EP0011715A1 - Liquid, cold-stable two-component washing agent and washing process - Google Patents

Abstract

A fluid, two-component washing agent consisting of two-components, A and B, of which component A is an aqueous dispersion of fatty acids and component B is an alkaline solution, wherein component A is a cold-stable aqueous dispersion consisting essentially of (a) from 25% to 35% by weight of a substantially unsaturated fatty acids, (b) from 10% to 16% by weight of a potassium soap of the fatty acids of (a), (c) from 15% to 25% by weight of an ethoxylated primary alcohol having 5 to 12 oxyethylene units, (d) from 4% to 10% by weight of a sodium C10-14 alkylbenzenesulfonate, (e) from 0.05% to 1% by weight of at least one optical brightener, (f) from 1% to 5% by weight of at least one hydrotropic compound, (g) from 2% to 10% by weight of at least one C1-3 alcohol, and (h) from 15% to 30% by weight of water, and wherein component B is an alkaline solution containing alkaline potassium compounds.

Description

Two-component detergents are understood to mean preparations consisting of two separately produced and stored detergent constituents which are only combined with one another immediately before or at the start of the washing process. The present invention relates to such an agent in which the liquid concentrate contains one component as a fatty acid and other surfactants and the other component contains the alkali required for soap formation.

From GB-PS 338 121 a washing method using a two-component detergent is known. The first component consists of soap-forming fatty acids, such as palmitic acid, stearic acid or oleic acid, which can be present in a mixture with emulsifiers or solvents, such as sulfated olive oil, hydrocarbons, turpentine and chlorinated hydrocarbons. The second component contains the alkalis required for soap formation, such as alkali metal hydroxides, carbonates, bicarbonates and silicates, and is only combined with the first component in the wash liquor. Bleaching components can also be added. This process has a number of disadvantages, particularly in commercial laundries high degree of automation play a role. It is difficult to automatically feed and dose the fatty acids mentioned, while the use of solvents from the range of hydrocarbons or chlorinated hydrocarbons poses considerable problems, such as increased risk of fire and explosion or toxicological concerns. In addition, the reaction between the fatty acids which are not sufficiently finely dispersed in the washing liquid and the alkali is relatively slow, in particular at washing temperatures below 65 C. The reaction is moreover inhibited or partially prevented by the laundry present, so that it forms fatty acid deposits on the Laundry can come.

Another method known from FR-PS 1 460 904 is based on aqueous fatty acid emulsions suitable for soap formation, which are combined with the washing alkalis in the wash liquor. The fatty acid, which is preferably technical oleic acid or a low-melting fatty acid mixture (titer 45 ° C.), is emulsified in water with a nonionic emulsifier, such as polyoxyethylene sorbitan monolaurate or monostearate, optionally with the addition of distilled tall oil . Substances with an alkaline reaction must not be added, as these will break the emulsions. It has now been shown that the cleaning power of the compositions is comparatively low, since the emulsifiers used do not make any notable contribution to the detergency. Furthermore, the stability, in particular the low-temperature stability, of the emulsions is poor, since segregation occurs below the freezing point, which cannot be easily reversed after heating.

Despite these problems, there is still interest in liquid agents of the aforementioned type _e, in particular in the form of highly concentrated preparations. Highly concentrated agents make it possible to keep packaging, transport and storage costs low. Also as liquid funds, they have the advantage of easy handling and _D osier- bility. This not only offers decisive advantages for commercial laundries that are equipped with appropriate batch and storage tanks, but also for the z. Household washing machines currently in development, equipped with storage and dosing devices. With these new devices, the detergent dosage is specifically matched to the respective washing program, which prevents undesirable or wastewater-incorrect dosing.

• a) 25 bis 35 Gew.-% einer Fettsäure mit 12 bis 18 Kohlenstoffatomen, die zu 60 bis 100 Gew.-% aus ölsäure besteht,
• b) 10 bis 16 Gew.-% einer Kaliumseife, die sich von einer Fettsäure der unter (a) angeführten Zusammensetzung ableitet,
• c) 15 bis 25 Gew.-% eines ethoxylierten primären linearen bzw. in 2-Stellung methylverzweigten Alkohols mit 8 bis 14 Kohlenstoffatomen und durchschnittlich 5 bis ¹² Ethylenglycolethergruppen
• d) 4 bis 10 Gew.-% eines Natriumalkylbenzolsulfonats mit linearen, 10 bis 14 Kohlenstoffatomen aufweisenden Alkylketten,
• e) 0,05 bis 1 Gew.-% mindestens eines optischen Aufhellers aus der Klasse der substituierten Stilbensulfonsäuren in Form des Na- oder K-Salzes,
• f) 1 bis 5 Gew.-% mindestens einer hydrotropen Verbindung aus der Klasse des Harnstoffs und der Na- oder K-Salze von Alkylbenzolsulfonaten mit 1 bis 2 Alkylgruppen, die insgesamt 1 bis 3 Kohlenstoffatome enthalten,
• g) 2 bis 10 Gew.-% mindestens eines Alkohols mit 1 bzw. 3 Kohlenstoffatomen,
• h) 15 bis 30 Gew.-% Wasser.

The invention, with which the disadvantages described are avoided or the problems mentioned are solved, is a detergent consisting of two components A and B, of which component A consists of an aqueous dispersion of soap-forming fatty acids with 12 to 18 carbon atoms and component B consists of one there is an aqueous solution of alkaline substances which are capable of complete soap formation with the fatty acids of component A and optionally sequestering compounds, characterized in that component A is composed as follows:

• a) 25 to 35% by weight of a fatty acid with 12 to 18 carbon atoms, which consists of 60 to 100% by weight of oleic acid,
• b) 10 to 16% by weight of a potassium soap which is derived from a fatty acid of the composition mentioned under (a),
• c) 15 to 25% by weight of an ethoxylated primary linear or methyl-branched alcohol in the 2-position with 8 to 14 carbon atoms and an average of 5 to ¹² ethylene glycol ether groups
• d) 4 to 10% by weight of a sodium alkylbenzenesulfonate with linear alkyl chains having 10 to 14 carbon atoms,
• e) 0.05 to 1% by weight of at least one optical brightener from the class of the substituted stilbene sulfonic acids in the form of the Na or K salt,
• f) 1 to 5% by weight of at least one hydrotropic compound from the class of the urea and the Na or K salts of alkylbenzenesulfonates with 1 to 2 alkyl groups which contain a total of 1 to 3 carbon atoms,
• g) 2 to 10% by weight of at least one alcohol with 1 or 3 carbon atoms,
• h) 15 to 30 wt .-% water.

The fatty acid listed under (a) consists of 60 to 100% by weight, preferably .65 to 95% by weight, of oleic acid. In addition to oleic acid, polyunsaturated fatty acids, e.g. Linoleic acid, in proportions of 0 to 25, preferably 1 to 15 wt .-% in the fatty acids. The proportion of saturated fatty acids with 12 to 18 carbon atoms is 0 to 35, preferably 2 to 20% by weight, the proportion expediently. the stearic acid should not exceed 5% by weight, in particular 3% by weight. Suitable fatty acid mixtures have, for example, the following composition (in% by weight):

The content of the fatty acids mentioned under (a) in the dispersion is preferably 30 to 34% by weight.

The potassium soap mentioned under (b) is derived from the fatty acids of the aforementioned composition and is preferably present in proportions of 12 to 15% by weight.

The ethoxylated alcohols listed under (c) are derived from native or synthetic alcohols, in particular oxo alcohols having 8 to 14, preferably 9 to 12, carbon atoms. The oxo alcohols can be linearly branched or methyl-branched in the 2-position. Mixtures of native alcohols and alcohols obtained by oxo reaction are also suitable. The number of ethylene glycol ether groups is on average 5 to 10, preferably 6 to 8. The proportion of ethoxylated alcohols in the dispersions should be 15 to 25, preferably 18 b ^i. s are 22% by weight.

The component (d) consists of linear sodium alkylbenzenesulfonate, in particular dodecylbenzenesulfonate, in proportions of 4 to 10, preferably 6 to 8,% by weight.

The optical brighteners listed under (e) are derived from compounds of the formulas

worin die einzelnen Symbole die folgende Bedeutung haben:

• Me = Na, K
• R_1' R₂ = -NHCH₃, -NCH₃(CH₂CH₂0H), -N(CH₂CH₂0H)₂
  
• R₃, R₄ = H, -CH₃, -Cl, -OCH₃, -COOCH₃, -CN, -S0₂NR₅R₆, -CONR₅R₆ mit R₅ und R₆,= H oder Alkylreste mit 1 bis 3 Kohlenstoffatomen.

where the individual symbols have the following meaning:

• Me = Na, K
• R _{1 '} R ₂ = -NHCH ₃ , -NCH ₃ (CH ₂ CH ₂ 0H), -N (CH ₂ CH ₂ 0H) ₂
  
• R ₃ , R ₄ = H, -CH ₃ , -Cl, -OCH ₃ , -COOCH ₃ , -CN, -S0 ₂ NR ₅ R ₆ , -CONR ₅ R ₆ with R ₅ and R ₆ , = H or alkyl radicals with 1 to 3 carbon atoms.

Optical brighteners of the formula I are preferably used, in which R ₁ and R _{2 represent} morpholino, diethanolamino or anilino residues. The optical brighteners are present in proportions of 0.05 to 1, preferably 0.1 to 0.7,% by weight.

The hydrotropic compounds listed under (f) can be present in the form of the Na or K salts from urea and / or from low molecular weight alkyl or dialkylbenzenesulfonates, such as toluene, ethylbenzene, cumene or xylene sulfonate. Their proportion is preferably 1.5 to 3% by weight.

The component (g) consists of aliphatic C ₁ -C ₃ alcohols, for example ethanol, propanol and in particular isopropanol, and of the mixtures of the alcohols mentioned. The content of these alcohols in the compositions is preferably up to 8% by weight. Agents with fractions of less than 4% of the alcohols mentioned can also contain hydrotropic ether alcohols which are derived from C ₁ -C ₄ monoalcohols and ethylene glycol or propylene glycol or diglycols. For example, the monomethyl, monoethyl, monopropyl, monoisopropyl or monobutyl ethers of ethylene glycol are suitable.

sind innerhalb eines Temperaturbereiches zwischen +50°C und -1₀ ⁰C unbegrenzt lagerbeständig. Sie werden zwar nach mehrwöchiger Lagerung bei einer Temperatur von -10 °c pastenartig, neigen jedoch selbst unter derartig extremen Bedingungen nicht zum Entmischen, sondern bilden nach dem Wiedererwärmen wieder gut gießbare, weitgehend klare Flüssigkeiten. ,The water content of the detergent concentrate is 15

are stable in storage within a temperature range between + 50 ° C and -1 ₀ ⁰ C. Although they become pasty after storage for several weeks at a temperature of -10 ° C, they do not tend to separate even under such extreme conditions, but instead form well-pourable, largely clear liquids after reheating. ,

Other additives may also include biocides, fragrances, dyes, stabilizers, sequestering agents, neutral salts and optical brighteners of other constitution, but the total amount of such additives should not exceed 10% by weight and preferably less than 5% by weight, in particular less than 2 wt .-%, so that a negative influence on the cold stability is avoided.

Component B, which is combined with the dispersion described above to form fatty acid soaps before or at the start of the washing process, consists of a. most technical cases from an aqueous solution of alkalis, for example the hydroxides, carbonates, silicates, phosphates and polyphosphates of sodium or potassium or of mixtures of the alkaline compounds mentioned. Their alkalinity and their amount should be such that the fatty acids are completely converted into the soaps and there is also an excess of alkali, so that the pH of the wash liquor is 9.5 to 14, preferably at least 10 and in particular 10.2 - is 13.5. In addition to the alkali or the sequestering acting polyphosphates, other compounds can be present sequestering acting _'. e.g. the Na or K salts of polycarboxylic acids, Hydroxy- or Ethcrpolycarboxylic acids, aminopolycarboxylic acids, hydroxyalkanephosphonic acids and aminopolyphosphonic acids. Examples of particularly common compounds are nitrilotriacetic acid, ethylenediaminotetraacetic acid, diethylenetriamineopentaacetic acid, 1-hydroxyethane-1,1-diphosphonic acid and 1-aminoethane-1,1-diphosphonic acid.

A liquid, easily metered and, in particular, cold-resistant solution of washing alkalis, which has proven to be particularly suitable as component B for use in automated laundry operations, has the following composition:

The mixing ratio of component A with liquid component B according to the above composition is 1: 1 to 1: 4, preferably 1: 2 to 1: 3, the total amount of all detergent components and washing alkalis in the washing liquor being 5 g to 30 g, preferably 10 is up to 25 g per kg of dry laundry.

The invention further relates to a washing process using the two components A and B in accordance with the aforementioned compositions, mixing ratios and use concentrations. Additional components can be added to these washing processes are, for example, sodium aluminum silicates capable of cation exchange according to DE-AS 24 12 837, graying inhibitors, such as cellulose ethers and cellulose mixed ethers, enzymes and bleaches containing active oxygen or active chlorine, optionally with the addition of bleach activators. Insofar as the stability of the compounds in question permits, they are also preferably in the form of solutions or dispersions, it being possible, if necessary, to counteract poor stability by encapsulating the active compounds.

Example: 1 e

The fatty acids (a) used in the recipes and the fatty acids contained in the potassium soaps (b) had the following composition (in% by weight):

An oxo alcohol of chain length C ₉ -C ₁₁ with 7 ethylene glycol ether groups was used as the ethoxylated alcohol (component c). Component d consisted of linear Na dodecylbenzenesulfonate. The sodium salt of the compound of the formula I was used as the optical brightener (component e), in which R ₁ and R ₂ meant morpholino radicals. Urea or K-toluenesulfonate was used as the hydrotrope (component f). Component g consisted of isopropanol. The component "salts" means small amounts of Na ₂ S0 ₄ and NaCl, which were present as accompanying substances of the alkylbenzenesulfonate and the optical brightener. The composition is shown in Table 2.

Zwecks Herstellung der Mittel wurden zunächst die Fettsäure mit der zur Seifenbildung erforderlichen Menge Kalilauge sowie dem Ethoxylat und dem Alkylbenzolsulfonat, das als 50 %ige wäßrige Lösung vorlag, miteinander vermischt, darauf der in Isopropanol gelöste optische Aufheller eingerührt und abschließend das Hydrotrop sowie Wasser bis zur angegebenen Menge zugefügt.

For the preparation of the agents, the fatty acid was first mixed with the amount of potassium hydroxide solution required for soap formation and the ethoxylate and the alkylbenzenesulfonate, which was in the form of a 50% strength aqueous solution, then the optical brightener dissolved in isopropanol was stirred in, and finally the hydrotrope and water up to specified amount added.

The concentrates were in the form of yellowish, clear to slightly iridescent solutions which were thin at room temperature and remained clear and homogeneous when stored for three weeks in a climatic cabinet at -10 ° C and +50 ° C. A multiple temperature change between +5 ₀ ° C and -10 ° C also did not lead to segregation. The concentrates were miscible with water in all proportions.

The following readings were used as alkaline component B (amounts in% by weight):

Die Lösungen erwiesen sich in einem Temperaturbereich von -10° bis +50 °C als stabil.

The solutions proved to be stable in a temperature range from -10 ° to +50 ° C.

The following proportions were combined with one another for washing treatment.

Soaking process

Two-eye procedure prewash

Plain wash

Bei einem Flottenverhältnis (kg Trockenwäschs pro l Waschlauge) von 1 : 4 bis 1 :10 unter Verwendung von enthärtetem Wasser wurden einwandfreie Waschergebnisse erzielt.

With a liquor ratio (kg of dry laundry per liter of wash liquor) from 1: 4 to 1:10 using softened water, perfect washing results were achieved.

Claims (11)

1. For two components A and B existing detergent, of which component A consists of an aqueous dispersion was anbildender fatty acids having 12 to 18 carbon atoms and component B of an aqueous solution of alkaline-reacting, capable of complete soap formation with the fatty acids of component A _r Sto fe and optionally sequestering compounds, characterized in that component A is composed as follows: a) 25 to 35 wt .-% of a fatty acid with 12 to 18 carbon atoms, the 60 to 100 wt .-% from oleic acid. stands, b) 10 to 16% by weight of a potassium soap which is derived from a fatty acid of the composition mentioned under (a), c) 15 to 25% by weight of an ethoxylated primary linear or methyl-branched alcohol in the 2-position with 8 to 14 carbon atoms and an average of 5 to ₁₂ ethylene glycol ether groups, d) 4 to 10% by weight of a sodium alkylbenzenesulfonate with linear alkyl chains having 10 to 14 carbon atoms, e) 0.05 to 1% by weight of at least one optical brightener from the class of the substituted stilbene sulfonic acids in the form of the Na or K salt, f) 1 to 5% by weight of at least one hydrotropic compound from the class of the urea and the Na or K salts of alkylbenzenesulfonates with 1 to 2 alkyl groups which contain a total of 1 to 3 carbon atoms, G)

3 carbon atoms, h) 15 to 30 wt .-% water.

3. Composition according to claim 1, characterized in that the potassium soap listed under (b) is derived from a fatty acid according to claim 2 and is present in proportions of 12 to 15 wt .-%. 4. Means according to claim 1, characterized; that the ethoxylated alcohols listed under (c) contain 9 to 12 carbon atoms and 6 to 8 ethylene glycol ether groups and are present in proportions of 18 to 22% by weight, 5. Composition according to claim 1 ', characterized in that the alkylbenzene sulfonate listed under (d) is present as Na dodecylbenzene sulfonate in proportions of 6 to 8% by weight. 6. Composition according to claim 1, characterized in that the optical brighteners listed under (e) consist of compounds of the following formulas:

where the individual symbols have the following meaning: Me = Na, K R ₁ , R ₂ '= -NHCH ₃ , -NCH ₃ (CH ₂ CH ₂ OH), -N (CH ₂ CH ₂ OH) ₂

R ₃ , R ₄ = H, -CH ₃ , = Cl, -OCH ₃ , -COOCH ₃ , -CN, -SO ₂ NR ₅ R ₆ : -CONR ₅ R ₆ with R ₅ and R ₆ = H or alkyl radicals with 1 to 3 carbon atoms. 7. Composition according to claim 1, characterized in that the hydrotropic compounds listed under (f) are present in proportions of 1.5 to 3 wt .-%. 8. Composition according to claim 1, characterized in that the alcohol listed under (g) consists of isopropanol and is present in proportions of 3 to 8 wt .-%. 9. Composition according to claim 1, characterized in that the water content is 16 to 22 wt .-%. 10. Washing method using a

Component A according to claims 1 to 9 and a further at least one alkaline hydroxide, carbonate silicate, phosphate or polyphosphate of sodium and / or potassium-containing component B in an amount that the combination of the two components before or at the beginning of the washing process the washing liquor a pH of 9.5 to 14, preferably from 10.2 to 13.5 and the total amount of all detergent components and washing alkalis in the wash liquor is 5 g to 30 g, preferably 10 to 25 g, per kg of dry laundry. 11. Washing method according to claim 10, characterized in that as component B a solution of the composition

in a ratio of A: B like 1: 1 to 1. 4 from 1: 2 to 1: 3 is used.