DE102015208116B3 - Hydrophobie-lending compound and fluorocarbon polymer-free preparations based on water and / or organic solvents, their use as a finish on fabrics and substrates obtained thereafter - Google Patents

Abstract

The present invention relates to preparations (Z) based on water and / or organic solvents and their use as a finish on fabrics containing (1) 10-90% of a reaction product (S) obtainable by reacting an etherified hexamethylolmelamine with a compound of the composition (2) 0-10% of a hydrophobic wax-based component, (3) 0-45% of an unblocked or blocked di-, tri- or polyisocyanate, and (4) optionally conventional emulsifiers. When used as a finish on fabrics, the formulations impart permanent hydrophobic properties to the treated fabrics.

Description

The invention relates to a hydrophobicity-imparting compound and compositions based on water and / or organic solvents and their use as a finish on fabrics.

It is known that, for finishing fabrics, aqueous based or solvent based formulations of silicone oils, paraffins, fluorocarbon polymers (hereinafter referred to as FCFC) and other additives which impart particular hydrophobic effects to the finished fabric, are resistant to rain To meet splash or moisture from other sources during use of the fabric.

For example, tent fabrics are treated with aqueous emulsions of paraffins, metal soaps and silicic acid salts of polyvalent metals to make the textile surface impermeable to rain or spray. Such formulations are also used to treat paper, also to improve the hydrophobic properties. From the German Auslegeschrift DE-AS 1001965 It is known to use reaction products of basic metal salts of higher molecular weight fatty acids or resin acids and low molecular weight di- or polyisocyanates for the dry hydrophobing of textiles.

All these known applications have in common that the fabrics can not be washed after their treatment with the chemicals mentioned or can be removed by other cleaning measures of any contamination. However, if substrate-dependent cleaning processes are necessary, there is always a drastic deterioration of the water-repellent properties. By refreshing the hydrophobicity by means of aftertreatment with suitable hydrophobizing agents, this disadvantage can be partially compensated for, with chemicals mostly being used on the same or a similar chemical basis as in the first finish.

Modern fabrics find a variety of applications in sports and leisure wear, but also for articles in the military or fire department or for other protective clothing. Such articles pollute very quickly, especially during intensive use, and are therefore frequently washed. This is usually done using detergents on industrial or domestic washing machines or by hand washing. In all washing processes in addition to a wetting of the fabric by the detergents used a more or less strong mechanical stress by walking, wrestling and upsetting. Due to the combined action of detergent and mechanical forces, the applied finishes are mostly removed from the fabrics and the substrates have only moderate or no water repellency after drying. A refreshing of the hydrophobicity by spraying or application in the washing machine or similar application methods succeeds with the currently marketed impregnation products to a satisfactory extent, because to achieve a good hydrophobicity, the treated surface should be heated after drying above the melting point of waxes used to coalescence of To produce wax particles and thus a continuous, optimally hydrophobic wax film.

In the case of the articles mentioned, it is therefore a prerequisite that in addition to a good initial hydrophobicity, there is also a resistance of the finish to multiple washes. Therefore, preparations have been developed early on which should improve the insufficient resistance to washing processes. So be in the DE-B 1 017 133 Hydrophobizing agents which are prepared by mixing a condensation product of hexamethylolmelamine hexamethyl ether, stearic acid, stearic acid diglyceride and triethanolamine with paraffin. In order to achieve good washing permanence, the presence of residual reactive methylol groups, if appropriate in etherified form, which are accessible to a later crosslinking reaction during application to textile substrates with the cellulosic OH groups is always important. The resulting flake or pebble-like products are brought before use by melting with hot water or steam and with the addition of acetic acid in an aqueous liquors applizierfähige emulsion form.

In order to achieve a particularly good washing resistance of the cellulose-based textile substrates treated with these water repellents, it is also always necessary to use crosslinking compounds of the hexamethylol-melamine hexamethyl ether type. This results in a hydrolysis-related formaldehyde elimination on the textile substrates during storage and use of the articles made from them, which exceeds the currently prescribed limit values of many countries.

In addition, it has been found to be disadvantageous in the fabrics and fiber materials treated therewith that, owing to the relatively high application rate, the chemical character of the preparation and, in particular, the crosslinking of the remaining reactive methylol groups still present in the fatty acid-modified methyloltriazine compound, if appropriate in their etherified form, With itself and the frequently added Hexamethylolmelaminhexamethylether and the functional groups of substrates on a native basis, a significant hardening of the grip character went along. Because of this reaction characteristic is a resistance to multiple washes, although given in the cellulosic substrates, such as cotton or viscose, but on lightweight, textile materials of synthetic fibers, as they are preferred for the equipment of sports and leisure articles use, but because of the fiber morphology As well as the substantial absence of functional groups, a crosslinking reaction does not take place to the same extent as cellulosic articles, which is why the washing permanence is insufficient. In addition, the handle hardening caused by the addition of crosslinking compounds of the hexamethylolmelamine hexamethyl ether type is perceived as unnatural.

Another significant disadvantage of the finish described has been shown in the application of these products in practice in that the preparations must be made in the finishing operation only immediately before use of the anhydrous, 100% melt. This is necessary because owing to the high reactivity of the methylolaminotriazine compound in the strongly acetic acid, aqueous emulsions, crosslinking within the emulsion particle can take place, which on the one hand reduces the reactivity with the textile substrate, on the other hand leads to crosslinking and agglomeration between the emulsion particles and thus to extreme viscosity increases , For the same reason, the preparation loses its hydrophobic effects in anhydrous dandruff, block or prill mold, so even before the emulsification, after prolonged storage and is increasingly difficult or impossible to emulsify. The aqueous emulsions also have limited shelf life and must be used up quickly before the reactivity is unduly reduced. Due to this behavior, aging-resistant emulsions of the described composition have hitherto not been known despite the overall positive wash permanence profile.

Another disadvantage of such preparations is the complicated preparation of the emulsion from the flakes. Under today's conditions, this is a factor of uncertainty in textile processing plants with often untrained personnel, which is not accepted. In addition, emissions of formaldehyde inevitably occur during application, in particular due to the addition of the crosslinking compounds of the hexamethylolmelamine hexamethyl ether type, which are no longer acceptable under today's ecology standards.

On modern fabrics, especially those made of synthetic materials, the described problem can be better solved by the use of aqueous or solvent based FC polymers. For example, describes the EP 0 325 918 B1 Preparations which consist of modified, perfluoroaliphatic groups containing polyurethanes and with which good oil and water repellency on textile substrates with good soft feel and satisfactory washing resistance can be achieved. In the EP 314 944-A It is recommended to use formulations of FC polymers with the addition of polyethylene and modified polysiloxanes, which emphasize a particularly smooth surface, soft feel.

In the EP 0 073 364 B1 reaction products of hexamethylol melamine ethers are described with Perfluoralkythiolen which impart the treated textile substrates excellent oil and water repellency with good wash permanence. However, the necessary for producing, partially fluorinated co-solvents make the production of these products obsolete out of ecotoxicological and commercial aspects.

WO 00/29663 A2 describes preparations for the permanent fiber finishing which contain reaction products of polyisocyanate-functional compounds with silicone-free and / or silicone-containing softening agents and which, according to the examples, preferably have a hydrophilizing radical.

Due to the washing resistances of hydrophobic and oleophobic effects to be achieved with FC formulations, combined with a good handle, to date such compounds, in particular for use on synthetic fabrics, are regarded as suitable products for the target to be achieved.

Perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) are important intermediates in the synthesis of FC polymers. Due to the high binding energy between carbon and fluorine, the compounds are not biodegradable in the environment. The hazard profile of PFOA and PFOS has become known in the meantime and has been confirmed by numerous studies. Both compounds are persistent, bioaccumulative and toxic substances that have severe and irreversible adverse effects on the environment and human health. In many countries, especially in the EU, legislative procedures have been initiated for some time in order to limit further use.

Under the limitation of PFOA to 2 ppb (parts per trillion) in products or the substrates equipped therewith, as proposed for example by the ECHA (European Chemical Agency), the use for the production of FC polymers for the textile application will also fall Degradation of the polymer chain in the final stage PFOA is formed.

The FC polymer manufacturing industry has attempted to avoid the problem by replacing the PFOA or PFOS with shorter chain FC residues, which while also being persistent and bioaccumulating, are considered to be less toxic active substances. For example, FC polymers are now available that biodegrade to PFHA (perfluorohexanoic acid) and PFBS (perfluorobutanesulfonic acid). A disadvantage of these compounds is the significantly poorer hydrophobicity and the production-related higher price. In addition, in the compounds prepared by telomerization always inevitably residual amounts of PFOA included. While these shares are small, it is unlikely to meet this threshold when the ECHA's proposed upper limit of 2 ppb comes into force.

It was therefore an object of the present invention to produce an active hydrophobicity-imparting compound and preparation which has optimum hydrophobic properties on fabrics with good wash fastness with only slight grip hardening. At the same time, the preparation should be free of FC polymers and should contain as few emission-capable components as possible. In particular, no latent cleavable formaldehyde should be included, as in the according to DE-B 1017133 produced compounds is the case. In addition, under conditions of use, the preparation should be compatible with other prior art formulations, such as the blocked polyisocyanate-based boosters commonly used in connection with FC polymers. Furthermore, under the usual storage conditions, the preparation should undergo no change in the product aspect, in particular no increase in viscosity of the emulsion, no phase separation and no losses in the desired hydrophobic effects on the substrates treated therewith.

Furthermore, it was the object of the preparation to be developed to completely or partially regenerate on fabrics by aftertreatment with the preparation of a multiwash decreasing hydrophobizing effect.

In the comparative study of the chemical structures of hydrophobically acting substances, some regularity can be recognized in that linear structures, such as paraffin or silicone polymers, provide less good hydrophobicity than can be achieved by cyclic structures, as exemplified previously listed DE-B 1017133 and EP 0 073 364 B1 are described. Following this postulate are in the PCT WO 03/078725 A1 and the DE10200702079 A1 Described compounds having an annular, dendrimer-like structure which provide optimum hydrophobic effects and good resistance to washing processes on textile substrates.

This object is achieved in terms of a hydrophobic reaction product with the features of claim 1, with respect to a preparation having the features of claim 7. With claim 9 uses of both the hydrophobic reaction product and the preparation may be mentioned. The respective dependent claims represent advantageous developments.

• (a1) eines veretherten Alkylolmelamins, das mindestens zwei veretherte Alkylolamingruppen aufweist, mit
• (a2) mindestens einer Komponente R¹-H, wobei R¹ ein hydrophober Rest, ausgewählt aus den nachfolgenden Resten
  
  wobei n für eine ganze Zahl von 12 bis 26, bevorzugt von 12 bis 18 steht, und
• (a3) einer gesättigten oder ungesättigten, eine Säureanhydridgruppe enthaltenden organischen Verbindung, wobei die Verbindungen (a2) und (a3) in einem stöchiometrischen Verhältnis von 30:70 bis 99:1 eingesetzt werden und bezüglich 1 Mol Ethergruppen des Alkylolmelaminethers mindestens 1 Mol der Summe der Verbindungen (a2) und (a3) verwendet wird.

Surprisingly, the aforementioned object could be achieved with a hydrophobic reaction product (S) according to the invention, which is obtainable by reaction

• (a1) an etherified Alkylolmelamins having at least two etherified Alkylolamingruppen with
• (a2) at least one component R ¹ -H, wherein R ^{1 is} a hydrophobic radical selected from the following radicals
  
  where n is an integer from 12 to 26, preferably from 12 to 18, and
• (a3) a saturated or unsaturated organic anhydride group-containing organic compound, wherein the compounds (a2) and (a3) are used in a stoichiometric ratio of 30:70 to 99: 1 and with respect to 1 mol of ether groups of the Alkylolmelaminethers at least 1 mol of the sum the compounds (a2) and (a3) is used.

The hydrophobic reaction product according to the invention can thus be obtained by reacting an alkylolmelamine ether with alcohols, carboxylic acids, amides, amines, thiols or glycerides and also downstream or simultaneous reaction with an acid anhydride.

In the event that a thiol is used in the reaction, it is also possible to further oxidize the sulfur atom contained after the reaction, for example, to a sulfoxide or sulfone group.

The sum of compounds (a2) and (a3) is used with respect to each ether group present in the alkylol melamine in a stoichiometric ratio of at least 1: 1, i. at least as much of the compounds (a2) and (a3) is added as are ether groups in the alkylol melamine. For example, it is also possible to work with an excess of the compounds (a2) and (a3).

Thus, in the reaction according to the invention, a substitution of the ether moiety takes place, the ether group being substituted on the one hand by the radicals R ^{1 of} the compound R ¹ -H or by the acid anhydride (with opening of the acid anhydride).

According to a preferred embodiment, the etherified alkylolmelamine (a1) is etherified hexamethylolmelamine, preferably hexamethylolmelamine etherified with an aliphatic alcohol having from 1 to 4 carbon atoms, more preferably methanol-etherified hexamethylolmelamine.

It is furthermore advantageous that the etherified alkylol melamine (a1) has at least 3, preferably at least 4, more preferably at least 5, particularly preferably at least 5.5, etherified alkylolamine groups.

The degree of etherification of the alkylolmelamine used is determined over the entirety of all alkylolamine groups, so that the degree of etherification can assume deviating degrees of etherification even of integers.

It is particularly preferred if the compounds (a2) and (a3) are used in a stoichiometric ratio of 40:60 to 90:10, preferably 50:50 to 80:20.

In particular, suitable compounds (a2) are stearyl alcohol, stearic acid, behenic acid, octadecanethiol, glyceryl distearate and / or mixtures or combinations thereof.

wobei
R² bei jedem Auftreten gleich oder verschieden ist und ausgewählt ist aus einer Gruppe, bestehend aus Wasserstoff und linearen oder verzweigten Alkyl- oder Alkenylresten mit 8 bis 36 Kohlenstoffatomen, bevorzugt ein Rest der nachfolgend abgebildeten Formel ist -(CH₂)-CH=CH-(CH)_n-CH₃ wobei n die zuvor genannte Bedeutung besitzt. The compound (a3) is preferably selected from the group consisting of

in which
R ^{2 is the} same or different at each occurrence and is selected from a group consisting of hydrogen and linear or branched alkyl or alkenyl radicals having 8 to 36 carbon atoms, preferably a radical of the formula depicted below - (CH ₂ ) -CH = CH- (CH) _n -CH ₃ where n has the abovementioned meaning.

Particularly preferred is 2-octadecen-1-yl-succinic anhydride. In addition, the underlying object is achieved by providing a preparation (Z) based on water and / or organic solvents 10-90% by weight at least one previously described hydrophobic reaction product (S), 0-50% by weight at least one hydrophobic component based on wax, 0-45% by weight at least one unblocked or blocked di-, tri- or polyisocyanate, as well as possibly. usual emulsifiers solved.

Surprisingly, the object could be achieved on the basis of this postulate described above by the use of a preparation containing a novel component (S), optionally known from the prior art wax components of various origins, optionally blocked with a protective group polyisocyanate and aqueous preparations to emulsify essential emulsifiers. The formulations thus obtained are distinguished by superior hydrophobic properties with high washing permanence, the aqueous-based emulsions during storage showing no tendency to premature crosslinking and concomitant viscosity increase of the emulsion.

The constituents contained in the preparation preferably complement each other with water and / or organic solvents contained to 100 wt .-%. Particular preference is given to preparations which completely dispense with organic solvents and are thus formulated only on the basis of water. To prepare the preparation, organic solvents, preferably volatile organic solvents such as, for example, isopropanol, acetone, etc., can be used as intermediates, which serve to facilitate the homogenization of the composition. However, these volatile organic solvents can also be removed again.

A particularly preferred embodiment provides that the composition 60-50% by weight at least one hydrophobic reaction product (S) as described above, 10-30% by weight at least one hydrophobic component based on wax, 0-25% by weight at least one unblocked or blocked di-, tri- or polyisocyanate, as well as 0.1-5 usual emulsifiers contains or consists of.

Another object of the invention is the application of the reaction product (S) or the preparations of the invention as a finish on fabrics. As such, for the textile application area, for example, woven fabrics, knitted fabrics and pre-bonded nonwovens of native fibers, such as wool or cotton or synthetic fibers, in particular PES, PA and regenerated fibers or mixtures thereof are used.

The application to the textile fabrics is generally carried out with runs of 1-5 wt .-%, but preferably 3-5 wt .-% of the solid substance of the preparation according to the invention based on the weight of the fabric to be treated. Usually, a liquor in the desired concentration by means of a forced application of aqueous medium on the pad with 40-200% liquor pickups, then predrying at 80-110 ° C and a subsequent heat treatment at 130-170 ° C for 1-5 minutes. The duration of the heat treatment depends on the temperatures used.

Another possible application to textile fabrics is given by the exhaust process known to the expert.

When applied to textile fabrics, the preparations according to the invention can also be combined with the textile auxiliaries customary in the textile industry. Worth mentioning are agents which improve the Entknitterungseigenschaften, for example, methylol compounds of Dihydroxyethylenharnstoffes or Methylolmelaminether different degrees of methylolation. Further suitable textile auxiliaries are those which improve the flame resistance or impart a preferred feel to the fabric. However, the goods handle can be controlled by a favorable combination of components (1) to (3) in the desired direction, which is why in these cases can be dispensed with further textile auxiliaries.

If, in addition to good hydrophobic properties, an oil and dirt repellency is desired on the treated fabrics, FC polymers can be added to the application liquors as textile auxiliaries.

The sheets may also be made of paper, which may be made by the known papermaking methods and from all common in this field of application basic materials. The preparations according to the invention can be applied either as an additive to the paper pulp or by application to the surface of the machine-smooth paper by means of coating lines using roll, doctor blade or air brush coating methods and subsequent infrared, hot air or cylinder drying.

Leather sheets are also well suited for finish with the formulations of the present invention. If the application is carried out in the tannery downstream dressing processes, this can be done with the known application method or by spraying or watering.

The treatment of other fabrics is also possible. Thus, mineral sheets, such as e.g. non-glazed tiles, ceramic parts or even wall surfaces obtained by impregnation with the finishing liquor according to the invention excellent water repellency.

The treatment of the fabrics can be done by different methods, for. B. by application of a liquor of the preparation according to the invention by means of spraying, patting, brush or sponge application, optionally in foam form. In general, runs of 1-5 wt .-%, preferably However, 3-5 wt .-% of the solid substance of the preparation according to the invention based on the weight of the sheet to be treated used.

Another object of the invention is the use of the formulations according to the invention according to claim 3 on textile substrates, wherein the finishing takes place as a post-treatment of washed textiles.

Many made-up items are either washed at home on household washing machines or on industrial washing machines. The latter applies to a large extent to the workwear of members of the fire brigade, police, military and other professions, which often have to be outdoors and thus exposed to the weather. The usually oil-, water- and dirt-repellent finished clothes undergo a loss of these properties through the laundry. Frequently, therefore, these properties are refreshed and revitalized by a post-treatment with repellents. The preparations according to the invention can be used for this application.

The revitalizing treatment of the industrially washed, ready-made articles takes place in the washing or centrifugal drum by pouring a liquor of the preparations according to the invention on the spin-dried laundry articles and subsequent drying in a tumbler. In household washing machines, the finish can be done by means of the usual aftertreatment rinse cycle or a dosing ball system.

Another object of the invention is the application of the preparations of the invention as a finish on fabrics with the proviso that the application is carried out from organic solvents in the impregnation or dipping process.

Many garments are not washed but subjected to cleaning in organic solvents. As in the case of the after-treatment of washed articles, the hydrophobic properties can also be revitalized here by refreshing with products based on the preparations according to the invention.

The revitalizing treatment of the finished articles purified in organic solvents takes place in the cleaning drum of the chemical cleaning machines by pouring or spraying a liquor of the preparations according to the invention onto the moist, cleaned articles and then removing the solvents in the tumbler at elevated temperatures. The chemical character of the cleaning agent is irrelevant, i. the treatment can be carried out either on modern machines in closed systems with perchlorethylene or on those which are suitable for treatment with hydrocarbon-based solvents such as Isopar J.

Another object of the invention is the application of the preparations according to the invention as a finish on fabrics with the proviso that the application is carried out from organic solvents by means of spraying.

Instead of a revitalizing treatment of textile fabrics after washing or cleaning processes by application of the preparations according to the invention from continuous, aqueous or solvent-containing liquors, application of the preparations according to the invention can also be carried out by means of various spraying methods for domestic use (consumer care). For this purpose, phobizers, formulated in organic solvents and propellant gases from spray cans or by pumping mechanisms are offered. In particular, for the shoe care area is to achieve significant improvement in water repellency and thus the wearing comfort.

All percentages of the preparations according to the invention relate to the total composition of the active substances of the preparation according to the invention and are percentages by weight. Preferred ranges for the component (S) are a range of 10-80%, more preferably 10-50%. If the wax-based hydrophobic component is added, its concentration is preferably in the range of 1-40%, especially 5-35%. If an addition of the non-blocked or blocked di-, tri- or polyisocyanate of the isocyanates, their concentration is preferably in the range of 1-40%, in particular 5-35%. The preferred concentration of the emulsifier emulsifier is in the range of 4-25%, more preferably in the range of 7-15%, based on the sum of the active substance of the components (1), (2) and (3) used.

The hydrophobic reaction product (S) is in particular obtainable by reacting 1 mol of a C ₁ to C ₄ -alcohols etherified hexamethylolmelamine (a1), hereinafter abbreviated to HMME, with 3 to 5 mol of a compound (a2) of the composition R ¹ is -H and 1 to 3 moles of the anhydride of an organic dicarboxylic acid of the composition (a3).

The resulting in this reaction, the chemical structure of the reaction product thus has an inner, heterocyclic core with an overlying shell of polar intermediate groups, and another, outer shell, which has a higher than average proportion of terminal hydrophobic residues and at the polar branching groups of these hydrophobic Remains has a pronounced tendency to crystallize. The structure thus has similar structures, as they are postulated in dendrimers and as they are for example in the WO 03/078725 A1 as reaction product (S) are described.

The reaction is a condensation reaction in which in the first reaction stage the alcoholic component of the HMME (a1) etherified with C ₁ to C ₄ alcohols is exchanged for the hydrophobic radical R ^{1 of} the compound (a2) and the resulting alcohol distilled off becomes. In a second reaction stage, the anhydride of an organic dicarboxylic acid of composition (a3) is esterified with the remaining, free methoxy groups of the C ₁ -C ₄ -alcohol HMME (a1). The molar ratio of the educts is chosen so that at the end of the reaction all free methoxy groups are completely replaced by the higher molecular weight, hydrophobic residues of the compounds (a2) and (a3) to on the substrates treated therewith a hydrolysis-induced regression of formaldehyde from residual free , Not according to the invention implemented to avoid etherified with C ₁ to C ₄ alcohols methylol groups. The condensation or addition reaction can also be carried out simultaneously by simultaneous reaction of all components as an alternative to the two-stage process; however, a two-stage method of preparation is preferred.

For the transetherification or esterification reaction, the concomitant use of an acid catalyst is not absolutely necessary, but advantageous. In particular, low-volatility inorganic or organic acids come into consideration, such as sulfuric acid, phosphoric acid, p-toluenesulfonic acid or oxalic acid in amounts of 0.05 to 0.5, in particular from 0.1 to 0.25 wt .-% based on the total reaction mass.

The reaction is carried out by mixing the compounds (a1) and (a2) in the desired molar ratios, adding the acidic catalyst and, while stirring, expediently taking place in a 4-necked flask equipped with stirrer, gas inlet tube, internal thermometer and descending distillation condenser Inert gas atmosphere, with temperature increase to at least 145 ° C with each other. The temperature is increased with a gradient of 0.5-2 ° C / min to 145-200 ° C, preferably to 160-180 ° C and left at the desired final temperature for another 30 minutes. During the reaction, the C ₁ to C ₄ -alcohol released by the transetherification is distilled off. To complete the reaction and remove the residual amounts of the liberated alcohol is advantageously applied for 1-2 hours at the desired Endtemparatur vacuum. Subsequently, the compound (a3) is added in the desired molar ratio and left for a further 30-120 minutes at the desired final temperature with stirring.

Alternatively, the reaction can also be carried out by mixing the compounds (a1), (a2) and (a3) in the desired molar ratios, adding the acidic catalyst and the reaction according to a temperature / time profile, as in previously described two-stage method is performed performs.

The reaction product (S) thus obtained, after cooling, forms a smooth, brittle, hard-wax-like mass, the melting point of which may be between 40 and 90 ° C., depending on the chosen molar ratio and the type of educts (a2) and (a3) used.

The compounds HMME (a1) used for the preparation of the reaction product (S) are known. They are, for example, according to the method of GB-PS 611,013 accessible. By HMME are meant those in which the melamine is completely methylolated and the methylol groups are largely etherified. For economic reasons, because of the ready availability and because of the high reactivity, up to 95 mol% of methanol-etherified hexamethylol melamine derivatives are particularly preferred.

The compounds (a2) used for preparing the reaction product (S) are, in particular, fatty alcohols, fatty acids, fatty acid amides, fatty acid amines, alkylthiols or fatty acid diesters of glycerol, the chain length of the alkyl group contained therein being between 12 and 26, preferably between 12 and 18 carbon atoms. The alkyl radical may be mono- or polyunsaturated and present in linear or branched form. Preferably, however, the saturated and linear compounds are used.

The compounds (a3) used to prepare the reaction product (S) are, in particular, the anhydrides of maleic acid, phthalic acid or succinic acid. Particularly preferred are the hydrophobically modified derivatives of succinic acid such as 2-alkene-1-yl-succinic anhydride wherein the alkyl moiety has between 12 and 28, preferably 12 to 18 carbon atoms.

The addition of the hydrophobic wax-based component is optional. This component is a wax and may consist of the usual hydrocarbons of various provenances which are well known to the person skilled in the art. Both natural waxes such as beeswax or carnauba wax and synthetic waxes such as polyethylene waxes and Fischer-Tropsch waxes can be used. However, particularly preferred are linear paraffin waxes, optionally with a proportion of 1-5 wt .-% of short-chain, liquid at ambient temperature, linear hydrocarbons. From the state of the art, optimum melting points of the paraffins used are known with regard to the hydrophobic effects. Thus, low-melting paraffins with a melting point <50 ° C significantly lower hydrophobicity values than those with melting points> 60 ° C. Paraffin waxes having a melting range of 40-70 ° C., but especially those having a melting range of 60-70 ° C., are therefore particularly preferred.

The addition of the isocyanates of the unblocked or blocked di-, tri- or polyisocyanate is optional. Compounds of this type are referred to as boosters and they cause a partially significant improvement in the hydrophobic effects on the treated fabrics. This pronounced synergism with the reaction products (S) is based essentially on a co-crystallization between the star-shaped, hyperbranched and on the outer shell with above average many, terminal hydrophobic residues equipped reaction product (S) during the common heating and cooling with the non-blocked or Blocked di-, tri- or polyisocyanates on the thus treated fabrics.

At the same time, owing to the polyfunctionality of the polyisocyanate, crosslinking is effected with the -OH, -COOH or -NH ₂ groups always present on most substrates and, if appropriate, unreacted functions of the reaction product (S), which markedly improves the resistance to washing processes and the resistance is increased against abrasion.

The isocyanates can be used both in unblocked and in blocked form. The unblocked forms of the isocyanates are predominantly used in applications of non-polar media, because this undesirable, premature reaction of the free NCO groups is avoided with the reactive active hydrogen atoms of the application medium.

The non-blocked di-, tri- or polyisocyanates suitable for preparing the isocyanates or di-, tri- or polyisocyanates (IC) to be converted into partially blocked isocyanates are disclosed in US Pat DE-A-100 17 651 , Paragraphs 0032 to 0037 inclusive described.

Particularly preferred di-, tri- or polyisocyanates (IC) are, for example, 2,4-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4-methylcyclohexane-1,3-diisocyanate, 4,4'-diphenylmethane diisocyanate, the mixtures of monomers Diphenylmethane diisocyanates and higher-chain homologs of diphenylmethane diisocyanate (polymeric MDI), tetramethylene diisocyanate, tetramethylene diisocyanate trimers, hexamethylene diisocyanate, hexamethylene diisocyanate trimers, isophorone diisocyanate, isophorone diisocyanate trimers, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate and dimer diisocyanate. Dimer diisocyanate is available from Cognis Corp., 300 Brookside Avenue, Ambler, PA 19002, USA, under the designation DDI 1410.

If the isocyanates from application media are to be applied to fabrics carrying active hydrogen atoms, it is often necessary to protect the reactive NCO groups by blocking with suitable blocking agents. In these cases, the preparation of the isocyanates by processes in which the complete blocking of the free NCO groups of di-, tri- or polyisocyanates is carried out with a blocking agent and optionally in an organic solvent. In order to achieve complete blocking, usually a small stoichiometric excess of blocking agent is used. If products are to be prepared for aqueous applications, the blocked di-, tri- or polyisocyanates, if appropriate dissolved in organic solvent, must be converted into the emulsion form using suitable emulsifiers.

In a particular embodiment, non-blocked di-, tri- or polyisocyanates can be used as boosters, their self-emulsifying ability in water by partial reaction of the isocyanate groups with Polyalkoxymonoalkylethern with the aid of appropriate catalyst systems Urethanes is improved. By attaching hydrophilic side chains to the di-, tri- or polyisocyanates, the HLB value of the urethane thus produced is changed so favorably that the per se water-insoluble compound gets self-emulsifying properties. In the case of the hydrophilic side chains, a certain selection of the nature and amount of the radical is advantageous. Preferably, between 4 and 20 ethylene oxide radicals are used, optionally together with 2-6 propylene oxide radicals, which may also be present in blocks within the alkoxy chain. In such mixed alkoxylated side chains, however, the proportion of ethylene oxide always outweighs that of propylene oxide. As catalysts for urethane synthesis, the systems known to those skilled in the art based on tertiary amines and / or organotin compounds, such as, for example, dibutyltin dilaurate, dioctyltin dilaurate or diacetate, can be used.

When used, the urethanes thus produced spontaneously form fine-particle emulsions with high stability to shear forces and good compatibility with the other components of an application liquor when introduced into water. Because of the reactivity of the remaining, unreacted NCO groups with water, only limited pot lives of up to 8 hours are possible in these special forms in the application liquor.

The addition of the isocyanates is carried out in particular in cases where particularly high demands are placed on the washing resistance of the treated fabrics. Preferably, then 5-25% of this compound are used, which can be used for the application of solvent-containing, anhydrous media directly and without formulation auxiliaries. Insofar as the application takes place from an aqueous medium, preferably emulsions of isocyanates with 15-35% solids content are used which are present using emulsifiers (= emulsifier) based on ethoxylated fatty amines, optionally present in quaternary form, and optionally other emulsifying auxiliaries, such as, for example, solubilizing agents be prepared based on ethylene glycol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, mono- or diethylene glycol monobutyl ether or N-methypyrrolidone. The emulsification can be done with the aid of Hochdruckhomogenisiermaschinen.

Commercially available products of the isocyanate type are available on the market under the names RUCOGUARD WEB and NET (RUDOLF CHEMIE, Germany). These are aqueous emulsions of blocked isocyanates, as described, for example, in US Pat WO 99/52961 or WO 92/17635 in terms of design and manufacture will be described.

If the preparations (Z) according to the invention are present on an aqueous basis, preference is given to using emulsifiers. The emulsifiers used for the formulation of the preparations according to the invention are known. Suitable emulsifiers are, for example, ethoxylation products of fatty acids, fatty acid amides, fatty alcohols, fatty amines, the latter also in the form of their salts with low molecular weight organic acids or mineral acids and quaternary ammonium compounds, such as cetylbenzyldimethylammonium chloride and preferably ethoxylated octadecylmethylammonium chloride. Such emulsifiers are described, for example, in "Römpp Lexikon Chemie" (10th edition, 2nd volume, page 1149 and 1150).

The usual application rates of the emulsifiers are preferably between 4 and 25 wt .-%, based on the sum of the active substance of the components (1), optionally (2) and optionally (3).

To prepare the emulsions, the known methods for the formation of secondary emulsions are used. The emulsification temperature is usually above the melting range of the active substances of the components (1) used, if appropriate (2) and optionally (3), preferably between 50 and 80 ° C. In order to produce highly finely divided, particularly stable emulsions, a coarse-particle pre-emulsion is often first prepared, the particles of which are subsequently reduced to the necessary average particle size between 0.1 and 10 micrometers with the aid of high-pressure homogenizers.

To achieve particularly finely divided emulsions, it is advantageous to bring the component (1) and optionally the wax-based hydrophobic component into a low-viscosity, dissolved form before emulsification and homogenization in an inert, organic auxiliary solvent (LM). In particular, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate or amyl acetate are used.

If desired, the inert organic solvents (LM) added before emulsification and homogenization may be removed by distillation after emulsification to avoid organic hydrocarbons which may be emitted.

The following examples illustrate the invention. The application of the finishes on textile fabrics was carried out on a laboratory padder with subsequent drying and heat treatment on a laboratory clamping frame. If spray application was carried out, this was done in a closed hood by manual and one-sided application by means of pump spray on the stretched fabric with subsequent drying at room temperature for 24 hours. The liquor pickup was determined by weighing the finished test samples before and after the application.

The examination of the hydrophobic effects did not take place immediately after the application, but only after a conditioning of the substrates in the standard climate for 24 hours, in order to level influences on these properties by overdrying. Amounts and the conditions of the hot treatment are listed in Table 2 together with the phobic effects to be achieved.

The water repellency was tested on the fabrics by spray test according to AATCC Standard Test Method 22. The test according to this method is carried out by spraying water under controlled conditions on the textile substrate to be tested and then visually comparing the wetting pattern to images of an evaluation standard listed in the test method. The numerical values given here refer to the appearance of the surface after spraying the water and have the following meaning: 100 = No adhesion of water droplets or wetting of the upper surface 90 = Occasional sticking of water droplets or wetting of the upper ones surface 80 = Wetting of the upper surface at the points of impact of the water 70 = Partial wetting of the whole upper surface 50 = Complete wetting of the whole upper surface 0 = Complete wetting of the whole upper and lower Surface (Durchnetzt).

In order to test the resistance of the finished fabrics to washing processes, the test samples according to EN ISO 6330: 2000 were washed at 60 ° C. and dried.

Comparative example

The preparation of the comparative emulsion listed in Table 2 (preparation (Z) 1) is carried out according to DBP 1 017 133, Example 1.

General manufacturing instructions for the reaction products (S)

In a suitably dimensioned four-necked flask equipped with distillation condenser, controllable stirrer and internal thermometer, the components (a1) and (a2) and p-toluenesulfonic acid indicated in Table 1 are melted as catalyst in the amounts stated there in grams under dry nitrogen as inert gas and stirring. Subsequently, the molten mixture is heated with a gradient of 1 ° C / min to the end temperature (T) indicated in Table 1 and stirring is continued until no more reaction alcohol distilled off. Subsequently, a vacuum of 50-100 mbar is applied at this temperature for 30 minutes in order to remove the optionally still present reaction alcohol. Subsequently, the compound (a3) is added and left for a further 45 minutes at the same final temperature with stirring. The resulting reaction product (S) is poured out after cooling to 90 ° C and processed after further cooling to room temperature to dandruff.

Emulsions (E):

General Preparation Instructions for Emulsions (E) from the Reaction Product (S)

Oily phase: In a suitably sized beaker, the amounts shown in Table 1 in grams of reaction product (S), optionally the hydrophobic component based on wax, present in the aforementioned isopropyl acetate and heated with stirring to 65-70 ° C until a gives a clear, homogeneous solution.

Aqueous phase: The quantities indicated in Table 1 are dissolved in grams of emulsifiers (Em) (= emulsifier) in the stated amount of water at 65 ° C. in a suitably dimensioned beaker. Under a high speed stirrer, both phases are stirred into a coarse preemulsion and then homogenized at 65 ° C on the high pressure homogenizer at 300-500 bar until an average particle size of between 0.1 and 10 microns is reached. Subsequently, the solvent (LM) is removed on the rotary evaporator in vacuo by azeotropic distillation. Optionally, the pH of the resulting emulsion is adjusted to 5-7 with acetic acid 60%, the resulting white emulsion filtered through a 20 micron filter and adjusted to a solids content of 20% with water.

Preparation of the preparations (Z) according to the invention

The emulsions (E) listed in Table 2, comprising the components (1), if appropriate the components (2) and (3) and optionally water, are mixed in the stated weight ratios, the formulations (Z) mentioned in Table 2 being obtained become.

Appreturbeispiele

Application of preparations (Z) on aqueous basis to textile fabrics:

Equipment conditions and test results are listed in Table 2.

Use of Solvent-Based Compositions (Z) on Textile Fabrics (Not Listed in Table 2):

 

For this application, 23 g of the reaction product (S) listed in Table 1 in column number 4 are dissolved in 231 g of n-heptane. By means of a pump sprayer, the solution is sprayed from a distance of about 30 cm onto the cotton and polyester substrates described in table 2 until the surfaces are uniformly wetted. It is then dried for 24 hours at room temperature. The treated cotton poplin test fabrics show a water repellency according to AATCC Standard Test Method 22 of 90, the polyester test fabrics one of 100.

Claims (11)

A hydrophobic reaction product (S) obtainable by reacting (a1) an etherified alkylolmelamine having at least two etherified alkylolamine groups with (a2) at least one component R ¹ -H, wherein R ^{1 is} a hydrophobic group selected from the following groups

where n is an integer from 12 to 26, preferably from 12 to 18, and (a3) a saturated or unsaturated organic anhydride group-containing organic compound, wherein the compounds (a2) and (a3) are in a stoichiometric ratio of 30: 70 to 99: 1 are used and with respect to 1 mol of ether groups of the alkylol melamine ether at least 1 mol of the sum of the compounds (a2) and (a3) is used. Hydrophobic reaction product (S) according to claim 1, characterized in that the etherified Alkylolmelamin (a1) is etherified hexamethylolmelamine, preferably etherified with an aliphatic alcohol having 1 to 4 carbon atoms Hexamethylolmelamin, more preferably etherified with methanol hexamethylolmelamine. Hydrophobic reaction product (S) according to any one of the preceding claims, characterized in that the etherified Alkylolmelamin (a1) at least 3, preferably at least 4, more preferably at least 5, more preferably at least 5.5 etherified Alkylolamingruppen. A hydrophobic reaction product (S) according to any one of the preceding claims, characterized in that the compounds (a2) and (a3) are used in a stoichiometric ratio of 40:60 to 90:10, preferably 50:50 to 80:20. A hydrophobic reaction product (S) according to any one of the preceding claims, characterized in that the compound (a2) is selected from a group consisting of stearyl alcohol, stearic acid, behenic acid, othadecenthiol, glyceryl distearate and / or mixtures or combinations thereof. A hydrophobic reaction product (S) according to any one of the preceding claims, characterized in that the compound (a3) is selected from the group consisting of

wherein R ² at each occurrence is identical or different and is selected from a group consisting of hydrogen and linear or branched alkyl or alkenyl group having 8 to 36 carbon atoms, preferably a radical of the formula depicted below is - (CH ₂ ) -CH = CH- (CH) _n -CH ₃ where n has the abovementioned meaning, in particular 2-octadecen-1-yl-succinic anhydride. Preparation (Z) based on water and / or organic solvents, comprising: 10-90% by weight at least one hydrophobic reaction product (S) according to one of the preceding claims, 0-50% by weight at least one hydrophobic component based on wax, 0-45% by weight at least one unblocked or blocked di-, tri- or polyisocyanate, as well as possibly. usual emulsifiers. Preparation (Z) according to the preceding claim, characterized in that 60-50% by weight at least one hydrophobic reaction product (S) according to one of the preceding claims, 10-30% by weight at least one hydrophobic component based on wax, 0-25% by weight at least one unblocked or blocked di-, tri- or polyisocyanate, as well as 0.1-5 usual emulsifiers. Use of a hydrophobic reaction product (S) according to any one of claims 1 to 7 or a preparation (Z) according to any one of claims 7 to 8 as a finish on fabrics, especially on textile substrates, paper, leather and mineral fabrics. Use according to the preceding claim, characterized in that the application takes place by means of spraying, by brush or sponge application, and / or from organic solvents by impregnation or dipping method or by spraying and / or by means of forced application or by exhaustion and / or as aftertreatment washed textiles done. Use according to one of the two preceding claims, characterized in that the use is carried out together with formulations of fluorocarbon polymers to achieve oil-repellent effects.