PL88986B1 - - Google Patents

Description

The invention relates to a method of fixing non-woven (pile) fiber materials of glass or natural fibers or of synthesis tic, especially polyamide, polyester, polyacrylonitrile, polypropylene or wi-fi bevels, foam method with the use of means binding agents and auxiliary foam-forming agents or CH.

In the production of non-woven materials (fleece first a fibrous layer is produced output (rune).

However, such a fleece is characterized by a complete one lack of strength and therefore it is by means of binding agents applied in by fularding process or by spraying pad with increased pressure or foam method.

The foam method has the advantage that allows the material to dry faster, because The solution contains a foam applied in the form of a foam up to 50 ° / t air instead of water, and this advantage, that this method of application facilitates point-dropping giving a fixative at the points of the cross the fibers. Together in the foam method while the fixative is used considerable content of postnatal active substances, what after necessitating additional treatment consist leaching substances from the surface cayroiej from the preserved material and therefore also the man foam toda despite its advantages is now relatively not often used * According to the known method in the foam method The binding agent is first diluted with the answer with the amount of water, emulsifies in water, and then adds surfactant and intensifier do not mix in order to introduce as much as possible amount of air. This procedure basically works the day is not sufficient for the introduction of a given amount of air and therefore into the mixture air is additionally forced through the nozzles o subtle cross-section or the so-called means which is e.g. sodium acid carbonate and acid acetic or azodicarbonamide or the so-called relationships promotujaee or activating.

It has been found that the washing process can be eliminated cia when using the foam method, if instead hitherto generally used agents surfactants will be introduced below salty reactive tensides.

Used in the method according to the invention compounds referred to as "reactive tensides" are with surfactants dissolved in both in water and organic solvents characterized by their ability to reduction of the surface tension of the dissolving both, and being cross-linked in response their conditions, especially in the environment acidic or at elevated temperature. IN these compounds are deprived of the result of cross-linking properties of the surfactant and turns into insoluble products. 88 98 688 986 The invention relates to a method of fixing non-woven fabrics, foam method using there are five binders and foaming agents as in the fact that non-woven (pile) materials are stretched it is heated at room temperature, the water is heated a shaft with a pH value of 2-4.5 containing a solvent new or water-dispersible agent binding and as auxiliary foaming agent a reactive tenside which is a high surface activity, such as hydrated hydroxymethylene melamine or etherified a hydrated hydroxymethylene urea or a condensate initial aminoplast containing etherified hydroxymethylene urea or hydroxy- methylene melamine, being a reactive surfactant contains residues of monohydroxy compounds o at least 4 carbon atoms and the amine residues contain hydroxyl groups or glycol residues polyethylene or hydroxyl residues in which some of the carbon atoms are bound to the groups of formula Me-08S, where Me is an alkali metal or aliphatic hydroxy-acid residues carboxylic acid through hydroxyl groups we are associated with hydroxymethylene melamine or with hydroxymethylene urea and possibly the remainder of you containing amines containing hydroxyl groups, including that the above-mentioned reactive surfactant, corresponding to under certain conditions, it is characterized by ability the ability to cross-link and turn into connection zek insoluble, irreversibly deprived the properties of the surfactant, a the material is then heat treated in temperature 60-190, preferably 90-150 ° C.

The tensors used in the method according to the invention dy, referred to as "reactive surfactants" are represented especially the condensates resulting from the reaction urea lulb melamine with formaldehyde. Tensy Such methods are known, for example, from French descriptions Patent No. 1,065,686 or 1,381,811, or 1470103 or 1581989.

As nitrogen compounds capable of being formed from a mold with maldehyde in the condensates designated as "re active tensides "include: 1,3,5-aminotria- sines, such as N-substituted melamines, e.g. N-butyl melamine, N-trichloromethylmelamine, like ammeline, guanamine, e.g. benzoguanamine, ace- toguanamine as well as diguanamine. Even Alkyl and aryl ureas and thio are not suitable ureas, alkylene ureas, e.g. propylene urea, acetylene diurea or 4,5-dihydroxyimide- zolidone-2 and its derivatives, e.g. 4,5-dihydroxyimine dazolidone-2 bound via the hydroxyl group located at position 4, with the group of formula CH2OH2CONH-CH2OH. They are especially suitable compounds prepared with hydroxymethylolate urea and melamine, and in particular excretion products made of compounds substituted with many clusters hydroxymethylene memories. As output products Both monomolecular are suitable as well as more condensed preliminary condensates.

Aminoplast pre-condensates used as output products for the production of reactive surfactants can also exist as alkanol ethers with 1 to 3 carbon atoms, in particular methyl ether chloride.

As reactive in the method according to the invention A number of different surfactants can also be used tensides of non-ionic nature, anionic and cationic. Especially the they are not reactive tensides of a compound nature nonionics such as hardenable cones group-containing aminoplast pre-densates etherified hydroxymethylene * • partially with hydroxyl compounds marked with symbols lem 1, such as the hydroxyl compounds of formula HO- / CH2CH2-0- / n-H, where n is a number total 2—115 and which are partially verified with an alcohol having 4-18 carbon atoms.

As the above-mentioned compounds marked with The pain and pain are especially polyethylene glycols new, and as alcohols, amyl alcohol, hexa- nol- (l), 2-ethylbutanol- (l), dodecanol, petrol alcohol venom, stearyl alcohol, and in particular n-butanol.

Especially preferred as reactive surfactants are hardenable hydroxymethylene urine ethers nika or hydroxyimethylene melanin in which the hydroxymethylene groups are partially etherified polyethylene glycol with a total weight 1000-5000, and partially with alkanol o 4-7 carbon atoms, such as, for example, reactive ten the compounds mentioned in the French patent specification dimension No. 1381811.

Also suitable as non-ionic reactive tensides are low molecular weight compounds, especially monomeric reactive surfactants produced from carbamides. Compounds of this type can be made cut from mono-hydroxymethylene derivatives carbamide by hydrophobic etherification or a hydrophilic hydroxyl compound, na- stepwise reacting with formaldehyde or a compound capable of cleaving formaldehyde du and subsequent verification of the introduced in this method of the second hydroxymethylene group, as in with the help of a hydroxyl compound by nature 40 hydrophobic or hydrophilic so as to obtain The reactive tenside contained at least one into a hydrophilic group and one hydrophobic group.

Suitable low molecular weight reactive ten The judges are derived from monohydroxymethylene 45 acyclic urea derivatives, such as in particular black monohydroxymethyleneurea.

These reactive tensides can be made, e.g. if a compound marked with the symbol Ib, representing amine of the general formula H2N-CO-NH-O-R, in which R is an alkyl or alkenyl radical with 6-22 carbon atoms, the radical alkylcyclohexyl- or alkylphenyl with 2 to 12 carbon atoms, preferably 6-10 carbon atoms in the alkali residue or cycloalkyl with 8-12 carbon atoms, 55 is reacted with formaldehyde or a compound capable of releasing formaldehyde and the obtained product etherifies the polyalkylene glycol The ball with an average molecular weight does not indicate from 2,000 and preferably between 106 and 1,500.

The symbol R is preferably an alkyl radical or alkenyl of 6-22, especially 10-18 atoms coal.

As reactive tensides of a compound nature anionic condensates are suitable 65 aminoplasts with hydroxymethylene groups 88 986 6 partially verified with monohy- hydroxyl groups of at least 4 atoms carbon and partially etherified with alkanols incl having at least two hydroxyl groups we and containing the groups o the formula MeOjS where Me is a met atom alkaline thallium, also such as sodium, potassium or lit. As particularly suitable tensides of this of the type mentioned are primarily zetcher valid hydroxymethylene ureas or hydroxyme- Tylenomelamines in which the hydroxyimethyl groups flax plants are partially verified with alkanols of 4-18 carbon atoms and partly with alkanols of the general formula N- / OCH2CH2 / a-OH where m means a number, an integer not higher than 25, and which they contain groups of formula on the carbon atoms MeOa-S-, wherein Me is metal al- calcareous. Anionic tensides of this type are high mentioned in French Patent No. 1470103.

Other interesting reactive tensides pre-condensates are anionic aminoplasts with hydroxymethylene groups partially verified with monohy- hydroxyl with 4 to 22 carbon atoms, and partially aliphatic hydroxycarboxylic acids o 2 to 4 carbon atoms and possibly partially etherified alkanolamine having 2 to 6 carbon atoms gla. Of these types of reactive tensides, especially hydroxymethylene ureas and hydroxymethylene melamines having hydroxy groups methylene, partially etherified alkali nols with 4 to 22 carbon atoms, and partially carbon with saturated hydroxyalkyl acids locarboxylic acids with 2 to 5 carbon atoms, and possibly partially etherified, ethanol-, diethanol- or triethanolamine. Anionic tensides / of this type are listed in French o- Patent No. '1I58H989.

As the so-called cationic reactive surfactants pre-condensates of aminoplasts o partially etherified hydroxymethylene groups alkanol or fatty acid o 4 carbon atoms and partially etherified al canolamine having 2 to 6 carbon atoms. Especially preferred surfactants of this type are hydroxyme- tylenmelamine with hydroxymethylene groups partially etherified with an alkanol of 4-22 atoms coal and partially etherified atanol, diethanol- or triethanolamine. Reactive, cationic, such tensides are listed in French Patent No. 1,065,686.

Reactive anionic and cationic tensides are more preferred than nonionic reactive ten sydów.

In the method according to the invention, the reactions are carried out it is favorable in the aquatic environment, but can Also use solvent environment organic, especially mixing with ox, such as alcohol, glycol or solvent mixtures organic with water.

In the method according to the invention, the reactive tensor can be made irreversibly insoluble by various methods, with which it is necessary to replace especially the application, higher temperature, setting the solution to appropriate pH value, adding appropriate substances that bind to tensides or to con¬ tions pre-densates of aminoplasts creates a high v 5 molecule products, especially the addition of yes known as hardening catalysts, i.e. compounds acidic in nature.

If the curing reactions are carried out. in sro in water, then the mixture is favorable the pH is adjusted to 2-4.5, and especially 2.8-3.5, with the help of low-molecular aliphatic carboxylic acids, such as sough like formic acid, acetic acid, citric acid or inorganic acids such as phosphoric acid or its salts as well as acidic or hydrolysable salts such as aluminum sulfate, titanium oxychloride, magnesium chloride, ammonium salts of strong acids, such as ammonium chloride, ammonium nitrate, sulfate or ammonium dihydrogen phosphate. It is also possible use oxidizing agents causing oxidation formaldehyde to formic acid such as hydrogen peroxide. The table is especially preferred volatile acids.

As binding agents, in the method according to bed, you can use all measures previously time used in preservation processes, preferably not, however, such agents that are soluble in water or suspendable in water day. He mentions as appropriate binding measures for example, acrylic resins, a shoe copolymer diene (styrene, butadiene / acrylonitrile copolymer), poly styrene limers, melamine resins, epoxy plastic, polyester, polyurethane, phenolic resins, polyurethane vinyl acetate, [polyvinyl alcohol, poly chloride vinyl, natural latex, and especially products obtained from epoxy compounds.

They are particularly suitable as binders reaction products of epoxy compounds with amines us aliphatic and with basic polyamides 40 or dicarboxylic acids.

Such products are made of epoxy dies, aliphatic amines and basic polyamines, for example by reacting a basic polyamide in an organic solvent environment, w At a temperature of up to 95 ° C, with the reaction product being evaporated formed from at least one epo xydowe marked with the symbol a), which is a compound containing at least 2 epoxy groups in the molecule and from at least one high 50 molecule aliphatic amines of 12-22 atoms coal, marked with the symbol b), while holding the ratio of the equivalent to the epoxy groups for amines, such as 1: 0.1-0.85, with the proviso that the liamide used in this reaction is produced by 55 condensing the compound marked with the symbol pain c), constituting an unsaturated polymeric fatty acid, with the compound marked with the symbol pain c '), constituting a polyalkylene polyamine, at 'maintaining the equivalent proportion of epo groups / 60 x ingredients marked with symbols a) and b), to the amino groups of the basic polyamide made of components c and c 'as IM up to 1: 6, preferably 1: 1-1: 5, with the latest addition being upon completion of the reaction, such an amount is optionally added 05 acid to make a sample of the po7 reaction mixture the water had a pH value 2-8.

The term "equivalent proportion" applies quantities of substrates expressed in grams, no 1 mol of monoamine or 1 mol epoxy groups.

The reaction products obtained are also suitable scanned from epoxy plates, aliphatic amate and dicarboxylic acids. Products ta¬ which are produced in an organic environment in solution a solvent of at least one compound is designated by connected by the symbol a), which is related to the epo with at least a molecule two epoxy groups and at least one of the amine marked with the symbol b), which is a high molecule aliphatic amine and with at least less one acid marked with the symbol c), which is an aliphatic saturated diacid carboxyl with at least 7 carbon atoms, and optionally from an acid anhydride marked with Cg), which is an aromatic anhydride tic dicarboxylic acid by at least 8 carbon atoms or an aliphatic diacid or monocarboxylic acid of at least 4 atoms coal and possibly a subsequent re-treatment shares of this product with one or more ingredients such as a compound marked with the symbol d) which is a pre-condensate of aminopJastu with a thickness of Alkyl ether armpits, compound marked with the symbol pain e) being an aliphatic diol of 2-22 atoms coal mining and a compound marked with the symbol f), constituting an organic polyfunctional compound, especially bifunctional * which is functional the groups or atoms contain labile halogen atoms, vinyl or ester groups or at most one acid, nitrile, hydroxyl or epo accountant together with at least one other group functional or an atom of the above-mentioned type, the reactions being optionally carried out in at elevated temperature in organic dissolution in the dilute until the end product is obtained containing a free carboxyl group, then the resulting product is subjected to of the reaction with the base marked with g) becomes loose ammonia or a water-soluble organism any principle, such as especially the aliphatic tertiary Regular monoamine or polyamine, where O.R. the reaction medium is optionally alkalinized with strength of ammonia or water-soluble additives the organic carbon so that a sample of the mixture reaction on dilution with water showed pH value 7.5-42.0 * Epoxy compounds marked with the symbol above a) derive especially from multivalued ones phenols or polyphenols such as resorcinol, to produce and the condensation of phenols with re-type formaldehyde zon 'or novolaks. For making compounds of epoxy nols, such as di- (4-hydroxyphenylmethane) and in particular Chia 2,2-di- (4'-hydroxyphenyl) propane.

Epoxy compounds are especially preferred 2,2-di- (4'-hydroxyphenyl) Mpcopane gas #: epoxy peaks of 1.8-5> 8 equiv per 1 kg of the compound, determined by the formula given in the drawing, in which the symbol z denotes a switch course 8 the thinnest value 0—0.65. I received two bundles is known by reacting epichldrohydrin, with 2-2- (4'-hydroxyphenyl) propane.

As suitable high molecular weight amines aliphatic marked with the symbol above b) belongs name in particular mono-amines of 12-22 atoms carbon, represented by the formula CH, - (CH2) XNH2, in which rhyme X means the total value of Hczbowa 11-21, especially 17-2 * 1. Suitable amines are you can also see e.g. lauryl-, palmityl-, stea- rykr-, arachidyl- or behenylamine. Also mixtures of these amines can be used as a technical product.

These amounts of labeled ingredients are selected above symbols a) and b) to make an epoxy compound there was an abundance, that is, to 1 group amine of the compound marked with the symbol b) ex more than 1 epoxy group died.

To obtain a surfactant suitable for In the method according to the invention, they are selected such proportions of the two components mentioned above so that 1 epoxy group falls on 0.1- 0.5 amino groups, that is, the amount of the epoxy compound equivalent to 1 epoxy equivalent it fell to 0.1 — fr, 5 equivalents amino groups. Preferably the compound is used epoxy and amine compound respectively v the equivalent ratio of epoxy groups to amine such as 1: 0.1-0.5, especially 1: 0.25-0.5.

Reactions between the components marked above the symbols a) and b) are preferably carried out as temperature 80-1200C, especially 100 * C.

The components marked above with the symbol c) preparation of basic polyamides which constitute Glucose unsaturated fatty acids are especially with dimers or t-timerates of aliphetic acids of greasy words containing unsaturated ethylene dust. Requests are particularly appropriate products produced in the reaction of polyitoleenopoHamin ^ marked above with the symbol c '), with those marked above by symbol c) alipha dimers or trimers fatty acids with unsaturated an ethylene bond, derived from acids monocarboxylic acids with 1-22 carbon atoms. Yeah 45 acid monofcarphoxylic acids are tlu¬ acids containing at least one, preferably not 2-5 ethylenically unsaturated bonds. Before the representatives of this type of acid are acids such as e.g. oleic acid, hiragonic acid, eleostearic acid, li- canal, peanut, clupanodone, and especially linoleic and linolenic. The mentioned oxygen acids can be obtained from natural oils in which they are especially in the form of glycerol deeds. 55 The aforementioned dimers and trimers of the toluic acids are produced in a known manner by di- merizations of monocarbofcsylic acids above of a given type. So-called fatty acid dimers usually contain a certain amount of persistence as M and a small amount of monomeric acids.

As a component marked above with the symbol c) di- or trierized is particularly suitable linoleic acid and hib linolenic acid. Technical product it usually contains these acids in an amount of 75-GS * / * wt grams as dlmerized acids and 4—-25 * / q8B * » le femoral triraer and trace amounts of monomer. Tue » carrying up to $ 9J by weight. Molar FTfraction tee- the ru 4o trimer is typically 521- ^ 6: 1, As a component marked above with the symbol c *) od¬ especially pohainines, such as diethyl nottriamine, tripletsJenotmrmtm or tetramethyl- nopentamine as well as amines of the formula H ^ N-ZCHj-CH, - -NH / ^ - CHr ^ Hr ^ NHip where n is Tosc Hcabowa 1, 2 or *.

If a mixture of amines is used, the symbol «t in the above-mentioned formula it may be a little bit Hello, the average figure is between 1 and 1. Jarko the alkaline half is particularly preferred a liamide made from dimerized or trimmed Rised Knotic Acid i * Unotenomgo i polyamines © of the above formula NHj-ZCHj-CH, - As organic baby animals, in which the individual components of the exchange are given to the reaction especially soluble in organic matter solvents, namely those that have they go with water in any quantity. As a solution This type of solvent is mentioned as ap. dioxane, isopropaanol, etami and methanol, glycol o-butite ether ethylene colum and glycol monobutyl ether ditheite These reactions can also be carried out in the some water-insoluble solvents organic, e.g. gasoline hydrocarbons, like gasoline or petroleum ether, in benzene, in ch! o ~ grooved or substituted low rod alkyls, benzene, such as toluene, xylene, robenzea, in aticyclic compounds such as tetra rope, or eyclohexene, in chlorinated carbon dons like methylene chloride, methylene bromide, chloroform, carbon tetrachloride, ethylene chloride, ethylene bromide, s-tetrachloroethane, and especially trichlorethylene or pencbitaroethylene.

Reaction products of epoxides with amines a and a and a ~ tics and pottamide, they can also be produced possibly with the use of the third component, marked with the symbol w), which is another mo¬ no- or bifunctional compound, including what functional groups or noms, labile chlorine atoms grooves, vinyl, acid, ester, wildebeest groups py acid anhydrides, isocyanate- we U4> epoxy Marked above with the symbol w) single-function The compound uses the toe intentionally in a proportion of 0.25 M per 1 revnowataik of the amine groups pohanudn, ale this amount may be increased to e.g. 0.5 M aa 1 the equivalent of the amine groups. If the relationship azaa * czoiiy symbol w) apply * in the form of a relationship bifunctional, then it is introduced in The amounts of OfiS are aa 1 amine equivalent polyamine midu. As a component marked with the symbol w) uses forces, especially artaalkito-hib aikilphafloge- nek, nitrile, amide hA acid methylolaroid series acrylic, atiCetycaae or aromatic acids kaibotayi or their eUry or anhydrides like alphatic or aromatic isocyanates, epoxies or eipibaieigenehydtryin.

As a single-function ingredient marked above by the symbol w), alkyl halides are used, such as bro ethyl mce or butyl chloride, aralkyl halide- ki, like benzyl chloride; nitriles, amides or methyl-, lotoamlides of acrylic or methacrylic acid, such as acrylonitrile, acrylic acid amide or N- -raethylol acrylamide. Instead of methylolacrylamines- you can also use a mixture capable of the production of methyl acrylamide in situ, i.e. mercury shanine from acarylamide and formaldehyde or a compound capable of cleaving formaldehyde.

It is also possible to use acids - alkanecarboxyl - we have no more than 1B carbon atoms, such as fatty acids, such as coconut acids or stearics new, or their esters with alkanols, not more than carbon atoms, e.g. with methanol, ethanol or n-butanol or their anhydrides, such as acetic acid hydride; aromatic isocyanate ny, such as phenylisocyanine, or aliphatic or aro- matte epoxy compounds such as propyleneoxide butyleneoxide, dodecenoxide or styroloxide.

A particularly suitable bifunctional compound marked with the symbol w) is epichlorohy- dryna.

Also marked with special convenient compounds the above symbols w) are alkyleneoxides o no more than 12 carbon atoms, alkane- 2 $ we with no more than 16 carbon atoms, monocy- klicnte aryloatllohalogenides or acrylonitrile.

The order in which the polyamide reacts with monofunctional compounds and ref the action of epoxy with aliphatic amines does not he plays no role and so poHamid may surrender reacted first with one of the normal function and then with the reaction product epoxide with amine, or these reactions can be carried out today in reverse order.

In some cases, if reactivity individual reagents are in the same row, then you can react simultaneously all ingredients.

Reactions leading to the production of products ^ from the ingredients marked with the above symbol a) and b), with components marked with symbols c) and: &) t is carried out in such a way that you obtain a water-soluble or water-soluble polyadhesive the form of suspensions, the reaction medium 45 leads sfig dc- pH value of 2— €, preferably 2-7, and in particular 5-4 with, for example, inorganic acids organic or organic, preferably by means of organic acids with high volatility, Like acid 50 formic or acetic. The procedure is preferably in this way that they immediately pre-started reaction of the basic polyamide with epoxide is added them efe a certain amount of acid, and then over time the duration of this reaction is introduced continuously or in portions 55 to the reaction environment further amounts of acid. Re¬ these actions are preferably carried out at temperature to i (f * C, e.g. 85 ° -0 ° C, especially 45 ° -70 ° C. solutions or suspensions in this way may be used of the reaction product obtained in the above-mentioned conditions at pH conditions and deliberately diluted with organic solvent and especially water to concentration —46i / ». Preferably 10-30% are characterized by high stability and have a different appearance from the last solution to a constant opalescent solution. 85 Products with equally beneficial properties 3S88 986 11 12 can also be obtained in this way that after a do giving acid and water, the resulting mortar It is cured at ambient temperature or at elevated temperatures, e.g. within 4 hours in temperature of 70 ° C or for a longer period 5 time at a correspondingly lower temperature.

As an ingredient marked with the above symbol Ci) especially alkylene dicarboxyl acids are preferred xyl groups of 7-14 carbon atoms, as a rule, as dicarboxylic acids of the formula HOOC- / CH2 / y- 10 -CÓOH, where y is an integer value total 5-12, preferably 6-10.

Acids are used as such ingredients dicarboxylic acid, such as pimelin, cork, aze- lainic or sebacic and nona-, decano-, 15 acids undecanolib dodecane dicarboxylic acid. Composition the symbol Ci) above may be stacked valid as such, or possibly together with the component defined above by the symbol c2) is preferably an aromatic imo-2o anhydride no- or bicyclic dicarboxylic acid having 8-12 carbon atoms or an aliphatic acid dicarboxylic acid with 4-10 carbon atoms. As especially suitable anhydrous is replaced monocyclic aromatic acid anhydrides 25 dicarboxylic acid with 8-40 carbon atoms. Jul optionally substituted with cl pa methyl phthalic acid anhydride.

As ingredients marked above with c2) Anhydrides such as, for example, anhydrides may be used maleic or phthalic acid hydride. If is used to produce the end product also the component marked with the above symbol d), then this component, calculated as the total number of ingredients marked with symbols a), b), 35 Ci) and d) are used in the amount of 10-90, especially 40-70% by weight.

As a component denoted above by the symbol d) table the initial condensate of the aminoplast is removed by a total of ditch or especially partially eroded 40 methylol groups, derived from the compound nitrogen compounds capable of forming such con densates, e.g. urea and urea derivatives, such as ethylene urea, propylene urea or monuria nicglyoxal. 45 However, especially etherified ones are beneficial methylolaminotriazines, such as, for example, the alkyl ethers of highly methylolated mines, incl having 1-4 carbon atoms in the alkyl residue. As especially suitable alkyl residues 50 such as methyl, ethyl, n-propyl, isopropyl wa, n-butyl and n-hexyl.

In addition to the abovementioned alkyl residues, the molecule of this compound may be different residues you, such as polyglycol. Especially suitable 55 are generally n ^ utylethers of melamine with excl high degree of methylolation. As melamine, Fr. high degree of methylolation is called melting mines containing 5, preferably 5.5, methyl groups lowe. 60 If the ingredient is also used marked with the symbol e) above as appropriate A component of this kind is used in a diol, especially is an aliphatic diol with 2 to 6 carbon atoms in which The atoms that entered the chain are possibly over 65 separated by oxygen atoms. As a particularly suitable Mention is made of alkylene diols having 2 to 6 atoms carbon or di- or triethylene glycol. Spo among the particularly preferred alkylene diols with 2 to 6 carbon atoms are mentioned e.g., ethylene glycol, 1,4-butandiol, in particular hexandiolJl, 6.

As optionally used polyfunctional, a in particular the bifunctional ingredients marked with excl zej symbol f), the compounds that as they preferably contain functional groups or atoms halogen atoms bound to the alkyl moiety, res vinyl or esterified carboxy groups one or at most one epoxy group, carboxy or hydroxy together with another group functional pa or other labile atom. As such compounds are particularly suitable bifunctional organic compounds, which as a function they contain tional groups or atoms related to the rest alkyl, chlorine or bromine atoms, vinyl groups or alkyl esterified carboxyl groups we, aflbo at most one epoxy group or carboxyl together with another functional group or another labile atom.

Bifunctional organisms are particularly suitable numerous aliphatic compounds, such as, for example, epihalohy- dryin such as epibromohydrin or especially epichlorohydrin.

Other suitable bifunctional compounds- Meats are, for example, glycerin dichlorohydrin, acrylic acid acrylonitrile, methyl acrylamide and acrylonitrile.

As ingredients marked above with the symbol g), od¬ In particular, aliphatic tertiary classes are suitable monoamines, ammonia or an amine containing co at least two amino groups and only basic a nitrogen atom in which the amino groups contain ray at least one hydrogen atom bonded to nitrogen atom.

Particularly suitable tertiary amines There may be mentioned trialkylamines having 3-1-2 carbon atoms gla, e.g. triethylamine, tri-n-propylamine or tri-n-butylamine.

Component marked with g) above. can be diamines of an aliphatic nature or cycloaliphatic containing in particular at least less one primary amino group i a second amino group in which at least one the hydrogen atom is bonded to the nitrogen atom. As a component of this type may also be used ammonia, however, are particularly suitable primary aliphatic or cyclo-diamines aliphatic.

Particularly suitable aliphatic amines there are polyamines, such as diethylene triamine, triethyl lenotriamine or tetraethylene pentamine, and amines of formula NH2- (CH2CHzNH / n-CHBCH2NH2) where n is a numerical value of 1, 2 or 3, and if a mixture of amines is used, it may taking an average value, e.g. between 1 and 2.

Suitable cycloaliphatic amines are especially diamines with two groups I-row wyeh, which, in addition to the two nitrogen atoms, the ami¬ the new ones contain only carbon and hydrogen atoms, and in which there are 5-6 membered rings carbocyclic groups, one of the amino groups is bound to the carbon atom of one ukla-1 * ring, and the other amino group is bound to It is a carbon atom of the second ring via the -CH2- group.

Examples of such amines are mentioned 3,5,5-trimethyl-1-amino-3-aminomethylcyclohexane or 1-amino 1 -aminomethylcyclopentene.

The products are manufactured by known methods, by reacting the individual components in any order.

It is deliberately done in this way with a reaction gives up with each other the ingredients marked symbols a) and b), or a) together with b) and Ci). Re¬ action between component Cj) and finished product the result obtained from components a) and b) can be requested also in the presence of component c). Reactions with components d) or Ib) leads from re¬ guly only at the very end, that is, before the landing giving the resulting reaction product with the composition by g). Equality is often possible early reaction between the component m and a), b) and c) and possibly c2), and will then be obtained the new product is optionally reacted with with components d), e), and f). According to this variant, re the actions are preferably carried out in such a way that components a), b) and c) are reacted at a temperature from 80 to 120 ° C, preferably at 100 ° C, whereby the amounts of the individual ingredients are selected according to the price so many proportions so that with 1 group equivalent epoxy, proportion of the ami¬ group equivalent to carboxyl groups was 0.1- $ 0: i — 0.55.

You can also react the composition first Niki a) and b), and then subject the obtained product reaction with component ci and possibly in the third phase, condense the resulting product with its composition nikami d), e) or f). According to this method of production the product is rolled from the components a) and b), preferably at a temperature of 80-120 ° C, especially 100 ° C. Second the reaction phase, i.e. condensation with the component ej is preferably carried out at a temperature of 80-110 ° C, and especially at a temperature of around 100 ° C, at what are the amounts of ingredients selected so that 1 equivalent epoxy groups proportion amine equivalents to carbohydrate groups xyl compounds, was 0.1-0.5: 1-0.55; converted on the aliphatic amine marked with the above symbol lem b), and acid, denoted by the symbol c2). For obtaining a product suitable for the application such is used in the method of the invention the amount of epoxy compound a) to be equal to the sum novelties of amine groups and acid groups less than 1 equivalent of epoxy groups dropped out data.

The product obtained under these conditions contains So the end carboxyl groups. Con-product As a rule, it is characterized by an acid number -80, preferably 35-60.

Reacts with the component marked with the symbol d) is usually carried out at a temperature of 60-105 ° C, preferably around 100 ° C. Usually these reactions is carried out in the presence of a small amount of organisms an organic solvent such as, for example, n-bu- tanol.

Reactions with component e) are carried out as W3r- mentioned above simultaneously in application 986 14 the ej component. On the other hand, reactions with component f) carried out before the reaction with component g), w temperature of about 60-120 ° C. \ Reactions with component g) are carried out at the ambient temperature or at an elevated temperature in such conditions that the mixture was reacted or is only neutralized during the production salt if tertiary amine is not used or the reaction is completely complete.

However, in both cases you get the product polyaddition dissolved or dispersed in water, but immediately after finishing In order to react, the mixture will become alkaline, to such an extent that a sample of the mixture is water showed a value after dilution pH 7.5 ° C 12 "0, especially 8-10. Alkali mixture is based on inorganic bases or organic, especially easily volatile bases, like ammonia. The reactions with component g) are carried out preferably at a temperature not higher than 80 ° C, e.g. 60-70 ° C. If as component g) apply ammonia or III-row-base, then reactions is carried out expediently at ambient temperature.

The reaction products obtained in this way, basically after the task and preferably diluted organic solvent or water to steady state 10-40% are solutions or suspensions livid, characterized by high stability.

As organic solvents in the presence of end products are used mainly water-soluble organic baths, i.e. those that are mixed with water in any proportions. As solvent-, such elements, for example, diaxon, iso- propanol, ethanol and methanol, n-butyl glycol ether of ethylene and monobutyl ether of di- ethylene.

Reactions can also be conducted in the presence of water-insoluble solvents 40 organic, e.g. in hydrocarbons such as petrol, toluene, xylene, in halogenated hydrocarbons such as methylene chloride, methylene bromide, chloroform, carbon tetrachloride, ethylene chloride, ethylene bromide, S-tetrachloroethane, and especially 45 trichlorethylene.

When a sample of the mixture is fed in, the reaction up to a pH of 2-8 or 7.5-1) 2, sample diluted with water to the corresponding concentration —40% of the content of the reaction product. 50 As binders, they are also suitable so-called acrylic resins, such as ester copolymers isobutyl acrylic acid, acrylonitrile and acrylic acid.

Binding agents are intentionally used in the form of 55 solutions or suspensions containing next to reactive surfactant and other additives we, like an emulsifier or an organic solvent.

After treating the fleece, mortar with a binding agent it foams with the mixture, the material yields is heat treatment, especially dry sewing and then heating to temperature 60-120 ° C, preferably 100-150 ° C. Drying was carried out operates favorably at ambient temperature.

Due to the fact that a number of 65 is relatively low in viscosity, so the production of 88M ii the foam falls off very quickly and therefore It is necessary to increase the viscosity of the solution by means of thickeners. Come on the thickening agents used should be of the nature of the be resistant to acids like and should result in a significant increase in viscosity sci when adding them in a small amount * Quality suitable compounds of this type are mentioned ethers celluloses * carubic acid derivatives, esters polyacrylic acid, especially ethyl cellulose.

These measures are added to the taking solution both the set viscosity of the binder emulsion and the thickening effect of the product, with re¬ the use of a thickener is sufficient it in the amount of 2-30 g, and especially 3-20 g per 1 liter solution.

Reactive surfactants are expediently used in concentration 2-100 g / liter, preferably 5-50 g / liter bath, while binders require application in an amount of 100-700 g, preferably 170-330 g especially 250 g per 1 liter of capsule * Mortars used in the method according to the invention a strip for fixing fleece materials can also contain other additives not to obtain the results of detergents, such as material resistance rial to the action of microorganisms. The right ones the products are also preliminary condensates, noplasts with the help of which to obtain especially beneficial effects, especially if these densates will be used together with the binding agent made from components a), b), c) and C |), and in particular the components a), b) and optional not Cg), except that condensation is optionally used pre-aminoplast sat containing al- kiloether. Pre-condensate is used in * in the above-mentioned case, in an amount greater than 40% by weight head, based on the total amount of mixing nina. The resulting mixture is used together with reactive tenside.

Mortar of a reactive tenside with a fresh agent how to treat fleece materials in a known by surfacing. Preferably, the repair is on foulard at ambient temperature until obtained increase the weight gain of fibers by 30-80%, and not 40-70%.

A wide variety of pile materials can be used the first kind, as well as fiberglass, but fortunately fiber materials are generally preferred polyamide, chopped viscose fiber, fiber polyester, polyacaryl nitrile or polypropylene we and any mixtures of these fibers.

The method according to the invention is explained by the interface given examples with manufacturing methods *. casting of reactive tensides - examples I-X, and the binding agent in the examples XI-XVIII, as well as mortar and maintenance of fleece materials - examples XIX-XXVIII.

In the examples of these parts unless indicated otherwise, they mean parts by weight.

EXAMPLE 1 Method for the production of reactive dissolves 126 parts of melamine with the addition of 10 parts of 25% water ammonia in 590 parts 36.5% methanol, aqueous * formaldehyde solution at 8 ° C.

The reaction mixture heats up to 4empam- » rounds $ 0 ° C and dagm 28 rninwt addet * y * oats under the reduced cisnianSam 18fc parts of the city methanol with water, then suction asked 400 parts of n-butanol and subjected to further distillation, under reduced pressure, separating the mixture Vedas with A-butanal, n-butanal is turned back to na¬ action after separating 118 caesci in * - ' dy. It is then added to the reaction mixture 3 parts of 85% formic acid dissolve in parts of n-butaziol, then p * d- gives distillation until removal of 452 caesci n-fcu * tanotau which distills with the rest of the water * One obtains 532 parts of a colorless resin. sticks, mixing sit t benane at any time proportions. The obtained product was marked with the name Iak resin A. 445 parts of the drug resin A does 50 parts polyethylene glycol medium heavy and: 4000 zaetecfckowy, then heated to temperature; 9 ° -108 ° C and add * 3 parts of ice this acetic acid. Then heat the mixture it turns back to 95-108 ° C and tftray- keep at this temperature until the sample is the mixture will dissolve clearly in water, after whereof to the reaction mixture is added f0 cue- from triethanolamine, mixed and heated for 2 hours at 10 ° C. After cooling down, you got I feel a waxy substance that is dancing in water at a temperature of «0 ° CL After dilution water after reaction mixture, acidifies sle ia with a small amount of acetic acid in evaporation and: | and a 50% methyl fenside solution is obtained with a pH of 6.1- * 0.2.

This solution, after dilution with water, list at a concentration of 5%, the ability to reduce the voltage surface water, from -72J & dyn / cm to 41fi dyn / / cm. The obtained product was designated as reactive new tenside I. 40 Example 12. IM parts of melamine and 6t0 Jun- 30% of formaldehyde after adjusting to the value The pH value of 3.2 warms up in about 8.5 days at a temperature of 90 ° C until the appearance of meta n-bulanaiu, then adds a hundred of 1600 parts of n-bulanaiu 45 and 8 parts of glacial acetic acid and heats up so long under a reflux condenser until the solution was alive so many will become Idarowrry. Come on, let's go eat under reduced pressure butanol and vice until the water is completely drained and obtained 50 distillate completely clear after cooling down. Down residues add 869 parts of glycol pofcet- flax with a molecular weight of 4800 and warms further under reduced pressure at temperature 90 ° C while distilling off more butanol 55 and water. Heating is carried out as long as possible a taken sample of the reaction mixture will be dissolved brawling clearly in the water, and then the background becomes post-reaction nina add 18 parts tnójetaaoto * amines, mix and cool. It gets bcscoloured, in a waxy substance easily dissolvable in beef day. The product obtained was designated as reactive new tenside II.

Example III. 206 parts of a 36.5% solution aqueous formaldehyde, 170 parts of butanaka and 68 05 parts of urea are mixed with 8 parts of 25% water1? 881M mp ammonia solution and heated at 90 ° C for 2 hours in a fitted rotary evaporator into the coolers and distilling .32 parts of the mixture n-butanol with water. Then the mixture, cool It works up to 50 ° C and asks for 1 part & 5 ° h phosphoric acid dissolved in 20 parts n-butanol and then heated under reduced pressure evaporation to 80 ° C and distilled off a mixture of water and n-butanol, separates the water and the n-butanol is returned to the re-mixture stock. After 4 hours of distillation, it is obtained practically anhydrous product, miscible with with benzene in any proportions. Received the product is neutralized with 5 parts of triethanol amine and evaporates under reduced pressure to obtain a volume equivalent to 212 parts by weight. This product was referred to as la resins kowa B. 150 parts of the wax resin B are placed in the tab a rotary steam equipped with coolers, and then 100 parts of glycolic acid buyl ester were treated kolewego and 3 parts of glacial acetic acid and heated under reduced pressure, temperature of -80-90 ° C while distilling n- -butanol.

Within 1.5 hours, 63 parts of n- -butanol and then added to the reaction mixture a solution of 40 parts of solid hydroxide was added Tasu in 200 parts of ethanol and all kept boiling within 30 minutes, which caused the the initially clear solution became cloudy.

The reaction mixture was then evaporated to dryness under reduced pressure, receiving 185 parts of the colorless solid dissolve clears in water with strong foaming niu. Aqueous solution with a pH value of 8 * 0 it has high emulsifying capacity. If this solution acidified with acetic acid, then with solution a white resinous precipitate is lost, not dissolved in excess of lug. A similar product can be also get if instead of butyl ester the glycolic acid equivalents will be used the appropriate amount of lactic acid ethyl ester wego. The resulting surfactant was described as reactive new tenside III.

Example IV. For 206 parts of 9fi, 5% solution 230 parts of 25% of aqueous formaldehyde are added of ammonia water, and the mixture is heated to a temperature of 60%, add BO parts of urea ka, boiled and distilled 3? parts methanol-water mixtures. Then adds up a mixture of 1 part tfrh of phosphoric acid in 24 parts of n-butanol, mix 15 minutes and distances it catches a mixture of water under reduced pressure dy with ti-butanol, butanol being separated off is returned to the reaction vessel. After distancing Lining 134 parts of water-containing butanol, you add 2? parts of the ethylene wheel and 30 parts lauric alcohol and under reduced pressure OdestyiDouble 216 parts of rn-butanol, removing this way the last residual water. Next condensation is carried out during 1 hour in 95-100 ° C, then added 15 parts of dry acidic sodium sulfate and after heating pouring the reaction mixture for 30 minutes at at 100 ° C the product is easily obtained water-soluble. We will get the product it goes with 6 parts of the tri-marl and cools * One obtains 270 parts of vivid transparencies a highly viscous product that dissolves easily in water with high foaming.

This product was referred to as Reactive Tenside IV.

Example V. 126 parts of meiamine, at the bottom A dish of 1 $ of Ammonia water * dissolves in 590 parts d $ JPk of a methanol-water solution formaldehyde at 00 ° G, then the reaction mixture is warmed to temperature 80QC and under reduced pressure within 24 minutes nut, 132 parts of the metal mixture are distilled off tanol with water.

Then 400 parts of n-butanodium are added and a half distils again under reduced pressure 118 parts of a mixture of n-butanol and water, separate The water is heated and the butanol is returned to the reaction vessel after which 3 parts of 85% acid are added Formic acid dissolved in 5 parts n-t »- tanol and re-distills 452 parts of n-bu- tanoiu with the rest of the water.

532 parts of a colorless resin are obtained high viscosity, miscible with benzene in the bottom free proportions. This product was identified as wax resin C. 532 parts of melamine-n-butanol resin kowa C {containing l * / o melamdny) and IM caesci triethane amines, by stirring, keep the soy in the water per at least 120 ° C for 1.5 hours, then for a further 90 minutes at 185- 140 ° C, with 75 parts of ta-bu- tanol. After cooling, 560 parts of the clause are obtained an equal high viscosity product that is dissolved It digs very easily in 10% acetic acid solution wego. This acidic solution characterizes the sieve excellent emulsifiability.

From this solution at a pH value of 4 /) a little elevated temperature gives off an aero- permeable resin. This ability to go pro the product into an insoluble resin the product obtained as a reactive surfactant. Pro this product contains 9–85% solids.

The obtained reactive surfactant was in the form of a 5% solution the formation causes a reduction in surface tension new water from 72.75 dyafcm to 37j6 djWem, This product has been reported as reactive tenside V.

Example VI. 187 gttM raosiometriccritinoch * nika containing 7 g of water, [obtained according to Honben-Weyr "Methods of ckezoii oiwnicmel" vol 14 part 2, p. 348, ed. 41, asks 500 g of n-bu tanol and 4 g. Glacial acetic acid and heat wa at 100 ^ C until the moment a sample of the taken reaction mixture will be transparent after cooling, which is usually required heating for a few minutes. Then mix 334 g of dodecanol, i.e. 2 moles of 06% of the product at a temperature of 55-8t ° C, under reduced pressure, within 2 hours from 380-800 g of n-butanol are distilled. Received dodecyl ether is neutralized with 10 g of triethanol amine and inflicts 200 g of ethanol and 200 g (2.4M) 36.5% formaldehyde solution and stirring 40 45 50 5519 88 * 86 it is at 85 ° C for 2 hours after with which - while hot, it drains the resulting insolation permissible resin. The resulting monododec ether low ^ divumethylolurea dissolves easily in with hot ethanol, from which partially crystallized after cooling down. The rest of the product is obtained from mother liquors by thickening them. 2.8 g of monododecyl ether dimethylol urea The filter is condensed under reduced pressure with 60 g of medium polyethylene glycol molecular weight 600, in the presence of 1.0 g high acetic acid under reduced pressure m: down to 20 mm / Hg at 90-100 ° C. IN 2.5 g of the mixture is isolated during the condensation water with acetic acid. After 75 minutes 2.1 g of tris are added to the reaction mixture ethanolamine and everything is cool. You get a shadow tenside easily dissolving when foaming sitting in the water. The aqueous solution shows a value of pH 7.9. The product obtained is identified as reactive tenside VI.

Example VII. According to the method described in Example VI, the monomethylol ether is prepared urea, carrying out etherification with copper alkanol mixtures with 12-15 carbon atoms, with a diameter of it is a molecular weight 207.

The ether obtained is reacted with formaldehyde hydem to obtain a dimethylol urea derivative. 31 g (about 0.1 M) of monoalkanol diethyl ether methylolurea is condensed under low pressure, at a temperature of 90-130 ° C, in the presence of 1 g of glacial acetic acid, with 40 g medium weight polyethylene glycol molecular weight 400.

1.6 g is distilled off from the reaction mixture water with acetic acid and then mixed It is neutralized with 2.6 g of triethanolamine.

After cooling, the product is obtained as highly viscous liquids.

This product dissolves easily in water at foaming strongly, forming a thin solution.

The obtained product was described as reactive surfactant VIIa.

A product with similar properties can be discarded form by condensing the monoalkanol ether of dimethylol urea, with 30 g of polyglycol Tylen with an average molecular weight of 300.

This product was referred to as a reactive surfactant VIIb.

Example VIII. 342 g (1%) of stearyl monomethylolurea ether prepared from n- -butyl ether by cross-conversion reactions with al stearic alcohol, is condensed with lithium formaldehyde in a slightly alkaline solution alcohol and, after filtering off the produced liquid, of permissible resin, 340 g of monoste are obtained aryl ether dimethylol urea (M-372). 37.2 g (0.1 M) of the product obtained is condensed onto it steppe with 154 g of polyethylene glycol ether o molecular weight average 1540, in the presence of 1 g of glacial acetic acid, reduced pressure at 90-100 ° C for 90 minutes. Then 2 g of triethanol are added amines and, after mixing, the mixture is cooled.

A waxy product that is easily dissolved is obtained water-soluble when forming a thin solution ru. An easy-to-foam water solution of this pro of the product has favorable washing properties and surfactants. The obtained product may be it has a typical reactive property tensides, i.e. it undergoes acidification very quickly completely destroyed when heated, and after slow destruction at ambient temperature, the insolubles separating from the solution to resin, and the solution loses its foaming ability, Aug. The product obtained in the above manner was determined salt as reactive surfactant VIII.

Example IX. It is done as it is described in Example VII, but with the difference that Instead of stearyl ether, oleyl ether is used mono-methylolurea, and the resulting The tylol derivative of urea condenses with the ether medium weight polyethylene glycol in a molar ratio of 1000, in a molar ratio of 1: 1, w the presence of glacial acetic acid or acid form. The post-reaction mixture was neutralized they eat morpholine or triethanolamine and obtain soft, waxy, easily soluble in water product, designated as Reactive Tenside VIII, showing a hardenability like pre-condensates.

Example X. 90 g (0.25 M) Hydrabiethyl- monomethylolurea ether (prepared by from monomethylolurea butyl ether by strength of the conversion reaction with hydrogen alcohol ethanol), dissolved in 500 g of ethanol, po 30 g of a 36.5% solution of formaldehyde are added and such an amount of triethanolamine that the solution shows it has a pronounced alkaline reaction and is stirred at the temperature 70 ° C within 2 hours.

Then the reaction mixture is evaporated dry and get 98 g (0.25 M) of ether monohydroabietyl dimethylolurea.

The obtained product is subjected to condensation with 150 g of polyethylene glycol ether, medium thin kills the molecular weight of W '600, in the presence of 4 g of ice acetic acid, carried over 90 minutes, under reduced pressure and temp rush 90-95 ° C. During the condensation, in the receiver 6 g of water and acetic acid are collected. Received many a liquid, sticky product is brought down slightly alkaline with triethanol amines.

The product dissolves easily in water at foaming and creates a solution with a constant opalescence.

If the resulting solution is treated with acid, do to obtain a slightly acid reaction against the indicator Congo, then from the solution of this stored at ambient temperature will start slowly evolve white insoluble resin, precipitate this falls out very quickly after heating the solution, the solution loses its foaming ability.

The obtained tenside was designated as reactic ten syd X.

Example XI. The method of producing the agent binding. 196 g [1 equivalent of epoxy groups ] epoxy compound prepared from 2l · 2- -two- (4'-hydroxyphenyl) -propane and epichlorohy- The dryin is stirred for 1 hour at temperature at 100 ° C, together with 155 g (0.5 equiv 40 45 50 95 6021 88 986 22 amine) mixtures of 1-aminoejicosan with 1-amine nodocosan and the reaction mixture with chlorine today, up to the ambient temperature. He places 150.5 g of the above-obtained solution in a rotary evaporator and heated to temperature batch 60 ° C, then into the reaction mixture 37.2 g of polyamide is instilled in 30 minutes, made from linoleic acid and dimethylene triazines (0.15 amine equivalent), dissolved in 16 g of n-butylglycol and stirred continue at the same temperature for 5 hours.

It is then added to the reaction mixture 3.9 g (0.03M) 1,3-dichloro-2-propanol and stirred for further 1 hour at 60 ° C, after 24 g of glacial acetic acid were added in w 133 g of deionized water and stirring continued without heating tions. A solution of medium viscosity is obtained, having a pH value of 4.8 and 40% solids value. Received product was referred to as the binding agent of A.

Example XII. The method of producing the agent binding. 08 g (0.5 equiv. Epoxy e) epoxy compound made from 2,2- - di- (4'-liydroxyiphenyl) propane and epichlorohy dryin is boiled for 1.5 hours, under reflux condenser, together with 77.5 g (0.25 amine equivalent), the amines yielded the one in example 11, and 94.5 g of isopropanol. Na¬ stepwise, to the reaction mixture is dripped in Within 1 hour a solution of 247 g of the above-described product liamide, i.e. 1 equivalent of amino groups, v 328 g of isopropanol, followed by further stirring hours at the boiling point under the cooler feedback. 53.5 g are added to the reaction mixture {0.75 M) acrylamide and 22.5 g {0.75 M) para- maldehyde and stirring continued for 8 hours at boiling point under reflux. Have The post-reaction shame is diluted with 60 g of ice cold acetic acid dissolved in 1500 g of deionization water and a low viscosity solution is obtained with a pH value of 4.6 and a dry substance content of 20 hey. The product obtained is called the agent binding B.

Example XIII. 98 g (0.5 groups equiv elioxide) of the epoxy compound was formed from 2,2-di (4'-hydroxyenyl) propane and epi chlorohydrin and 31 g of a mixture of 1-amino-acid dip with 1-amino-docosan - (containing 0.1 eq of the amine group) and 55.5 g of glycol bu- the hindquarters, heated with stirring for 3 hours at 100 ° C. Then to the mixture 10.2 g (0.1 M) of methylolacrylium are added to the reaction of lamide and stirred for 3 hours at temperature 100 ° C, then 146.9 g of glycol of bu- back and stir until cool. I get clear, low viscous solution * characterized acid number 6. Obtained product has been described as the binding agent of C.

Example XIV. 98 g (0.5 groups equiv of epoxy) of the epoxy compound formed from 2,2-di (4'-hydroxyphenyl) propane and epi chlorohydrin, while stirring, is heated to a temperature of 100 ° C for 3 hours together with 31 g (0.1 equivalent to amino groups) of the mixture 1- -amino-eicosan and 1-amino-docosan and 50 g nH-butylglycol. Then to the reaction mixture 17.7 g (0.3 eq. of hygr droxyl), hexandiol-1,6 and 50,5 of setoacid of tin (0.5 eq. acid groups) and stirring continued for 3 hours at temperature 100 ° C, then 4.6 g (0.05 M) of epichloro rohydrin and mixes for the next 3 hours at 100 ° C. The mixture pore the stock is diluted with 131.8 g of n-1-butylglycol i mix until cool. Obtains clear low viscosity solution with an acid number of 43.6.

The obtained product is referred to as a linking agent cy D.

Example XV. A solution of 49.4 g of a con- densation of the polymerized linoleic acid from diethylenetriamine (with an equivalent weight of ami¬ molecular weight 247), and 49.4 g of methanol, e.g. can be obtained with vigorous stirring for 24 minuit to the solution heated to 51 ° C 38.4 g epoxy, (made from 2,2-di- / 4'-hy- droxyphenes, V-propane and epichlorohydrin, equal to 191), in 38.4 g of methanol, the reaction mixture is maintained at a temperature of 51-53 ° C and after 8 and 18 minutes from the beginning of adding the solution is added 3 g of glacial acetic acid each, and after 24 minutes 2 g more glacial acetic acid and re the action continues for 2 hours and 35 minutes notes at a temperature of 55-60 ° C. You get a pro product easily soluble in water. Aqueous solution This product is opalescent. Then no, while stirring, 4 g of glacial acid are added of vinegar and 273.4 water and becomes yellowish, dense, % solution with a pH value of 5.2.

Example XVI. 68.5 g (0.1 equiv epoxy groups) of an epoxy compound with a thinner molecular weight 685, made from 196 g (1 equator of epoxy groups), 2,2-di- / 4'- -hydroxyiphenyl) -propane and epichlorohydrin, such as 40 out of 155 g (0.5 amine equivalent) of each sham amlin with 1-amino-eicoses and 1-amiino-deco dip, dissolve in 37 g of isopropanol and heat up to 68 ° C. Then to the fabricated solution is added within 30 minutes. 45 zones with 24.7 g (0.1 amine equivalent) polyamide (made of polymerized linoleic acid and diethylenetriamine) in 24.7 g isopropanol and 15 g isopropanol. Mixture the reaction temperature is kept at 88 ° C, under 50 reflux condenser, stirring for 5 hours, after 1.85 g (0.02 M) epichlorohydrin is added and after 10 minutes a solution of 16 g is added of glacial acetic acid deionize in 312 g water and stir until cool. Received A solution containing 20% of dry substance is mixed Hey, characterized by low viscosity and low value pH 4.6.

Example XVII. 90 g of epoxy (0.5 eq vase of epoxy groups) made of 2.2- 60-di- (4'-hydroxyphenyl) -pTopane and epichlorohy Dry, while stirring, are heated together with 31 g of the mixture shafts of amines (0.1 equivalent of the amine groups) 1-amino-eicosan and 1-amino docosan, and from 50 g butylglycol, at a temperature of 100 ° C for 3 hours 65 days 15.6 g of neopentylglycol23 are then added (0.3 eq. * Of hydroxyl groups) and 50.5 g sebacic acid <0.5 eq owls) and stirred for 3 hours at temperature IGO5 *: followed by adding 13.0 g (0.15 M) of epichlo- rohydrin and stirred for a further 3 hours at temperature 100 ° C. The diluted post-reaction mixture 159 g perchlorethylene are poured on and stirred until cold going on. A clear solution is obtained with an average viscosity, characterized by an acid number of 20, 109 grams of a held 50% resin solution is mixed then with 62 * & g SOtye of butanol solution hexamethylolamine di- and trsdbwphcyl ether, then 10 g of 50Vd is added to this solution product solution of the addition of 70 M ethoxide lene to a mixture of Cu-Cjs amines and a mixture emulsifies. It is dropped into the resulting mixture 56.5 g of deionized water and is replaced subtly zAyspergowana emuJsje with 30 * / resin content.

Example XVIII. For the preparation vessel bathing is introduced with 30 l of water, then 2000 g of reactive surfactant I, prepared in example I, and 300 g of a 2% aqueous solution it is ethyl cellulose as a thickening agent and have it until the final spread of the ka. 25,006 g of the binder is then added A, prepared according to Example XI and by mixing adjusts the mixture to the pH value of 3, with formic acid, followed by a bath top up with water up to 100 liters and set the agitator so that a funnel was formed in the solution allowing suction of large amounts of entrust into the canal weeding Mixing is carried out until the volume of the chute as a result of foaming, it will increase to volume 200 1, then the resulting foam is repaired with a fleece polyester fiber on a double-rolled foulard, until 56-40% gain in fiber weight is obtained.

After saturation, the fiber is dried at temperature 140% in 10 minutes and cures. During the holiday the sis-fiber reactive tenside loses its properties surfactants. You get a permanent fleece made permanently.

Example XIX. It is done as follows bu described in Example XVIII, but with this difference ca that reactive is used instead of tenside I teaside, prepared according to example II. Received It also has a good fixation of the fleece fibers as in example XVIiL Example XX. It is done as it is described in Example XVIII, but with the difference, that instead of binding agent A, an agent is used B-binding produced according to the belted method in example XX.

A good fixation of the fiber is also obtained as in example XVIII.

Example XXI. In a crafting vessel in the bath place 70 liters of cold water (at a temperature of environment), then add 20 kg of the agent a binding agent, prepared according to the method of administration in example XIII. Then adds up 1000 g of an aqueous solution of ethylcellulose and start The high-speed agitator breaks down precisely spread the thickener then add it 5060 g of reactive tenside XVIII are eaten, produced by according to the method given in the example III and the bath is adjusted to a pH of 3, a 45 50 55 60 65 14 with formic acid, the bath replenishes water up to 100 liters and the speed of the stirrer yes sets to create a enabling entry pouring a large amount of air into the solution. I> o In the bath, additional air is blown in for so long until the bath volume increases from 100 to 200 1. Off created foam bath fleece, with polyester fibers, reinforced by stitching, on a foulard with two parallel cylinders or in special screening devices for surfacing up to 50-70V # fiber weight gain. Next the fibers are dried and hardened at temperature 140 ° C within 5 minutes. In the curing process the reactive tenside loses its surface properties inactive. The pile material is hardened permanently. Test of the ability to wet of fleece material. 2 test material a round shape with a diameter of 4 cm is embossed.

The sample was then hung on the hook of an apparatus equipment of a structure similar to that of the test apparatus the surface tension of the liquid, and then the sample was "immersed" in water at 20 ° C.

The results shown in the following were obtained the table where the material treatment method is given and the period of time from immersion to sinking shapes.

T. Material surfacing partially spoiled only the middle binding Binding agent4- reactive surfactant binding agent reactive tenside! wed € fe binding +] reactive surfactant binding agent + reactive tenside a b 1 i c a Tempe rature drying in ° C 140 140 and 1 * 0 120 140 ' | j Time zwHzarria immediately] over 10 minutes] immediately j immediately immediately | 9 over 10 minutes j i. 1. ii »nf Example XXII. It is followed by "after" described in the example XHX, 'with this difference, ** the reactive tenside IV, prepared in the debt of example IV, instead of the reactive tenside III One receives similarly perfectly recorded pile fibers.

Example XXIII. Follow the rules of described in example XXI, but with this difference ca 1000 g are used instead of formic acid magnesium chloride. A fleece fiber is obtained new with a similar permanent fix.

Example XXIV. Follow the rules of described in example XX2, but with this different Not that, instead of a binding agent C is used Binding agent D prepared according to the method described in example XIV. Receives .sie fibers with a similar permanent fixation.

Example XXV. Fibers made of wel-45 were fixed * & * 86 * cut with the saturation of the foam drip o in the composition given below. 200 g of a binding agent, prepared according to Example XV 170 g water; & 0 g of a 2.5% solution of hydrotesyethyl cellulose; 6 g of reactive tenside VI (by the example Y »; 50 g of 40% acetic acid solution.

The bath is brought to a reaction. pH 3 ° C after approx strength of formic acid, then stirring the mixture forcefully and blows in the air until the volume drops bathing capacity by 100%. This bath is saturated fiber on a two-shaft roll day for the weight gain to be 40-50%. Process drying is carried out for 10 minutes at a temperature temperature of 110 ° C, which at the same time causes loss of performance tenside activity. Upon drying, the tenside of the hive decomposition, and it loses its properties surfactants important for fularding and therefore, washing the fibers becomes unnecessary. Mon. Good results are obtained with the materials pile of polyester fibers and polypropylene new.

Example XXVI. Pile made of chopped wool of lulosic material is fixed on the foam dripping bathtub new with the following composition: 200 g. 50% water an emulsion of an acrylic resin binder formed by copolymerizations of the following monomers: 85 parts of N-tetylacrylate; acrylonitrile parts; acrylic acid parts; 4 g of reactive tenside VII; 50 g of water; 40 g of 2.5% carboxymethylcellulose solution; ml of 20% magnesium chloride solution.

Above mentioned, the bath is brought to the odor a deed with a pH value of 3.0 with the help of formic acid and mixing as described in the example XXI leads to foaming. Fiber fu- up to 30-60% weight gain, then dried within 10 minutes at 140 ° C.

Upon drying, the reactive surfactant loses its effect hydrogilic activity.

Instead of the reactive tenside XII, it can be used sativa reactive tenside X produced according to Example X. Instead of carboxymethylcellulose you can also use methylcellulose, metho- xycellulose or polyolate ester.

Instead of chopped wool fleece, mozz a similar fleece of polyamide fibers should be used or polyester.

Example XXVII. Polyester fleece Strengthened by stitching, it is pressed mortar of the following grade is placed on the foulard day; 20O g of P-binding agent, prepared according to example XV; 4 g of reactive tinxide VI; 50 g of a 5% solution of seed flour thickener Swietojanski bread and 80 & water.

The bath is brought to a pH value 3.0 with formic acid and then proceed funnel according to the method described in example XXI.

Fulardization is carried out up to 40-60% ab weight of the fibers, then the fibers are dried, w within 10 minutes at 100 ° C, in effect the reactive tenside loses its iydrophic properties lowe.

Instead of the reactive tenside VII, it is possible to use wac reactive tenside VIII obtained according to example VIII.

Instead of polyester fiber you can also use a fleece of cut polyamide poly- and propylene or chopped woolen. Also you can use mixtures of these fibers as well other containing, for example, polyacrylate fibers, lowe.

Example XXVIII. Polyamide pile fiber of the new needle rug, Fr. with the following composition: 200 g of binding agent C, prepared according to of example XIII, or a 50% suspension of but- diene-styrene-latex; 3 g of reactive surfactant IX prepared in example IX debt; 40 g of 5% methylceiulose; 150 g of water; ml of 20% magnesium chloride; 50 g of butylglycol.

The bath brings about a value reaction pH 2.8 with formic acid and progress them further according to the method described in the example XXI, the fiber fulards up to 40-50% growth scales, and then dried at 90 ° C. In pro¬ the drying process loses its reactive surfactant properties surfactants which enables elimination drying process.

Claims (29)

Patent claims 35 1. The method of fixing non-woven (pile) fabrics made of glass fibers, natural or synthetic fibers, especially polyamides, polyester, polyacryionitrile, polypropylene or viscose, foam method with the use of binders and auxiliary foaming agents, characterized by that non-woven (fleece) fabrics are treated, at room temperature, with a water-based mortar with a pH of 45-2-4.5, containing "a water-soluble or dispersible binder and possibly a thickening agent, and as auxiliary foam-forming agent, a reactive surfactant, which is a compound with a high surface activity, such as etherified hydroxymethylene methylamine or etherified hydroxymethylene urea aSfoo aminoplast precondensate containing etherified hydroxymethylene glycol groups or reactive hydroxymethylenemethyl contains menohydroxy moieties of at least 4 atoms carbon and amine residues containing hydroxyl groups or polyethylene glycol residues or alcohol residues containing at least two pheydroxy groups in which the carbon atoms are bonded to groups of the formula Me-OjS, in which Me is an alkali metal atom , or contains aliphatic hydroxycarboxylic acid residues linked via hydroxyl groups to hydroxyl methylenelamine or to hydroxymethylene mesium and optionally residues of amines containing hydroxyl groups, the above-mentioned tenside, at the heat treatment temperature of the material, has the ability to cross-link and converting into an insoluble compound, irreversibly devoid of surfactant properties, and then the material is heat treated at a temperature of 60-190, preferably 90-150 ° C. 2. The method according to claim A process as claimed in claim 1, characterized in that the reactive surfactant is an aminoplast precondensate containing hydroxymethylene groups partially etherified with a hydroxyl compound of the formula HO- / CH2-CH2-0 / n-H, in which the symbol n represents an integer value. 2-115 and partly with a monohydric alcohol having 4-18 carbon atoms. 3. The method according to p. A process as claimed in claim 2, characterized in that the reactive surfactant used is hardenable hydroxymethylene urea or hydroxymethylene melamine ethers with methylol groups etherified with an alkanol of 4-7 carbon atoms and polyethyleneglycol with an average molecular weight of 1000-5000. 4. The method according to p. A compound according to claim 1, characterized in that the reactive surfactant is a compound of the formula HgN-CO-NH-CHjj-OR, wherein R represents an alkyl or alkenyl group of 6 to 22 carbon atoms, an alkylcyclohexyl or an alkylphenyl group of 2 - 12 carbon atoms in the alkyl residue or a cycloalkyl group with 8-12 carbon atoms in the ring, condensed with formaldehyde or formaldehyde donating agent and etherified with a polyalkylene glycol with an average molecular weight not higher than the numerical value of 2000. 5. The method according to p. The process of claim 1, wherein the reactive surfactant is an aminoplast pre-condensate with methylol groups partially etherified with a hydroxyl compound with at least 4 carbon atoms and partially etherified with alcohols of at least two hydroxyl groups containing the bound with carbon atoms of the group of formula Me-OsS- where Me is an alkali metal atom. 6. The method according to p. A process as claimed in claim 1, characterized in that the reactive surfactant is a etherified hydroxymethylenemeside or a hydroxymethylene methylamine in which the methylol groups are etherified partially with an alkanol of 4-18 carbon atoms and partially with an alcohol of the formula H- (OCH2-CHj). jj-OH, in which m is a total number not greater than 25, containing groups of the formula Me-08S, in which Me is an alkali metal bonded to carbon atoms. 7. The method according to p. A process as claimed in claim 1, characterized in that the reactive surfactant is an aminoplast precondensate containing methylol groups partially etherified with monohydroxy compounds with 4 to 22 carbon atoms and partially etherified with aliphatic hydroxycarboxylic acids with 2 to 4 carbon atoms, and optionally a partially etherified alkanolamine having 2 to 6 carbon atoms. A method according to claim 1, characterized in that the reactive surfactant is hydroxymethyl-lenourea or hydroxymethylene melamine, in which the methyl groups are partially etherified with an alkanol having 4 to 22 carbon atoms and partially etherified with saturated hydrocarbons. - 5 droxyalkane carboxylic acids having 2 to 4 carbon atoms and, if appropriate, partially etherified ethanolamine, diethanolamine or triethanolamine. 9. The method according to p. The process of claim 1, wherein the reactive surfactant is an aminoplast precondensate in which the methylol groups are partially etherified with an alkanol or a etherified fatty acid derivative with at least 4 carbon atoms, and a partially etherified alkanolamine with a 2- 6 carbon atoms. 10. The method according to p. The process as claimed in claim 9, wherein the reactive surfactant is hydroxymethylenemelamine, in which the methylol groups are partially etherified with an alkanol having 4-22 carbon atoms and partially etherified with ethanol, diethanol or triethanolamine. 11. The method according to p. The method of claim 1, wherein the mortar is adjusted to a pH value of 2.8-3.5 with a volatile acid. 25 12. The method according to p. The method of claim 1, wherein the binder is products which are polymers or copolymers of olefinically unsaturated compounds. 13. The method according to p. The method of claim 12, wherein the binder is polymers derived from compounds of the acrylic acid series, butadiene or styrene. 14. The method according to p. The method of claim 13, wherein the binder is a copolymer of 85 parts of N-butyl acrylate, 10 parts of acrylonitrile and 5 parts of acrylic acid. 15. The method according to p. The binder according to claim 1, wherein the binder is the product of the condensation of epoxy compounds with fatty amines and basic polyamines or dicarboxylic acids. 16. The method according to p. 15, characterized in that the binder is the product of condensation of epoxy compounds with fatty amines and basic polyamines produced in an organic solvent environment by reacting the polyamide in the presence of an organic solvent with the product produced with the symbol a ) at least one epoxy compound with at least 2 epoxy groups in the molecule and at least one high molecular weight amine with 12-22 carbon atoms, denoted by b), while maintaining the equivalent proportion of epoxy groups in the compound denoted by a) to amine groups of the compound denoted by b), such as 1: 0.1 to 1: 0.05, except that the polyamide used in this reaction is a basic polyamide obtained by condensing the compound denoted by 00, which is a polymeric unsatisfactory Yellow fatty acid, with the compound marked with the symbol c '), which is a polyalkylene polyanate, keeping the proportion equal to of the novel epoxy groups of the compound prepared from the components denoted above with symbols a) and b), 'to the amine groups of the basic polyamide, such as 1: 1 to 1: 6, carried out under such pH conditions obtained later' beziposrednlio after the completion of the reaction after. With the aid of acid addition, a sample of the reaction mixture, after adding water, shows a pH value of 2 to 8. 17. The method according to p. The binder according to claim 15, characterized in that the binder is the condensation product of epoxy compounds with fatty amines and basic polyamines prepared in an organic solvent environment by reacting at least: a) one epoxide compound with at least two groups epoxy in the molecule, b) a fatty amine with a high molecular weight, cx) an aliphatic saturated dicarboxylic acid with at least 8 carbon atoms or an aliphatic mono- or dicarboxylic acid with at least 4 carbon atoms and possibly one or more components such as: d) an aminoplast pre-condensate containing alkylether groups, e) an aliphatic diol with 2 to 22 carbon atoms, and f) a polyfunctional, preferably difunctional, organic compound containing as functional atoms or labile groups halogen atoms, vinyl groups or ester or at most one acid, nitrile, hydroxyl or epoxy group together with at least one other group a functional group or other labile atom, condensed where appropriate, optionally at elevated temperature, with ammonia or a water-soluble organic base while maintaining an alkaline environment by adding ammonia or water-soluble basic amine in during the condensation or immediately after the completion of the reaction, so that a sample of the reaction mixture, in the environment of an organic solvent, after dilution with water, showed a pH value of 7.5-12. 18. The method according to p. The binder according to claim 1, characterized in that the binder is a mixture consisting of an aminoplast precondensate containing alkylether groups and an epoxy compound with a fatty amine and a basic polyamide or an epoxy compound with a fatty amine and an aliphatically saturated dicarboxylic acid. and possibly with an acid anhydride. 19. The method according to claim The process of claim 17, wherein the epoxy compound is 2,2-di (4'-hydroxyphenyl) propane polyglycidyl ether, containing in 1 kg of the compound at least 5 equivalents of epoxy groups. 20. The method according to claim A process as claimed in 19, characterized in that the epichlorohydrin reaction product with 2,2'-di- (4'-hydroxyphenyl) propane is used as the epoxy compound. 21. The method according to p. The process as claimed in claim 16, characterized in that the polymerically unsaturated fatty acid is a dimer or trimer of an ethylenically unsaturated aliphatic fatty acid. 22. The method according to claim The method of claim 17, wherein the polyamine is a polyalkylene polyamine of the formula H 2 N- / CH 2 CH 2 · NH / n-CH 2 -CH 2 -NH 2, where n represents a numerical value of 1, 2 or 3. 23. The method according to claim The process of claim 17, wherein the dicarboxylic acid is an acid of formula HOOC- / CH2 / y-COOH in which Y is a total value of 5-12. 24. The method according to claim 17, characterized in that the anhydride is an aromatic anhydride of a mono- or bicyclic dicarboxylic acid with 8-12 carbon atoms, an aliphatic dicarboxylic acid with 4-10 carbon atoms or a monocarboxylic acid with at least 4 carbon atoms . 25. The method according to claim A process as claimed in claim 17, characterized in that an alkyl ether of highly methylated melamine having alkyl residues of 1-4 carbon atoms is used as the pre-condensate of the aminoplast. 26. The method according to claim A process according to claim 17, characterized in that the aliphatic diol is a diol having 2 to 6 carbon atoms and having a carbon chain optionally separated by oxygen atoms. 27. The method according to claim 17. The process according to claim 17, characterized in that an organic compound is used as the difunctional organic compound which contains functional groups bound to the alkyl moiety, such as halogen atoms, vinyl groups or ester groups of carboxylic acids, or at most one epoxy, carboxyl or hydroxyl group, together with a different functional group or with a different functional atom. 28. The method according to claim 17. The process as claimed in claim 17, wherein the water-soluble organic base is an aliphatic tertiary amine or an amine containing at least two amino groups and an exclusively basic nitrogen atom in which at least each amino group contains one hydrogen atom bonded to the atom. nitrogen. 29. The method according to claim The binder according to claim 16, characterized in that the binder is the reaction product of an epoxy compound, a fatty amine and a polyamide and a mono- or difunctional organic compound, different in structure from an epoxy compound, a fatty amine, a polymerically unsaturated fatty acid and a polyalkylene oxide. polyamines. 88 986 nu H2C-CH LVC ^^ C ^^ - O-CHjCHOH-CH ^ O- ^ C - ^) - CH, -0CH2 HC-CH, Bltk 826/77 r. 115 copies A4 Price PLN 10