CH631206A5 - Detergent suitable for cold washing - Google Patents

Description

The invention further relates to a process for washing mono- or dialkylphenols having 6-14 carbon atoms in the alkyl

of textiles using the most inventive. In addition to these water-soluble nonionics are also

Laundry detergent. This process is characterized in that 45 polyglycol ethers which are not or are not completely water-soluble, with the textiles in an aqueous washing liquor containing 2-7 ethylene glycol ether residues in the molecule of interest, in particular

Temperature between 10 and 30 ° C, especially 15 to 25 ° C especially if they are combined with water-soluble non-ionic

moved or seen manually or mechanically for 10 to 60 minutes or anionic surfactants are used.

these washing liquors are the detergents defined above. Furthermore, the non-ionic surfactants are the water-soluble

Contains amounts of 1.0 to 12.0 g / 1, preferably 4.0 to 10.0 g / 1, 50 chen, 20-250 ethylene glycol ether groups and 10-100 propy-

and that the textiles are then separated off from the wash liquor containing addition products containing glycol ether groups and washed with fresh water until ethylene oxide on polypropylene glycol, alkylenediamine-poly-

the washing liquor components rinses. propylene glycol and on alkyl polypropylene glycols with 1-10

If the washing liquor contains a peroxy compound usable as bleaching carbon atoms in the alkyl chain, in which the medium, the washing process in the cold polypropylene glycol chain can act as a hydrophobic residue after the washing process. It is also possible to use th washing liquor by heating this washing liquor to nonionic surfactants of the amine oxide or sulfoxide type at temperatures of preferably 60 to 95 ° C. for a time, for example the compounds N-coconut

a desired bleaching effect on the textile-N, N-dimethylamine oxide, N-hexadecyl-N, N-bis (2,3-dihydro-

lien can be achieved. xypropyl) amine oxide, N-tallow alkyl-N, N-dihydroxyethylamine oxide.

The following is a more detailed description of the most important ones in eo. The expression “nonionic surfactants (nonionics)” comprises the detergents contained in the detergents according to the invention, and accordingly does not include the hydroxyal

parts, sorted by substance classes. alkylated polyamides.

The surfactants contain at least one hydro- in the molecule. The zwitterionic surfactants are preferably

phobic organic residue and a water-solubilizing addition to derivatives of aliphatic quaternary ammonium compounds

anionic, zwitterionic or nonionic group. At 65 fertilizers, in which one of the aliphatic residues consists of one of the hydrophobic residues is usually an aliphatic Cs-Cig residue and another is an anionic water-soluble

contains a hydrocarbon radical with 8-26, preferably 10-22 and lending carboxy, sulfo or sulfato group,

are in particular 12-18 carbon atoms or an alkyl aromatic representative of such surface-active betaines

1

5 631206

for example the compounds 3- (N-hexydecyl-N, N-di-speaking monomeric carboxylic acids with one another or methylammonio) propane sulfonate; 3- (N-tallow alkyl-N, N-dimethyl- with ethylenically unsaturated compounds such as ethylene, pro-ammonio) -2-hydroxypropanesulfonate; 3- (N-hexadecyl-N, N-pylene, isobutylene, vinyl methyl ether or furan. Bis (2-hydroxyethyl) ammonium) -2-hydroxypropyl sulfate; 3- (N- Suitable inorganic, non-complexing salts are

Cocosalkyl-N, N-bis (2,3-dihydroxypropyl) -ammonio) -propansul- 5 the bicarbonates, carbonates, borates, sulfates or silicates of the fonate; N-tetradecyl-N, N-dimethyl-ammonioacetate; N-hexad alkali; of the alkali silicates are, in particular, the sodium silicyl-N, N-bis (2,3-dihydroxypropyl) ammonium acetate. with a Na20: SiCh ratio of 1: 1 to 1: 3.5

The foaming power of the surfactants can be combined.

increase or decrease nation of suitable surfactant types; another scaffold because of its hydrotropic

Reduction can also be achieved by adding non-ten properties, mostly used in liquid agents, such as organic substances. A reduced are the salts of the non-capillary active, 2-9 C atoms containing foaming power, which is desirable when working in machines with the sulfonic acids, carboxylic acids and sulfocarboxylic acids, can be achieved in many cases by combining various alkali, benzene, alkali salts, for example Toluene, xylene surfactant types, e.g. B. of sulfates and / or sulfonates with non- or cumene sulfonic acids, sulfobenzoic acids, sulfophthal-ionics and / or with soaps. In the case of soaps, the foam acid, sulfoacetic acid, sulfosuccinic acid and the salts of the fung increase with the degree of saturation and the C number of the fatty acid re-acetic acid or lactic acid. As soles mediators are also on; Soaps of the saturated C2o-24 fatty acids are suitable for acetamide and urea.

therefore especially as a foam damper. Dirt carriers can also be contained in the preparations

The non-surfactant-like foam inhibitors are those which keep the dirt detached from the fibers in the liquor generally suspended in water, mostly aliphatic, and thus prevent graying. For this purpose, compounds containing C8-C22 carbon residues. Suitable are water-soluble colloids mostly organic in nature, non-surfactant foam inhibitors are such. B. the N-alkylami- such as the water-soluble salts of polymeric car-notriazines, d. H. Reaction products of 1 mole of cyanuric chloride, acids, glue, gelatin, salts of ether carboxylic acids or with 2-3 moles of a mono- or dialkylamine with essentially ether sulfonic acids of starch or cellulose or salts, 8-18 carbon atoms in the alkyl radical. Also suitable are propo- of acidic sulfuric acid esters of cellulose or starch, xylated and / or butoxylated aminotriazines, e.g. B. the implementation- Water-soluble acidic polyamides containing 1 mole of melamine with 5-10 mole of propylene oxide are suitable for this purpose. Furthermore, soluble and additionally 10-50 mol of butylene oxide and the aliphatic starch preparations and starch pro-cis-C40-ketones other than those mentioned above, such as. B. Stearon, the fatty ketones from hardened products such. B. degraded starch, aldehyde starches ter tranfatty acid or tallow fatty acid etc. and also the 30 etc. Polyvinylpyrrolidone is also useful.

Paraffins and halogen paraffins with melting points below Among the bleaching agents in water H2O2 100 ° C and silicone oil emulsions based on polymeric silicon-providing compounds have sodium perborate tetrahyganic compounds. drat (NaBCh • O2 • 3 H2O) and the monohydrate (NaBCh • H2O2)

Particular importance is given as organic and inorganic builders. However, other H2O2-providing weakly acidic, neutral or alkaline reacting salts, 35 borates can also be used, e.g. the Perborax Na2B407-4 H2O2. These, in particular alkali salts, which precipitate calcium ions or compounds can bind partially or completely by other complexes. Of the inorganic, com-active oxygen carriers, in particular by peroxy hydrates, such as plexifying salts, are the water-soluble alkali metal or peroxy carbonates (Na2CC> 3 • L5H2O2), peroxypyrophosphates, alkali polyphosphates, in particular the pentasodium triphosphate citrate perhydrates, urea-H20C- or melamine-H20C-melamine -sphat, of particular importance. These phosphates can fertilize 40 and peracid salts providing H2O2, e.g. cion ions can be replaced in whole or in part by organic complexing agents for cal-caroates (KHSOs), perbenzoates or peroxyphthalates. This includes connections of the type.

the aminopolycarboxylic acids, such as. B. nitrilotriacetic acid, it is recommended to use conventional water-soluble and / or

Ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid-insoluble stabilizers for the peroxy compounds acid as well as higher homologs. Suitable phosphorus-containing 45 together with these in amounts of 0.25-10% by weight of single-organic complexing agents are the water-soluble salts of the two. As water-insoluble stabilizers, the z. B. 1 -8, pre-alkane polyphosphonic acids, amino and hydroxyalkane poly tensile 2-7% of the weight of the entire preparation ausma-phosphonic acids and phosphonopolycarboxylic acids, such as. B. chen, the magnesium silicates MgO: SiC> 2 = 4: 1 to 1: 4, pre-methane-l, l-diphosphonic acid, aminotrimethylene triphosphonic 50, which are usually obtained by precipitation from aqueous solutions, the compounds methane diphosphonic acid, dimethylaminogen, are suitable preferably 2: 1 to 1: 2 and in particular 1: 1. In their place, acid, l-hydroxyethane-l, l-diphosphonic acid, 1-phosphono-other alkaline earth metal or tin silicates of corresponding ethane-l, 2-dicarboxylic acid, 2-phosphonobutane-l, 2,4-tricarbon composition can be used. Also water-containing oxides of acid. Tin are suitable as stabilizers. Water soluble stabilizers

Among the organic framework substances are the N- and gates, which can be present together with water-insoluble P-free polycar-55 which forms complex salts with calcium ions, are the organic heavy metal complexing agents, bonic acids, for which purpose also polymers containing carboxyl groups, amount 0.25-5 , preferably count 0.5-2.5% of the weight of the sate, of particular importance. Are suitable for. B. can make up entire preparation.

Citric acid, tartaric acid, benzene hexacarboxylic acid and tetra-um when washing already at temperatures below hydrofuran tetracarboxylic acid. Also 80 ° C containing ether groups, in particular in the range of 40-60 ° C, a satisfactory polycarboxylic acids can be used, such as 2,2'-oxydibernstein-60 to achieve a bleaching effect, are preferably active acid and partially or completely etherified with glycolic acid. bleach components containing gates incorporated into the preparations, polyhydric alcohols or hydroxycarboxylic acid, as activators for perverbin

for example biscarboxymethylethylene glycol, carboxymethyl fertilizers are used to form N-acyl or O-acyl compounds, in particular saccaride, which form peracid succinic acid organic with this H2O2 and carboxymethylated or oxidized polymers. Furthermore, the polymeric carboxylic acids 65 are suitable acetyl, propionyl or benzoyl compounds, as well as carbons with a molecular weight of at least 350 in the form of the acid or pyrocarbonic acid esters. Useful compounds of water-soluble salts, such as. B. polyacrylic acid, poly-a-hydroxy- include: N-diacylated and N, N'-tetraacylated acrylic acid, polymaleic acid, and the copolymers of the ent amines such as. B. N, N, N ', N' -Tetraacetyl-methylenediamine or

631 206

-ethylenediamine, N, N-diacetylaniline and N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoins, alkyl-N-sulfonyl-carbonamides, e.g. B. N-methyl-N-mesyl-acetamide, N-methyl-N-mesyl-benzamide, N-methyl-N-mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide, N-acylated cyclic hydrazides, acylated triazoles or urazoles such as. B. the Monoacetylmaleinsäurehy-drazid, 0, N, N-trisubstituted hydroxylamines such. B. O-ben-zoyl-N, N-succinyl-hydroxylamine, 0-acetyl-N, N-succinyl-hydro-xylamine, 0-p-methoxybenzoy] -N, N-succinyl-hydroxylamine, Op-nitrobenzoyl-N , N-succinylhydroxylamine and 0, N, N-tria-cetyl-hydroxylamine, N, N'-diacylsulfurylamides, such as, for. B. N, N'-DimethyI-N, N'-diacetyl-sulfurylamide, and N, N'-diethyl-N, N'-dipropionyl-sulfurylamide, triacylcyanurates, e.g. B. triacetyl or tribenzoyl cyanurate, carboxylic anhydrides, e.g. B. benzoic anhydride, m-chlorobenzoic anhydride, phthalic anhydride, 4-chlorophthalic anhydride, sugar esters, such as. B. glucose pentaacetate, 1,4-diacyl-4,5-diacyloxy-imidazolidine, for example the compounds 1,3-diformyl-4,5-diacetoxyimidazolide-din, 1,3-diacetyl-4,5-diacetoxy-imidazolidine, l, 3-diacetyl-4,5-dipropionyloxy-imidazolidine, acylated glycolurils such as e.g. B. tetrapropionylglycoluril or diacetyl-dibenzoylglycoluril, diacylated 2,5-diketopiperazines, such as. B. 1,4-diacetyl-2,5-dike-topiperazine, 1,4-dipropionyl-2,5-diketopiperazine, 1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine, acetylation or benzoylation products of propylene diurea or 2,2-dimethyl-propylene diurea (2,4,6,8-T etraaza-bicyclo- (3,3,1) -nonane-3,7-dione or its 9,9-dimethyl derivative), sodium salts of p- (ethoxycarbonyloxy) benzoic acid and p- (propoxycarbonyloxy) benzene sulfonic acid.

The detergents can contain, as optical brighteners for cotton, in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Are suitable for. B.

Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which have a instead of the morpholino group Carry a diethylamine group, a methylamino group or a 2-methoxyethylamino group. Possible brighteners for polyamide fibers are those of the 1,3-diaryl-2-pyrazoline type, for example the compound l- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and compounds of the same structure which instead of the sulfamoyl group z. B. the methoxycar-bonyl, 2-methoxyethoxycarbonyl, the acetylamino or the vinyl sulfonyl group. Useful polyamide brighteners are also the substituted aminocoumarins, e.g. B. the 4-methyl-7-dimethylamino or the 4-methyl-7-diethylaminocumaine. The compounds 1 - (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) ethyl and 1-ethyl-3-phenyl-7-diethylamino-carbostyril are also useful as polyamide brighteners. The brighteners for polyester and polyamide fibers are the compounds 2,5-di- (2-benzoxazolyl) -thiophene, 2- (2-benzoxazolyl) -naphtho [2,3-b] -thiophene and 1,2-di - (5-methyl-2-benzoxazolyl) ethylene suitable. Brighteners of the substituted 4,4'-distyryldiphenyl type may also be present; e.g. B. the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

As water-soluble organic solvents, the lower alcohols, ether alcohols, glycols or ketones with 1-6 carbon atoms, such as. B. methanol, ethanol, propanol, isopropyl alcohol, ethylene glycol, propylene glycol, di-ethylene glycol, methyl glycol, ethyl glycol, butyl glycol or acetone and methyl ethyl ketone.

Examples

The production of some hydroxyalkylated polyamides which can be used according to the invention is described first.

The ethoxylation or ethoxylation / propoxylation of the polyamides was carried out according to the following rule:

In a 2000 ml stirred autoclave, a mixture of 56.3 g of the polyamide (0.5 mol based on the monomer unit), 200 ml of dioxane and 0.3 g of sodium methylate was used to add the ethylene oxide and, if appropriate, additional propylene oxide in various the individual products specified quantities, in portions of about 20 g with nitrogen at a temperature of about 150-175 ° C pressed. After reaching constant pressure, in the event that a further reaction with propylene oxide was provided, this was reacted in the same way; or after reaching constant pressure, the reaction temperature was maintained for a further hour. After cooling, the reaction product was mixed with 600 ml of dioxane. The mixture was then neutralized with dilute hydrochloric acid and suctioned off in the heat for insolubles. The filtrate was evaporated to dryness on a rotary evaporator. The reaction products are pale yellowish masses which are obtained as pasty or waxy products after the solvent has been stripped off. The cloud points were determined in water according to DIN 53917.

Product I:

The reaction product of the polyamide from hexamethylenediamine, adipic acid and e-caprolactam (Ultramid 6A) with ethylene oxide, in a weight ratio of 1: 1.37; Cloud point> 100 ° C.

Product II:

The reaction product of 56.3 g of the polyamide Ultramid 6A and 66 g of ethylene oxide; Cloud point> 100 ° C.

Product III:

The reaction product from 56.3 g of the polyamide Ultramid 6A first with 48 g of ethylene oxide and then with 87 g of propylene oxide; Weight ratio polyamide: epoxides such as 1: 2.4; Cloud point 37-39 ° C.

Productive:

The reaction product from 56.3 g of the polyamide Ultramid 6 A with 385 g of ethylene oxide and then 103 g of propylene oxide; Weight ratio polyamide: epoxides such as 1: 8.6; Cloud point> 100 ° C.

Product V:

The reaction product from 56.3 g of the polyamide Ultramid 6A with first 77 g of ethylene oxide and then 103 g of propylene oxide; Cloud point 47-49 ° C.

Product VI:

The reaction product of the polyamide from hexamethylenediamine, adipic acid, e-caprolactam and 4,4'-diamino-l, l'-dicyclohexylmethane (Ultramid IC) with ethylene oxide in a weight ratio of 1: 1.56; Cloud point> 100 ° C.

Product VII:

The reaction product of the polyamide from hexamethylenediamine and adipic acid (Ultramid A3) with ethylene oxide in a weight ratio of 1: 4.1; Cloud point> 100 ° C.

Product VIII:

The reaction product of the polyamide from e-caprolactam (Ultramid B3) with ethylene oxide in a weight ratio of 1: 4.4; Cloud point> 100 ° C.

Product IX:

The reaction product of a poly-e-caprolactam and ethylene oxide, with an ethylene oxide content of approx. 77% by weight; Cloud point> 100 ° C (commercial product Lurotex A25 from BASF).

6

5

10th

15

20th

5

30th

35

40

45

50

55

60

65

7

631206

20th

25th

30th

Product X:

The reaction product of the polyamide from hexamethylenediamine and sebacic acid (Ultramid S4) with ethylene oxide in a weight ratio of 1: 5.3; Cloud point> 100 ° C.

Working instructions for the implementation with Glycid:

Approx. 20 g of the granulated polyamide were placed with about 10 ml of glycid in a 250 ml three-necked flask with a stirrer, thermometer, reflux condenser and dropping funnel. Then the air in the apparatus was replaced by nitrogen and the reaction vessel was immersed in an oil bath preheated to approx. 200 ° C. After the reaction had subsided, the remaining amount of glycide was added dropwise, with stirring and passing through nitrogen, in such a way that the internal temperature remained constant. After the reaction mixture had subsequently been kept at 200 ° C. for about a further hour, the mixture was cooled. The glycation products were obtained as yellowish waxy masses which were completely soluble in water or alcohol (cloud points> 100 ° C.).

Product XI:

The reaction product of 22.6 g (0.2 mol) of the polyamide Ultramid 6 A and 107.5 g (1.45 mol) of glycid; Weight ratio 1: 4.75; Reaction temperature 200-205 ° C.

Product XII:

The reaction product of the polyamide Ultramid 6A with glycid; Weight ratio 1: 2.75; Reaction temperature 235-240 ° C.

Product XIII:

The reaction product of the polyamide Ultramid IC with glycid; Weight ratio 1: 3.54; Reaction temperature 200-205 ° C.

Product XIV:

The reaction product of the polyamide Ultramid IC with glycid; Weight ratio 1: 2.41; Reaction temperature 240-245 ° C.

Product XV:

The reaction product of the polyamide Ultramid B3 with glycid; Weight ratio 1: 6.6; Reaction temperature 195-205 ° C.

Product XVI:

The reaction product of the polyamide Ultramid B3 with glycid; Weight ratio 1: 4.2; Reaction temperature 235-250 ° C.

The following examples describe the composition and effect of some detergents according to the invention and the implementation of the washing process according to the invention. The above-described hydroxyalkylated polyamides I-XIII were used as active ingredients.

55

example 1

This example describes the composition of a foam-dampened cold detergent, which is particularly suitable for machine washing.

6.0% by weight sodium dodecylbenzenesulfonate; 60

1.0% by weight adduct of 1 mole of tallow alcohol and 14 moles of ethylene oxide;

1.0% by weight of adduct from 1 mol of ethyl / cetylic alcohol and 10

Moles of ethylene oxide;

1.0% by weight of hydroxyalkylated polyamide 65

3.0% by weight of soap (sodium salt of cis-C22 fatty acids); 60.0% by weight sodium triphosphate;

2.0% by weight of water glass (Na2Ü + 3.35 SiCh);

0.2% by weight sodium ethylenediaminetetraacetate;

1.2% by weight carboxymethyl cellulose sodium salt;

Balance sodium sulfate and water.

To demonstrate the cold washing ability, Launde 5 rometer tests were carried out with the hydroxyalkylated polyamides under the following conditions:

Washing temperature 20 ° C; Water hardness 16 ° d; Detergent concentration 4.0 g / 1; Liquor ratio 1:30 with refined cotton and polyester / cotton fabric; Washing time 30 to minutes. A comparison was made with a detergent which additionally contained 1% by weight of sodium sulfate or 1% by weight of sodium dodecylbenzenesulfonate instead of the hydroxyalkylated polyamide. From the following numerical values of the degree of lightening measured on the test fabrics, the prominent improvement in the washing power when using the detergent according to the invention becomes clear.

Table 1

laundry detergent

% Remission

according to example 1

cotton

Cotton/

refined

polyester

equipped

1 a) with 1% product VI

61.9

47.8

lb) with 1% product VIII

65.8

49.8

ld) with 1%

Sodium dodecylbenzenesulfonate

53.8

44.6

le) with 1% sodium sulfate

53.2

44.3

There now follows a table with further examples of washing and cleaning agents according to the invention. The salt-like constituents of the detergents or cleaning agents mentioned in the examples — salt-like surfactants, other organic salts and inorganic salts — are present as sodium salts, unless expressly stated otherwise. The names or abbreviations in the examples have the following meaning:

"ABS": the salt of an alkylbenzenesulfonic acid obtained by condensing straight-chain olefins with benzene and sulfonating the resulting alkylbenzene with 10-15, essentially 11-13 carbon atoms in the alkyl chain;

“Olefin sulfonate”: a mixture of hydroxyalkane, alkane and disulfonates obtained by sulfonating α-olefins with 12-18 C atoms with SO3 and hydrolyzing the sulfonation product with sodium hydroxide solution;

“Fs-estersulfonate”: a sulfonate obtained from hydrogenated palm kernel fatty acid methyl ester by sulfonation with SO3;

"Alkanesulfonate": a sulfonate obtained from the sulfoxidation of C12-i8 paraffins;

"Soap": a soap made from a hardened mixture of equal parts by weight of tallow and rapeseed oil fatty acid (iodine number = 1);

"TA + x ÄO": the addition products of ethylene oxide (ÄO) with tallow fatty alcohol (TA) (iodine number = 0.5), where the numerical values for x indicate the molar amount of ethylene oxide attached to 1 mol of alcohol;

"Bleach activator": the compound tetraacetylglycoluril;

"Perborate": a technical product with the approximate composition NaB02 * H202-3H2O;

«EDTA»: the salt of ethylenediaminetetraacetic acid;

"NTA": the salt of nitrilotriacetic acid;

"CMC": the salt of carboxymethyl cellulose.

The constituents of the detergents according to the invention, in particular the builders, are selected so that the preparations react neutral to clearly alkaline, so that the pH of a 1% solution of the preparation is in the range from 7 to 12. Delicates have neutral to weak

631206

8th

alkaline reaction (pH = 7-9.5), while soaking, prewash and cooking detergents are more alkaline (pH = 9.5-12, preferably 10-11.5).

The examples in the following table are powdery detergents with bleaching action in the case of examples 2, 3 and 9, powdery detergents and main detergents without bleaching action in the examples 4 and 5, while examples 6 to 8 are a powdery mild detergent or represent a liquid detergent or a powdered phosphate-free detergent. The desired improvement in detergency is also achieved if other hydroxyalkylated polyamides according to the invention are used in the detergent formulations in Table 2.

Table 2

Ingredients Detergent ingredients in% for examples

Ingredients Detergent ingredients in% for examples

8th

Potassium toluene

sulfonate

-

-

-

-

-

4.0

-

-

hydroxyalky-

lated

polyamide

Product II

1.0

-

-

1.5

1.5

-

-

1.5

Product V

-

-

1.0

-

-

1.8

-

-

Product IX

-

1.0

-

-

-

-

1.5

-

NasPsOio

40.0

30.0

60.0

55.0

40.0

-

-

40.0

NTA

-

5.0

-

5.0

-

-

-

-

K4P2O7

-

-

-

-

-

10.0

-

EDTA

0.2

0.2

-

-

-

-

0.2

0.2

Perborate

15.0

15.0

-

-

-

-

20.0

25.0

SECTION

TA + 14ÄO

TA + 5ÄO

Fs-ester

sulfonate

Alkanesulfonate

Olefin sulfonate

Tallow alcohol

3ÄO sulfate

Soap

6.0 1.0 1.0

6.5

1.5

6.0

1.0 1.0

3.0

3.0

1.5

6.0 -

4.0

8.0

6.0 1.0 1.0

6.020 bleach activator 15.0 2.5 water glass 3.0 1.5 soda

Mg silicate 2.0 CMC 1.5

- 25 isopropyl alcohol

15.0 3.0

2.0 1.8

4.0 3.0

5.0 3.0

3.5

1.5 1.4

15.0 6.0 2.0 1.2

5.0

3.5 3.5 2.5 3.0

4.0 0.5

3.0 3.0

Rest: Na sulfate, enzymes, opt. Brightener, perfume, water

Rest of water

3.0

2.0 1.5

G

Claims (4)

631206 1.Textile detergent, characterized in that it is a combination of at least one surfactant from the group of anionic, nonionic and zwitterionic surfactants and a water-soluble hydroxyalkylated polyamide which contains at least half of its weight bound ethylene oxide and / or glycide and / or propylene oxide or Butylene oxide The invention relates to a new textile detergent which contains, the weight ratio of the surfactant to hydro- and especially cold water, and xyalkylated polyamide 50: 1 to 2: 1. a washing process. 2. Detergent according to claim 1, characterized, 10 In order to achieve a satisfactory washing result, it is necessary for the hydroxyalkylated polyamide to wash with warm washing liquors at least to two thirds. The availability of its weight contains bound ethylene oxide and / or glycidity of hot water from hot water devices and / or propylene oxide or butylene oxide. by washing machines with heaters is therefore 2nd PATENT CLAIMS in quantities of 4.0 to 10.0 g / 1. 3rd 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 631206 3. Detergent according to claim 1 or 2, characterized - not only a prerequisite for good washing success, but also that the weight ratio of the surfactant to hydride is also an important cost factor in washing. Although xyalkylated polyamide is 20: 1 to 2: 1. can be seen in recent times that 4. Detergent according to any one of claims 1 to 3, including because of changing consumer habits and because of the corresponding water-soluble hydroxyalkylated poly penetration of easy-care textiles made of synthetic fibers amides, which has a cloud point in water - determined by the previously usual hot wash more and more by so-called DIN 53917 - above 20 ° C. 20 called 60 ° C laundry is displaced, which is undoubtedly also 5. Detergent according to one of claims 1 to 4, containing an energy saving. However, in order to save more heat 0.5-2.5% by weight of the hydroxyalkylated polyamide when washing and also in the cases with a surfactant content of 5-50% by weight, which is preferred len, in which only cold water is available, with good wise to be able to wash from synthetic anionic surfactants of sulfonate success, the task was, one and sulfate type, and / or nonionic surfactants, and / or zwit-25 detergent for the To develop cold wash that also combines with terionic surfactants. not heated water, i.e. with water from 10 to 30 ° C, 6. Detergent according to one of claims 1 to 5, characterized in particular 15 to 25 ° C, as it generally indicates from the water that it comes as a hydroxyalkylated polyamide leads to a good washing result. Reaction products of polyamides with ethylene oxide and / This object is achieved according to the invention by one or with ethylene oxide and then propylene oxide in the detergent, which is characterized in that it contains a weight ratio as defined in claim 1. Combination of at least one surfactant from the group of 7. Detergent according to one of claims 1 to 6, characterized anionic, nonionic and zwitterionic surfactants and is characterized by the following composition: a water-soluble, hydroxyalkylated polyamide, which a) 5-50, preferably 5 to 25 wt .-% at least one at least half, preferably at least two third-party surfactants from the group of sulfonate and sulfate surfactants and 35 parts by weight of bound ethylene oxide and / or glycide nonionic surfactants of the ethoxylated alkanol type, and / or propylene oxide or butylene oxide, wherein the alkenols and alkylphenols, weight ratio of the surfactant to the hydroxyalkylated poly b) 0.5-2.5% by weight of the defined hydroxyalkylated polyamide is 50: 1 to 2: 1, preferably 20: 1 to 2: 1. amides, the constituents a) and b) preferably being used as water-soluble hydroxyalkylated polyamides in Weight ratio 20: 1 to 2: 1 are present, "o the detergents according to the invention preferably use those c) 0-8, preferably 0.2 to 5% by weight of a foam inhibition reaction product, the water solubility of which is essentially from the group of alkali soaps is characterized by a cloud point in water - determined according to DIN Cis-C22 fatty acid residues and the non-surfactant foam foam 53917 - of above 20 ° C. bittern, for the production of the hydro- d) 50-94.5, preferably 55 to 90% by weight of powdered xyalkylated polyamides, known commercial and / or liquid carriers from the group of powdered polyamides can be used. Suitable such polyamides gene organic and inorganic builders, which can in a known manner by polycondensation of a, water-soluble lower alcohols, diols and ether alcohols tD-C2-Ci2-diaminoalkanes such. B. of tetra-, penta- or and of water, optionally including a bleaching hexamethylene diamine, or cycloaliphatic diamines such as component, and so z. B. 4,4'-diamino-l, l '-dicyclohexyl-methane, and C4-Ci2-Dicar- e) 0-10, preferably 0.5 to 10 wt .-% additives for washing acids such as. B. succinic acid, glutaric acid, adipic acid, medium from the group of optical brighteners, enzymes, pimelic acid, sebacic acid, terephthalic acid, etc. are given dirt carriers, fabric softeners, antimicrobial effects. Other substances, dyes and fragrances suitable for the production of polyamides. The starting materials are the polyamide-forming oAminocarbon 8. A method of washing textiles using 55 to 4 carbon atom acids such as e.g. Co-aminobutter dung of the detergent according to claim 1, characterized - acid, a> -aminocaproic acid, co-aminocaprylic acid, co-Aminoca-records that the textiles in an aqueous washing liquor, pric acid etc. or that correspond to these co-aminocarboxylic acids -At a temperature between 10 and 30 ° C during 10 to 60 lactams. The output minutes capable of polyamide formation are moved manually or mechanically, and these detergents can also be used as mixtures. The poly liquor of the detergent defined above in amounts of 1.0 to 60 amides generally have an average molecular weight Contains 12.0 g / 1 and that the textiles are then between 500 and 30,000. the wash liquor is separated off and rinsed with fresh water until the hydroxyalkylation of the polyamides is rinsed in a known gene removal of the wash liquor components. Way with the polyamides in powder or granule form 9. The method according to claim 8, characterized, performed. In the presence or absence of this, the temperature of the wash liquor is between 15 to 25 ° C. 65 of a suspending or swelling agent such as acetone, dioxane, tetra. hydrofuran, toluene etc. as well as with and without catalyst 10. The method according to claim 8 or 9, characterized. If more than one epoxy is drawn in during the hydroxyalkylation, the washing liquor sets the detergent defined above, for example the combination of ethylene oxide and propyl. enoxide, glycid / propylene oxide or glycid / ethylene oxide, the first epoxy is preferably reacted first and the second epoxy component is reacted only after the addition of the one epoxy component has ended. Reaction products with two different epoxides are in particular produced in such a way that the more hydrophilic component is added first and then the more hydrophobic component. Cloud point measurements to determine the water solubility of the substances were carried out up to 100 ° C. If the substance was soluble in boiling water,> 100 ° C was specified for the cloud point. Surprisingly, it was found that even a small amount of the hydroxyalkylated polyamide with the surfactant or surfactant mixture brings about a synergistic increase in washing power, which is particularly effective in the cold washing liquor. Accordingly, preferred detergents according to the invention contain 0.5 to 2.5% by weight of the hydroxyalkylated polyamide together with a surfactant content of 5 to 50% by weight, which is preferably composed of synthetic anionic surfactants of the sulfonate and sulfate type, and / or non-ionic surfactants and / or zwitterionic surfactants. The detergents according to the invention preferably contain at least one further customary detergent constituent from the group of inorganic and / or organic builders, foam inhibitors, optical brighteners, dirt carriers, enzymes, antimicrobial active ingredients, colorants and fragrances. In addition to or instead of water, liquid embodiments can also contain low molecular weight, water-miscible organic solvents, in particular from the group of the aliphatic alcohols, diols and ether alcohol. The detergent according to the invention enables the usual washing operations for washing by hand and machine washing with cold water, as is directly available from the water pipe, to be carried out successfully. The agents according to the invention can also contain bleaching additives consisting of peroxy compounds as active oxygen carriers, in particular sodium perborate, stabilizers and optionally activators. As a result, when washing at elevated temperatures, i. H. achieves an additional bleaching effect in the case of 60 ° C. washing or in the case of hot laundry. Even when washing at these elevated temperatures in the washing machine, the hydroxyalkylated polyamides used according to the invention advantageously contribute to the overall washing effect. For the preparation of the hydroxyalkylated polyamides used according to the invention, for example, the following commercially available types of polyamide can be used: A polycondensate of hexamethylenediamine and adipic acid, melting point about 260 ° C (Ultramid A3 from BASF); a polycondensate of hexamethylene diamine, adipic acid and e-caprolactam, melting point about 185 ° C (Ultramid 6A, BASF); a poly-e-caprolactam, melting point about 220 ° C (Ultramid B3, BASF); a polycondensate of hexamethylenediamine, adipic acid, e-caprolactam and 4,4'-diamino-l, l'-dicyclohexyl-methane, melting point about 185 ° C (Ultramid IC, BASF); a polycondensate of hexamethylenediamine and sebacic acid, melting point about 215 ° C (Ultramid S4, BASF). The hydroxyalkylation of the preferably granulated or powdered polyamide with ethylene oxide is preferably carried out in the presence of a dispersing or swelling agent such as dioxane and an alkaline catalyst. Suitable catalysts are e.g. B. the compounds sodium methyl, sodium hydroxide, sodium hydrogen carbonate, triethylamine or trimethylbenzylammonium hydroxide (Triton B). Preferred631206 Sodium methylate is used. The reaction with ethylene oxide is preferably carried out in a stirred autoclave by pressing the calculated amounts of ethylene oxide in portions in a nitrogen atmosphere at the selected reaction temperature of 100-200.degree. C., preferably 150-180.degree. C. and after the pressure has reached constant temperature for some time at the reaction temperature holds. After cooling, the reaction mixture is removed from the autoclave, and further organic solvent in which the product is soluble, for example dioxane or ethanol, is added. The reaction mixture is then neutralized with dilute hydrochloric acid, the insoluble material is filtered off with heat and the filtrate is evaporated to dryness in vacuo. In the case of hydroxyalkylation with glycid, the finest possible polyamide is mixed with part of the glycid at room temperature. Then the air in the reaction vessel is replaced by nitrogen and the mixture is heated to approx. 200 ° C. After the reaction with the glycid has subsided, the remaining glycid is added dropwise so rapidly while stirring and passing nitrogen through that the internal temperature remains constant. When reacting with glycid, an organic solvent and a catalyst are not used. In the case of the hydroxyalkylation of the polyamides with 2 different epoxides, the second epoxide, for example the propylene oxide, is reacted when the addition reaction with the first epoxide, for example ethylene oxide, has ended. Reaction products of the polyamides with ethylene oxide and with ethylene oxide / propylene oxide are preferably used in the proportions given in the agents according to the invention; These hydroxyalkylated polyamides combine easy accessibility with a high increase in washing power. The composition of the detergent according to the invention can be subject to certain fluctuations depending on the intended use. If the preparations according to the invention are to be universally usable and can also be used as cooking detergents, this is achieved by adding a peroxy compound, in particular sodium perborate, which together with a stabilizer and optionally an activator for the peroxy compound 10 to 40, in particular 15 to 35 Can make up% by weight of the total detergent. The composition of the detergent according to the invention is generally in the range of the following formulation: a) 5-50, preferably 5 to 25% by weight of at least one surfactant from the group of the sulfonate and sulfate surfactants and the nonionic surfactants of the ethoxylated alkanols, alkenol and alkylphenols type, b) 0.5-2.5% by weight of the above-defined hydroxyalkylated polyamide, components a) and b) preferably being present in a ratio of 20: 1 to 2: 1, c) 0-8, preferably 0.2 to 5% by weight of a foam inhibitor from the group of alkali soaps with essentially cis-C22 fatty acid residues and the non-surfactant foam inhibitors, d) 50-94.5, preferably 55 to 90% by weight of powdered and / or liquid carriers from the group of powdered organic and inorganic builders, the water-soluble lower alcohols, diols and ether alcohol and water, optionally including a bleaching component , and e) 0-10, preferably 0.5 to 10% by weight of conventional additives for detergents from the group of optical brighteners, enzymes, dirt carriers, fabric softeners, antimicrobial active ingredients, colorants and fragrances. Detergents according to the invention, which have a particularly pronounced detergent capacity both in the cold and at elevated temperature or cooking temperature, contain together as the surfactant component a) a sulfonate surfactant 4th with a nonionic surfactant, in particular of the type see rest with 6-18, preferably 8-16 aliphatic C-Ato- ethoxylated aliphatic Cio-C2o alcohols. Invention. moderate preparations, the surfactant component a) exclusively. As anionic surfactants z. B. soaps from natural nonionic surfactants, in particular from ethoxylated or synthetic, preferably saturated fatty acids, against aliphatic Cio-C2o alcohols are also 5 usable also from resin or naphthenic acids, moves. Suitable synthetic anionic surfactants are those of A particularly good washing effect is observed when the type of sulfonates, sulfates and synthetic carboxylates. these nonionic ethoxylation products as mixtures. Alkylbenzene sulfo- of products with different medium ethoxylates (C9_15-alkyl), olefin sulfonates, d. H. Mixtures of alkene degree and are in this mixture the ratio of 10 and hydroxyalkanesulfonates and disulfonates as they are Addition products of 8 to 20 moles of ethylene oxide to one mole, for example of Cu-Cis monoolefins with end or inside of an aliphatic Cio-C2o alcohol to the ethoxylation double bond by sulfonation with gaseous Products with 2 to 7 moles of ethylene glycol per mole of alcohol 5: 1 sulfur trioxide and subsequent alkaline or acidic to 1: 3. Hydrolysis of the sulfonation products is considered. - The detergent according to the invention with weak foaming is also suitable for the alkanesulfonates which, from C 1 -C 2 -alkanes, contain 0.2-0.8% by weight of a non-surfactant by sulfochlorination or sulfoxidation and subsequent Foam inhibitor or 0.5-5% by weight of an alkali soap from hydrolysis or neutralization or by bisulfite addition to essential Cts-C22 fatty acids, or a mixture from which olefins are obtainable, and the esters of a-sulfofatty acids, non-surfactant foam inhibitor and the soap in a z. B. the a-sulfonated methyl or ethyl ester of the hydrogenated Amount of 0.2-5% by weight. 20 coconut, palm kernel or tallow fatty acids. The detergents according to the invention are in powder form. Suitable surfactants of the sulfate type are the sulfuric acid. Precious, pasty or liquid preparations. monoester primary alcohols (e.g. from coconut fatty alcohols, The liquid to pasty preparations are preferably tallow fatty alcohols or oleyl alcohol) and those secondary produced in such a way that the surfactant component a) in the alcohols. Sulfated ones are also suitable Solvent d) dissolves, then the hydroxyalkylated polyamide b) 25 fatty acid alkanolamides, sulfated fatty acid monoglycerides are added and the mixtures are homogenized by stirring and given or sulfated reaction products of 1-4 mol ethylene oxide if heated and optionally pre-mixed with the primary or secondary alcohols or alkyl phenols. and other components c) and e) and finally given. Any powdered framework substances provided according to other suitable anionic surfactants are the fatty acid d) mixes 30 esters or amides of hydroxy or amino carboxylic acids The production of pourable powdered preparations or sulfonic acids, such as. B. the fatty acid sarcosides, glycolates, can by the usual methods, e.g. B. by cold and hot lactates, taurides or isethionates. Spray drying. Preferred are the hydroxyalky- The anionic surfactants can in the form of their sodium, polyamides b), the paste-like potassium and ammonium salts at room temperature and as organic or soluble salts. are wax-like, on which powder particles of the remaining pre-35 bases, such as mono-, di- or triethanolamine, are present, preferably by spraying-on. Addition products of hen - for example as an alcoholic solution - on a part 1-40 are nonionic surfactants , preferably 2-20 moles of ethylene oxide in 1 mole of fatty alkali or builder substances, for which sodium triphosphate and hol, alkylphenol, fatty acid, fatty amine, fatty acid amide or sodium sulfate forms with bulk densities of 200 to 500 g / 1 alkanesulfonamide can be used. The particularly suitable ones are particularly important, or - in the case of bleach-containing pre-adducts of 8-20 mol ethylene oxide on coconut oil - by spraying on finely powdered sodium perbo or tallow fatty alcohols, on oleyl alcohol or on secondary advice. Alcohols with 8-18, preferably 12-18 C atoms, as well as