EP0616071A1 - Process for the treatment of fibrous materials with triazin derivatives - Google Patents

Abstract

Cyanuric acid, cyanuric chloride, partial hydrolysates of cyanuric chloride, metal salts of these compounds or of polyoxyethylene derivatives of these compounds are suitable for treating cellulosic fibre materials, for example textiles. On textiles these formaldehyde-free crosslinkers confer crease resist and easy care properties. The novel process for treating fibre materials requires relatively low drying temperatures and can be combined with a reactive dyeing.

Description

The invention described below relates to a process for the treatment of fiber materials which consist of 20 to 100% by weight of cellulose fibers.

It is known to treat fiber materials, such as textiles, which contain cellulose fibers or consist of cellulose fibers, with certain products in order to give them shrink or wrinkle resistance properties. For this purpose, products are used which can be obtained by adding formaldehyde to amide groups. These N-methylol compounds normally still contain residues of free formaldehyde, and they release formaldehyde to a certain extent during thermal treatment, which can lead to unpleasant odors and intolerance. This disadvantage of N-methylol compounds can be reduced or avoided by using low-formaldehyde or formaldehyde-free products as crosslinkers for cellulose. Products that have etherified N-methylol groups or products that do not contain any -N-CH₂-O groups are possible. An example of the last-mentioned class of compounds are N, N'-dialkyl-4,5-dihydroxiimidazolidinones (N, N'-dialkyl-dihydroxyethylene ureas), which can be obtained by reacting N, N'-dialkylureas with glyoxal. Etherification products of the last-mentioned compounds with polyhydric alcohols are also known as crosslinking agents for cellulosic materials, see for example EP-A 0 330 979.

The disadvantage of previously known formaldehyde-free cellulose crosslinking agents is that the desired level of effect is not achieved in all cases. In addition, known products often require temperatures of 150 ° C. or higher for a sufficient crosslinking reaction with cellulose, which, apart from energy costs, can also be undesirable for other reasons. Previously known formaldehyde-free crosslinkers also require relatively high or very high ones Amounts and requirements and often lead to undesirable yellowing tendency of the treated fiber materials.

The object on which the invention described below was based was to develop a process for the highly effective formaldehyde-free finishing or crease-resistant finishing of fiber materials which contain cellulose fibers or consist of cellulose fibers. The process should allow the crosslinker to react with cellulose (condensation) at relatively low temperatures, i.e. Carry out temperatures of less than 150 ° C, and should lead to a higher level of crease-resistant or easy-care effect than is possible with known formaldehyde-free crosslinkers.

aufgebracht wird, worin R¹, R² und R³ unabhängig voneinander jeweils für Cl oder OR⁴ stehen und alle anwesenden R⁴ unabhängig voneinander für Wasserstoff, ein Metall oder für

stehen, wobei n eine Zahl von 1 bis 6, vorzugsweise von 1 bis 4, ist.The object was achieved by a process for the treatment of fiber materials which consist of 20 to 100% by weight of cellulose fibers, which is characterized in that at least one product of the general formula (I)

is applied, wherein R¹, R² and R³ each independently represent Cl or OR⁴ and all R⁴ present independently of one another for hydrogen, a metal or for

stand, where n is a number from 1 to 6, preferably from 1 to 4.

This method is suitable for the crease-resistant finishing of fiber materials which contain at least 20% by weight of cellulose fibers. With a content of less than 20% by weight, the effect of the anti-shrink or anti-crease finish is too small to show the advantages of the process. The fiber materials can contain cellulose fibers in a mixture with other fibers, in particular polyester or polyamide, or they can consist exclusively of cellulose fibers. Cellulose fibers include both natural fibers such as cotton and fibers from regenerated cellulose such as Viscose in question.

Suitable fiber materials which can be treated by the process according to the invention are, above all, textile fabrics or knitted fabrics.

The process according to the invention has a number of advantages: The fiber materials to which the above-mentioned products have been applied can be dried at 80 to 130 ° C. in order to achieve good easy-care effects: temperatures up to 150 ° C. and more, such as they are required if known formaldehyde-free crosslinkers are used, do not have to be used. In the process according to the invention, the application of an alkaline liquor containing crosslinking agents can also be carried out by means of the wet residence process. This means that after application and a squeezing process, e.g. as part of a padding process, the fiber material, e.g. in the form of a textile fabric, protected against drying out, stored at room temperature and after a certain dwell time of e.g. Rinsed with water for 20 hours and dried. At least partial crosslinking takes place during storage in the wet state.

After the crosslinking agent has been applied in the wet crosslinking process, the finished and dried fiber materials often have a higher degree of whiteness than when known processes are carried out. The protection against rotting of the finished fiber materials is in many cases considerably better than with known processes. The method according to the invention can also advantageously be combined with other processes, such as e.g. with reactive staining in an alkaline medium or other processes to be carried out in an alkaline medium. The method according to the invention also offers the advantage in many cases of less impairment of the light fastness in the case of substantive and reactive dyeings than is the case with known methods.

In the process according to the invention, at least one product of the formula (I) given above and in claim 1 is applied to the fiber materials, which are preferably textile fabrics or knitted fabrics. However, mixtures of several products covered by the formula (I) can also be applied. In addition, one or more products of the formula (I) can be used to apply other desired products to the fiber materials, such as, for example, agents for water-repellent, oil-repellent or flame-retardant finishing. It has been shown, for example, that the process according to the invention can be carried out in such a way that the fiber materials are treated with aqueous solutions or dispersions which, in addition to one or more products which come under the formula (I) given above and in claim 1, also contain ammonium phosphate , Contain ammonium polyphosphate and / or a phosphate of an organic base. The organic base can be, for example, guanidine, urea, dicyandiamide or guanyl urea. In this way, very good flame-retardant treatment of the treated fiber materials is achieved. Such product mixtures can be applied by means of a single treatment liquor, for example by padding, if these product mixtures are homogeneous mixtures. Particularly advantageous For economic and ecological reasons, it is to carry out the process according to the invention in such a way that a product of the formula (I) or a product mixture in the form of an alkaline aqueous solution or dispersion of this product or these products is applied to the fiber materials and the fiber materials are then dried. Drying is preferably carried out in a temperature range from 80 to 130 ° C; If necessary, however, other temperatures can also be used, for example up to 140 ° C. In addition to the addition of other products to the treatment liquor mentioned, in a preferred embodiment of the method according to the invention the combination of the easy-care or crease test equipment with reactive dyeing in a single operation can be considered. In this case, in addition to one or more products of the formula (I) and optionally further products, a reactive dye is added to the treatment liquor. This preferred embodiment of the method according to the invention is particularly suitable for alkaline treatment liquors whose pH at 20 ° C. is preferably in a range from 7 to 13.

With regard to the stability of the solutions or dispersions, it is normally advantageous if the solutions or dispersions to be used for the process according to the invention, preferably aqueous solutions or dispersions, have a pH during storage which is not below 7.0 and not above 10 , 0, in some cases does not exceed 9.0. If higher pH values result in the production of solutions of partial hydrolyzates of cyanuric chloride which are to be used for the process according to the invention, it is advisable to subsequently adjust the solutions or dispersions to a pH value of 7 to 10 and in this form to store. The setting or stabilization of the desired pH, e.g. in the range of 7 to 10, e.g. by Na₂CO₃, K₂CO₃, KHCO₃ or NaHCO₃. The amount of alkali, e.g. NaOH or KOH are added, which is required for the treatment of the fiber materials (crosslinking reaction with cellulose) and / or for the reactive dyeing.

The products (1.3.5-triazine derivatives) of the formula (I) include, inter alia, cyanuric chloride and its partial hydrolyzates or the cyanuric acid formed by complete hydrolysis of cyanuric chloride. The partial hydrolyzates and the cyanuric acid, which are derived from cyanuric chloride by replacing one or more chlorine atoms with hydroxyl groups, can be used in free form (R⁴ = hydrogen) for the process. However, they are preferably used in the form of metal salts (R⁴ = metal), ie in the form of alkaline treatment liquors, preferably in the form of aqueous solutions or dispersions which have a pH in the range from 7 to 13 at 20.degree. In the vast majority of cases, the method according to the invention is carried out with alkaline treatment liquors.

Cyanuric acid, cyanuric chloride and partial hydrolyzates of cyanuric chloride have long been known compounds. Partial hydrolysates of cyanuric chloride with a predetermined degree of hydrolysis or their metal salts can be prepared by hydrolysis of cyanuric chloride with water or an aqueous metal hydroxide solution. The temperature at which this hydrolysis is carried out can be used to control whether one, two or three chlorine atoms of the cyanuric chloride are substituted. This is described in "Ullmann's Encyclopedia of Technical Chemistry" , Verlag Chemie GmbH, Weinheim, Bergstrasse, 4th edition (1975), volume 9, page 651. By setting an alkaline pH, the metal salts (R⁴ = metal) of these hydrolyzates or cyanuric acid can be obtained.

Als einwertige Metalle bzw. Metallkationen sind Natrium und Kalium besonders bevorzugt. Die Natrium- oder Kaliumsalze der Cyanursäure oder der Teilhydrolysate des Cyanurchlorids sind deshalb besonders bevorzugt, weil es sich hierbei um wasserlösliche Produkte handelt. Eine bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens besteht somit darin, wasserlösliche Produkte der Formel (I) zu verwenden; diese wasserlöslichen Produkte sind vor allem Na- oder K-Salze, die in wäßrigen Ausrüstungsflotten eingesetzt werden. Kommen nur diese Na- oder K-Salze zur Anwendung, handelt es sich hierbei vorzugsweise um alkalische wäßrige Lösungen. Bei Anwesenheit weiterer Zusätze, die wasserunlöslich, aber wasserdispergierbar sind, wird das erfindungsgemäße Verfahren vorzugsweise unter Verwendung wäßriger Dispersionen durchgeführt. Die für die Dispergierung solcher zusätzlicher Ausrüstungsmittel in Wasser erforderlichen Dispergatoren sind dem Fachmann bekannt. Auch die wäßrigen Dispersionen, welche neben mindestens einer Verbindung der Formel (I) weitere Produkte enthalten, weisen vorzugsweise alkalische pH-Werte im Bereich von pH 7 bis 13 auf.The metal salts present in the alkaline aqueous medium, which fall under the formula (I) and are suitable for the process according to the invention, need not be salts of monovalent metal cations. R⁴ in formula (I) can also stand for a polyvalent metal cation.
In this case, of course, two or more anions of cyanuric acid or the partial hydrolyzate of cyanuric chloride are present for each metal ion R⁴. In a preferred embodiment of the process according to the invention, however, all R⁴ present in the product of the formula (I) are hydrogen or a monovalent metal or

Sodium and potassium are particularly preferred as monovalent metals or metal cations. The sodium or potassium salts of cyanuric acid or the partial hydrolyzates of cyanuric chloride are particularly preferred because they are water-soluble products. A preferred embodiment of the process according to the invention thus consists in using water-soluble products of the formula (I); These water-soluble products are primarily Na or K salts, which are used in aqueous finishing liquors. If only these Na or K salts are used, these are preferably alkaline aqueous solutions. In the presence of further additives which are water-insoluble but water-dispersible, the process according to the invention is preferably carried out using aqueous dispersions. The dispersants required for dispersing such additional finishing agents in water are known to the person skilled in the art. The aqueous dispersions which, in addition to at least one compound of the formula (I), contain further products also preferably have alkaline pH values in the range from pH 7 to 13.

Die Zahl der durchschnittlich anwesenden Oxyethyleneinheiten wird durch n wiedergegeben und beträgt zwischen 1 und 6. Vorzugsweise besitzt n einen Wert von 1 bis 4.Instead of cyanuric acid, cyanuric chloride, partial hydrolyzates of cyanuric chloride or the metal salts described (R⁴ = metal), polyoxyethylene derivatives of cyanuric acid or partial hydrolyzates can also be used for the process according to the invention. These polyoxyethylene derivatives can be obtained by adding ethylene oxide to cyanuric acid or to partial hydrolyzates of cyanuric chloride. In this case, R⁴ in formula (I) is

The number of oxyethylene units present on average is represented by n and is between 1 and 6. Preferably, n has a value from 1 to 4.

Diese Teilhydrolysate sind durch milde Hydrolyse von Cyanurchlorid besonders leicht zugänglich. Als Metallkationen für die neutralisierten Formen kommen wiederum insbesondere Natrium- oder Kaliumionen in Frage. Das in der ersten Hydrolysestufe aus Cyanurchlorid gebildete und mittels Alkalimetallhydroxid neutralisierte Produkt der Formel (I), bei dem R¹ und R² für Cl stehen und bei dem R³ für ONa oder OK steht, hat sich als besonders geeignet für das erfindungsgemäße Verfahren erwiesen.Products are particularly preferably used for the process according to the invention in which in formula (I) R¹ is Cl, R² is Cl or OR⁴ and R³ is OR⁴, ie products obtained by hydrolysis of one or two C-Cl bonds of cyanuric chloride will. The CO bonds formed here can be in the form of C-OH bonds (R⁴ = H) or in neutralized form (R⁴ = metal) or in the form of the respective oxyethylene adducts

These partial hydrolyzates are particularly easily accessible through mild hydrolysis of cyanuric chloride. Sodium or potassium ions are again particularly suitable as metal cations for the neutralized forms. The product of the formula (I) in which R 1 and R 2 stand for Cl and in which R 3 stands for ONa or OK has been found to be particularly suitable for the process according to the invention in the first hydrolysis step from cyanuric chloride and neutralized by means of alkali metal hydroxide.

The fiber materials can be treated by the method according to the invention by generally known methods. An application of solutions or dispersions which contain at least one product of the formula (I) by padding is very suitable. This treatment is expediently carried out with an aqueous liquor which contains 1 to 12% by weight, based on the entire liquor, of one or more products of the formula (I). After the subsequent squeezing, the fiber material normally contains about 1 to 6% by weight of the product of the formula (I), based on the total weight of the finished fiber material. The subsequent drying can be carried out in known devices and is preferably carried out in a temperature range from 80 to 130 ° C. A temperature gradient may be present during the drying process. A reaction (crosslinking) of product of formula (I) with cellulose takes place simultaneously with the drying. This reaction is promoted by the presence of an alkaline pH.

Crosslinking with the OH groups of cellulose is thus favored by the presence of alkaline compounds. Even if alkaline compounds of the formula (I), for example metal salts of partial hydrolyzates of cyanuric chloride (see claims 4 and 5) are already used for the process according to the invention, the addition of further alkaline compounds to the treatment liquors is recommended. Sodium hydroxide and potassium hydroxide are particularly suitable for this. Instead of the additional addition of these alkaline compounds to the treatment liquors, the process according to the invention can also be carried out in two stages. This is done, for example, by applying a first aqueous treatment liquor which contains a product of the formula (I) and a pH to the fiber materials in the first stage has, in which this liquor has high stability, for example a pH of 7 to 10. This first aqueous treatment liquor can contain other products, such as reactive dyes. This first treatment liquor can be applied by padding. After squeezing, the fiber material is dried. In a second stage, a second aqueous treatment liquor is applied which contains the amount of alkaline compound required for crosslinking with cellulose. This alkaline compound is preferably sodium hydroxide or potassium hydroxide. After the second liquor has been applied, drying is carried out, for example at 80 to 130 ° C., the crosslinking taking place. The second treatment liquor can be, for example, an aqueous sodium hydroxide or potassium hydroxide solution of a relatively high concentration, for example between 30 and 60% by weight.

At the applied temperatures of e.g. 80 to 130 ° C in the presence of alkaline compounds crosslinking (condensation) with cellulose takes place. For this reason, the treatment of the fiber materials with treatment liquid is preferably carried out at a pH in the range from 7 to 13 (measured at 20 ° C.).

The fiber materials treated by the process according to the invention are notable for good easy-care or crease-resistant properties. These properties can be determined quantitatively, for example, by determining the crease angle (crease recovery angle) or indirectly via the water retention capacity (DIN 53814). The determination of the crease angle is carried out according to DIN 53890 (1972 edition) (dry crease angle) or according to the method described in Melliand, Textile Reports 39 - 5/1958, pages 552 to 554 (wet crease angle).

The invention is now illustrated by means of exemplary embodiments.

example 1

74 g (0.4 mol) of cyanuric chloride and 500 g of demineralized water are placed in a flask. With vigorous stirring, 64 g (0.8 mol) of sodium hydroxide solution (50%) are then added dropwise at 5-10 ° C. over the course of about 60 minutes. The mixture is subsequently stirred at 20-25 ° C. for 3 hours, the pH being kept in the alkaline range by adding a total of 1-3 g of sodium hydroxide solution (50%). The result is a clear solution with very little undissolved portions. A further 6 g of Na₂CO₃ are added and the mixture is stirred at 20-25 ° C for 30 minutes. After filtration, a water-clear solution with about 12% active substance is obtained, which contains the sodium salt of 2,4-dichloro-6-hydroxy-1.3.5-triazine as the main product.
Equipment: A cotton poplin sample is dipped into a liquor containing 340 g / l of the above reaction mixture (containing about 0.2 mol of the above-mentioned Na salt) and 32 g / l of aqueous NaOH (50%) (Weight per square meter approx. 120 g), followed by padding, the liquor absorption being approx. 75%. The mixture is then dried for 10 minutes at 110 ° C. and rinsed with water until the pH is around 7. Then it is dried again. In a second experiment, a cotton batiste (80 g / m²) was used instead of the poplin pattern (liquor absorption approx. 100%, other conditions as above).

Example 2 (comparison):

In a comparative experiment approx. 140 g / l (containing approx. 0.4 mol of a modified N, N'-dimethyl-dihydroxyethylene urea (DMDHEU)); the modification consists in partial etherification of the two OH groups with 1,6-hexanediol ) a commercially available formaldehyde-free cellulose crosslinking agent (KNITTEX® FF from Pfersee Chemie) in the form of an aqueous liquor which additionally 20 g / l MgCl₂. 6 H₂O and 0.2 g / l NaBF₄ contained. With this liquor, the above-mentioned patterns of poplin and cotton batiste were treated, padded (liquor absorption approx. 75% for poplin and 100% for cotton batiste) and further treated, as indicated above, with the difference that after drying, post-condensation occurred 150 ° C was carried out for 4 minutes. Without this post-condensation, no acceptable equipment results could be obtained.

The results (crease angle, swelling value, shrinkage, resistance to hot water) show that the effect achieved in the process according to the invention (sodium salt of the triazine derivative) is comparable to that after drying at 100 to 110 ° C without post-condensation Comparative experiment can only be achieved when post-condensation is carried out at 150 ° C. In contrast to the comparative test described, wet crosslinking could be carried out in example 1 according to the invention described above using the cold residence process. This was not possible in Comparative Example 2, because in the case of the crosslinking agent known from the prior art, post-condensation (150 ° C.) is absolutely necessary. The whiteness of the finished goods was better for both textile samples in the case of example 1 than in the case of example 2. The protection against rotting which was obtained in the textile samples of example 1 was better than that obtained in the case of example 2.

In further experiments, colored tissue samples were treated on the one hand by the method according to the invention and on the other hand with a liquor known from the prior art (containing DMDHEU). Patterns stained by both reactive and noun staining were used as tissue samples. It was found that in the samples treated by the method according to the invention, the impairment in light fastness was significantly less than in the case of the comparison samples.

Example3

The example described below shows that the process according to the invention allows the simultaneous use of crosslinking agent (triazine derivative) and reactive dye in an alkaline aqueous liquor. Fleet A: 140 g / l KNITTEX® FF 20 g / l MgCl₂. 6 H₂O 0.2 g / l NaBF₄ Fleet B: 340 g / l Product manufactured according to Example 1 32 g / l aqueous NaOH (50%) Fleet C: like B with additional 20 g / l Reactive dye '' Cibacron® -Rot F-B '' and 5 g / l aqueous NaOH (50%) Fleet D: water

One cotton swatch and one cotton batiste are each immersed in the liquors A to D and squeezed off at room temperature. (Fleet intake: poplin approx. 75%, batiste approx. 100%). It is then dried under tension at 110 ° C. for 10 minutes. The samples were then halved, each half was post-condensed at 150 ° C for 5 minutes. The samples from fleet B were rinsed with water until the rinsing water had a pH of about 7 and dried at 100 ° C. for 10 minutes; the samples from fleet C were aftertreated at boiling temperature with an aqueous solution which contained 2 g / l "Tinovetin®JUN '' and 1 g / l soda, then rinsed neutral with water and dried at 100 ° C. for 10 minutes JUN (manufacturer: Ciba-Geigy) contains water and a surface-active agent.

The crease angle values can be found in the following table: Pattern dried Cotton batiste A B C. D Crease angle Chain 60 ° 76 ° 72 ° 53 ° (dry) Shot 61 ° 78 ° 77 ° 57 ° Crease angle Chain 94 ° 119 ° 125 ° 92 ° (wet) Shot 99 ° 126 ° 119 ° 93 ° Post-condensed pattern Cotton batiste A B C. D Crease angle Chain 81 ° 79 ° 85 ° 51 ° (dry) Shot 86 ° 80 ° 85 ° 59 ° Crease angle Chain 107 ° 119 ° 126 ° 88 ° (wet) Shot 113 ° 112 ° 125 ° 93 ° Pattern dried Cotton poplin A B C. D Crease angle Chain 66 ° 78 ° 84 ° 60 ° (dry) Shot 73 ° 86 ° 89 ° 68 ° Crease angle Chain 88 ° 110 ° 114 ° 78 ° (wet) Shot 90 ° 112 ° 113 ° 83 ° Post-condensed pattern Cotton poplin A B C. D Crease angle Chain 85 ° 96 ° 82 ° 55 ° (dry) Shot 89 ° 91 ° 93 ° 70 ° Crease angle Chain 104 ° 109 ° 117 ° 66 ° (wet) Shot 100 ° 121 ° 113 ° 81 °

A higher value for the crease angle means a better effect of the crease resistant finish.

Another cotton batiste pattern is soaked in liquor B and subjected to a wet crosslinking process using the cold dwell process. A dry crease angle of approximately 72 ° and a wet crease angle of approximately 118 ° were measured. After a hot wash, these crease angles remain unchanged.

Example 4

148 g (0.8 mol) of cyanuric chloride and 440 g of demineralized water are placed in the flask and 200 g (1.6 mol) of aqueous potassium hydroxide solution (45%) are kept under constant cooling at 5 - 10 ° C for about 2 hours. added dropwise with vigorous stirring. The mixture is then stirred for a further 2 hours at 20-25 ° C., the pH being kept in the alkaline range by adding a total of about 2 g of aqueous KOH (45%). Finally, 8 g of solid potassium carbonate are added and this is dissolved for 15 minutes at 20-25 ° C. After filtering, a clear, low-viscosity solution with approx. 22% active substance is obtained.
Equipment: With a treatment liquor which contained 200 g / l of the solution thus obtained (containing about 0.2 mol of potassium salt of the 2,4-dichloro-6-hydroxy 1.3.5-triazine) and 32 g / l of 50% aqueous NaOH solution. the same tissue samples as described in Example 1 were treated. An effect level as with the product from Example 1 was obtained.

Claims (9)

Process for the treatment of fiber materials which consist of 20 to 100% by weight of cellulose fibers, characterized in that at least one product of the general formula (I) is formed on the fiber materials

is applied, wherein R¹, R² and R³ each independently represent Cl or OR⁴ and all R⁴ present independently of one another for hydrogen, a metal or for

stand, where n stands for a number from 1 to 6, preferably from 1 to 4. Process according to Claim 1, characterized in that water-soluble products of the formula (I) are used. Process according to Claim 1 or 2, characterized in that all R⁴s present independently of one another are H, Na or K. Method according to one or more of claims 1 to 3, characterized in that R¹ is Cl, R² is Cl or OR⁴ and R³ is OR⁴. Process according to Claim 1, characterized in that R¹ and R² stand for Cl and R³ stands for ONa or OK. Method according to one or more of claims 1 to 5, characterized in that a reactive dye is applied to the fiber materials together with a product of formula (I). Method according to one or more of claims 1 to 6, characterized in that an aqueous dispersion or aqueous solution containing at least one product of the formula (I) contains, onto which fiber materials are applied and that the fiber materials are then dried. Process according to Claim 7, characterized in that the aqueous solution or dispersion has a pH in the range from 7 to 13 at 20 ° C. Process according to Claim 7 or 8, characterized in that the fiber materials are dried at a temperature in the range from 80 to 130 ° C.