KR900004494B1 - Detergent composition - Google Patents

Abstract

A detergent compsn. having improved dispensibility in automatic washing machines contains a builder mixt. of a water-soluble alkali metal carbonate such as sodium carbonate and a water-insol. particulate carbonate seed crystal for calcium carbonate, e.g. calcite is claimed. The compsn. comprises a ternary active system containing 30-70% anionic active such as an alkyl benzene sulphonate, 20-27% of nonionic active such as an ethoxylated alcohol and at least 10% soap. The soap must exceed 10% of the compsn. as a whole.

Description

Detergent composition

The present invention relates to detergent compositions, in particular detergent compositions intended for use in textile washing in automatic washing machines, and more particularly detergent compositions containing materials containing little or no phosphorus.

Detergent compositions generally contain, in addition to detergent active materials, in particular detergent builders which serve to remove hard ions from the wash liquor which, if not removed, reduce the effectiveness of the detergent active materials. Water-soluble phosphate materials have been widely used as detergent builders. However, there have been hopes of using the patented sodium carbonate, alkali metal salt of carbonate instead of phosphate, for a variety of reasons, including nutritional promotion and cost, which are supposed to be caused by phosphates. However, the alkali metal salt cleaning power builder of carbonic acid has various problems. Firstly, the reaction of alkali metal salts of carbonic acid with calcium ions contained in hard water results in the formation of insoluble calcium carbonate, which, depending on the conditions, aggregates in the washed fabric and remains in that form. Secondly, the reaction of alkali metal salts of carbonic acid with calcium ion of hard water is particularly slow at low temperatures and is easily inhibited by substances acting as calcium carbonate precipitate growth inhibitors, referred to herein as poisons. This result indicates that some free calcium ions can still be used to reduce the effect of detergent actives, since the concentration of calcium ions in the wash liquor does not decrease to the desired extent or as fast as desired.

In order to solve this problem, it has been proposed to contain an insoluble substance in the detergent composition which acts as a seed crystal of precipitated calcium carbonate and can absorb the poison from the wash liquor. Granular calcite among other materials has been proposed as such material (see British Patent No. 1437950).

The detergent active substance may be selected from various kinds of substances, but it is preferable to use a mixture of anionic non-soap detergent active substance, nonionic detergent active substance and soap.

However, detergent compositions containing these three-component active systems, together with alkali metal salts and calcite of carbonic acid, have poor partitioning properties in automatic washing machines when compared to equivalent detergent compositions containing phosphates as a cleaning power builder. In such a washing machine, a user puts an appropriate amount of detergent powder into a dispenser in which the detergent powder is held until needed by the washing machine. At the appropriate time in the wash cycle, water enters the dispenser and, together with the detergent powder, reaches the laundry room of the washing machine through the supply line. If the powder is not substantially washed off from the dispenser during the washing operation, it is not only wasteful, but after repeated use the powder builds up and eventually clogs the dispenser and / or the feed tube. Therefore, the user needs to wash the dispenser well after each washing cycle.

In some washing machines, the cause of poor partitioning of carbonate / calcite base powders has not been fully understood, but we have surprisingly found that relatively good partitioning can be achieved with selected three-component activators.

Therefore, according to this invention, the detergent composition containing the following component is provided. That is, (i) a detergent active system composed of a mixture of the following substances; (a) anionic non-soap detergent active materials, (b) nonionic detergent active materials, and (c) soaps, (ii) water-soluble alkali metal salts of carbonic acid; And (iii) a soluble particle carbonate substance that is a seed crystal of calcium carbonate.

Here, the content of (a) is 30% to 70%: the content of (b) is 20% to 27%: and (c) based on the total weight of components (a), (b) and (c) Is at least 10%, but not more than 10% of the total composition weight.

British Patent No. 2104912A describes, in Example 8, a calcite / carbonate build composition having a three component active system in which the proportions of anion, nonionic and soap in the three component system are within the previously specified range. However, since the soap content is described at 12%, this composition is not entirely within the above limits. Moreover, the previous English specification does not suggest, specify or imply how a calcite / carbonate build tricomponent system can obtain improved distribution properties.

Although our invention requires soaps in amounts not exceeding 10% by weight of the total composition, it is preferred that this value does not exceed 8%.

The composition preferably contains from 5% to 40% by weight, preferably 25% by weight or less of detergent.

Patent useful results were obtained when the detergent active mixture contained about 35% to 60% anionic active material, about 21% to 26% nonionic active material and about 15% to 35% soap.

Non-soap (synthetic) anionic detergent active compounds are generally water-soluble alkali metal salts of organosulfuric and sulfonic acids with alkyl radicals containing from about 8 to about 22 carbon atoms, and the term alkyl includes alkyl moieties of higher acyl radicals. do. Examples of suitable synthetic anionic detergent compounds include sodium sodium sulfate and potassium (especially sodium and potassium alkyl sulfates obtained by sulphating higher (C ₈ -C ₁₈ ) alcohols produced from tallow or coconut oil), alkyl (C ₉ -C ₂₀ ) Sodium Benzenesulfonate and Potassium (Patented Linear Secondary Alkyl (C ₁₀ -C ₁₅ ) Sodium Benzenesulfonate), Alkyl Glyceryl Ether Sulfate (Derived from Higher Alcohols and Petroleum Derived from Patented Tallow or Coconut Oil) Sodium or potassium salts of the above esters of synthetic alcohols, coconut oil, fatty acid monoglycerides and sodium sulfonates, sulfates of higher (C ₈ -C ₁₈ ) fatty alcohol-alkylene oxides (especially ethylene oxide reaction products) , Reaction products of fatty acids, such as coconut acid, esterified with isethionic acid and neutralized with sodium hydroxide, sodium and potassium salts of fatty acid amides of methyltaurine, alpha Alkanesulfonates induced by the reaction of -olefins (C ₈ -C ₂₀ ) with sodium bisulfite and paraffins with SO ₂ and Cl ₂ Alkanomones derived by hydrolysis with a base to produce a random sulphonate Sulfonates, and olefinsulfonates (the term describes a substance obtained by neutralizing and hydrolyzing this reaction product after the reaction of olefin patent C ₁₀ -C ₂₀ alpha-olefins with SO ₃ ). Preferred anionic detergent compounds are (C ₁₁ -C ₁₅ ) alkyl benzenesulfonate sodium and (C ₁₆ -C ₁₈ ) sodium sulfate.

Suitable nonionic detergent compounds include reaction products of patent hydrophobic groups and compounds having reactive hydrogen atoms (e.g. aliphatic alcohols, acids, amides or alkylphenols) with alkylene oxides (especially ethylene oxide or ethylene oxide / propylene oxide). . Certain nonionic detergent compounds are generally alkyl (C ₆ -C ₂₂ ) phenol-ethyleneoxide condensates having 5 to 25 EO per molecule (ie, 5 to 25 units of ethylene oxide per molecule), typically 5 to 40 EO. Condensation products of ethylene oxide with aliphatic (C ₈ -C ₁₈ ) primary or secondary linear or branched alcohols, and products obtained by condensation of propylene oxide with ethylenediamine and ethylene oxide. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxide crude dialkylsulfoxides.

The term " soap " as used herein generally means not only alkali metal and alkaline earth metal salts of fatty acids but also organic salts produced by complexes of fatty acids with nitrogen-containing organic materials such as amines and derivatives thereof. Soaps generally comprise salts of higher fatty acids containing 8 to 24 carbon atoms, preferably 10 to 20 carbon atoms, or mixtures thereof, in the molecule.

Examples of preferred soaps are sodium salts of sodium stearate, sodium palmitate, tallow, sodium salts of coconut oil and palm oil, and stearic and / or palmitic fatty acids and / or tallow and / or coconut oil and / or Or water-soluble alkanolamines and morpholines such as palm oil and ethanolamine, di- or tri-ethanol amine, N-methylethanol amine, N-ethylethanol amine, 2-methylethanol amine and 2,2-dimethylethanol amine , 2'-pyrrolidone and complexes with N-containing cyclic compounds such as methyl derivatives of these substances.

It is also possible to use mixtures of soaps.

Particular preference is given to the sodium and potassium salts of mixed fatty acids derived from coconut oil and tallow, ie sodium and potassium tallow and coconut soap.

An essential component of the composition is a water soluble carbonate as a builder. This material is preferably sodium carbonate or potassium or mixtures thereof for reasons of cost and effectiveness. Carbonates are preferably fully neutralized, but may be partially neutralized (e.g. sesquicarbonate may be used as a partial substitute for normal carbonates), and these partially neutralized salts are less effective because they tend to be less alkaline. . The content of the water-soluble carbonate substance in the detergent composition may vary widely, although the content may be used up to 75% by weight if desired for a particular product, but the content is at least 5% by weight, preferably 10-40% by weight, Patent 10 It should be -35% by weight. Even if the water-soluble carbonate is hydrated before or when incorporated into the detergent composition, the content of this carbonate is determined based on the anhydrous state. It should also be noted that it is also desirable to limit the content of carbonates to low levels within the above-described range so as to reduce the risk of internal damage resulting from, for example, some inadvertent intake by children.

The composition necessarily contains insoluble particulate carbonates. This material should be able to act as a seed crystal of the precipitate resulting from the reaction between the calcium hard ions of the water and the water-soluble carbonate. Therefore, this insoluble particulate matter is the seed crystal of calcium carbonate, such as calcium carbonate itself.

Insoluble particulate carbonate material should be subdivided and have a surface area of at least 10 m ² / g, preferably at least 15 m ² / g. Particular preference is given to materials having a surface area of 30-100 m ² / g. If economically available, insoluble carbonate materials having a surface area exceeding 100 m ² / g may be used.

Surface area is measured by nitrogen absorption using a standardized Brewer, Emmet & Teller (BET) method. A suitable machine for carrying out this method is the Carlo Erba Sorpty 1750 instrument, which is operated by the manufacturer's instructions.

High surface area materials are most preferably prepared in the absence of poisons in order to preserve their seed activity.

Insoluble carbonate materials generally have an average particle size of less than 10 microns as determined by sieve analysis, but may be granulated for ease of handling.

If the insoluble carbonate material is calcium carbonate, it can be used in any crystalline form or mixtures thereof, but calcite is preferred because aragonite and batterite are difficult to commercially purchase, and calcite at normal washing temperatures. Slightly less soluble than aragonite or batterite. When aragonite or batterite is used, it is generally mixed with calcite. In later general description the term "calcite" is used to mean calcite itself or any other suitable insoluble calcium carbonate seed material.

The content of calcite in the overall composition depends on the specific surface area as described above. The content of calcite used in the composition should be 5 to 60%, preferably 5 to 30%.

In addition to insoluble carbonates, detergent actives and water-soluble carbonates, it is possible to contain traces of other detergency builders, provided that the total content of the detergent builders does not exceed 85% by weight to leave room for other desired components in the detergent composition. Can not be done.

Except for calcite, detergent actives and detergent builders, detergent compositions may optionally contain any conventional ingredients in amounts normally contained in textile laundry detergent compositions.

One such optional component is the alkali metal salt of silicic acid, in particular neutral, alkaline, meta- or sodium orthosilicate.

Low content of phosphates, for example 5-10% by weight silicates, are generally advantageous for reducing the corrosion of the metal parts of the fabric washing machines and provide advantages in the manufacturing process. If a high content of silicate is used, up to a maximum of 30% by weight, for example from 10% to 20% by weight, the water soluble carbonate material content can be somewhat reduced and a noticeable improvement in cleaning power can be made. This effect has been found to be patently useful when water with moderate levels of magnesium hardness is used as the wash liquor. Silicate may also be used to some extent to control the equilibrium pH of the wash liquor, generally within the range of 9-11, preferably 10-11, for a recommended concentration of detergent solution. It should be noted that high pH (ie 10.5 and higher) tends to be more effective in terms of cleaning power, but is not safe for home use. Sodium silicate is usually supplied as a concentrated aqueous solution but its content is calculated on the basis of anhydrous state.

Examples of other optional ingredients include foam accelerators such as monoethanol amide derived from alkanolamides, in particular palm seed and coconut fatty acids, foam inhibitors, oxygen-releasing bleaches such as sodium perborate and sodium percarbonate, perchloric acid bleaching precursors, triclo Chlorine-releasing bleach, such as leuisocyanuric acid. Fabric softeners, inorganic salts such as sodium sulfate, and enzymes, fungicides and colorants, such as fluorescent agents, fragrances, proteases and amylases, which are generally present in extremely trace amounts.

The detergent composition is prepared by any technique commonly used in the manufacture of textile laundry detergent compositions, including slurry-forming and spray-drying processes for the preparation of detergent powders.

The invention will now be described by way of the following non-limiting examples.

[Examples 1 to 7]

The compositions were prepared by the following formulation. Each composition was prepared in the form of a powder by spray drying a slurry of the above-mentioned ingredients except for sodium silicate, sodium perborate and TAED (if used) separately added to the spray dried base powder. This powder was sprayed at the desired moisture content of 3-4%.

week.

1-Alternatively, Dovan 113 (Shell Chemicals) sulfonated to produce sodium benzenesulfonate having an alkyl group containing from 10 to 15 carbon atoms.

2-Synferonic A7 (an ICI product-alcohol having an alkyl chain length of 13-15 carbon atoms ethoxylated with an average of 7 ethylene oxide groups per molecule).

3- Examples 1 and 4 use a 50:50 mixture of cured tallow sodium soap and cured rapeseed sodium soap, and in other examples cured tallow sodium soap.

4- Measured as anhydrous.

Sokal U3 (Solvay) with a surface area of 5-100 m ² / g.

6-1 Hydrate form.

In each example, 150 g of powder was placed in the dispenser of a Hoover® automatic washer. Cold water was allowed to enter the dispenser for 2 minutes at a rate of 2 liters per minute. This water had a hardness of 24 ° FH (ie free calcium ion concentration of 24 × 10 ⁻⁴ molarity). The pressure of this water was 5 psi. After allowing the water to naturally drain out of the dispenser, the weight of the powder residue in the dispenser was measured. The results were as follows. It is considered acceptable if the weight ratio of residues in this experiment is less than 20 g. The following table also shows the percentage of anionic, nonionic and soap in each formulation.

The residue in Example 3 was 7 g when 30% sodium carbonate was replaced with 35% sodium carbonate and 10% sodium perborate was replaced with 5.3% sodium perborate with 2.3% TAED as the bleaching agent. .

These results indicate that the compositions according to the present invention (Examples 1 to 7) leave significantly less residues than the comparative compositions A to D in terms of residues.

Claims (11)

A detergent active system consisting of a mixture of (i) an anionic non-soap detergent active material, (b) a nonionic detergent active material and (c) a soap, (ii) a water-soluble alkali metal salt of carbonic acid, and (iii) a carbonic acid A detergent composition containing an insoluble particle carbonate material that is a seed crystal of calcium, wherein the content of (a) is 30% to 70% based on the total weight of components (a), (b) and (c), (b) And a content of 20% to 27%, and (c) at least 10% but no more than 10% by weight of the total composition. The detergent composition according to claim 1, wherein the soap content of the total composition does not exceed 8% by weight. The detergent composition according to claim 1 or 2, wherein the detergent active system is 5 to 40% by weight of the total composition. The detergent composition according to claim 3, wherein the detergent active system does not exceed 25% by weight of the total composition. The detergent composition according to claim 1, wherein the anionic non-soap detergent active material is a water-soluble alkali metal salt of organosulfuric acid or sulfonate having an alkyl radical containing from about 8 to 22 carbon atoms. The nonionic detergent active material according to claim 1, wherein the nonionic detergent active material is C ₆ -C ₂₂ having 5 to 25 units of ethylene oxide per molecule, alkylphenol-ethylene oxide condensate, C ₈ having 5 to 40 units of ethylene oxide per molecule. -C ₁₅ detergent composition, characterized in that it is selected from condensation products of primary and secondary or branched alkylene alcohols, and products obtained by condensation of propylene oxide and ethylene diamine with ethylene oxide. The detergent composition according to claim 1, wherein the soap is an alkali metal and alkaline earth metal salt of a fatty acid or a fatty acid salt having a nitrogen-containing organic portion complexed thereto. The detergent composition according to claim 1, wherein the content of the water-soluble carbonate substance in the total composition is at least 5% by weight. 9. A detergent composition according to claim 1 or 8, wherein the water soluble particulate carbonate material is calcite. 10. The detergent composition according to claim 9, wherein the calcite constitutes 5% to 60% of the total composition. The detergent composition according to claim 1, further comprising an alkali metal salt of silicic acid.