EP0033115A2 - Process for finishing textiles - Google Patents

Abstract

Process for finishing textile goods made of cellulose, which has been pretreated with liquid ammonia, by impregnating the goods with a finishing agent based on an aminoplast former and heating for 10 seconds to 6 minutes at 110 to 230 ° C. in the presence of an acidic or potentially acidic catalyst, where as a finishing agent a substance of formula III <IMAGE> is used, in which the radicals R¹ and R² independently of one another are hydrogen, methyl, ethyl, propyl or methoxyethyl and R² also represents the radical of an ethylene and / or propylene oxide chain of 1 to 20 monomer units can.

Description

The invention relates to a process for finishing textile goods made from natural or regenerated cellulose, which has been pretreated with liquid ammonia, using N-monomethylol or N-monoalkoxymethyl compounds of 4-hydroxy or 4-alkoxy-5.5- dimethyl propylene ureas as finishing agents.

By "equipping" is meant the shrink and wrinkle-resistant equipment - also called "easy-care equipment". This is done with aminoplast formers, that is to say substances which contain methylolated amide groups on the nitrogen, in particular methylolated urea and its derivatives, methylolated melamine and methylolated carbamate. During "hardening" or "fixing", the N-methylol groups react under the influence of heat and catalysts with the hydroxyl groups of the cellulose with acetal formation and crosslinking. It is usually difficult to avoid that the mechanical strength of the cellulose drops significantly. For example, tensile strength losses of the order of 30 to 40% and more are the order of the day. This is a serious disadvantage of the textile equipment (which is indispensable in terms of shrink and wrinkle resistance in today's requirements). Of course, it is particularly strong when it comes to purely cellulosic textiles, i.e. fabrics and knitted fabrics that consist exclusively of natural or regenerated cellulose, i.e. primarily exclusively of cotton, linen, rayon or rayon wool, the strength of which cannot be based on synthetic fibers that have been processed to carry. In addition, there is generally, not only with purely cellulosic textiles, a more or less disturbing hardening of the textile handle by the equipment.

in der die Reste R¹ bis R⁶ Wasserstoffatome oder niedermolekulare Alkylreste sind, als Textilausrüstungsmittel vorgeschlagen worden. Sie haben zwar gewisse Vorteile (z.B. im Hinblick auf Hydrolysebeständigkeit, Lichtechtheit von Färbungen und Chlorechtheit), vermögen aber die beiden genannten Probleme hinsichtlich der mechanischen Festigkeit und des Griffs nicht befriedigend zu lösen.There has been no shortage of attempts to solve these problems. For example, in DE-PS 14 69 269 and US-PS 35 02 672 are double methylolated cyclic ureas of the formula I.

in which the radicals R ¹ to R ^{6 are} hydrogen atoms or low molecular weight alkyl radicals have been proposed as textile finishing agents. Although they have certain advantages (for example with regard to resistance to hydrolysis, lightfastness of dyeings and chlorinefastness), they are unsatisfactory in solving the two problems mentioned with regard to mechanical strength and grip.

in der R¹ einen Alkylrest mit 1 bis 18 Kohlenstoffatomen, R², R³ und R⁶ Wasserstoffatome oder niedermolekulare Alkylreste und R⁴ und R ⁵ niedermolekulare Alkylrest e bedeuten, vorgeschlagen worden (vgl. DE-OS 20 06 516). Sie sind zwar in der Lage, die beiden genannten Probleme weitgehend zu lösen, doch haben sich die damit erzielbaren Ausrüstungseffekte in der Praxis als unzureichend erwiesen.There are also finishing agents based on compounds of the formula II

in which R ^{1 is} an alkyl radical having 1 to 18 carbon atoms, R ² , R ³ and R ^{6 are} hydrogen atoms or low molecular weight alkyl radicals and R ⁴ and R ^{5 are} low molecular weight alkyl radicals e (cf. DE-OS 20 06 516). You are able to address the two problems mentioned largely to be solved, but the equipment effects that can be achieved in practice have proven to be inadequate.

One way to increase the mechanical strength (among other important properties such as gloss and smoothness) of textiles made of cellulose is by mercerizing or leaching, i.e. a treatment with concentrated hot alkali with or without mechanical treatment. A variant of this old method which has recently become increasingly practical, particularly in the USA, consists in replacing the alkali with liquid ammonia (cf., for example, US Pat. Nos. 19 98 551, 34 06 006, 35 60 140 and 10 65 514 and DE-OS 25 23 433; also J. Müller, Chemical Fibers and Textile Industry 25 (1975), 5, pages 449-450 and K.Bredereck, Textilveredelung 13 (1978), 12, pages 498 to 506). The currently most important process on this basis is the SANFOR-SET process from the Sanforized Company, USA. With these processes, for example, the tear strength of cellulosic textiles can be improved by an order of magnitude of 10-15%. However, this is not enough to compensate for the loss of tensile strength in the order of 40% in the subsequent easy care equipment to such an extent that the ultimate tensile strength was sufficient.

The invention was therefore based on the object of developing a finishing process for textiles made of cellulose pretreated with liquid ammonia, which combines high finishing effects (improvement in the shrink and wrinkle resistance) with the least possible influence on the textile handle and, above all, on the tear strength.

This object is largely achieved by the method according to the claim: sufficient levels of smoothness (according to Monsanto), dry and wet crease recovery angles and low shrinkage values are obtained without this significant tensile strength losses compared to the goods would arise before the ammonia treatment. The totality of the properties of the goods equipped according to the invention is more favorable than with equipment using known methods.

mit R³ gleich Wasserstoff oder Methyl sein. Hierbei wird R³ = Methyl weniger bevorzugt gegenüber R³ = Wasserstoff oder eine Mischung von Wasserstoff und Methyl. Insbesondere soll R³ nicht ausschließlich Methyl darstellen, wenn R¹ Propyl ist, weil dann das gesamte Molekül nicht mehr ausreichend wasserlöslich wäre. Ausreichende Wasserlöslichkeit der Verbindungen der Formel III ist selbstverständlich Voraussetzung für ihre Brauchbarkeit.The substances of formula III of claim can by reacting urea with isobutyraldehyde and formaldehyde in a molar ratio of 1: 1: 1 in aqueous solution or in an alcohol of formula R ² OH and in the presence of a non-oxidizing mineral acid at temperatures between 30 and 120 ° C and subsequent further alkaline reaction with 1 mol of formaldehyde. The resulting monomethylol compound can be etherified with an alcohol R ¹ OH in an acidic medium. As can be seen from the meaning of R ² in formula III, the alcohol _R ² OH can also be a glycol of the formula

with R ³ being hydrogen or methyl. Here R ³ = methyl is less preferred than R ³ = hydrogen or a mixture of hydrogen and methyl. In particular, R ³ should not be exclusively methyl if R ^{1 is} propyl, because then the entire molecule would no longer be sufficiently water-soluble. Sufficient water solubility of the compounds of formula III is of course a prerequisite for their usability.

The synthesis is thus completely analogous to the known synthesis of the substances of the formula I, but with correspondingly less formaldehyde, so that only the monomethylol compound is formed. B. The methylolation with one mole of formaldehyde, as the nuclear magnetic resonance analysis shows, almost results exclusively the 1-monomethylol compound, and only in a minor amount the 3-monomethylol compound and / or the 1,3-dimethylol compound in addition to the non-methylolated starting compound. "Substances of the formula III" means the reaction mixture actually present, with an average of one methylol group. As I said, it corresponds largely, but not 100%, to Formula III, but this definition should also apply to the (unlikely) case that Formula III should prove to be wrong late.

Examples of substances of the formula III obtainable in this way are: N-monoethoxymethyl-4-ethoxy-5,5-dimethylpropyleneurea, N-monomethoxyethoxymethyl-4-methoxyethoxy-5,5-dimethylpropyleneurea and, because of them Easy accessibility preferred, N-monomethylol-4-hydroxy-5,5-dimethyl-propyleneurea (IV), N-monomethylol-4-methoxy-5,5-dimethyl-propylene urea (V) and N-monomethoxymethyl-4-methoxy -5,5-dimethyl-propyleneurea (VI).

The finishing agents of the formula III come on the market as 40 to 60% aqueous solutions or dispersions and are diluted with water for use. They have proven themselves particularly well on textile material made of cellulose, which has been pretreated with ammonia. You can click on for the application of N-methylol compounds The usual textile processes can be used. These are processes in which the material to be finished is impregnated with an aqueous solution or dispersion of the finishing agent and an acidic or potentially acidic catalyst and is reacted with the finishing agent as described at the beginning, this reaction (fixing, hardening) either in the wet Condition of the textile goods can be carried out or between the impregnation and the chemical conversion a partial or complete drying of the textile goods and, if desired, a longer storage and / or processing into garments in the impregnated but not yet or not fully implemented state can be carried out.

The concentration of the finishing bath of substances of the formula III is generally between 40 and 200 g / l. Preference is given to impregnating a foulard. The soaked material is freed in a known manner by squeezing off excess impregnation liquid. The fiber application to substances of the formula III should be in the range from 50 to 100, preferably 60 to 70,% by weight, based on the textile material to be finished.

The impregnated fiber material is heated in the presence of acidic or potentially acidic catalysts to a temperature of 110 to 230 ° C., preferably 120 to 210 ° C. Under these conditions, the reaction is generally completed in 10 seconds to 6 minutes, preferably in 20 seconds to 2 minutes.

Acidic or potentially acidic catalysts are known and used for the purpose of finishing with N-methylol or N-alkoxymethyl compounds. As such there are, for example, as for the process according to the invention: inorganic and organic acids, such as sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, oxalic acid, and salts which react acidically or which form acids, for example by hydrolysis, during their use, for example ammonium salts of strong acids , Magnesium chloride, zinc chloride and zinc nitrate. Mixtures of several catalysts can often also be used with advantage. As mentioned, the reaction of the substances of formula III with the textile material is carried out in the presence of these catalysts. This can be done by applying the catalysts, preferably in the form of aqueous solutions, to the material before or after impregnating the material to be finished with the new substances. However, the catalysts are preferably added directly to the impregnating bath containing the substances of the formula III. In general, catalyst concentrations between 1 and 40 g / l have proven useful for the equipment.

Together with the new finishing agents to be used according to the invention, the usual hydrophobicizing, softening, leveling, wetting and finishing agents can also be used. Hydrophobing agents are, for example, aluminum or zirconium-containing paraffin wax emulsions and silicone-containing preparations. Oxygenation products of higher fatty acids, fatty alcohols or fatty acid amides, higher molecular weight polyglycol ethers, higher fatty acids, fatty alcohol sulfonates, N-stearylurea compounds and stearylamidomethylpyridinium chloride may be mentioned as plasticizers. As leveling agents, for example, water-soluble salts of acidic esters of polybasic acids with ethylene oxide or propylene oxide adducts of longer-chain basic compounds which can be alkoxylated can be used. Examples of wetting agents are salts of alkylnarthalene sulfonic acids, the alkali salts of sulfonated amber acidic edioethyl ester and the add-on products of alkylene oxides to fatty alcohols, alkylphenols, fatty amines and the like. Suitable finishing agents are, for example, cellulose ethers or 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 their esters and amides, and of corresponding polymethacrylic compounds, polyvinylpropionates Polyvinylpyrrolidone, from copolymers, for example from vinyl chloride and acrylic acid esters, from butadiene and styrene or acrylonitrile or from 1,1-dichloroethylene, β-chloroalkylacrylic acid esters or vinyl ethyl ether and acrylic acid amide or the amides of crotonic acid or maleic acid or from N-methylol methacrylic acid amide and others polymerizable compounds. These additional auxiliaries are generally used in amounts of 0.3 to 4%, preferably 1 to 2.5%, based on the weight of the dry textile goods; in special cases these quantities can also be exceeded.

The experience according to the invention results in a cellulose-pretreated ammonia-treated equipment that provides sufficient shrink and cut resistance with high chlorine resistance, does not significantly influence the textile feel and has sufficient hydrolysis resistance for use purposes with a loss of tensile strength of rarely more than 20%, based on the tensile strength of the goods pretreated with ammonia. Further advantageous properties emerge from the examples.

The invention is explained in more detail below with the aid of examples. Unless otherwise noted, the parts and percentages given in the examples relate to the weight.

example 1

• Eine Mischung aus 1070 Teilen Methanol, 500 Teilen Harnstoff, 625 Teilen einer 40 %igen wäßrigen Formaldehydlösung und 40 Teilen 50 %iger wäßriger Natronlauge wird 1 Std. bei 50°C in einem Rührgefäß gerührt. Der pH-Wert wird mit 75 %iger Schwefelsäure auf 5,0 gestellt und 670 Teile Isobutyraldehyd unter Kühlung zugegeben. Darauf wird 30 min bei 50°C gerührt. Unter Kühlung werden dann 300 Teile 75 %ige Schwefelsäure zugegeben und das Ganze bei 80 bis 85°C 8 Std. am Rückfluß gekühlt. Man läßt abkühlen und stellt dann den pH-Wert mit Ätznatron auf 7,0. Von ausgefallenem Natriumsulfat wird abfiltriert und die Lösung bei 60°C im Vakuum eingedampft. Die Ausbeute, 1350 Teile 5,5-Dimethyl-4-methoxypropylenharnstoff, wird mit 625 Teilen 40 %iger Formaldehydlösung und 20 Teilen 50 %iger Natronlauge versetzt. Nach 2stündigem Rühren bei 50°C und einem pH-Wert von ca. 10,5 wird der pH-Wert mit 75 %iger Schwefelsäure auf 7,0 gestellt. Anschließend wird mit 1100 Teilen Wasser eine Lösung mit einem Feststoffgehalt von 50 % hergestellt.

The aqueous solutions mentioned below were prepared using a compound of formula III as a finishing agent, where R ^{1 is} hydrogen and R ^{2 is} a practically equimolar "mixture" of hydrogen and methyl. The connection is established as follows:

• A mixture of 1070 parts of methanol, 500 parts of urea, 625 parts of a 40% aqueous formaldehyde solution and 40 parts of 50% aqueous sodium hydroxide solution is stirred in a stirred vessel at 50 ° C. for 1 hour. The pH is adjusted to 5.0 with 75% sulfuric acid and 670 parts of isobutyraldehyde are added with cooling. The mixture is then stirred at 50 ° C. for 30 minutes. 300 parts of 75% sulfuric acid are then added with cooling and the whole is refluxed at 80 to 85 ° C. for 8 hours. Allow to cool and then adjust the pH to 7.0 with caustic soda. Precipitated sodium sulfate is filtered off and the solution is evaporated at 60 ° C. in vacuo. The yield, 1350 parts of 5,5-dimethyl-4-methoxypropylene urea, is mixed with 625 parts of 40% formaldehyde solution and 20 parts of 50% sodium hydroxide solution. After stirring for 2 hours at 50 ° C. and a pH of approximately 10.5, the pH is adjusted to 7.0 with 75% sulfuric acid. A solution with a solids content of 50% is then prepared with 1100 parts of water.

35 x 50 cm samples of Sanfor-set cotton fabric were made. Solutions 1 to 4 prepared according to Table 1 were padded onto 3 samples per bath with a liquor absorption of 65% at room temperature. The mixture was then dried at 107 ° C. for 1 min and condensed as indicated in Table 1 (duration and temperature). The dried and condensed samples were tested according to the standard test instructions. The results are shown in Table 2.

• 1. Formaldehydgeruch am ausgerüsteten Gewebe im verschlossenen Behälter nach der AATCC-Prüfmethode 112-1975.
• 2. Abriebfestigkeit nach der Accelerotormethode (AATCC--Prüfmethode 93-1974)

The following were also checked:

• 1. Odor of formaldehyde on the finished fabric in the closed container according to the AATCC test method 112-1975.
• 2. Abrasion resistance according to the accelerator method (AATCC - test method 93-1974)

The results are shown in Table 3.

The equipment according to the invention thus results in a formaldehyde odor level (at or below 1000 ppm) which is sufficiently low for the clothing industry and low abrasion losses at various condensation temperatures.

Example 2

• 14,0 % Ausrüstungsmittellösung nach Beispiel 1,
• 0,2 % anionischem Netzmittel nach Beispiel 1,
• 1,9 % Katalysatorlösung nach Beispiel 1 und
• 1,0 % handelsüblicher anionischer Polyethylenemulsion
• (25 % Feststoffgehalt), Rest Wasser.

A fleet is made up of

• 14.0% equipment solution according to Example 1,
• 0.2% anionic wetting agent according to Example 1,
• 1.9% catalyst solution according to Example 1 and
• 1.0% commercially available anionic polyethylene emulsion
• (25% solids content), balance water.

Das Ausrüstungsmittel nach Beispiel 1 zeigt sehr wenig oder keine Reißfestigkeitsverluste durch Chlor nach der Wäsche mit chlorhaltigem Waschmittel.Shirting (100% cotton, sanfor-set; calico) was padded with the liquor to 60 to 70% liquor absorption. The fabric was then dried in a stenter at 107 ° C. for 60 seconds. The fabric thus dried was condensed on the tenter for 90 seconds at various temperatures in accordance with Table 4. The test was again carried out according to the usual AATCC test methods, in particular for smoothness, shrinkage (warp and weft) and loss of tensile strength due to possible damage from chlorine. The evaluation is shown in Table 4.

The finishing agent according to Example 1 shows very little or no loss of tensile strength due to chlorine after washing with chlorine-containing detergent.

Example 3

• 2 % handelsübliche anionische Polyethylenemulsion (25 % Feststoffgehalt),
• 2 % handelsüblicher, nichtionischer, flüssiger Weichmacher
• 1,7 % Magnesiumnitratkatalysator nach Beispiel 1 und
• 0,2 % anionisches Netzmittel nach Beispiel 1, Rest Wasser.

The finishing agent according to Example 1 was applied to samples of a sheet cloth (50 parts of cotton, 50 parts of polyester, 109 g / m ² ) and condensed. For comparison, aqueous dimethyl-4,5-dihydroxyethylene urea solution with a solids content of 45% was applied to other samples of the same product. In each case, 12% crosslinking agent solution was added to an aqueous dispersion of the following composition:

• 2% commercially available anionic polyethylene emulsion (25% solids content),
• 2% commercial, nonionic, liquid plasticizer
• 1.7% magnesium nitrate catalyst according to Example 1 and
• 0.2% anionic wetting agent according to Example 1, the rest water.

The fleet intake was 60% in each case. The samples were dried and condensed at 205 ° C for 20, 60 and 120 seconds.

The condensed samples were checked for discoloration. The test for smoothness, shrinkage (warp and weft), free formaldehyde content and chlorine damage according to the test methods described in Example 1 only extended to the samples condensed for 20 seconds. The results are summarized in Table 5.

In comparison to the cross-linked DMDHEH, the finishing agent according to Example 1 delivers flawless and in some respects excellent results.

Claims (1)

Process for finishing textile goods made of cellulose, which has been pretreated with liquid ammonia, by impregnating the goods with a finishing agent based on an aminoplast former and heating for 10 seconds to 6 minutes at 110 to 230 ° C. in the presence of an acidic or potentially acidic catalyst, characterized in that a substance of formula III

uses in which the radicals R ¹ and R 2 independently of one another hydrogen, methyl, ethyl, propyl or methoxyethyl and R ^{2 can} also represent the remainder of an ethylene and / or propylene oxide chain from 1 to 20 monomer units.