laundering.
• the previously used hydroxymethyl or alkoxymethyl compounds containing nitrogen, as well as finishing agents not containing nitrogen, can be used conjointly with the new agents. It is also possible to use, conjointly, the customary water repellents, softeners, levelling agents, wetting agents, etc., such as, in particular, polymer solutions or dispersions.
• water repellents are paraffin wax emulsions containing aluminum or zirconium, preparations containing silicones, and perfluorinated aliphatic compounds.
• Softeners which may be mentioned are oxyethylation products of higher fatty acids, fatty alcohols or fatty acid amines, higher-molecular polyglycol ethers, higher fatty acids, fatty alcohol sulfonates, N-stearyl-N, N -ethylideneurea and stearylamidomethylpyridinium chloride.
• levelling agents which can be used are water-soluble salts of acid esters of polybasic acids with ethylene oxide adducts or propylene oxide adducts of long-chain basic starting material which can be oxyalkylated.
• wetting agents are salts of alkylnaphthalene-sulfonic acids, the alkali metal salts of sulfonated succinic acid dioctyl ester and the adducts of alkylene oxides to fatty alcohols, alkylphenols, fatty amines and the like.
• finishes which can be used are cellulose ethers or cellulose esters and alginates, and also solutions or dispersions of synthetic polymers and polycondensates, for example of polyethylene, polyamides, oxyethylated polyamides, polyvinyl ethers, polyvinyl alcohols, polyacrylic acid or its esters and amides and corresponding polymethacrylic compounds, polyvinylpropionate, polyvinylpyrrolidone and copolymers, for example those of vinyl chloride and acrylates, of butadiene and styrene or acrylonitrile or of vinylidene chlorde, B-chloroalkylacrylates or vinyl ethyl ether and acrylamide or the amides of crotonic acid or maleic acid, or of N-methylolmethacrylamide and other polymerizable compounds.
• additional auxiliaries are in general employed in amounts of 0.3 to 4 percent, preferably l to 2.5 percent, relative to the weight of the dry textile goods;
• EXAMPLE 1 2 parts of 50 percent strength sulfuric acid are added to 540 parts of a 40 percent strength formaldehyde solution and the mixture is heated to C. 157.8 parts of a 68.5% strength urea solution are introduced at this temperature over a period of 30 minutes.
• the pH is l to 1.1.
• the reaction mixture is heated at 90C for 30 minutes and is then cooled to 45C, and its pH is adjusted to pH 6.8 withapprox. 1.2 parts of 50 percent strength sodium hydroxide solution.
• This solution contains approx. 33 percent of the urea in the form of urones. 157.8 parts of a 68.5 percent strength urea solution are introduced into this mixture, whilst stirring.
• the reaction solution is heated at 50C for 4 hours whilst maintaining a pH of 6.8 to 7.0.
• the free formaldehyde content is 0.8 percent.
• EXAMPLE 2 percent strength sodium hydroxide solution whilst at approx. 54 percent of the urea in the form of urone. 526 parts of a 68.5 percent strength urea solution are added at 45C. The reaction mixture is stirred for 4- hours at 50C whilst keeping the pl-lat 7.2-7.4 by adding triethanolamine. 2,150 parts of a 48 percent strength solution of the-finishing agent-according to the invention, containing 2.1 percent offree-formaldehyde, are obtained.
• 1,440 parts of 2160 percent strength methylolation mixture of "urea' with formaldehyde fin the'molar ratio of 1:4, are heated to 100C andstirredwith 4 parts byvolume of 75 percent strength sulfuric acid for min utes at 100C.
• fabric 120 'g/m isz-padded with a; finishing liquoryvhich contains 120 parts of the product prepared according to Example 1 and 3 parts of ammonium chlorideper liter.
• the wet pickup is 70 percent.
• the fabric is dried out and then the condensation reaction is carried out for 4 mi nutes at 140C (the test results are given in column'Aof the table).
• Untreated fabric Product according to Example 2 Dimethylolurea Dry crease angle according to DIN 53,890 Warp weft After I wash at 60C Monsanto rating after one wash at 60C Compale AATCC Technical Manual 88A-1964 T.
• EXAMPLE 4 780 parts of crystalline urea are added to the reaction mixture. The reaction solution is heated at C for three hours whilst maintaining a pH of 7.2-7.6 by means of triethanolamine. 3,950 parts of an approx. percent strength aqueous solution are obtained.
• An embossed effect produced on a ribbed calendar prior to the condensation reaction shows similar durability to laundering in both products.
• a process for the manufacture of a liquid finishing agent for cellulosic textiles which is stable on storage wherein a reaction mixture obtainable by reaction or urea or methylolated urea or a water-soluble urea-formaldehyde polycondensation product with formaldehyde in an overall molar ratio of urea: formaldehyde of from 1:3 to 1: 10 in aqueous solution at a pH of from 0 to 3 is adjusted to a pH of from 6 to 10 and urea is added at a temperature of from 20 for C to provide an overall molar ratio of urea to formaldehyde of from 121.5 to 1:25.
• reaction mixture is obtained by reaction of urea or methylolated urea or a water-soluble urea-formaldehyde condensation product with formaldehyde in an overall molar ratio of urea: formaldehyde of from 1:4 to 1:6 in aqueous solution at a pH of from O to 3.
• reaction mixture is obtained at a pH of from 1.5 to 2.5.
• a process as claimed in claim 2 wherein the formaldehyde for reaction with the urea, methylolated urea or water-soluble urea-formaldehyde condensation product is provided in the form of a polymer or acetal thereof.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Phenolic Resins Or Amino Resins (AREA)

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Cited By (7)

Citations (6)

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• 1972
  • 1972-10-07 DE DE2249320A patent/DE2249320A1/de active Pending
• 1973
  • 1973-09-26 US US40072073 patent/US3920390A/en not_active Expired - Lifetime
  • 1973-09-28 BR BR756273A patent/BR7307562D0/pt unknown
  • 1973-10-02 IT IT5286773A patent/IT996237B/it active
  • 1973-10-03 CH CH1412173A patent/CH548480A/xx not_active IP Right Cessation
  • 1973-10-05 FR FR7335657A patent/FR2202188B1/fr not_active Expired
  • 1973-10-05 SE SE7313606A patent/SE407417B/xx unknown
  • 1973-10-05 GB GB4662373A patent/GB1435827A/en not_active Expired
  • 1973-10-08 JP JP11243573A patent/JPS4971296A/ja active Pending

Patent Citations (6)

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