DE1032532B - Process for the preparation of new curable derivatives of aldehyde condensation compounds of the aminotriazine or urea group - Google Patents

Description

Process for the preparation of new curable derivatives of aldehyde condensation compounds of the aminotriazine or urea group The invention relates to new curable Derivatives of aldehyde condensation compounds of the aminotriazine or urea group as well as derivatives of the ethers of these compounds with low molecular weight alcohols. These derivatives contain at least one basic nitrogen atom to which a Rest is bound to an epoxy group.

The new derivatives are obtained when ä) aldehyde condensation products of compounds of the aminotriazine or urea group or their ethers with low molecular weight Alcohols or derivatives derived from such compounds with higher molecular weight Hydrocarbon radicals, b) primary, secondary or tertiary amines or their substitution products or their quaternary ammonium salts, c) if the compounds mentioned under b) do not contain residues with epoxy groups, compounds that introduce such residues capable, and d) optionally compounds which the hydrophilicity on noninogenic Ability to introduce ways increasing atom groups, converts with each other, with the molar ratio between the reaction components is chosen such that im End product at least one methylol group etherified with a lower alcohol or at least one free methylol group is present. The presence at least a free methylol group or a methylol group etherified with a lower alcohol in the end product is necessary so that the latter remains hardened.

As formaldehyde condensation products of the aminotriazine group (component a) In principle, all products can be used that have at least one free -% letliylolgruppe or at least one etherified with a low molecular weight alcohol Contain methylol group. Among these compounds are primarily reaction products of formaldehyde and 2,4,6-triamino-1,3,5-triazine, usually called melamine, are mentioned. Such condensation products can contain from one to six methylol groups, usually they represent mixtures of different compounds. There are also methylol compounds of those descendants of melaniins that still contain at least one amino group -en.keep, e.g. B. methylol compounds of melain, melem, ammeline, or ammelide of halogen-substituted aminotriazines, such as 2-chloro-4,6-diamino-1,3,5-triazine; also methylol compounds of guanamines, such as. B. of benzoguanamine, acetoguanarnine or formoguanamine.

The ethers with low molecular weight alcohols can also be used differ from the compounds mentioned and methylol alcohol, ethyl alcohol, propyla.lkoholen or butanols. For example, methyl ethers can be derived from Methylolme.laminen with three to six methylod groups, in which two to six methylol groups are etherified are to be used. the. The formaldehyde condensation products can also have further substituents .. You can ester, ether or acid amide groups contain. The ester-like compounds include, for example, those those by esterification of a methylolmelamine or an ether derived therefrom with a low molecular weight alcohol with higher molecular weight asiphatic carboxylic acids, such as lauric acid, palmitic, stearic, behenic. C51 or trailing fatty acids, or aromatic carboxylic acids, such as benzoic acid and its substitution products, or with cycloaliphic acids, such as abietic acid or \ taphthenic acids, are available. Among the compounds that contain further ether groups there are those into consideration that by Verätherurig the methylol compounds mentioned or their Ethers with low molecular weight alcohols with higher molecular weight aliphatic or araliphatic alcohols, such as octyl, dodecyl, 2-butyloctyl, cetyl> oleyl, Octadecyl alcohol or benzyl alcohol are available. Starting compounds with amide groups can differ from, the acid amides or the 1 \ T-Methvlolsäureamiden of the above both Derive acids mentioned esters. In the connections of the Component a) can also increase the hy drophilität in a nonionic way Components d) containing atomic groups are introduced. Come as such Compounds with polyglycol ether chains or a plurality of hydroxyl groups in Consideration, and in principle all connections can be used for this purpose, which contain or can form several hydroxyl groups or polyglycol ether chains and can react with the methylene derivatives or their ethers. As connections, which contain several hydroxyl groups are the aliphatic polyalcohols, such as Glycerine, erythrite, pentite or hexite, e.g. B. sorbitol or mannitol, as well as corresponding Polyoxycarboxylic acids, such as glucuronic or Galacturonic acids, called. Such connections can by etherification or esterification or transetherification with the methylol compounds or their ethers are implemented.

There are also compounds containing several hydroxyl groups also polyvinyl alcohol, partially saponified polyvinyl esters and ethers, polymerisation products of acrylic or methacrylamides containing hydroxyl groups and finally oligo-, Poly saccaride into consideration.

As compounds that contain and introduce polyglycol ether chains are able to, the polyglycols are used in particular. Preferably: be the commercial types used that have an average molecular weight of 600, 1000, 1500, 3000 or even more. Also derivatives of such polyglycols, such as one-sided ethers or esters, e.g. B. a polyglycol acetate, or a Polyglykolme: ethyl ether or a glycerine etherified with one to three polyglycols can be used.

As compounds that contain several hydroxyl groups or polyglycol ether chains able to introduce, the low molecular weight aliphatic alkyleiloxides, such as propylene oxide, butylene oxide, glycide and especially ethylene oxide can be used.

Furthermore, formaldehyde condensation products can be used for the purposes of the present invention of formaldehyde and guanyl melamines, as specified in the German patent 946 805 are accessible, can be used. Such condensation products can derive from Mono-, Di- or Trigunaylmelamill or mixtures thereof that are available are when you dicyandiamide in an inert solvent in the heat with gaseous Treated halogenated hydrogen and from the resulting salts the free amines separated by the addition of strong alkalis. Substituted guanylmela.mine can also be used for the production of formaldehyde condensation products.

The formaldehyde condensation products of the aminotriazine group can be used in a predominantly monomeric or partially condensed state. The monomeren compounds are, if they are not pronounced hydrophobic residues contained in large numbers, soluble in water. A suitable starting material is e.g. B. a water-soluble I-lexaine: thylo-iinelainiiihexamethyläther.

In principle, all products can be used as formaldehyde condensation products of the urea group for the purposes of the present invention, provided they have at least one free methylol group or at least one methylol group etherified with a low molecular weight alcohol. As compounds of the urea group, there may be mentioned, for example, urea, thiourea and compounds with the atomic grouping such as dicyandiamide, dicyandiamidine, guanidine, acetoguanidine or biguanide. A suitable starting material is e.g. B. the dimethylolurea.

Compounds capable of introducing an epoxy group and as a reaction component under c) are in particular those; which introduce the epoxypropyl residue can. Examples include glycidic and glycidic acid and their functional ones Derivatives. In particular, epihalohydrins, preferably epichlorohydrin, are used: The primary, secondary or tertiary amines that are used as reactants are among b) may be the aromatic, hydroaromatic; araliphatic, heterocyclic or preferably belong to the aliphatic series. As aliphatic Amines are suitably alkylamines, dialkylasnines, oxyalkylamines, bis (oxyalkyl) amines and NT ', N'-dia.lkylalkylenediamines used for the implementation. Both straight chain as well as branched, saturated and unsaturated representatives of these compounds with z. B. 1 to 18 carbon atoms can be used. Examples include methylamine, Ethylamine, propyl, #amine, isopropylamine, butylamine, isobutylamine, allyl, 1 amine, Mono- and diethanolamine, propanolamine, diisohutylamine, N ', 2 # T'-diethyl-ethylenediamine, also Polv alkylenpo: lyainine, such as diethylenetriamine, triphylenetetramine, Tetraätliylenpentainin or no higher malecular polyalkylene polyamines. There are also such amines into consideration, the one higher molecular weight, non-aromatic and preferably one have aliphatic hydrocarbon radical. Under the term higher mo: lecular Hydrocarbon radicals are to be understood as meaning those radicals which are approximately 8 to 40 and preferably contain from 12 to 18 carbon atoms. Examples are Resin amines such as Abietylainin, and also fatty amines such as laurylamine, oleylamine, octadecylamine and their commercially available mixtures. The higher molecular weight hydrocarbon radical does not need to be bound directly to the nitrogen atom. It can also go through Heteroatoms with interrupted bridges can be interposed, as in the case of ethylene-diethanolamine-monol: olcosfatty acid ester or in the case of triethanolamine mono-octadecyl ether.

Finally, di- and polyamines with a higher molecular weight can also be used Hydrocarbon residue can be used. Such connections are for example accessible by the addition of acrylonitrile to an amine with a higher molecular weight Hydrocarbon radical and reduction of the nitrile group to the amine. Also the di- and Polyamines with those mentioned for component a) which increase the hydrophilicity Atom grouping rules are usable. These can be achieved by implementing the above Prepare amines with components d).

Of the hydroaromatic amines, for example, cyclohexylamine, Dicyelohexylamine or N-methyl-cyclohexylamine can be mentioned.

The araliphatic amines are preferably derived from benzylamine from, benzylamine itself and its core by z. B. halogen, alkyl or derivatives substituted by alkoxy groups. 11 G The aromatic Amines can be mononuclear or polynuclear and, if appropriate, be further substituted. Preferably, aniline and its core substitution products, such as. B. o or p-Toluidine, various chloroanilines, o- or p-anisidine are used. But also naphthylamines, such as a- or 13-naplithvlainin and their core substitution products can be used for the implementation according to the invention are used.

The usable heterocyclic amines can (#iii or more Contain heteroatoms. Piperidine, a-pipecolin, morpholine, pyrrolidine, Imidazole, benzimidazole, 2-amino-thiazole, 5-aminotetrazole and tetrahydroquinoline.

Of the tertiary amines those are expediently used, which a bound to an oxygen, sulfur or other non-basic nitrogen atom, contain reactive hydrogen atom. They preferably belong to the aliphatic Row on. Tertiary alkanolamines such as triethanolamine, diethanolamine, Tripropanolamine, / 3-oxyethylmorpholine, also condensation products of such Alkanolamines with polyglycoals or alkylene oxides, furthermore partial esters of such alkanolainines with carboxylic acids, such as triethanolamine stearic acid mono-ester, ethereal reaction products of alkanolamines with N-methylolamides, e.g. B. the Reaction products of 1 mol of Triäthanola.min- with 1 or 2 mol of stearic acid-N-methylola.mid. The compounds, which in addition to the tertiary nitrogen atom still have another one, do not have a basic nitrogen atom, are mainly derived from aliphatic polyamines from, which in addition to at least one tertiary amino group, also contain a primary, which is acylated. Such a compound is, for example, that with stearic acid acylated N ', N'-diethyl-ethylenediainine.

Finally, it is also possible to use amines which contain epoxy groups contain, and in this case it is not necessary to use further radicals with epoxy groups to introduce into the condensation products.

Instead of using single. Connections for the Production process listed as reaction components under a), b), c) and d) , mixtures of several such compounds can of course also be used can be used.

The preparation of the compounds to be used according to the invention can be carried out in such a way that first the compounds mentioned under a) condensed with those mentioned under c) and the condensation product thus obtained with those mentioned under b) or that the ones mentioned under a) and b) are first implemented Components combined and the product obtained then with those mentioned under c) Reacts compounds, or further that one first the compounds mentioned under h) and c) condensed with one another and the condensation product thereupon with those mentioned under a) implements. Finally, it is also possible to use all three components at the same time to implement. The procedure is preferably such that first the components a) and b) are combined and that this binary condensation product with the component c) is implemented.

The individual reactions are expediently carried out under the conditions known for similar condensations. The components become beneficial at higher temperature, preferably at temperatures above 80 ° C, e.g. B. at 100 up to 200 ° C. The reactants can be merged in a simple manner or they are reacted in the presence of an inert solvent. It may be appropriate to carry out the reactions under reduced pressure and / or in one Inert gas, e.g. B. in a stream of nitrogen.

The molar ratio between the components used is mainly based on the number of methyl alcohol present in component a) or methylol ether groups. The strength of the cation activity of the condensation products can also be varied by the amount of component b) and the amount used Choice of amines. In general, it is useful to make connections the more than one, e.g. B. two to four cation-active groups per Mo, l aminotriazine compound contain. This can be achieved by adding several to 1 mole of component a) Moles of a monoamine or 1 or more moles of a polyamine are used.

If epihalohydrins are used as component c), then arise the egg products in the form of their salts. Primary or secondary amines serve as a component b), amine salts, especially hydrochlorides, are formed. When tertiary ainine are used, quaternary ammonium salts are formed, the anion of which is usually represents the chloride. There can be compounds with one or more quaternary Ammonium groups are produced. Products are preferably produced that. more as one, e.g. B. contain two to four epoxy groups.

A particularly useful embodiment of the present manufacturing process is the one according to which the proportions of the starting materials are chosen so that the reaction product has at least two tertiary amino groups or quaternary ammonium groups contains and at each nitrogen atom, these groups have a finite residue of an epoxy group is bound and that you can obtain the only tertiary. Amino groups and none quaternized products containing ammonium groups.

So you can dkondensationsverhindungen in derivatives of aldehydes the aminotriazine or urea series or their ethers with low molecular weight alcohols, which have at least two basic, tertiary nitrogen atoms, the latter quaternize with agents that are able to introduce epoxy groups at the same time, where such derivatives of the aminotriazine or urea series are advantageous as Starting materials used, which increase the hydrophilicity in a non-ionic way Contain atom groupings. There come z. B. such alkylol compounds, in particular Methylolverbin.dungen the aminotriazine or urea series into consideration, in which at least two alkylol groups by aliphatic or heterocyclic-aliphatic Residues are etherified which contain at least one tertiary amino group, where between the. Alkylolsauerstoffa.tomen and the tertiary nitrogen atoms still each a polyglycol ether chain may be present.

The condensation products obtainable by the process according to the invention are at least in the form of their salts with the customary acids soluble in water or can be distributed therein. They are suitable for improving materials, in particular textile materials made of synthetic fibers, with regard to the surface conductivity. For the reason just given, they are preferably used in the form of their water-soluble salts for this purpose, and the treatment is carried out in aqueous solutions. However, it is also possible for the treatment in non-aqueous. Media, e.g. B. in the solvents used in dry cleaning, in which case the free bases or salts soluble in these solvents are used. For the treatment in aqueous solution, the customary impregnation processes known in the textile industry are used. If curable products are used, it is expedient to cure at higher temperatures after impregnation and drying. B. at 120 to 150 ° C. In these cases, it is advantageous to use hardening catalysts. As such, the generally customary curing catalysts such. B. acids such as hydrochloric acid, sulfuric acid or formic acid into consideration; salts of strong acids with weak bases, e.g. B. ammonium salts of strong, inorganic and organic acids: such as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium oxalate or ammonium lactate can be used. Will solutions in organic. Solvents used, those catalysts come into consideration which are soluble in the organic solvents, for. B. stronger organic acids, such as formic acid, acetic acid, chloroacetic acid, or compounds which split off acids when heated, such as tartaric acid diethyl ester or triacetin and amines having a reactive hydrogen atom; Furthermore, the German patent application C 2365 IV b / 39c describes water-soluble condensation products from alkylol compounds: indungen of at most weakly basic compounds containing N H or N H2 groups and alkylolamines. When treating man-made fibers such as nylon or acetate gray with these. known products, no or at most a weak antistatic effect can be achieved, the latter also not being washable. In contrast, when treating z. B. nylon or Acetatreyon with the new derivatives, as mentioned above, achieve an effective antistatic finish, which is also very resistant to washing, especially in Acetatreyon.

In the following examples, parts mean parts by weight if nothing else is noticed. Example 1 68 parts of piperazine are added in a stream of nitrogen heated to 130 ° C, whereupon 69.6 parts of ethylene oxide as a finely divided gas stream initiates at 130 to 140 ° C. Most of the dioxyethylpiperazine thus obtained boils at 183 to 192 ° C under a pressure of 13 mm of mercury.

18 parts of hexamethylolmelamine - hexamethyl ether and 13.2 parts of the Dioxyäthylpiperazins just described are in a stream of nitrogen for 2 hours Heated to 120 to 125 ° C. The temperature is first increased within 1 hour to 160 ° C. and then to 200 to 205 ° C. for a further 2 hours. Finally, stir one for 30 minutes under reduced pressure (12 mm mercury column) in a Bath from 200 to 205 ° C.

The above-mentioned methylol melamine ether can be obtained as follows: 324 parts (1 mol) of finely powdered hexamethylolmelamine are stirred at room temperature entered in 2000 parts of methyl alcohol containing 100 parts of concentrated hydrochloric acid. After 10 minutes the methylol compound has dissolved. The solution is immediately with about 160i parts of calcined soda stirred until it reacts neutrally to litmus. The deposited salt is filtered off and the solution is evaporated to a syrup in vacuo. The syrup, which has been concentrated to about 99 ° / a, is then used to remove the rest Salt filtered hot.

25 parts of the condensation product described in the second paragraph and 5.9 parts of epichlorohydrin are boiling in a nitrogen stream for 3½ hours Stirred water bath. After this time, the reaction product is due to severe thickening no longer touchable. It forms a thread-drawing, easily soluble in water and methyl alcohol viscous mass and can be used as an antistatic agent. Example 2 18 parts of hexamethylol melamine - Hexamethyl ether (see below for preparation) and 13.2 parts of N, N-dioxy- 'ethyl piperazine (Obtainable, for example, by introducing 2 moles of ethylene oxide into 1 mole of anhydrous piperazine at 120 to 130 ° C in the presence of a small amount of metallic sodium) in a stream of nitrogen for 2 hours in a heating bath at 120 to 125 ° C Stirring heated, whereupon the Ternperatur of the heating bath within. 1 hour on 160 ° C and within a further 2 hours to 200 to 205 ° C. Last heated one for 30 minutes at a pressure of about 12 mm of mercury in a Bath from 200 to 205 ° C.

25 parts of the condensation product obtained in this way are combined with 5.9 parts Epichlorohydrin for 31/2 hours in a stream of nitrogen in a boiling water bath heated. After this time, a strong thickening of the reaction product has occurred. The latter is soluble in water as well as in methanol.

To make the Hexame@th.ylo used above: imelamine hexamethyl ether one can proceed as follows: To obtain the methylolmelamine methyl ether 324 parts (1 mol) of finely powdered hexamethylolmelamine with stirring at room temperature entered in 2000 parts of methyl alcohol containing 100 parts of concentrated hydrochloric acid. After 10 minutes the methylol compound has dissolved. The solution is immediately with about 160 parts of caleined soda are stirred until it reacts neutrally to litmus. That The deposited salt is filtered off and the solution is evaporated to a syrup in vacuo. The syrup, concentrated to about 99%, is then used to remove the rest Salt filtered hot.

The quaternized in the manner indicated above with epichlorohydrin Condensation product can be used as an antistatic agent. Example 3 Heating is carried out 43.8 parts of triethylene tetramine to 120 ° C and passes ethylene oxide as finely divided Gas stream at 120 to 160 ° C until 79.2 parts are added.

20.5 parts of the oxethylation product thus obtained and 36 parts of the hexamethylolmelamine - hexamethyl ether described in more detail in the third paragraph of Example 2 are in the manner described in the second paragraph of Example 2 to 200 to 205 ° C heated.

33.9 parts of the reaction product thus represented are 13.8 Share epichlorohydrin during 31l2 hours in Sticks.toffstroin and heated with stirring in a boiling water bath. After that, the reaction product has heavily thickened. To clean it, it is boiled several times with acetone. It educates a water-soluble, viscous mass and can be z. B. use as an antistatic agent.

Example 4 108 parts of that described in the third paragraph of Example 2 Hexamethylolmelamine hexamethyl ethers and 53.4 parts of dimethylethanolamine are in the Nitrogen flow for 2 hours. in a heating bath from 120 to 125 ° C with stirring heated. Man: the temperature of the bath is first increased within 1 hour 160 ° C and then for 2 hours to 200 to 205 ° C. Finally, the heating is stopped continued for 30 minutes in the vacuum of the water jet pump.

50.2 parts of this condensation product are heated with 28 parts Epichlorohydrin for 6 hours with stirring in a boiling water bath, whereby nitrogen is passed through the reaction mixture. Then you continue heating continued for 1 hour in the vacuum of the water jet oil pump. The new reaction product is soluble in water. It can be used in the manner described in Example 2 of triethylene tetramine to improve the surface conductivity of nylon fabrics be used. Example 5 103 parts of diethylene triamine are heated in a stream of nitrogen in a stirred vessel provided with a descending condenser to 140 to 150 ° C and then carries 540 parts of technical stearic acid in small amounts within 4 hours Shares a. The mixture is heated for a further 4 hours to 160 to 165 ° C, with one constantly Passing nitrogen through.

80 parts of the acylation product thus obtained are added heated by 0.8 parts of sodium to 110 ° C, whereupon at 110 to 130 "C ethylene oxide introduced as a finely divided gas stream until the increase in weight is 108 parts.

53.8 parts of this Oxäthylierungsproduktes and 9 parts of the third Sales of. Example 1 described Hexamethylolinelamin-H exainethyläthers be heated according to the information in the first paragraph of example 4, last to 200 up to 205 ° C.

24 parts of the reaction product described above are mixed with 2.8 parts of epichlorohydrin and stirred initially for 6 hours while passing through of nitrogen in a boiling water bath and terminates the reaction by 1 hour Heating in the vacuum of the water jet pump in a boiling water bath.

The product thus obtained is suitable as an antistatic z. B. for tissue made of nylon or polymerized caprolactam. Example 6 44.5 parts of dimethylethanolamine are heated to 110 ° C and conducts ethylene oxide as a finely divided gas stream at 110 to 130 ° C until the weight gain is 132 parts.

53 parts of this Oxäthylierungsprodukte, s and 18 parts of Hexainethylolnielamin-hexainethyläther are according to the procedure described in the first paragraph of Example 4 Heated between 200 and 205 ° C.

39.6 parts of the condensation product described above are mixed with 14.8 parts of epichlorohydrin and heated for 6 hours in a boiling Wasserhad, passing a stream of nitrogen through the reaction mixture.

This condensation product is also a z. B. suitable for nylon Antistatic.

Example 7 36 parts of triethylene tetramine are heated to 110 ° C. and introduces ethylene oxide as a finely divided gas stream at 110 to 130 ° C, up to 195 parts are included.

46.9 parts of the oxethylation product thus obtained and 18 parts of the hexamethylolmelamine-hexamethyl ether described in more detail in the third paragraph of Example 2 are heated to 120 to 125 ° C. for 2 hours in a stream of nitrogen. The temperature is raised first to 160 ° C. over the course of 1 hour and then to 200 to 205 ° C. over 2 hours. Finally, the mixture is stirred for 30 minutes under reduced pressure (12 mm mercury column) in a bath at 200 to 2050 ° C.

33 parts of the reaction product shown in this way are 16.8 Share epichlorohydrin for 6 hours in a stream of nitrogen and with stirring in one heated boiling water bath while bubbling nitrogen through the reaction mixture. The heating is then continued for 1 hour in the vacuum of the water jet pump away. The new reaction product is clearly soluble in water. Example 8 Heat is applied 43.8 parts of triethylene tetramine to 120 ° C and passes ethylene oxide as finely divided. Gas stream at 120 to 160 ° C until 158.4 parts are added.

67.4 parts of the oxyethylation product thus obtained and 36 parts of the Hexamethylolmelamin.-hexamethyläthers described in more detail in the third paragraph of Example 2 are in the manner described in the second paragraph of Example 1 to 200 to 205 ° C heated. 76.2 parts of the reaction product represented in this way are equal to 37.4 parts Epichlorhyd.rin for 6 hours in a stream of nitrogen and with stirring in a boiling Heated water bath. The heating is then continued for 1 hour in vacuo the water jet pump. The new reaction product is clearly soluble in water.

Claims (3)

PATENT CLAIMS: 1. Process for the preparation of new curable derivatives of aldehyde condensation compounds of the aminotriazine or urea group or their ethers with low molecular weight alcohols, which derivatives have at least one basic Contain nitrogen atom, this nitrogen atom being a radical with an epoxy group is bound, characterized in that a) aldehyde condensation products of Compounds of the aminotriazine or urea group or their ethers with low-malecular ones Alcohols or derivatives derived from such compounds with higher molecular weight Hydrocarbon radicals, b) primary, secondary or tertiary amines or their substitution products or their quaternary amino salts, c) if the compounds mentioned under b) contain no residues with epoxy groups, Ties that such To introduce leftovers ver :. like, and 'd) optionally compounds that increase the hydrophilicity able to introduce atomic groups which increase in a non-ionogenic way, -with each other converts, the molar ratio between the reaction components selected in such a way becomes that in the end product at least one methylol group etherified with a lower alcohol or at least one free methylol group is present. 2. The method according to claim 1, characterized in that the proportions of the starting materials sa selects that the reaction product has at least two tertiary amino groups or quaternary ammonium groups contains and at each nitrogen atom of this group a radical with an epoxy group is bound, and that one can obtain the only tertiary Am, ino groups and none Products containing quaternary ammonium groups are quaternized. 3. The method according to claim 2; characterized in that derivatives of aldehyde condensation compounds of the aminotri azine, or urea series or their ethers with low-molecular alcohols; which have at least two basic, tertiary nitrogen atoms, the latter being quaternized with agents which are capable of introducing epoxy groups at the same time. 4. - The method according to claim 3, characterized in that such derivatives of the aminotriazine or urea series are used as starting materials which contain the hydrophilicity in a nonionic way increasing atomic groups. Considered publications German Patent No. 833 707; German patent application C 2365 IV b / 39 c; U.S. Patent Nos. 2,476,127, 2,528,360, 2,594,452, 2,626,251. A test report was laid out when the application was published.