EP0044003B1 - Liquid washing agent with a content of discolouration inhibiting additives - Google Patents

Abstract

1. A liquid detergent containing a) from 5 to 18 % by weight of an alkyl polyglycol ether corresponding to the following formula see diagramm : EP0044003,P5,F1 in which R**1 is a straight-chain alkyl group and from 20 to 75 % by weight of R**2, based on the alcohol on which the alkyl polyglycol ether is based, is a C1 -C4 alkyl group and the remainder is hydrogen, the total number of carbon atoms in R**1 and R**2 amounting to between 11 and 15, and n has a value of from 5 to 9, n being selected in such a way that the ethylene oxide content of the alkyl polyglycol ether amounts to between 50 and 65 % by weight, b) from 5 to 18 % by weight of an alkyl polyglycol ether corresponding to formula I, in which R**1 is a straight-chain alkyl group and R**2 is either hydrogen of from 20 to 75 % by weight of R**2, based on the alcohol on which the alkyl polyglycol ether is based, is a C1 -C4 alkyl group and the remainder is hydrogen, the total number of carbon atoms in R**1 and R**2 amounting to between 6 and 10, and n has a value of from 3 to 8, n being selected in such a way that the ethylene oxide content of the alkyl polyglycol ether amounts to between 55 and 70 % by weight, c) from 1 to 10 % by weight and preferably from 2 to 6 % by weight of a fabric-softening quaternary ammonium salt selected from the derivatives of ammonia and/or imidazoline preferably containing 2 long-chain aliphatic radicals in the molecule, the weight ratio of a) to b) preferably amounting to between 2:1 and 1:2, characterized in that it additionally contains d) up to 50 % by weight, based on the quantity of components a) and b), of a cationic starch ether containing ammonium groups, the quantitative ratio of c) to d) preferably amounting to between 3:1 and 1:3.

Description

The present invention relates to a liquid washing and cleaning agent based on nonionic surfactants and laundry softening quaternary ammonium compounds, which additionally contains cationic starch ethers, as a result of which the dye transfer from colored textiles to white or light-colored textiles is counteracted during washing together.

The dye transfer when washing colored with white or light-colored textiles has been a problem for a long time, for which there have already been some proposed solutions, but not all of them can be completely satisfactory, because they are only marginal compared to a number of colors or textiles Have effect. So z. B. from DE-B-2 232 353 an agent is known whose discoloration-inhibiting additive is polyvinylpyrrolidone. DE-A-2420561 describes a detergent with a combination of alkali metal percarbonate and polyethylene glycol of a certain molecular weight or polyvinyl pyrrolidone. DE-A-2 309 099 relates to an agent with proportions of two different organic compounds which contain basic nitrogen atoms in the molecule. DE-A-2 828 619 describes a detergent composed of nonionic surfactants, zwitterionic or semipolar surfactants and cationic surfactants in certain proportions. US-A-4005029 and 4 006 092 describe compositions containing per-compounds. EP-A1-5 850 discloses a liquid detergent based on two different nonionic surfactants with a special cationic fabric softener; the dye transfer properties of this detergent are not fully satisfactory.

It has now been found that a liquid detergent based on nonionic surfactants, which contains conventional quaternary ammonium compounds as a softening constituent, has very good discoloration-inhibiting properties due to the addition of ammonium group-containing cationic starch ethers. Cationic starch ethers are known commercially available substances that are used as additives to improve the quality of paper and cardboard manufacture. The starch ethers can be prepared in a manner known per se, e.g. by reacting the starch, for example potato starch, with ethyleneimine (see US Pat. No. 3,303,184) and then partially or completely quaternizing the amino group. However, such ethers are preferably used as a discoloration-inhibiting additive in combination with textile-softening quaternary ammonium compounds which are obtained, for example, by reacting starch with 2,3-epoxypropyltrialkylammonium salts or 3-chloro-2-hydroxypropyltrimethylammonium salts, in particular with 2,3-epoxypropyltrimethylammonium chloride. Such reaction products are described for example in GB-A-1 136 842. The quaternary salts can be used as halides, especially chlorides, sulfates, alkyl sulfates, nitrates, phosphates and as salts of organic acids, e.g. B. present as acetates, citrates or lactates. A typical product is Empresol N from Emsland -force GmbH, Emlichheim, Federal Republic of Germany. This is a cationic potato starch derivative with tertiary and quaternary nitrogen atoms, the cationic charge of which is evenly distributed over the entire starch chain.

The concentration of the starch ether additive in the detergent is between 5 and 50% by weight, based on the amount of nonionic surfactants used, and the ratio of the starch ether to the plasticizing quaternary ammonium compound is between 3: 1 and 1: 3.

The quaternary ammonium compounds are, in particular, derivatives of ammonia, ie the quaternary salts obtainable by alkylation of long-chain secondary amines, such as, for example, the compounds distearyldimethylammonium chloride or ditalgalkyldimethylammonium chloride. In addition to the chloride, bromide, methyl sulfate, ethyl sulfate, methane, ethane or toluenesulfonate are also suitable as anions. Other possible quaternary ammonium compounds are the imidazoline compounds obtainable by reacting 1 mol of an aminoalkylethylenediamine or hydroxyalkylethylenediamine with 2 mol of a long-chain C ₁₄ -C ₂₆ fatty acid or its ester, which are then converted into the quaternary imidazolinium compounds by alkylation.

Typical preferred textile plasticizers are, for example, the commercial products Präpagen WK "and Präpagen WKT" (Hoechst), Adogen 442 "(Ashland), which are ditallow alkyl dimethyl ammonium salts. These compounds are 1 to 10, preferably 2 to 6% by weight in contain the detergent according to the invention.

• a) 5-18 Gew.-% eines Alkylpolyglykolethers der Formel
  
  in der R' eine geradkettige Alkylgruppe und R² zu 20 bis 75 Gew.-% - bezogen auf den dem Alkylpolyglykolether zugrunde liegenden Alkohol - eine C,-C_4-Alkylgruppe und im übrigen Wasserstoff bedeuten, wobei die Gesamtzahl der Kohlenstoffatome in R^I und R² 11 bis 15 beträgt, und n einen Wert von 5 bis 9 bedeutet, und wobei n so ausgewählt ist, dass der Ethylenoxidanteil des Alkylpolyglykolethers 50 bis 65 Gew.-% beträgt,
• b) 5-18 Gew.-% eines Alkylpolyglykolethers der Formel I, in der R' eine geradkettige Alkylgruppe und R² entweder Wasserstoff, oder zu 20 bis 75 Gew.-% - bezogen auf den dem Alkylpolyglykolether zugrunde liegenden Alkohol - eine C₁-C₄-Alkylgruppe und im übrigen Wasserstoff bedeuten, wobei die Gesamtzahl der Kohlenstoffatome in R' und R² 6 bis 10 beträgt und n einen Wert von 3 bis 8 bedeutet, und wobei n so ausgewählt ist, dass der Ethylenoxidanteil des Alkylpolyglykolethers 55 bis 70 Gew.-% beträgt,
• c) 1-10, vorzugsweise 2 bis 6 Gew.-% eines textilweichmachenden quartären Ammoniumsalzes, ausgewählt aus den Derivaten des Ammoniaks und/oder des Imidazolins mit vorzugsweise 2 langkettigen aliphatischen Resten im Molekül, wobei das Mengenverhältnis von a) : b) vorzugsweise 2 : 1 bis 1 : 2 beträgt,

und ist dadurch gekennzeichnet, dass es zusätzlich

• d) 5 bis 50 Gew.-%, bezogen auf die Menge der Komponenten a) + b), eines Ammonium-Gruppen enthaltenden kationischen Stärkeethers enthält, wobei das Mengenverhältnis von c) : d) vorzugsweise 3 : 1 bis 1 : 3 beträgt.

The nonionic surfactant component consists of a combination of two different nonionic surfactants, as described in DE-A-2 817 834. The liquid detergent according to the invention contains

• a) 5-18 wt .-% of an alkyl polyglycol ether of the formula
  
  in which R 'is a straight-chain alkyl group and R ² is 20 to 75% by weight, based on the alcohol on which the alkyl polyglycol ether is based, is a C 1 -C ₄ -alkyl group and, moreover, hydrogen, the total number of carbon atoms in R ^I and R ^{2 is} 11 to 15, and n is a value of 5 to 9, and where n is selected such that the ethylene oxide content of the alkyl polyglycol ether is 50 to 65% by weight,
• b) 5-18% by weight of an alkylpolyglycol ether of the formula I in which R 'is a straight-chain alkyl group and R ^{2 is} either hydrogen, or 20 to 75% by weight, based on that of the alkylpo alcohol based on lyglycol ether - a C ₁ -C ₄ alkyl group and hydrogen in the rest, the total number of carbon atoms in R 'and R ^{2 being} 6 to 10 and n being a value of 3 to 8, and where n is selected in this way that the ethylene oxide content of the alkyl polyglycol ether is 55 to 70% by weight,
• c) 1-10, preferably 2 to 6% by weight of a textile-softening quaternary ammonium salt, selected from the derivatives of ammonia and / or imidazoline with preferably 2 long-chain aliphatic radicals in the molecule, the quantitative ratio of a): b) preferably 2 : 1 to 1: 2,

and is characterized in that it is additional

• d) 5 to 50% by weight, based on the amount of components a) + b), of a cationic starch ether containing ammonium groups, the ratio of c): d) preferably being 3: 1 to 1: 3.

The alkyl polyglycol ethers of the formula I which are suitable as constituent a) are derived from alcohols which are prepared by reacting linear olefins with carbon monoxide and hydrogen in accordance with the known oxo process by hydroformylation and subsequent hydrogenation. Commercially available oxo-alcohol mixtures which are suitable for the preparation of the surfactant component a) are, for example, the oxo-alcohols available from the Deutsche Shell Chemie Gesellschaft under the trade name Dobanol ⁱⁱ , which have about 25% by weight of 2-alkyl branches. Other suitable oxo alcohols are available under the name Synprolli from Imperial Chemical Industries Ltd. available alcohol mixtures with about 50 to 70 wt .-% 2-alkyl branches. Other suitable products based on oxo alcohols are, for example, various Lutensol® types from BASF with approx. 30 to 35% by weight of branched alcohols and some Lial® types from Liquichimica SpA with approx. 60% by weight of branched alcohols.

As component a), particular preference is given to alkyl polyglycol ethers which are ethylene oxide condensates of the aforementioned oxo alcohols having 13 to 15 carbon atoms and an average ethylene oxide content of approximately 55 to 65% by weight. Typical preferred products are, for example, Dobanol 45-7®, which consists of at least 95% C ₁₄ / C ₁₅ oxo oxo alcohol with an average of 7 moles of ethylene oxide, and Lutensol AO-B ", which is a C ₁₃ / C ₁₅ oxo Represents alcohol ethoxylate with an average of 8 moles of ethylene oxide.

As component b), preference is given to alkyl polyglycol ethers whose alcohol base is natural or synthetic primary fatty alcohols or oxo alcohols which contain 9 to 12 carbon atoms and have an ethylene oxide content of approximately 60 to 70% by weight. Typical preferred products include the commercial product Marlipal KF "(Chemische Werke Hüls), which is a C ₁₀ / C ₁₂ fatty alcohol ethoxylate with an average of 6 moles of ethylene oxide, and the Lutensol ON-70®, which is a C ₉ / C ₁₁ - Oxo-alcohol ethoxylate with an average of 7 moles of ethylene oxide Suitable fatty alcohols as the basis for preferred alkyl polyglycol ethers are also the commercial products Lorol C-8 to 12® (Henkel).

The ratio of the amount of component a) used to the amount of component b) essentially determines the parameters of washing power, foaming behavior and softening effect. Optimal results are obtained if the ratio of a): b) is between approximately 2: 1 and 1: 2.

In general, amounts of component a) and component b) of 10 to 30% by weight, based on the total weight of the detergent, are used, an amount of 15 to 30% by weight being preferred.

Preferred detergents according to the invention contain, as constituent a), compounds whose radicals R ¹ + R ^{2 have} 11 to 13 carbon atoms and in particular 55 to 65% by weight of ethylene oxide. The detergents according to the invention preferably contain, as component b), compounds whose radical R ^{1 has} 7 to 10 carbon atoms and whose radical R ^{2 is} hydrogen, and which in particular have 60 to 70% by weight of ethylene oxide.

Water is preferably used as the solvent for the detergents according to the invention. However, organic solvents can also be used in amounts of up to 20, preferably up to 16% by weight of the total liquid detergent. Such additional solvents are either lower alkanols or lower diols or polyols such as ethanol, isopropyl alcohol, ethylene glycol, propylene glycol or glycerin. Optionally, polyols with ether compounds such as methyl, ethyl, butyl or diethylene glycol or their acetates (for example products of the "Cell-solve _{" type} from Union Carbide Corp.) can also be used.

To improve the solubility of the surfactants, it is often expedient to use solubilizers, so-called hydrotropes, in addition to or instead of the organic solvents mentioned above. The preferred hydrotropes are non-surfactant organic sulfonates, such as. B. C ₆ -C ₁₀ alkanesulfonates, and the salts of toluene, xylene and cumene sulfonic acid, preferably their alkanolamine and alkali salts, especially their potassium salts. Urea is also suitable as a hydrotrope. Hydrotropes are added in amounts of 2 to 12, preferably 3 to 9,% by weight, based on the total liquid detergent.

To improve certain properties, further auxiliaries, which are usually also effective in small amounts, can be added to the detergents according to the invention. These are, for example, opacifiers and viscosity regulators, which are usually present in the detergent to about 0.05 to 2% by weight. This is e.g. B. esters of alkanols or partial esters of polyols with longer-chain fatty acids, e.g. Palmitic or stearic acid. A typical product is ethylene glycol stearate.

Formalin is usually used as a preservative in an amount of 0.05 to 1% by weight.

To avoid discoloration of the detergent during longer storage, which can be caused by impurities such. B. can be caused with heavy metal ions in the manufacture, complexing agent for heavy metal ions is added. Common complexing agents are the sodium, potassium or triethanolamine salts of aminopolycarboxylic acids, such as, for example, ethylenediaminetetraacetic acid or nitrilotriacetic acid. They are used in amounts of 0.1 to 1% by weight.

Examples of suitable fragrances are substances with a floral / fresh or fruity fragrance or those designated as cosmetic or creamy.

Suitable dyes are e.g. water-soluble red xanthene dyes, such as rhodamine B extra.

• a) 10-12,5 Gew.-% eines Alkylpolyglykolethers der Formel 1, in der R^l und R² zusammen 11 bis 13 Kohlenstoffatome aufweisen und wobei der durchschnittliche Ethylenoxidgehalt des Alkylpolyglykolethers 55 bis 65 Gew.-% beträgt;
• b) 10-12,5 Gew.-% eines Alkylpolyglykolethers der Formel I, in der R¹ 7 bis 10 Kohlenstoffatome aufweist, R² = H ist und wobei der durchschnittliche Ethylenoxidgehalt des Alkylpolyglykolethers 60 bis 70 Gew.-% beträgt;
• c) 2-6 Gew.-% eines Ditalgalkyldimethylammoniumsalzes, vorzugsweise des Chlorids und/oder des Methylsulfats;
• d) 2-6 Gew.-% eines kationischen Stärkeethers;
• e) Rest Wasser und organische Lösungsmittel sowie gegebenenfalls weitere übliche, in geringen Mengen anwesende Zusätze wie Farb- und Duftstoffe, hydrotrope Mittel, Komplexierungsmittel für Schwermetallspuren sowie Konservierungs-, Trübungs- und Viskositätsstellmittel, wobei sich alle Mengenangaben der Komponenten a) bis e) auf die Gesamtmenge des Mittels beziehen.

An agent which is particularly preferred with regard to balanced product properties has the following composition:

• a) 10-12.5% by weight of an alkylpolyglycol ether of the formula 1 in which R ¹ and R ² together have 11 to 13 carbon atoms and the average ethylene oxide content of the alkylpolyglycol ether is 55 to 65% by weight;
• b) 10-12.5% by weight of an alkylpolyglycol ether of the formula I in which R ^{1 has} 7 to 10 carbon atoms, R ² = H and the average ethylene oxide content of the alkylpolyglycol ether is 60 to 70% by weight;
• c) 2-6% by weight of a ditallow alkyldimethylammonium salt, preferably the chloride and / or the methyl sulfate;
• d) 2-6% by weight of a cationic starch ether;
• e) the rest of water and organic solvents and, if appropriate, other customary additives present in small amounts, such as colorants and fragrances, hydrotropic agents, complexing agents for traces of heavy metals, and preservatives, opacifiers and viscosity regulators, all of the amounts of components a) to e) being based on obtain the total amount of the agent.

The detergents according to the invention can be used for washing and simultaneously improving the touch of colored and light-colored or white textiles made of cotton, linen, wool, cellulosic chemical fibers, synthetic fibers such as polyester, polyacrylonitrile, polyamide and mixtures of cotton, wool linen, cellulosic chemical fibers and synthetic fibers, the dye transfer is largely suppressed. The washing and softening process can take place at washing temperatures up to about 60 ° C. The application concentration of the agents is generally 2 to 20 ml per liter of wash liquor, preferably 3 to 8 ml per liter. The textiles are not only cleaned properly, but also get a pleasant grip. The good foaming behavior allows the agents to be used both in the washing machine and for hand washing. Examples

example 1

• 11,0 Gew.-% C₁₄/C₁₅-Oxo-Alkohol-Ethoxylat mit durchschnittlich 58 Gew.-% Ethylenoxid (Dobanol 45-7^%, Shell);
• 11,0 Gew.-% C₁₀/C₁₂-Fettalkohol-Ethoxylat mit durchschnittlich 60 Gew.-% Ethylenoxid (Marlipal KF", Chemische Werke Hüls);
• 2,8 Gew.-% Ditalgalkyldimethylammoniumchlorid (100%ig), eingesetzt als 75%ige Paste, Rest Isopropanol und Wasser, (Präpagen WK⁹, Hoechst);
• 1,2 Gew.-% kationischer Kartoffelstärkeether (Empresol N", Emsland-Stärke GmbH);
• 7,0 Gew.-% Ethanol/1,2-Propylenglykol;

Rest Wasser und geringe Mengen Konservierungsmittel, Farbstoff, Duftstoff.A detergent of the following composition was produced:

• 11.0% by weight of C ₁₄ / C ₁₅ oxo alcohol ethoxylate with an average of 58% by weight of ethylene oxide (Dobanol 45-7 ^% , Shell);
• 11.0% by weight of C ₁₀ / C ₁₂ fatty alcohol ethoxylate with an average of 60% by weight of ethylene oxide (Marlipal KF ", Chemische Werke Hüls);
• 2.8% by weight of ditallow alkyldimethylammonium chloride (100%), used as a 75% paste, the rest isopropanol and water, (Prepagen WK ⁹ , Hoechst);
• 1.2% by weight of cationic potato starch ether (Empresol N ", Emsland-Starch GmbH);
• 7.0% by weight ethanol / 1,2-propylene glycol;

Balance water and small amounts of preservative, dye, fragrance.

Example 2

For comparison, an agent of the composition of Example 1 was prepared with the exception of the potato starch ether, which was replaced by the same amount of ditallow alkyl dimethyl ammonium chloride. This detergent corresponds to an agent of the prior art.

Example 3

Another agent was prepared which had a composition similar to that of Example 2, except that the ditallow alkyl dimethyl ammonium chloride was replaced with the same amount of water.

Example 4

With the detergents of Examples 1 to 3, washing tests were carried out in a commercially available drum washing machine. Cotton bleaching nettle, white, was washed at a liquor ratio of 1 20, without contamination, in the presence of a section of fabric weighing approx. 20 g, which was colored with 3.5% Sirius light red F 4 BL, 154%. 84 g of the detergents from Examples 1 to 3 were added to a drum filling and, after washing, the reflectance values were measured using the Zeiss Elrepho RFC3, filter R 560.

_"Die Ergebnisse zeigen die überlegene Verfärbungsinhibierende Wirkung des erfindungsgemässen Waschmittels von Beispiel 1.The result is shown in Table 1.

_" The results show the superior discoloration-inhibiting effect of the detergent according to the invention from Example 1.

Similar results are obtained with textile samples made of terry cloth, lycra, cotton, polyester / cotton, dralon, nylon, etc.

Claims (10)

1. A liquid detergent containing

a) from 5 to 18% by weight of an alkyl polyglycol ether corresponding to the following formula

in which R¹ is a straight-chain alkyl group and from 20 to 75% by weight of R², based on the alcohol on which the alkyl polyglycol ether is based, is a C₁-C₄ alkyl group and the remainder is hydrogen, the total number of carbon atoms in R¹ and R² amounting to between 11 and 15, and n has a value of from 5 to 9, n being selected in such a way that the ethylene oxide content of the alkyl polyglycol ether amounts to between 50 and 65% by weight,

b) from 5 to 18% by weight of an alkyl polyglycol ether corresponding to formula 1, in which R¹ is a straight-chain alkyl group and R² is either hydrogen or from 20 to 75% by weight of R², based on the alcohol on which the alkyl polyglycol ether is based, is a C_l-C, alkyl group and the remainder is hydrogen, the total number of carbon atoms in R¹ and R² amounting to between 6 and 10, and n has a value of from 3 to 8, n being selected in such a way that the ethylene oxide content of the alkyl polyglycol ether amounts to between 55 and 70% by weight,

c) from 1 to 10% by weight and preferably from 2 to 6% by weight of a fabric-softening quaternary ammonium salt selected from the derivatives of ammonia and/or imidazoline preferably containing 2 long-chain aliphatic radicals in the molecule, the weight ratio of a) to b) preferably amounting to between 2: 1 and 1 : 2, characterized in that it additionally contains

d) up to 50% by weight, based on the quantity of components a) and b), of a cationic starch ether containing ammonium groups,

the quantitative ratio of c) to d) preferably amounting to between 3 : 1 and 1 : 3.

2. A liquid detergent as claimed in Claim 1, characterized in that component a) and component b) together make up from 10 to 30% by weight and preferably from 15 to 30% by weight, based on the total weight of the detergent.

3. A liquid detergent as claimed in Claims 1 and 2, characterized in that R' and R² of component a) together contain from 11 to 13 carbon atoms.

4. A liquid detergent as claimed in Claims 1 to 3, characterized in that the ethylene oxide content of component a) amounts to between 55 and 65% by weight.

5. A liquid detergent as claimed in Claims 1 to 4, characterized in that, of component b), R' contains from 7 to 10 carbon atoms and R² is hydrogen.

6. A liquid detergent as claimed in Claims 1 to 5, characterized in that the ethylene oxide content of component b) amounts to between 60 and 70% by weight.

7. A liquid detergent as claimed in Claims 1 to 6, characterized in that component c) is a quaternary ammonium salt of which the anion is selected from the group comprising chloride, bromide, methyl sulfate, ethyl sulfate, methane, ethane and toluene sulfonate.

8. A liquid detergent as claimed in Claims 1 to 7, characterized in that component c) is a ditallow alkyl dimethyl ammonium salt.

9. A liquid detergent as claimed in Claims 1 to 8, consisting of

a) from 10 to 12.5% by weight of an alkyl polyglycol ether of formula I in which R¹ and R² together contain from 11 to 13 carbon atoms, the average ethylene oxide content of the alkyl polyglycol ether amounting to between 55 and 65% by weight;

b) from 10 to 12.5% by weight of an alkyl polyglycol ether of formula I in which R¹ contains from 7 to 10 carbon atoms, R² = H, the average ethylene oxide content of the alkyl polyglycol ether amounting to between 60 and 70% by weight;

c) from 2 to 6% by weight of a ditallowalkyl dimethyl ammonium salt, preferably the chloride and/or the methyl sulfate;

d) from 2 to 6% by weight of a cationic starch ether;

c) remainder water and organic solvents and, optionally, other standard additives, such as dyes and perfumes, hydrotropic agents, complexing agents for traces of heavy metals and preservatives opacifiers and viscosity regulators, present in small quantities,

the quantities indicated for components a) to e) all being based on the detergent as a whole.

10. A liquid detergent as claimed in Claims 1 to 9, characterized by a content of cationic starch ether obtainable by reacting starch with 2,3-epoxypropyl trimethyl ammonium salts.