DE2004721A1 - Softener, rinsing agent - Google Patents

Abstract

A "softener" rinsing agent for use with articles which have already been washed contains, in aq. dispersion opt. together with other customary constituents, bisquaternary NH4 cpds. (where R1 and R2 are pref. satd. 18-24 esp. 12-20C alkyl, R3-R6 are 1-8, pref. 1-3C alkyl, or mono- or dihydroxy alkyl with 2-4C, Y is opt. branched 2-24 pref. 2-20C aljylene X- is anion of a sulphonate o sulphate type tenside, or of a soap).

Description

"Softener" The invention relates to an aqueous dispersion present fabric softener for washed laundry, especially machine-washed laundry Laundry.

After drying, washed textiles, especially those made from Cotton or similar cellulose fibers is a significant hardening of the handle especially when these textiles are washed in drum washing machines have been, in which the textile is washed with strong mechanical agitation will. The undesired hardening of the textile material can be avoided in that a fabric softener, which is usually cationic, is added to the last rinse Contains compounds with at least two longer-chain alkyl radicals in the molecule. There are liquid fabric softeners on the market, which are effective koiaponents dialkyldimethylammonium salts, generally in the form of the halides, contained in an aqueous dispersion.

It is known that such fabric softeners in contact with anionic Surfactant solutions form precipitates that have no finishing properties. Is used in the washing process, as is customary, a detergent containing anionic surfactants used, it can easily be done in practice due to insufficient rinsing, that any anionic surfactants still present with the above-mentioned cationic ammonium compounds unwanted reaction products form in the form of a greasy precipitate fail. Such deposits can settle on the textile fibers and so affect the softness and absorbency of the laundry.

It has now been found that the disadvantages outlined can be avoided if a liquid fabric softener is used which is characterized in that it contains bisquaternary ammonium compounds of the formula I as a softening agent in an aqueous dispersion, optionally together with customary ingredients of fabric softeners contains, in which R1 and R2 preferably saturated alkyl radicals with 8-24, preferably 12-20 carbon atoms, R3-R6 alkyl radicals with 1-8, preferably 1-3 carbon atoms, or mono- or dihydroxyalkyl radicals with 2-4 carbon atoms, Y a straight-chain or branched alkylene radical with 2-24, preferably 2-12 carbon atoms, and X is the anion of a surfactant of the sulfonate or sulfate type, optionally also a soap.

The active ingredients used according to the invention are distinguished by their Insensitivity to anionic surfactants and confer with them treated laundry, especially cotton textiles, a high degree of softness and fluffiness. In addition, the treatment with the inventive Agents in textiles, especially those made from synthetic fibers, are undesirable static charge largely prevented.

The alkyl radicals R1 and R2 of the formula I can be straight-chain or branched be; there are, for example, the octyl, decyl, lauryl, myristyl, palmityl, Stearyl and arachidyl radicals can be considered individually or as a mixture. Particularly preferred Alkyl residues and R2 are those derived from hardened tallow fatty acids. the R3 - R6 radicals are preferably methyl, ethyl or propyl; in particularly preferred All four radicals R3-R6 are the same for compounds of the formula I.

As the anion X, the anionic residues of the surfactants come from the sulfonate or sulfate type, such as alkylbenzenesulfonates, alkanesulfonates, fatty acid sulfonates, Fatty acid ester sulfonates, olefin sulfonates, fatty alcohol sulfates, fatty alkyl diol sulfates, Fatty alcohol polyglycol sulfates and, if appropriate, natural soaps or synthetic fatty acids.

The bisquaternary ammonium compounds used according to the invention of formula I are by reacting bisquaternary ammonium halides with the Alkali salts made of anionic surfactants. These are the aqueous solutions the starting materials mixed, the mixture optionally heated, the reaction product separated from the aqueous phase, optionally washed with water and dried. In practice, the moist reaction product can be used directly to produce the fabric softener be used. The compounds of formula I prepared in this way can contain traces of Contain alkali halides, which however do not interfere with further processing.

The bisquaternary ammonium halides to be implemented as well as their production is known. As alkali salts, especially sodium salts, more anionic Surfactants can be used as anionic washing active substances that are practically customary in detergents surfactants used are used, as described in more detail below 'r earth.

The fabric softeners according to the invention can be composed as follows: 1.0-25.0% by weight bisquaternary ammonium compound of the formula I, 0.0-8.0% by weight ' non-ionic, capillary-active dispersant or emulsifier, 0.0-30.0% by weight water-soluble organic solvent.

In addition to water, the remainder can also contain other common constituents of Fabric softeners such as optical brighteners, antimicrobial agents, Contain acidulants and complexing agents, fragrances and dyes.

The composition of the invention is particularly interesting in practice Fabric softener can be within the following formulation: 1.0-18.0, preferably 2.0-10.0% by weight bisquaternary ammonium compound of the formula I, 0.2-6.0, preferably 0.2-3.0% by weight of nonionic capillary-active dispersant or emulsifier, 0.2 - 30.0, preferably 0.2-10.0% by weight of water-soluble, organic solvent, in particular isopropanol, 0.0-10.0, preferably 0.3-7.5 by weight - other common ones Ingredients of fabric softener, the rest water.

Other common fabric softener ingredients can be used on the total amount of the agent, the following may be included: 0.2-3.0% by weight antimicrobial agent, 0.1-3.0% by weight acidifying and complexing agent, 0.01 - 0.5% by weight cotton brightener, 0.01 - 0.5% by weight polyamide brightener, 0.01 - 0.5 th weight percent fragrance, 0.00001-0.05 weight percent dye.

As bisquaternary ammonium compounds of the formula I, for example the following are used: N, N, N ', N'-tetramethyl-N, N'-dipalmityl-trimethylene-diammonium dioctyl sulfate; N, N, N ', N'-tetramethyl-N, N'-dilauryl-trimethylene-diammonium didecyl sulfate; N, N, N ' , N-tetraethyl-N, N t dioctyl sulfate; N, N, N ', N'-tetramethyl-N, N'-dipalmityl-decamethylene-diammoniumdilaurylbenzenesulfonate; N, N, Nt, N'-tetramethyl-N, N'-ditallow alkyl dodecamethylene diammonium dioctyl sulfate; N, N, N ', N'-tetramethyl-N, N'-dimyristyl-trimethylene-diammonium dilauryl sulfate; N, N, N ', N'-tetramethyl-N, N'-dilauryl-trimethylene-diammonium bis-coconut alkyl-diethylene glycol ether sulfate; N, N, N ', N'-tetramethyl-N, N'-dilauryl-trimethylene-diammoniumdimyri styl sul fat; N, N, N ', N'-tetramethyl-N, N'-dilauryl-trimethylene-diammonium decanediol-1,2-disulfate; N, N, N ', N'-Tetramethyl-N, N'-dilauryl-trimethylene-diammonium di-capric acid-d-sulfonate.

The fabric softener according to the invention is produced by Dispersing the components in an aqueous phase. To speed up dispersion the aqueous phase can be warmed up.

The said surfactant anions X of the sulfonate and sulfate type and the nonionic surface-active agents which can be used as dispersants or emulsifiers Compounds contain at least one hydrophobic residue from 6 to 26 in the molecule, preferably 10-22 and especially 10-18 carbon atoms and at least one anionic or nonionic water-solubilizing group. The preferably saturated one The hydrophobic radical is usually of an aliphatic, possibly also of an alicyclic, nature; it can work with the water-solubilizing groups directly or via intermediate links be connected. Benzene rings or ether-like rings are used as intermediate links Residues of polyhydric alcohols, such as those of ethylene glycol, propylene glycol, of glycerine or corresponding polyether residues.

The surfactant anions of the sulfonate type include, for example, the alkylarylsulfonates, in particular the alkylbenzenesulfonates, which are, inter alia, preferably straight-chain aliphatic hydrocarbons with 9-15, in particular 10-14, carbon atoms by chlorination and alkylation of benzene or from corresponding terminal or internal Olefins by alkylating benzene and sulfonating the resulting alkylbenzenes receives.

Aliphatic sulfonates of the alkane sulfonate type are selected from, for example preferably saturated, 8-18 and preferably 12-18 carbon atoms in the molecule containing hydrocarbons by sulfochlorination with sulfur dioxide and chlorine or sulfoxidation with sulfur dioxide and oxygen and stirring of the resulting Products made into the sulfonates.

Aliphatic sulfonates are also alkene sulfonates and hydroxyalkane sulfonates and mixtures containing disulfonates, e.g. C8 to C18 and preferably C12 to C18 olefins by sulfonation with sulfur trioxide and obtain acidic or alkaline hydrolysis of the sulfonation products. With the so produced aliphatic sulfonates of the olefin sulfonate type is bound the sulfonate group is multiple on a secondary carbon atom; but you can also sulfonates obtained by reacting terminal olefins with bisulfite with terminal Use sulfonate group.

The type of fatty acid ester sulfonates includes the sulfonates of α-sulfo fatty acid esters with mono- or polyvalent, 1-10, preferably 1-4 and especially 1-2 carbon atoms containing alcohols. They also include the sulfonates of fatty acid esters Oxethanesulfonic acid or dioxypropanesulfonic acid and the sulfonates of the fatty alcohol esters of lower, 1 - 8 carbon atoms containing aliphatic or aromatic Sulfomono- or -dicarboxylic acids and the alkyl glyceryl ether sulfonates.

As surfactant anions of the sulfate type, fatty alcohol sulfates with 6 - 22, preferably 6-18 carbon atoms, in particular coconut fatty alcohols, tallow fatty alcohols or of oleyl alcohol and diol disulfates, which are produced from fatty alkyl-1,2-diols will be called. Terminal or internal C8 to C18 olefins can also be used Sulronation products of the sulphate type available. Furthermore belong to this group sulfated alkoxylation products of alkylphenols (C8 to C15-alkyl), fatty alcohols, Fatty acid amides or fatty acid alkylolamides, which in the molecule 0.5-20, preferably May contain 1-8 and in particular 2-4 ethylene and / or propylene glycol residues.

As non-ionic dispersants and emulsifiers, here below Known as "Nonionics", products that enhance their hydrophilic properties are suitable the presence of polyether chains, amine oxide, sulfoxide or phosphine oxide groups, Alkylolamide groups and, more generally, an accumulation of hydroxyl groups owe.

Of particular practical interest are those caused by the addition of Ethylene oxide and / or glycide on fatty alcohols, alkylphenols, fatty acids, fatty amines, Fatty acid or sulfonic acid amides, these nonionics 3 - 100, preferably 6-40 and in particular 8-20 atomic residues, especially ethylene glycol ether residues may contain per molecule. In addition, in these polyether residues or on the ends of which contain propylene or butylene glycol ether residues or polyether chains be.

The nonionics also include those under the trade name "Pluronics" or "Tetronics" known products. They are obtained from water-insoluble per se Polypropylene glycols or from water-insoluble propoxylated lower, 1 - 8, preferably 3 - 6 carbon atoms containing aliphatic alcohols or or from water-insoluble propoxylated alkylenediamines. These water-insoluble (i.e. hydrophobic) propylene oxide derivatives are athoxylated until they are water-soluble transferred to the nonionics mentioned. Finally, as nonionics, the as "Ucon-Fluid" known, partly still water-soluble reaction products of the abovementioned aliphatic alcohols with propylene oxide useful.

The nonionics also include fatty acid or sulfonic acid alkylolamides, e.g. from mono- or diethanolamine, from dihydroxypropylamine or others Polyhydroxyalkylamines, e.g. derived from the glycamines. You can get through amides from higher primary or secondary alkylamines and polyhydroxycarboxylic acids.

The capillary-active amine oxides include, for example, those of higher tertiary, one hydrophobic alkyl radical and two shorter ones, each with up to 4 carbon atoms containing amines containing alkyl and / or alkylol radicals.

Suitable acidifying and complexing agents are non-oxidizing, Inorganic and non-surface-active substances that are harmless to the fibers to be treated organic acids with 1 - 8 carbon atoms, such as amidosulfonic acid, Urea compounds of orthophosphoric acid, acetic acid, propionic acid, oxalic acid, Lactic acid, glycolic acid, citric acid, tartaric acid, benzoic acid, phthalic acid, gluconic acid etc..

The brighteners that can be used are mostly, if not exclusively, Derivatives of diaminostilbene sulfonic acid, diarylpyrazolines and aminocoumarins.

Examples of brighteners from the class of the diaminostilbene sulfonic acid derivatives are compounds according to formula II: In the formula, R1 and R2 can denote halogen atoms, alkoxyl groups, the amino group or residues of aliphatic, aromatic or heterocyclic, primary or secondary amines and residues of aminosulfonic acids, aliphatic residues present in the above groups preferably 1 - 4 and in particular 2-4 C- Contain atoms, while the heterocyclic ring systems are mostly 5- or 6-membered rings. The radicals of aniline, anthranilic acid or anilinesulfonic acid are preferred as aromatic amines. Lighteners derived from diaminostilbene sulfonic acid are mostly used as cotton lighteners. The following products derived from formula II are commercially available, where R1 represents the radical —NH — C6H5 and R2 can represent the following radicals —NH2, —NH — CH3, —NH — CH2 — CH20H, —NH — CH2 —CH2 -O -CH3, -NH-CH2 -CN2-CH2-O-CH3, CH3-N'-CH2-CH2OH, -N = <CH2-CH2OH) 2, morpholino-, -NH-C6H5, -NH-C6H4- SO3H, -OCH3. Some of these brighteners are to be regarded as transition types to the polyamide brighteners with regard to the fiber frinity, for example the brightener with R2 a -NH-C6H5.

One of the diaminostilbene sulfonic acid type cotton whiteners also the compound 4,4'-bis- (-q-phenyl-vicinaltriazolyl-2 -) - stilbene disulfonic acid-2,2 '.

The polyamide brighteners, some of which have a broken affinity for cotton fibers, include diarylpyrazolines of the formulas III and IV: In the formula EI, R3 and R5 denote hydrogen atoms, optionally substituted by carboxyl, carbonamide or ester groups, alkyl or aryl radicals, R4 and R6 hydrogen or short-chain alkyl radicals, Arl and Ar2 aryl radicals, such as phenyl, diphenyl or naphthyl, which have worlder substituents can, such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, carboxylic acid ester, sulfonic acid, sulfonamide and sulfone groups or halogen atoms. Commercially available brighteners of this type are derived from the formula IV, where the radical R7 can represent the groups C1, -SO2-NH2, -SO2-CH = CH2 and -COO-CH2-CH2-O-CH3, while the remainder R8 denotes a chlorine atom in all cases. 9-cyano-anthracene is also commercially available as a polyamide brightener.

Weiberin aliphatic or aromatic ones go well with the polyamide brighteners substituted aminocoumarins, e.g. 4-methyl-7-dimethylamino- or 4-methyl-7-diethylaminocoumarin. The compounds 1- (benzimidazolyl-2 ') - 2- (N-hydroxyethyl-benzimidazolyl-2') ethylene are also used as polyamide brighteners and 1-N-ethyl-3-phenyl-7-diethylamino-carbostyril can be used.

As brighteners for polyester and polyamide fibers, the compounds are 2,5-di- (benzoxazolyl-2 ') -thiophene and 1,2-di- (5'-methyl-benzoxazolyl-2t) -ethylene suitable.

Examples The following examples describe the composition some fabric softeners according to the invention.

Example 1 7.0% by weight of N, N, N ', N'-tetramethyl-N, N'-dipalmityl-trimethylenediammonium dioctyl sulfate; 1.0% by weight adduct of 1 mol of coconut fatty alcohol (012 / C14 cut) with approx. 3 mol of ethylene oxide; 0.05% by weight cotton whitening agent of the formula II on page 10, in which R1 is the anilino- and R2 is the dihydroxyethylamino radical; 1.0 wt% glycolic acid; 0.2 wt% Fragrance; 0.85 wt% isopropanol; Rest water.

Example 2 6.0% by weight of N, N, N ', N'-tetramethyl-N, N'-dilauryl-trimethylenediammonium-bis-cocoalkyl-diethylene glycol ether sulfate 1.5% by weight adduct of 1 mol of tallow fatty alcohol (C16 / C18 cut) with approx. 12 mol of ethylene oxide; 0.05 wt .-% cotton brightener of the formula II on page 10, in which R1 is the anilino and R2 is the dihydroxyethylamino radical; 1.0 wt% glycolic acid; 0.08 wt% Fragrance; 0.0015 wt. Dye; 1.25 wt% isopropanol; Rest water.

To use the fabric softener according to the invention, the Washed textiles are treated with a rinse aid containing the agent in concentrations from 0.05-5 g / l, preferably from 0.2-2 g / l.

The fabric softening effect of the active ingredients used according to the invention the formula I is nachgeu based on a rinse test. For this purpose, samples of pre-hardened cotton terry fabric with an aqueous active ingredient dispersion that Contains 0.5 g of active ingredient per liter, rinsed and the samples dried while hanging. Afterward the grip is judged independently by four people. The grip assessment will Expressed in grades between 1 and 6, where: 1 = fuller and very soft Handle 6 = very hard handle.

The mean values, which are compiled in the table below, are calculated from the assessments. The limit values 1 and 6 are defined as follows: Samples of new cotton terry cloth are treated for 240 hours in a washing machine under high-temperature washing conditions in water with the addition of small amounts of tripolyphosphate. After drying, the fabric pre-hardened in this way is given a handle rating of 6. Samples of new cotton terry cloth are de-treated and treated with a solution of 0.5 g / l ditallow alkyldimethylammonium chloride. The fabrics softened in this way are given a rating of 1. Active ingredient handle note after (Concentration 0.5 g / l) one-time Wash N, N, N ', N'-tetramethyl-N, N'-dipalmityl- trimethylene diammonium dioctyl sulfate N, N, N ', N'-tetramethyl-N, N'-dilauryl- trimethylene diammonium didecyl sulfate N, N, N ', N'-tetramethyl-N, N'-dilauryl- trimethylene-diammonium-dimyristyl- sulfate N, N, N ', N'-tetramethyl-N, N'-dilauryl- trimethylene-diammonium-bis-coconutalkyl-3.1 diethylene glycol ether sulfate The fabric softeners according to the invention give the fabric a remarkable softness and fluffiness again after only one treatment. In addition, the fabrics, in particular those made from synthetic fibers, are given an antistatic finish as a result of the treatment. Agents according to the invention which, in addition to the textile-softening active ingredients, also contain optical brighteners or antimicrobial active ingredients, also increase the whiteness of the treated textiles, or the textiles are provided with microbistatic protection against germs.

Claims (7)

Fabric softener for washed laundry, characterized in that it contains bisquaternary ammonium compounds of the formula I in an aqueous dispersion, optionally together with other customary ingredients: contains, in which R1 and R2 preferably saturated alkyl radicals with 8-24, preferably 12-20 carbon atoms, R3-R6 alkyl radicals with 1-8, preferably 1-3 carbon atoms, or mono- or dihydroxyalkyl radicals with 2-4 carbon atoms, Y a straight-chain or branched alkylene radical with 2-24, preferably 2-12 carbon atoms, and X is the anion of a surfactant of the sulronate or sulfate type, optionally also a soap. 2. fabric softener according to claim 1, characterized by the following Composition: 1.0-25.0% by weight bisquaternary ammonium compound of the formula I, 0.0-8.0% by weight non-ionic, capillary-active dispersant or emulsifier, 0.0 - 30.0 wt. Water-soluble organic solvent, the remainder water and others Ingredients such as optical brighteners, antimicrobial agents, acidic agents and Complexing agents, fragrances and dyes. 3. fabric softener according to claim 1 and 2, characterized by the the following recipe: 1.0-18.0, preferably 2.0-10.0 by weight bisquaternary ammonium compound of formula I, 0.2-6.0, preferably 0.2-3.0% by weight of nonionic capillary-active Dispersant or emulsifier, 0.2-30.0, preferably 0.3-10.0% by weight of water-soluble organic solvent, especially isopropanol, 0.0-10.0, preferably 0.3 - 7.5% by weight of other common ingredients in fabric softeners, the remainder being water. 4. fabric softener according to claim 1-3, characterized in that the other usual ingredients are made up as follows: 0.2 - 3.0% by weight antimicrobial agent, O, '- 3.0% by weight acidifying and complexing agent, 0.01 - 0.5% by weight cotton brightener, 0.01 - 0.5% by weight polyamide brightener, 0.01 - 0.5 wt% fragrance, 0.00001-0.05 wt% dye. 5. fabric softener according to claim 3, characterized gekennzeiclmet that the water completely or at least partially by water-soluble organic Can replace solvent. 6. fabric softener according to claim 1-5, characterized by a Content of N, W, N'JN'-tetramethyl-N, N'-dipalmityltrimethylene diammonium dioctyl sulfate. 7. fabric softener according to claim 1-5, characterized by a Content of N, N, N ', N'-tetramethyl-N, N'-dilauryltrimethylene-diammonium-bis-coconut-alkyl-diethylene glycol ether sulfate.