DE2226871A1 - Washing compsns - contg n-alkyl-polyhydroxyalkylamines as soil-suspending agents - Google Patents

Abstract

Washing compsns. comprising >=1 surfactant and >=1 builder salt selected from polymeric phosphates, sequestering agents and washing alkalis and conventional additives is improved by addition of 0.1-10 wt.% of a cpd. of formula (I) (in which R is a 10-22 (alkyl; m is 4 (pref.) or 3; n=2-6). These cpds. can be prepd. by reacting N-alkyl-alkylenediamines with aldoses under hydrogenation conditions and then ethoxylating the reaction product. Cpds. (I) act as soil-suspending agents not only with respect to cellulose fibres, but also with respect to synthetic fibres, such as polyester or polyolefine fibres, and modified cotton.

Description

Detergent with a content of anti-graying additives it is known that detergents and cleaning agents that contain surface-active compounds Adding substances that improve the dirt-carrying capacity of the washing liquors Substances referred to below as graying inhibitors prevent resorption the detached dirt on the cleaned surfaces. These are mostly around high molecular weight compounds, either from natural substances, in particular Cellulose, or made from polymeric or copolymeric vinyl compounds, Polyesters or polyamides are made and often free, capable of salt formation Have carboxyl or sulfonate groups.

Of the compounds in question, however, only carboxymethyl cellulose has Obtained a greater technical importance, especially as it is graying-inhibiting Effect surpasses all proposed synthetic polymers. The carboxymethyl cellulose and the majority of the synthetic polymers mentioned have the disadvantage, however, that their anti-graying effect is limited to cellulose fibers, while them when washing synthetic fiber material, chemically modified cellulose or refined cotton are largely ineffective. This disadvantage makes itself felt Especially compared to white textiles made of polyester or polyolefin fibers, non-iron Finished cotton and blended fabrics made from the aforementioned synthetic fibers with cellulose fibers noticeable, which turn gray during use despite frequent washing and are therefore unsightly Synthetic vinyl polymers often have the disadvantage over one another Cellulose derivatives strongly changed biological Degradability while Polyester and polyamides partially saponified by strongly alkaline detergent salts can be.

The task was to develop a remedy that would do the above Does not have disadvantages.

The invention relates to detergents with a content of at least one surface-active detergent substance and at least one synthesis salt from the class of polymer phosphates, sequestering agents and washing alkalis, characterized in that they contain 0.1 to 10 percent by weight of an N-alkyl polyhydroxyalkylamine of the following formula: in which R is an alkyl radical with 10 to 22 carbon atoms, m is 3 or 4 and n is an integer from 2 to 6.

The compounds according to the invention can be prepared by reaction of N-alkyl-alkylenediamines with aldoses under hydrogenating conditions and subsequent Ethoxylation of the reaction products.

As examples of the N-alkylalkylenediamines to be used as starting materials are to be mentioned: N-decylethylenediamine, N-octadecylethylenediamine, N-dodecyltrimethylenediamine, N-decylhexamethylenediamine, N-docosyltrimethylenediamine, N-tetracosylethylenediamine, N-tetradecyltetramethylenediamine, N-eicosyltrimethylenediamine, N-tetradecylpentamethylenediamine, N-decyltetramethylenediamine as well Mixtures of N-alkyl-alkylenediamines, those which are natural in relation to the chain length distribution in the longer-chain alkyl radical Corresponding fatty acid mixtures, for example N-cocoalkyl-trimethylenediamine, N-tallow-alkyl-trimethylenediamine.

Of the aldopentoses and aldohexoses to be used as starting materials Primarily glucose, mannose, arabinose and invert sugar come as well as theirs Mixtures in consideration.

They are reacted with the diamines in a molar ratio of 1: 1 with the addition of a suitable solvent, e.g.

Ethanol, as well as a hydrogenation catalyst, e.g. Raney nickel, under heated to temperatures between 50 and 1000C under a hydrogen pressure of 150 - 200 at. That obtainable after separating off the hydrogenation catalyst and the solvent The reaction product is then reacted with 2 moles of ethylene oxide. The ethoxyiation can in a solvent, s.B. in low molecular weight ethers or hydroxyl groups-free Glycol ether, e.g. diglycol dimethyl ether, can be made in the absence of catalysts. The compounds obtained can be used directly in the detergents or the pasty ones Premixes are incorporated.

In addition to the polyhydroxyalkylamines according to the invention, the detergents contain Usual surface-active washing active substances, such as anionic, nonionic and zwitterionic detergents, also non-surface-active building salts, for example condensed phosphates, sequestering agents and washing alkalis and possibly others, Auxiliaries and additives customary in detergent formulations.

Suitable washing raw materials are those of the sulfonate or sulfate type, for example alkylbenzenesulfates, in particular n-dodecylbenzenesulfonate, furthermore Olefin sulfonates, alkyl sulfonates, α-sulfo fatty acid esters, primary and secondary Alkyl sulfates and the sulfates of ethoxylated or propoxylated higher molecular weight Alcohols.

Further compounds of this class which may be present in the detergents are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, such as the alkali metal salts of the monoalkyl ethers or the monofatty acid esters of glycerol monosulfuric acid ester or

of 1,2-dioxypropanesulfonic acid. Furthermore, sulfates come from ethoxylated or propoxylated fatty acid amides and alkylphenols and fatty acid taurides and Fatty acid ethers in question. Alkali soaps are further suitable anionic detergent raw materials of fatty acids of natural or synthetic origin, e.g. sodium soaps of coconut, palm kernel or tallow fatty acids.

As zwitterionic detergent raw materials, there are alkyl betaines and in particular Possible alkyl sulfobetaines, e.g. 3- (N, N-dimethyl-N-alkylammonium) propane-1-sulfonate and 3- (N, N-dimethyl-N-alkylammonium) -2-hydroxypropane-1-sulfonate.

The anionic detergent raw materials can be in the form of sodium, potassium and ammonium salts and as salts of organic bases, such as mono-, di- or triethanolamine, are present. If the anionic and zwitterionic compounds mentioned have a have an aliphatic hydrocarbon radical, this should preferably be straight-chain and have 8 to 22 carbon atoms. In compounds with an araliphatic The preferably unbranched alkyl chains contain hydrocarbon radicals on average 6 to 16 carbon atoms.

As nonionic surface-active washing-active substances come in primarily polyglycol ether derivatives of alcohols, fatty acids and alkylphenols in question, the 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon radical contain. Polyglycol ether derivatives in which the number of Ethylene glycol ether groups is 5 to 15 and their hydrocarbon radicals of straight-chain, primary alcohols containing 12 to 18 carbon atoms or of alkylphenols with a straight chain having 6 to 14 carbon atoms Derive alkyl chain.

Other suitable non-ionic washing raw materials are the water-soluble, Containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups Polyethylene oxide adducts with polypropylene glycol, ethylene diamino polypropylene glycol and Alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain. The mentioned Compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Also non-ionic compounds of the amine oxide and sulfoxide type, which may also be used Can be ethoxylated are usable.

The polymer phosphates are primarily tripolyphosphates, in particular the pentasodium triphosphate in question. The triphosphates can also be mixed with higher condensed phosphates, such as tetraphosphates, or their hydrolysis products, such as acidic or neutral pyrophosphates.

The polymer phosphates can also be wholly or partially replaced by organic, aminopolycarboxylic acids with a complexing action be replaced. These include in particular Alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid. Suitable are also the salts of diethylenetriaminopentaacetic acid and the higher homologues of the aminopolycarboxylic acids mentioned. These homologues can, for example, by Polymerization of an ester, amide or nitrile of N-acetic acid aziridine and subsequent Saponification to carboxylic acid salts or by reacting polyethyleneimine with chloroacetic acids or bromoacetic acid salts are produced in an alkaline medium. More suitable Aminopolycarboxylic acids are poly (N-succinic acid) ethyleneimines and poly (N-tricarballyic acid) -ethylenimines, which are analogous to the N-acetic acid derivatives are available.

Furthermore, complexing polyphosphonic acid salts can be present be, e.g. the alkali salts of aminopolyphosphonic acids, especially aminotri- (methylenephosphonic acid), 1-hydroxyethane 1, 1 -diphosphonic acid, methylenediphosphonic acid, ethylenediphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned. Mixtures too the aforementioned complexing agents can be used.

As washing alkalis, see B. Alkali silicates in question, in particular Sodium silicate in which the ratio of Na20 Si02 is 1: 3.5 to 1: 1. Further suitable washing alkalis are carbonates, bicarbonates and borates of sodium or Potassium. The amount of alkaline reacting substances including alkali silicates and phosphates should be dimensioned so that the pH value of a usable alkali for coarse laundry is 9 to 12 for delicates 6 to 9.

Oxygen-releasing bleaches are another component of the mixture, such as alkali perborates, percarbonates, perpyrophosphates and persilicates and urea perhydrate in question.

Sodium perborate is preferred in anhydrous form or as tetrahydrate used. In order to stabilize the per compounds, the agents can use magnesia silicate contain, for example in amounts of 3 to 20 wt .-%, based on the amount of Perborate. Agents to be used for washing textiles at temperatures below 700C, so-called cold detergents, bleach activators from the class of N- and O-acyl compounds, especially tetraacetylethylenediamine or tetraacetylglycoluril, as a powder component contain. The ones from the bleach activator or from the per connection existing powder particles can be coated with coating substances such as water-soluble polymers or fatty acids coated to allow interaction between the per compound and the activator during storage.

The detergents can also contain optical brighteners, in particular Derivatives of diaminostilbene disulfonic acid or

their alkali metal salts. For example, salts of 4,4'-bis (-2 "-anilino-4" -morpholino-1,3,5-triazinyl-6 "-amino) -stilbene-2,2s-disulfonic acid are suitable or similarly structured compounds which, instead of the morpholino group, have a Diethanolamino group, a methylamino group or a ß-methoxyethylamino group wear. Furthermore, those of the type used as brighteners for polyamide fibers Diarylpyrazolines in question, for example 1 - (- p-sulfonamidophenyl) -3- (p-chlorophenyl) - g -pyrazoline and similarly structured compounds that replace the sulfonamido group carry a carboxymetllyl or acetylamino group. Substituted ones can also be used Aminocoumarins, e.g. 4-methyl-7-dimethylamino- or 4-methyl-7-diethylaminocoumarin. The compounds 1 - (2-benzimidazolyl) -2- are also used as polyamide brighteners (1-hydroxyethyl-2-bensimidazolyl) -ethylene and 1-thyl-3-phenyl-7-diethylamino-carbostyril useful. The compounds are used as brighteners for polyester and polyamide fibers 2,5-di- (2-benzoxazolyl) -thiophene, 2- (2-benzoxazolyl) -naphtho 2, 3- -thiophene and 1,2-Di- (5-methyl-2-benzoxazolyl) -ethylene are suitable. Furthermore, brighteners can be used Type of substituted Diphenylstyrile be present. Also mixtures of the aforementioned Brighteners can be used.

The agents can also include enzymes from the class of proteases and lipases and amylases or mixtures thereof. Bacterial strains are particularly suitable or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus obtained enzymatic active ingredients that oppose Alkali, per compounds and anionic detergent actives are relatively stable and also at temperatures between 500 and 70 0C are not yet appreciably inactivated.

Further components contained in the agents according to the invention are neutral salts, especially sodium sulphate, bacteriostatic substances, such as halogenated phenolic ethers and thioethers, halogenated carbanilides and salicylanilides as well as halogenated diphenylmethanes, as well as dyes and fragrances.

Liquid agents can also contain hydrotopes and solvents contain, such as alkali salts of benzene, toluene or xylene sulfonic acid, urea, Glycerine, polyglycerine) di- or triglycol, polyethylene glycol, ethanol, i-propanol and ethereal alcohols.

If appropriate, the detergents can also be known foam suppressants contain, such as saturated fatty acids or their alkali metal soaps with 20 to 24 Carbon atoms, higher molecular fatty acid esters or triglycerides, paraffins, Trialkylmelamines and silicone anti-noise agents, to further increase the dirt-carrying capacity can also use other known graying inhibitors, in particular sodium cellulose glycolate (Carboxymethyl cellulose) can be added. The joint use of the invention Compounds and the cellulose glycolate is particularly useful in the cleaning of textiles made of blended fabrics containing cellulose fibers and synthetic fibers are advantageous.

ple qualitative and quantitative composition of the detergent depends largely depends on their area of application. The content of those to be used according to the invention Graying inhibitors amounts in the compound detergents 0.1 to 10, preferably 0.2 to 5 percent by weight, the difference from 90 to 99.9, preferably 95 to 99.8% by weight are allotted to other detergent ingredients, their quantitative composition can correspond to the following scheme (data in percent by weight): 1 to 40% of at least one compound from the class of the anionic, nonionic and zwitterionic washing active substances, 10 to 80% of at least one building salt from the class of polymer phosphates, sequestering agents and washing alkalis, 10 up to 50% of a per compound, especially water-containing or anhydrous Sodium perborate, as well as their mixtures with stabilizers and activators, 0.1 to 20% other auxiliaries and additives.

The washing active substances can be up to 100%, preferably 5 to 70% % of compounds of the sulfonate and / or sulfate type, up to 100%, preferably 5 to 40% of nonionic compounds of the polyglycol ether type and up to 2; u 100 , preferably 10 to 50% soap. The building salts can contain up to 100 %, preferably 25 to 95% of alkali metal triphosphates and their mixtures with Alkali metal pyrophosphates, up to 100%, preferably 5 to 50 $ from an alkali metal salt a complexing agent from the class of polyphosphonic acids, nitrilotriacetic acid, Ethylenediamino tetraacetic acid and up to 100%, preferably 5 to 75% of at least a compound from the class of the alkali metal silicates, alkali metal carbonates and alkali metal borates.

The other auxiliaries and additives include the optical ones Brighteners in particular the foam inhibitors that are in the agents according to the invention in a lot up at 5%, preferably in an amount of 0.2 up to 3% can be present, furthermore the enzymes, which in an amount up to 5%, preferably 0.2 to 3% and the carboxymethyl cellulose, their Share can be up to 5%, preferably 0.2 to 3%.

Examples The graying-inhibiting effect of the following The compounds described in the examples were prepared by the known "soil redeposition" method checked (see H. STAPEL "Textil-Praxis" Vol. 3, page 264 (1954)). There were in a laboratory washing machine (Launder-O-meter, ATLAS, Chicago USA) Seweils 4 lobules from the tissue to be examined with a total weight of 8.3 g together with 1.3 g of one Artificially soiled cotton thread washed for 30 minutes up to three times.

The reflection value was then measured using a photometer (Elrepho der CARL ZEISS company, using filter no. 6).

The practical dust / sebum combination used for soiling the cotton yarn consisted of a mixture of kaolin, black iron oxide, carbon black and synthetic skin oil (from 1/3 fatty acids, 1/3 fat and 1/3 hydrocarbons). The cotton thread contained after soiling approx. 11% pigments and approx. 2% sebum.

A detergent of the composition (in percent by weight) was used: 8% n-dodecylbenzenesulfonate (Na salt) 3% tallow alcohol (JZ 50) with 10 ethylene glycol ether groups 3% Na soap from saturated C12-C22 fatty acids 40% pentasodium triphosphate 22 % Sodium perborate 3.5% sodium silicate (Na2O: SiO2 = 1: 3.3) 2.5% magnesium silicate 0.2% Na-ethylenediaminetetraacetate 0.3% optical brighteners.

4,96 graying inhibitors were added to this agent.

The difference up to 100 96 was due to sodium sulfate.

The application concentration of the detergents was 5 g / l, the hardness of water 100 dH. The textile samples made from synthetic fabric as well as the mixed fabrics Refined cotton and synthetic fiber were refined at 40 to 600C, from which Cotton washed at 950C. The weight ratio of textile goods to washing liquor (Liquor ratio) was 1:30 or 1:12. After a washing time of 30 minutes the textile samples were rinsed four times with distilled water. After three washes the whiteness of the samples was determined photometrically. For comparison were Washing tests carried out without the use of a graying inhibitor. The results are compiled in the following table.

From the reflectance values it can be seen that when using the Polyhydroxyalkylamines showed less graying of the textile fibers in all tests entry.

Instead of the agents according to the invention, carboxymethylcellulose was used used, so was used for the fabrics made of synthetic fibers or those made of equipped Cotton shows no significant improvement over the comparative value without a graying inhibitor achieved, i.e. the increase in reflectance values was less than 1 5 '.

The following compounds were used as graying inhibitors: 1. N-decyl-N'-pentahydroxyhexyl-N, N'-d-hydroxyethyl propylenediamine 2. N-dodecyl-N '-pentahydroxyhexyl-N, N' -dihydroxyethyl propylenediamine 3. N- Tetradecyl-N'-pentahydroxyhexyl-N, N'-d-hydroxyethyl-propylenediamine 4. N-coconut alkyl-N'-pentahydroxyhexyl-N, N'-dihydroxy-ethylethylenediamine 5. N-coconut alkyl-N'-penta'hydroxyhexyl-N, N'- dlhydroxyäthylhexamethylenediamine "Coconut alkyl" means a mixture of chain length C12-18 (mean chain length C13.2) obtained from coconut fatty acids. Cotton polypropylene polyester polyurethane polyester / highly refined cotton Example 95 ° C 1:12 95 ° C 1:30 60 ° C 1:30 60 ° C 1:30 60 ° C 1:30 1 61.8 25.7 50.8 66.5 66.4 2 61.2 28.7 51.4 68.3 70.3 3 63.9 30.7 58.2 68.6 70.2 4 64.2 30.5 59.1 69.0 71.4 5 63.9 31.2 58.8 69.2 70.0 without addition 54.6 24.4 38.3 64.1 58.5

Claims (3)

Claims 1. Detergents with a content of at least one surface-active washing substance and at least one synthesis salt from the class of polymer phosphates, sequestering agents and washing alkalis, characterized in that they contain in amounts of 0.1 to 10 percent by weight of an N-alkyl polyhydroxyalkylamine of the following formula: in which R is an alkyl radical with 10 to 22 carbon atoms, m is the number 5 or 4 and n is an integer from 2 to 6. 2. Means according to claim 1, characterized in that in the formula m = 4 means. 3. Means according to claim 1 and 2, characterized in that it is up to 5% by weight, preferably 0.2 to 3% by weight, of carboxymethyl cellulose, preferably contained in the form of alkali salts.