EP0011130A1 - Aliphatic aminoether compounds, process for their preparation and their use as fabric softeners - Google Patents

Abstract

Quaternary ammonium compounds of the formula I <IMAGE> and amino ethers of the formula II <IMAGE> are produced. The quaternary ammonium compounds of the formula I are suitable as fabric softeners for laundry care in laundry aftertreatment agents and for finishing textile fibers by impregnation in aqueous or aqueous / alcoholic liquors, for example in the padding process or in the exhaust process. They can be used together with other active ingredients, for example fatty acid polyamine amides and / or fatty alcohol polyglycol ethers. The treated softened textiles also have good absorbency.

Description

The invention relates to new quaternary ammonium compounds and new tertiary amines, each with two or three long-chain hydroxyalkyloxyalkyl radicals, processes for the preparation of the amines and the quaternary ammonium compounds from the amines as intermediates and the use of the quaternary ammonium compounds as textile softening agents for the treatment of textiles.

In the course of the manufacturing process of textiles and through the washing process, most textiles become embrittled to a certain degree. In order to remedy this disadvantage, finishing agents are applied which give the textiles softness and suppleness or redefine the character of the goods from a fashion point of view. In addition, technical requirements such as antistatic, crease recovery, yellowing, surface smoothness, etc. play a role.

It has long been known that quaternary tetraalkylammonium compounds with two long-chain, generally C ₁₆ -C ₁₈ -alkyl radicals are suitable as finishing agents. These textile softeners are used to a large extent on the one hand in textile production and on the other hand in textile care for both commercial laundries and household laundry. It is believed that these cationic quaternary ammonium compounds easily attract onto the textile substrate because of their positive charge.

The most commonly used fabric softener in this class of compounds is ditallow alkyl or distearyl dimethyl ammonium chloride. Although this textile softener has excellent softening properties as well as productivity, substantivity and applicability under all customary conditions, both in textile finishing and in textile care, they also have disadvantages. For example, at the drying and / or condensation or heat setting temperatures frequently used in the textile industry, the usual cationic softeners turn yellow, a property that cannot be accepted with white goods or pastel-colored articles. Another disadvantage of cationic finishing agents is the fact that the textiles finished with them acquire a hydrophobic character. In particular with cellulose fibers, which are precisely because of their excellent absorbency in hygiene articles, e.g. If cotton, diapers, bandages, tampons or for terry and tricot goods are used, this water-repellent property is not desirable.

In the finishing of synthetic fibers, in addition to the softening properties of the finishing agents, their antistatic effect also comes to the fore. Here, too, the state-of-the-art additives only have a medium effect. Those in textile care with these; Textiles treated with substances have a contrast; the untreated fabrics have reduced absorbency, which can be perceived as uncomfortable by the consumer - especially when the fabric softener is overdosed - for example in clothing that is worn in contact with the skin and in terry towels. Such textile softeners can often not be removed completely from the fabric during washing, so that - even with the correct dosage - the softening active substances sometimes accumulate, which likewise results in a reduced suction effect of the textiles.

Other serious disadvantages of these textile softeners are their relatively high production costs, since expensive secondary fatty amines must be assumed, which are obtained predominantly from native fatty acids or fatty alcohols of frequently fluctuating quality.

There has been no shortage of attempts to overcome these disadvantages. It is known from US Pat. No. 3,636,114 that the use of quaternary ammonium compounds with 2 long-chain 2-hydroxyalkyl radicals can improve the absorbency. Quaternary ammonium compounds with 2 long-chain 2-hydroxy-3-alkoxypropyl groups are known from DE-OS 22 56 234. The plasticizers known from DE-AS 16 19 043 contain quaternary ammonium compounds with only one long alkyl radical and three short alkyl radicals, it being possible for the 3 short alkyl radicals to contain hydroxyl and ether groups. Quaternary ammonium compounds are described in Dutch patent application 68/08958 and US Pat. No. 3,591,405, the hydrophobic radicals of which represent hydroxyalkyl groups or alkyl groups linked to the nitrogen via ethoxy groups. However, these attempts to solve the problem were not convincing because either the modified quaternary ammonium compounds were poorly accessible and therefore; here for a practical application or because the softening effect was too low.

The present invention was therefore based on the object to provide new quaternary ammonium compounds which can be obtained in a simple manner from readily available cheap raw materials, the textiles treated therewith in a finishing process or in laundry care with good softening effect, maintain the absorbency and remain without residue in the process Have the laundry of the textiles removed.

Another task was to provide new tertiary amines as precursors from which the quaternary ammonium compounds can be produced by quaternization.

in der R¹ eine aliphatische Kohlenwasserstoffgruppe mit 1 bis 21 Kohlenstoffatomen und R²H oder R¹ bedeuten, wobei die Summe der Kohlenstoffatome von R¹ und R² 6 bis 22 beträgt und im Falle R²= H die Gruppe R¹ 6 - 21 Kohlenstoffatome besitzt, R³ eine Alkylgruppe oder Hydroxyalkyl gruppe mit 1 bis 4 Kohlenstoffatomen oder einen Rest der Formel

The invention therefore relates to new quaternary ammonium compounds of the formula I.

in which R ^{1 is} an aliphatic hydrocarbon group having 1 to 21 carbon atoms and R ^{2 is} H or R ¹ , the sum of the carbon atoms of R ¹ and R ^{2 being} 6 to 22 and in the case of R ² = H the group R ¹ 6-21 Has carbon atoms, R ^{3 is} an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms or a radical of the formula

means R ^{4 is} an alkyl group having 1 to 4 carbon atoms, X and Y are hydrogen or the methyl group, but X and Y in the same ethoxy group are not both methyl, m, n and p are integers between 1 and 20 and A⊖ is An anion is present, is easily accessible from a preparative point of view and at the same time has excellent laundry finishing properties. A⊖ means an anion split off from the quaternizing agent, e.g. B. a chloride or methyl sulfate anion. However, the anion can also be another anion common in quaternary ammonium compounds, e.g. B. be the bromide or ethyl sulfate anion. The compounds of the formula I can be prepared in a simple manner from inexpensive starting materials in high yield via the tertiary amine of the formula II, in which R ¹ , R ² , R ³ , X, Y, m and n have the abovementioned meaning. The invention therefore also relates to the provision of the compounds of the formula II as valuable intermediates. The invention therefore furthermore relates to a process for the preparation of the new quaternary ammonium compounds and the new tertiary amines of the formula II on which they are based

Compounds of the formula I with 2 or 3 long radicals in which R is an alkyl group preferably having 8 to 18 carbon atoms and R ^{2 is} the hydrogen atom are particularly good to use as textile softeners with regard to the balance of their application properties. Depending on the desired hydrophilicity, the compounds can contain 1-20 ethoxy or propoxy groups in each long residue, products whose long residues containing the 1-3 ethoxy groups, in particular 1 ethoxy group, being preferred.

• Bis(5-hydroxy3-oxa-pentadecyl)-dimethyl-ammoniummethyl- sulfat,
• Bis(5-hydroxy-3-oxa-heptadecyl)-dimethyl-ammoniummethyl- sulfat,
• Bis(5-hydroxy-3-oxa-C_15/17-alkyl)-dimethyl-ammoniummethyl- sulfat,
• Bis(5-hydroxy-3-oxa-C_19/21-alkyl)-dimethyl-ammoniummethyl- sulfat,
• Bis(5-hydroxy-3-oxa-C_15/17-alkyl)-methyl-(2-hydroxyethyl- ammoniummethylsulfat,
• Bis(5-hydroxy-3-oxa-undecyl)-dimethyl-ammoniumchlorid,
• Bis(5-hydroxy-3-oxa-4-hexyl-tridecyl)-2-hydroxyethyl- methyl-ammoniumchlorid,
• Bis(5-hydroxy-3-oxa-4-octyl-nonadecyl)-dimethyl-ammoniumchlorid,
• Bis(5-hydroxy-3-oxa-2-methyl-heptadecyl)-dimethyl-ammoniumchlorid,
• Bis(n-hydroxy-3,6,9-trioxa-tricosyl)-dimethyl-ammoniumchlorid,
• Tris(5-hydroxy-3-oxa-pentadecyl)-methyl-ammoniumchlorid,
• Tris(5-hydroxy-3-oxa-pentadecyl)-methyl-ammoniummethyl- sulfat,
• Tris(5-hydroxy-3-oxa-C_15/17-alkyl)-methyl-ammoniumchlorid,
• Tris(5-hydroxy-3-oxa-heptadecyl)-methyl-ammoniunmethyl- sulfat,
• ris(5-hydroxy-3-oxa-C_19/21-alkyl)-methyl-ammoniumchlorid,
• Tris(5-hydroxy-3-oxa-undecyl)-methyl-ammoniumchlorid,
• Tris(5-hydroxy-3-oxa-undecyl)-2-hydroxyethyl-ammoniumchlorid,
• Tris(5-hydroxy-3-oxa-4-octyl-heptadecyl)-ethyl-ammoniumchlorid,
• Tris(5-hydroxy-3-oxa-4-pentadecyl-hexyl)-methyl-ammonium- methylsulfat,
• Tris(5-hydroxy-3-oxa-2-methyl-nonadecyl)-methyl-ammoniumchlorid,
• Tris(14-hydroxy-tetrapropoxy-pentacosyl)-methyl-ammonium- methylsulfat.

Typical compounds of formula I are e.g. B.

• Bis (5-hydroxy3-oxapentadecyl) dimethyl ammonium methyl sulfate,
• Bis (5-hydroxy-3-oxa-heptadecyl) dimethyl ammonium methyl sulfate,
• Bis (5-hydroxy-3-oxa-C _15/17 alkyl) dimethyl ammonium methyl sulfate,
• Bis (5-hydroxy-3-oxa-C _19/21 alkyl) dimethyl ammonium methyl sulfate,
• Bis (5-hydroxy-3-oxa-C _15/17 alkyl) methyl (2-hydroxyethyl ammonium methyl sulfate,
• Bis (5-hydroxy-3-oxa-undecyl) dimethyl ammonium chloride,
• Bis (5-hydroxy-3-oxa-4-hexyl-tridecyl) -2-hydroxyethyl-methyl-ammonium chloride,
• Bis (5-hydroxy-3-oxa-4-octyl-nonadecyl) dimethyl ammonium chloride,
• Bis (5-hydroxy-3-oxa-2-methyl-heptadecyl) dimethyl ammonium chloride,
• Bis (n-hydroxy-3,6,9-trioxa-tricosyl) dimethyl ammonium chloride,
• Tris (5-hydroxy-3-oxapentadecyl) methyl ammonium chloride,
• Tris (5-hydroxy-3-oxapentadecyl) methyl ammonium methyl sulfate,
• Tris (5-hydroxy-3-oxa-C _15/17 alkyl) methyl ammonium chloride,
• Tris (5-hydroxy-3-oxa-heptadecyl) methyl ammonium methyl sulfate,
• ris (5-hydroxy-3-oxa-C _19/21 alkyl) methyl ammonium chloride,
• Tris (5-hydroxy-3-oxa-undecyl) methyl ammonium chloride,
• Tris (5-hydroxy-3-oxa-undecyl) -2-hydroxyethyl-ammonium chloride,
• Tris (5-hydroxy-3-oxa-4-octyl-heptadecyl) ethyl ammonium chloride,
• Tris (5-hydroxy-3-oxa-4-pentadecylhexyl) methyl ammonium methyl sulfate,
• Tris (5-hydroxy-3-oxa-2-methyl-nonadecyl) methyl ammonium chloride,
• Tris (14-hydroxy-tetrapropoxy-pentacosyl) methyl ammonium methyl sulfate.

in der R und R² die zuvor genannten Bedeutungen haben mit einem Polyalkanolamin der Formel IV

in der R⁵ eine Alkylgruppe mit Kohlenstoffatomen oder einen Rest der Formel H(-OCHX-CH_Y)-_p bedeutet, wobei X, Y, m, n und p die zuvor genannten Bedeutungen haben, in Gegenwart eines Katalysators unter Normaldruck und erhöhter Temperatur zu dem tertiären Amin der Formel II umsetzt und anschließend mit einem die in Formel I des Anspruchs 1 definierte Gruppe R⁴ einführenden Alkylierungsmittel quaterniert.The process for the preparation of quaternary ammonium compounds of the formula I via the tertiary amines of the formula II is a further subject of the invention; it is characterized in that an epoxyalkane of the formula II

in which R and R ^{2 have} the meanings given above with a polyalkanolamine of the formula IV

in which R ⁵ denotes an alkyl group with carbon atoms or a radical of the formula H (-OCHX-CH _Y ) - _p , where X, Y, m, n and p have the meanings given above, in the presence of a catalyst under normal pressure and elevated temperature converted to the tertiary amine of formula II and then quaternized with an alkylating agent introducing the group R ⁴ defined in formula I of claim 1.

The epoxyalkanes and alkanolamines to be used as starting materials are cheap and available in large quantities. The epoxyalkanes are obtained in a known manner from the corresponding olefins or olefin mixtures. The 1,2-epoxyalkanes are obtained via 1,2-monoolefins which for example by polymerizing ethylene with organic aluminum compounds as catalysts or by thermal cracking of paraffin hydrocarbons. Examples of preferred epoxyalkanes are the compounds 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane and epoxy mixtures such as B. C _12/14 -1,2-epoxy with approx. 70 wt.%, C ₁₂ - and approx. 30 wt.% C ₁₄ -epoxyalkane or C _16/18 -1,2-epoxy with approx. 40% by weight of C ₁₆ and approx. 60% by weight of C ₁₈ epoxyalkane.

The internal epoxyalkanes are obtained, for example, by epoxidizing olefins or olefin mixtures which are prepared by catalytic dehydrogenation or by chlorination / dehydrogenation of linear paraffin hydrocarbons. Monoolefins with an internal double bond can also be prepared by isomerization of α-olefins. Internal epoxyalkanes of a C _11/14 olefin fraction which were preferably used contained approx. 22% by weight of C ₁₁ -, approx. 30% by weight of C ₁₂ -, approx. 26% by weight of C ₁₃ -, approx. 22% by weight. % C ₁₄ epoxyalkane. An epoxyalkane mixture of a C _15/18 olefin fraction likewise preferably used contained approx. 26% by weight of C ₁₅ ; approx. 35% by weight of C ₁₆ -, ica. 32% by weight of C ₁₇ and approx. 7% by weight of C ₁₈ epoxyalkane.

Di- or trialkanolamines used with preference are, for example, N-methyl-diethanolamine or triethanolamine. By using alkoxylated alkanolamines, the; The hydrophilicity of the end products can be varied within certain limits and adapted to the desired application.

Sodium alcoholate, in particular sodium methylate, has proven itself as a catalyst for the reaction of epoxyalkanes of the formula III with polyalkanolamines of the formula IV. The catalyst is preferably used in amounts of 0.1-1.0; % By weight, based on the total reaction mixture.

The reaction of the epoxyalkane with the alkanolamine proceeds without significant formation of by-products in high yield. The reaction to give compounds of the formula I is expediently carried out using a ratio of epoxyalkane to alkanolamine such that an alkanol equivalent is used per mol of epoxyalkane, ie one mol of epoxyalkane is reacted with 1/2 mol of dialkanolamine or 1/3 mol of trialkanolamine . If there is an excess of alkanolamine or if the reaction is incomplete as a result of the shortened reaction time, mixtures of compounds with _R ³ in formula I = alkyl on the one hand and hydroxyalkyl on the other hand are obtained. After their quaternization, these technical mixtures likewise have the desired textile softening properties while maintaining the absorbency of the softened textiles; Any unreacted starting products are expediently distilled off from the reaction product at low pressure and low temperature. This prevents the reaction products from becoming dark.

Suitable alkylating agents are e.g. B. methyl chloride, methyl bromide, dimethyl sulfate, diethyl sulfate, but especially methyl chloride and dimethyl sulfate. When carrying out the quaternization using methyl chloride as the alkylating agent, the reaction is expediently carried out under a pressure of up to 10 bar, preferably 3-6 bar and a temperature between preferably 80-120 ° C., optionally in the presence of solvents such as isopropyl alcohol and / or water. The quaternization with dimethyl sulfate as the alkylating agent can be carried out at normal pressure and temperatures between 50 and 100 ° C., preferably 60-80 ° C.

Quaternization is also possible by reacting the amines with a lower epoxy and then acid treatment to introduce the anion.

The new products can be easily dispersed in water and in mixtures of water and lower alcohols to form stable dispersions; textiles treated in a textile finishing process or in laundry care have a soft, fluffy feel with good absorbency and good wettability.

The compounds of the formula I can be used as textile plasticizers and, if appropriate, mixed without problems together with other textile plasticizers, antimicrobials, optical brighteners, nonionic and cationic surfactants and, if appropriate, other conventional constituents of finishing agents, and can be made up into, in particular, liquid preparations. The use of the new quaternary ammonium compounds as textile softeners in, in particular, liquid detergents for post-treatment in the rinsing bath of the washing process in hand or machine wash and in a tumble dryer, the detergents 1-40% by weight of the compounds of the formula I and at least one diluent and optionally contain other customary additives for liquid laundry aftertreatment agents is therefore a further subject of the invention.

The use of the fabric softening agents according to the invention in laundries and households for the aftertreatment of washed laundry can take place in various ways, depending on the choice of the drying method. If drying is carried out in a tumble dryer, the laundry can be sprayed directly with an active ingredient dispersion or the active ingredient can be brought into contact with the laundry via a carrier, for example by spraying the liquid agent on the inner walls of the drying device before loading the device with laundry, or by Loading a carrier with a large surface soaked in the liquid agent, the fabric softener being drawn onto the laundry during the drying process. Currently however, the laundry is mostly dried hanging; the use of the softening agent in the last rinsing bath of the washing process for hand washing and especially for machine washing therefore also predominates. Amounts of the agent according to the invention are dissolved in the washing liquor such that the concentration of the active ingredient of the formula I is 0.05-1.5 g / l, preferably 0.1-1.0 g / l.

Suitable diluents for liquid textile treatment agents are water and / or water-soluble organic solvents. Usable water-soluble organic solvents are the lower alcohols with 1-5 carbon atoms, such as. B. methanol, ethanol, propanol, isopropyl alcohol, n-butanol, isobutanol, amyl alcohol, further the lower ketones acetone and methyl ethyl ketone and ethylene glycol, propylene glycol, diethylene glycol and their mono- or diether derivatives with in particular methyl and ethyl radicals.

The active ingredients of the formula I are also suitable for the preparation of pourable textile aftertreatment agents in powder form. Suitable diluents for such powdery compositions are, for example, urea, acetamide, sodium sulfate and any other conventional constituents which may be present, provided these are in solid form.

Other common constituents of textile treatment agents include, for example, dispersants, optical brighteners, antimicrobial agents, acidic additives, solubilizers, colors and fragrances.

The connections of the. Formula I can also be used together with known textile plasticizers of the quaternary ammonium compound type, such as. B. Ditalgalkyldimethylammoniumchlorid, or with known textile plasticizers with amide structure from Type of the fatty acid condensation products can be combined with hydroxyalkyl polyamines, for example the concentration product of 1 mol of tallow and 1 mol of 2-hydroxyethylethylenediamine. The addition of known antimicrobial agents of the type of antimicrobial quaternary ammonim compounds, such as, for example, which are suitable for confectioning in textile treatment agents. B. benzyldodecyldimethylammonium chloride, and antimicrobial nitro alcohols or phenol derivatives or carbamates, etc. is possible.

The composition of practically particularly interesting liquid laundry aftertreatment agents in which the new active compounds of the formula I can be used is generally in the range of the following recipe:

At least one of the following components can be present in the specified amounts, based on the total detergent, as other customary constituents of post-washing agents:

In the text which follows, the constituents still present in the textile treatment compositions in addition to the active ingredient of the formula I are described in more detail according to substance classes.

As dispersants, such as those in liquid and powder form; Textile treatment agents can be included, the nonionic surfactants ("Nonionics") are particularly suitable. These include products which owe their hydrophilic properties to the presence of polyether chains, amine oxide, sulfoxide or phosphine oxide groups, alkylolamide groups and, quite generally, an accumulation of hydroxyl groups. Such nonionics contain at least one hydrophobic radical of 8 to 26, preferably 10 to 20 and in particular 12 to 18 carbon atoms in the molecule, and at least one nonionic water-solubilizing group. The preferably saturated hydrophobic radical is usually aliphatic, optionally also alicyclic in nature; it can be connected to the water-solubilizing groups directly or via intermediate links. Coming as links. e.g. B. benzene rings, carboxylic acid ester or carbonamide groups, ether or ester-linked residues of polyhydric alcohols, such as. B. that of ethylene glycol, propylene glycol, glycerol or corresponding polyether residues in question.

Of particular practical interest are the products obtainable by addition of ethylene oxide and / or glycide onto fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid or sulfonic acid amides, these nonionics being 4 to 100, preferably 6 to 40 and in particular 8 to 20 ether residues , especially ethylene glycol ether residues per molecule. In addition, propylene or butylene glycol ether residues or polyether chains can be present in these polyether chains or at their ends.

Nonionics also includes products that are obtained from water-insoluble polypropylene glycols or from water-insoluble propoxylated lower aliphatic alcohols containing 1 to 8, preferably 3 to 6 carbon atoms, or from water-insoluble propoxylated alkenediamines by ethoxylating them to water solubility.

Nonionics also include fatty acid or sulfonic acid alkylolamines, which are derived, for example, from mono- or diethanolamine, from dihydroxypropylamine or other polyhydroxyalkylamines, for example from glycamines. They can be replaced by amides from higher primary or secondary alkylamines and polyhydroxycarboxylic acids.

The capillary-active amine oxides include, for example, the products derived from higher tertiary amines, a hydrophobic alkyl radical and two shorter alkyl and / or alkylol radicals containing up to 4 carbon atoms.

In addition to the mostly water-soluble surfactants, suitable nonionic dispersants may also be water-soluble or water-emulsifiable or dispersible compounds which either do not contain any hydrophobic radicals in the sense of the nonionic surfactants described above, or in which the nature or the number of hydrophilic groups is sufficient to achieve one complete water solubility is not sufficient. The former include e.g. As solid or liquid polyethylene glycols, may be regarded as the one _K ondensa- .tionspolymere of ethylene oxide with ethylene glycol or water, etc., ethylene oxide adducts of glycerol and other polyalcohols .; to the latter z. B. fatty acid partial glycerides or not or not completely water-soluble alkoxylation products, for. B. those with 2-5 ethylene glycol ether residues in the molecule.

Acidic additives include inorganic and non-interfacial organic acids with 2 - 8 carbon atoms, such as. B. amidosulfonic acid, urea compounds of orthophosphoric acid, boric acid, oxalic acid, lactic acid, glycolic acid, citric acid, tartaric acid, benzoic acid, phthalic acid, gluconic acid, acetic acid and propionic acid as well as the benzene, toluene or xylene sulfonic acids, sulfoacetic acid or sulfobenzoic acids or these acids Roger that. Glycolic acid and citric acid are preferred acids because of their easy access and non-toxicity.

Antimicrobial active substances are to be understood here as bactericidal or bacteriostatic or fungicidal or fungistatic compounds. These active ingredients are said to be water-soluble either as such or in the form of their salts. The antimicrobial quaternary ammonium compounds which are suitable as additives are, in particular, those which, in addition to a long-chain aliphatic and two short-chain aliphatic hydrocarbon radicals, contain an aromatic organic radical linked to the nitrogen atom via an aliphatic carbon atom or an aliphatic organic radical having double bonds. Examples of such antimicrobial quaternary ammonium compounds are the following; gend: dimethyl-benzyl-dodecylammonium chloride, dimethyl-benzyl-tetradecylammonium chloride, dimethyl- (ethylbenzyl) -dodecyl-ammonium chloride, dimethyl-benzyl-decylammonium bromide, diethyl-benzyl-dodecylammonium chloride, diethyl-benzyl-octyl-ammonyl chloride, , Methylethyl-benzyl, ethyl-cyclo-hexyl-allyl and ethyl-crotyldiethylaminoethyl-dodecyl-ammonium chloride.

Other suitable antimicrobial agents are both bromine and by the nitro group sub- s _t ituierten lower alcohols or diols having 3-5 carbon atoms such. B. the compounds 2-bromo-2-nitropropane-1,3-diol, 1-bromo-1-nitro-3,3,3-trichloro-2-propanol, 2-bromo-2-nitro-butanol.

Also suitable as antimicrobial active substances are phenolic compounds of the halogenated phenol type with 1-5 halogen substituents, in particular chlorinated phenols; Alkyl, cycloalkyl, aralkyl and phenylphenols with 1-12 carbon atoms in the alkyl radicals and with 1-4 halogen substituents, in particular chlorine and bromine in the molecule; Alkyl bisphenols, in particular derivatives substituted by 2-6 halogen atoms and optionally lower alkyl or trifluoromethyl groups, with an alkylene bridge member consisting of 1-10 carbon atoms; Hydroxybenzoic acids or their esters and amides, especially anilides; which can be substituted in the benzoic acid and / or aniline residue in particular by 2 or 3 halogen atoms and / or trifluoromethyl groups; o-phenoxyphenols, which can be substituted by 1-7, preferably 2-5, halogen atoms and / or the hydroxyl, cyano, carbomethoxy and carboxyl group or lower alkyl; a particularly preferred derivative of o-phenoxyphenol is 2-hydroxy-2 ', 4,4'-trichlorodiphenyl ether,

Antimicrobial agents in the broader sense also include additives such as. B. understood formaldehyde, sorbic acid, sodium fluoride, which serve to preserve the preparations.

Another object of the invention is a process for the use of compounds of formula I for finishing textile material during the finishing process by impregnation by means of aqueous or aqueous / alcoholic liquors of agents containing compounds of formula I, optionally in combination with others, usually with the softeners, wetting agents, dispersants and other auxiliaries used in textile finishing.

The finishing of the textile materials during the finishing process is expediently carried out by spraying on, padding, patting or after the pull-out process. The treatment is usually carried out at temperatures between 10 and 50 ° C, but can also be carried out directly in the dye bath if the dyes used are cationic in nature. Woven fabrics, knitted fabrics or nonwovens, fibers, yarns, combs of natural or regenerated cellulose fibers, wool, polyamide, polyester or polyacrylonitrile fibers, and mixtures of such fibers with one another are suitable as textile material.

The amount to be used according to the method according to the invention depends on the form of application and should be between 2 and 10 g / l dry matter content in the padding method, the squeezing effects advantageously being between 50 and 100%. In the exhaust process, 0.1-0.6% by weight, based on the weight of the goods, is added in the form of an aqueous preparation. The duration of treatment is between 10 and 30 minutes. The pH of the equipment fleet should advantageously be 3 to 7.5. The pH can be adjusted by adding inorganic or preferably lower organic carboxylic acids such as formic or acetic acid.

In addition to a soft, supple feel, the treated textile materials show excellent hydrophilicity, which almost reaches the values of non-activated materials with cellulose fiber materials. Excellent antistatic effects are achieved with synthetic fiber materials. In contrast to known cationic softening agents, no signs of yellowing occur even after the application of higher temperatures during the further processing of the finished textile materials.

Ein zusätzlicher Gehalt an Parfümier- und Konservierungsmitteln kann zweckmäßig sein.The softening agents of formula I can be used in the softening of textile materials during the finishing process together with other cationic and / or nonionic softening agents commonly used to soften the textile. The following are particularly suitable: fatty acid polyaminamides from 1 mol of a C ₈ -C ₂₂ fatty acid and 1 mol of a polyalkylene polyamine or hydroxypolyalkylene polyamine, for example diethylenetriamine, tetraethylene pentamine or aminoethylethanolamine, and C ₈ -C ₂₂ fatty alcohol polyglycol ether, for example the adducts of 2-20 mol Ethylene oxide in 1 mole of C ₁₂ -C ₁₈ fatty alcohol. This provides a further possibility for controlling the hydrophilic, grip-influencing and softening properties, although consideration must be given to a certain tendency to yellowing of the fatty acid polyaminamides. Such combinations consist of, for example

An additional content of perfume and preservatives can be appropriate.

Both the claimed preparations, which contain only compounds of the formula I, and the combination products mentioned are preferably pre-aqueous or aqueous / alcoholic concentrates with 5 to 30% by weight. preferably 10 to 25 wt .-% solids content produced and placed on the market. Suitable additional solvents are lower alcohols or glycols with 2-6 C atoms, such as ethanol, isopropanol or ethyl glycol monobutyl ether. However, the products can also be manufactured and used in water and solvent-free form.

Example: 1 e

The description of the preparation of the new compounds follows first.

example 1

Preparation of tris (5-hydroxy-3-oxa-C _15/17 alkyl) methyl ammonium chloride:

To 298.4 g (2 mol) of triethanolamine and 6 g of 30% by weight methanolic sodium methylate solution, 1194 g (6 mol) of 1,2-epoxyalkane with approx. 70 were added at 180 ° C. under a nitrogen atmosphere and with stirring within 30 minutes % By weight of C ₁₂ and about 30% by weight of C ₁₄ epoxyalkane were added and the mixture was stirred for 1 h. 80 g of feed were then distilled off at 0.8 mbar and a bottom temperature of 240 °. 1407 g of tris (5-hydroxy-3-oxa-C _15/17 alkyl) amine with an amine number of 84.4 remained in the distillation flask as a residue. From this product, 664.7 g (1 mole) along with 95.4 g of water and 143 g of isopropyl alcohol were drawn into an evacuated 2-1 autoclave. At 100 ° C 5 bar methyl chloride were pressed. After 4 1/4 hours, the quaternization was almost completely completed (quaternary fraction 93.5% by weight, amine number of a sample 2.3). After cooling to room temperature and pressure equalization, a 75% by weight solution of tris (5-hydroxy-3-oxa-C _15/17 alkyl) methylammonium chloride was obtained.

Example 2 Preparation of bis (5-hydroxy-3-oxa-C _19/21 alkyl) dimethylammonium methyl sulfate

At room temperature, 276.8 g (1 mol) of 1,2-epoxyalkane with a proportion of approx. 40% by weight of C ₁₆ and approx. 60% by weight of C ₁₈ epoxyalkane was added to 59.5 g (0 , 5 mol) N-methyl-diethanolamine and added 1.5 g of 30 wt .-% methanolic Sodium methylate solution added. With stirring and nitrogen blanket, the reaction took place within 7 hours after heating to 180 ° C.

Subsequently, 25.6 g of feed were distilled off at a pressure of 0.4 mbar and a bottom temperature of 240 ° C. 314 g (0.5 mol) of the reaction product bis (5-hydroxy-3-oxa-C _19/21 alkyl) methylamine with an amine number of 92.6 g remained as a residue in the distillation flask. Without further purification, 63.1 g (0.5 mol) of dimethyl sulfate were added dropwise to this reaction product for quaternization at 70 ° C. while stirring and the mixture was subsequently stirred at 70 ° C. for 2 h. The quaternized product was mixed with 75.4 g of isopropyl alcohol and 50.3 g of water. The resulting 75% by weight solution was used for tests.

Before the quaternization in the IR spectrum, the reaction product of Example 1 no longer had any epoxy band at 831 cm ^-1 ; this showed that the epoxyalkane had been completely converted. Instead, the ether band appeared at 1120 cm ^-1 .

The maxima characteristic of the structure in the NMR spectrum were δ = 4.3; 3.6; 2.7 and 0.9 ppm. The integration ratio was 1: 5: 2: 3. When heavy water was added, the maximum disappeared at δ = 4.3 ppm. 'This maximum could thus be assigned to the hydroxyl group. The maxima at 1.3 and 0.9 ppm can be assigned to the methylene or methyl group of the long alkyl ester.

The maximum at δ = 3.6 ppm is to be assigned to the hydrogen atoms which are bonded to the carbon atoms adjacent to the oxygen atom. The maximum at δ = 2.7 ppm is to be assigned to the hydrogen atoms which are bonded to the carbon atoms adjacent to the nitrogen atom. Of course, the signal of the hydrogen atoms of the methylene groups of the long alkyl radical appears as the most intense maximum at 1.3 ppm.

Theoretically, the not yet quaternized reaction product from Example 1 should have maxima in the NMR spectrum at δ = 4-5 ppm and at δ = 3.4; 2.7 and 0.9 ppm, the integration ratio being 1: 5: 2: 3. The position of the maximas of the measured NMR spectrum and the integration ratio agree very well with the theoretical values for this compound.

As expected, the NMR spectrum of the reaction product from Example 2 shows, before the quaternization, in addition to the other maxima that are also present in the spectrum of the product from Example 1, a maximum at δ = 2.3 ppm, which for the N-CH ₃ - Group is characteristic. The measured integration ratio 2: 10: 4: 3: 6 also agrees with the theoretical integration ratio for this connection.

Example 3

This example describes the use of a compound of the formula I according to the invention in the finishing of washed laundry items. The product from Example 1 was tested for its softening effect and for the wetting behavior of fabrics treated with this product. The wetting behavior provides a statement about the absorbency of textiles, which plays an important role especially in terry towels and clothing that is worn in contact with the skin.

The softening effect was tested by washing hardened cotton or polyacrylonitrile fabric in an aqueous liquor (liquor ratio 1:20) containing 0.5% by weight (based on the fabric) of active substance for 3 minutes by repeated washing Room temperature was weak, then the fabrics were largely freed of adhering treatment liquor in a spin dryer and air dried. The softness of the dried tissue was haptically assessed by a group of people who had experience in this type of test.

The wettability was tested on 2 x 2 cm cotton fabrics treated as previously described by placing the samples on a water surface and measuring the time after which the sample begins to sink.

For comparison, a cationic commercially available textile softener of the type ditallow alkyldimethylammonium chloride was used as active ingredients.

Result:

Cotton and polyacrylonitrile textiles which had been treated with the product from Example 1 and the comparative product were all judged to be soft by the test subjects; only slight gradual differences were found.

• 

The following values were measured for wettability (Table 1):

• 

These values show that the wettability of the fabrics treated with the compounds according to the invention is extremely good.

Further recipe examples follow.

Example 4

Example 5

Example 6

Examples 9-16

Fully assembled laundry aftertreatment agents of the following composition (data in% by weight) were produced with the product from Example 1:

The items of laundry treated with these formulations had good grip and good absorbency.

The following examples 17-21 describe the use of a compound of the formula I according to the invention as a finishing agent in the finishing of textiles. They show that when used according to the invention, soft, smooth textiles with improved hydrophilicity and antistatic properties and a reduced tendency to yellowing are obtained,

Example 17

A Molton fabric made of pure cotton is padded in the usual way with a liquor containing 20 g / l of a 20% strength aqueous preparation of the compound prepared according to Example 1 with a liquor absorption of 80% and then dried at 110 ° C. for 3 minutes. The fabric has a full, soft feel. The following values were obtained when determining the suction speed against water according to the climbing height method (DIN 53 924) in the warp and weft directions:

The climbing height method checks the speed at which textile fabrics absorb water. The values specified under warp and weft are in _; mm climbing height.

In contrast, a fabric finished for comparison with the same amount of active substance _D i -stearyldimethylammonium chloride by the same method shows the following values:

The fabric accordingly has no hydrophilic properties, while the handle roughly corresponds to the fabric equipped according to the invention.

Example 18

A fabric made of cotton / polyester (65/35) is made in the usual way with a liquor containing 0.6% of the weight of a preparation made from equal parts of the compound prepared according to Example 1 and a fatty acid polyminamide from 1 mol of C ₁₄ -C ₁₈ fatty acid and 1 mol of diethylenetriamine, treated at 40 ° C. in a liquor ratio of 1:20 for 20 minutes and then dried at 110 ° C. The result is a material with a soft, full grip. The hydrophilicity of the goods according to the rising height method according to DIN 53 924 gave the values:

i In contrast, a strand equipped for comparison with the same amount of active substance of the fatty acid polyamine amide gave the values in spite of approximately the same handle:

Example 19

Viscose fibers are made in the usual way with a liquor containing 0 ₄ 5% of the weight of a preparation of 8 parts of the compound prepared according to Example 1, 10 parts of the fatty acid polyamine amide mentioned in Example 4 and 8 parts of a fatty alcohol polyglycol ether from 9 moles of a C ₁₄ - C ₁₈ fatty alcohol and 5 moles of ethylene oxide, treated at 45 ° C in a liquor ratio 1:10 at 20 ° C and then dried. A product is obtained which has a pleasant, soft to voluminous feel and which can be excellently spun after adding the usual melts. If water is applied to a fleece formed from these fibers with the help of a pipette, spontaneous spreading and wetting takes place.

On the other hand, water droplets remain on a product equipped with the same amount of distearyldimethylammonium chloride as active substance for longer than 30 minutes.

Example 20

A fabric made of diol loft is padded in the usual way with a liquor containing 3 g / l of a preparation of 14 parts of the compound prepared according to Example 2 and 6 parts of the fatty alcohol polyglycol ether mentioned in Example 5 and then dried at 110 ° C. for 2 minutes . The result is a soft fabric with a surface electrical resistance of 2 x 1 _{0 0} ⁸ ohms and a field decay half-life of 0, as measured under standard conditions.

Is the same fabric by the same method treated with distearyldimethylammonium chloride, results, with the same handle design a woven fabric having a surface electrical resistance of 2.5 x 10 ⁹ ohms, and an _F eldzerfallhalbwertzeit of 1.5 seconds, which electrical during further processing and in use to disruptive Charge would result.

Example 21

A bleached and optically brightened shirt poplin made of polyester / cotton (50/50) is padded in the usual manner with a liquor containing 4 g / l of the compound prepared according to Example 2 and dried at 110 ° C. for 2 minutes. If this fabric is then exposed to a temperature of 120 ° C for two minutes, no yellowing occurs.

Similarly, if a fabric is treated with a condensation product of 1 mole of a C _16-18 fatty acid and 1 mole of a hydroxylpolyethylene polyamine, the fabric exhibits a marked yellowing with the same hydrophilicity.

Claims (7)

1. Quaternary ammonium compounds of the formula I

in which R ^{1 is} an aliphatic hydrocarbon group with 1 to 21 carbon atoms and R ^{2 is} H or R ¹ , the sum of the carbon atoms of R ¹ and R ^{2 being} 6 to 22 and in the case R ² = H the group R ¹ 6 to 21 Has carbon atoms, R ^{3 is} an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms or a radical of the formula

means R ^{4 is} an alkyl group having 1 to 4 carbon atoms, X and Y are hydrogen or the methyl group, but X and Y in the same ethoxy group are not both methyl, m, n and p are integers between 1 and 20 and A⊖ is there is an anion. 2. Compounds of formula II

in which _R ¹ , R ² , R ³ , X, Y, m and n have the meaning given in Claim 1. 3. A process for the preparation of compounds of formula II according to claim 2, characterized in that an epoxyalkane of formula III

in which R ¹ and R ^{2 have} the meaning given in claim 1, with a polyalkanolamine of the formula IV

in which R ^{5 is} an alkyl group having 1-4 carbon atoms or a .rest of the formula H (-OCHX-CHY) -, where X, Y, m, n and p have the meanings given in claim 1, in the presence of a catalyst under Reacts normal pressure and elevated temperature to the tertiary amine of formula II according to claim 2. 4. A process for the preparation of compounds of the formula I according to claim 1, characterized in that a tertiary amine of the formula II according to claim 2 is prepared according to claim 3 and quaternized with an alkylating agent introducing the group R ⁴ defined in formula I of claim 1. 5. Use of compounds of formula I of claim 1 as a fabric softener. 6. Use of the compounds of formula I of claim 1 according to claim 5 in particular liquid agents for the aftertreatment of washed laundry in the rinsing bath of the washing process in the hand or in particular in the machine wash and in the tumble dryer, the agents 1-40% % of the compounds of the formula I and at least one diluent and, if appropriate, other customary constituents of laundry aftertreatment agents. 7. Use of compounds of formula I of claim 1 according to claim 5 for the finishing of textile material during the finishing process by impregnation by means of aqueous or aqueous / alcoholic liquors and subsequent drying.