DD270721A5 - LIQUID DETERGENT PREPARATION - Google Patents

Abstract

The invention relates to a liquid detergent preparation. It contains an active mixture consisting of (a) at least 50% anionic surface active agent, based on the weight of the mixture, including at least 20% alkyl benzene sulphonate, based on the weight of the surface active agent mixture, and (b) at least 2% to the weight of the surfactant mixture, a non-ionic ethoxylate having an HLB value less than 12, the water being present in an amount to form a spherulitic or lamellar formulation. From 5% to 25% of this mixture of surface-active agents contains water and so much dissolved electrolyte that a non-sedimenting spherulitic preparation is formed.

Description

Field of application of the invention

The invention relates to a liquid detergent preparation which has a stable spherulitic structure and contains a substantial proportion of a nonionic surfactant. The invention is particularly applicable to the formulation of liquid detergent mixtures having a controlled foam characteristic, e.g. B. Preparations suitable for use in a front loading machine. The invention is also valuable for the preparation of formulations suitable for use in low temperature washing operations.

Characteristic of the known state of the art

In the formulation of liquid detergents for washing purposes, a good balance of mobility and high useful load of useful ingredients is most readily achieved when the surfactants are limited to such that a spherulitic structure is achieved by the presence of an adequate concentration of an electrolyte Extinguish surfactant from an aqueous micellar solution and form therefrom Sphärolhhe, which are believed to consist of a number of concentric shells, each forming a curved surface-active agent bilayer and alternating with shells of aqueous electrolyte solution. When the sparolites are sufficiently densely packed, a stable structured liquid capable of suspending solid particles of builders is formed; preparations of this type are described in detail in British Patent Application 2153380, this description being in the following part to be the revelation. Relatively few individual surfactants are known which are capable of forming stable spherulitic preparations for themselves. They are characterized by very extended hydrophobic groups having a large cross-sectional area with respect to the hydrophilic groups, e.g. For example, some secondary or branched chain alkyl benzene sulfonates such as sodium dodeca-6-yl benzene sulfonate, dialkyl sulfosuccinates, and some olefin sulfonates. In general, these surfactants are expensive and have poor detergent properties. However, spherulites can be more easily obtained using mixtures of surfactants. In particular, mixtures of linear alkyl benzene sulfonates with alkyl ether sulfates, amine oxides or alkanolamides are all capable of forming stable spherulitic formulations and exhibit relatively inexpensive detergent properties, at least for natural fibers.

However, such formulations have two disadvantages relating to those markets where front-loading washing machines are commonly used, as well as to markets where the washing is carried out at low temperatures or ambient temperatures and / or the laundry contains a high proportion of synthetic fibers ,

First, surfactant blends have been found to form stable spherulites that form mixed high foaming systems. To formulate detergent formulations suitable for use in front-loaded washing machines, it has hitherto been necessary to use relatively large quantities of expensive antifoams, such as silicones. In addition to cost, silicones have a less ideal behavior because they tend to form weak foam in the wash, but to make some residual space in the rinse water. The consumer gets the impression that the detergent is not very effective and is not properly rinsed out. Second, it has not been found possible to prepare stable spherulitic formulations containing substantial levels of ethoxylated nonionic detergent surfactants. Mixtures containing the latter are generally more expensive to clean synthetic fibers and give improved performance at low wash temperatures, e.g. Below 40 ^° C. The detergent surfactants are generally defined as having an HLB value between 12 and 15. Surfactants outside this HLB range are not usually considered detergents.

Another problem that occurs with liquid detergents when they are exported or sold at a location remote from the surfactant manufacturing source is the transport cost of the water and the builder content of the liquid detergent. It is convenient to be able to transport the active material as a concentrate in a form suitable to mix and dilute at a location closer to the point of sale. Such preparations must be pourable and must not be separated, but should also be relatively concentrated. However, many surfactants sold as such are difficult to concentrate above about 30% because of the formation of immobile M phases.

It has now been found that certain mixtures of linear alkylbenzenesulfonates with non-ionic surfactants having an HLB value of below 12 form stable high-level spherulitic formulations in both natural and synthetic fibers and have substantially reduced foaming tendencies and / or improved W .-. Behavior at low temperatures.

It has further been found that when such mixtures are concentrated, adequate levels within the bleach of from 25 to 80% by weight of non-separating, pourable, spherulitic and / or G phase additions are obtained, which are easily diluted or with other detergent ingredients can be mixed and which are relatively cheap in terms of transport and storage.

Object of the invention

The aim of the invention is, js, to eliminate the identified deficiencies of the prior art.

Explanation of the essence of the invention

The invention relates to a liquid detergent preparation consisting of water, sufficient amounts of an active mixture (hereinafter referred to as "system") consisting essentially of: an active mixture of (a) at least 50% by weight, based on the total weight of surfactants present, of anionic surfactants consisting of at least 20%, based on the total weight of surfactants present, of an alkylbenzenesulfonate, and of (b) at least 2% by weight, based on the total weight of surface active agents present alkoxylated nonionic surfactant having an HLB value below 12, and sufficient water to provide a non-separating, pourable, spherulitic or G phase formulation, to provide a total surfactant concentration of from 5 to 25% by weight of the composition.

Further, the preparation consists of sufficient amounts of dissolved, the surfactants of the solubilizing electrolyte to provide a non-sedimenting spherolytic preparation.

Preferably, the surfactant concentration of the detergent system is greater than 28%, e.g. Over 30%, and preferably between 30 and 80%. Usually, the concentration of surfactants is greater than 35%, e.g. B.

to 75%, in particular 50 to 70% by weight.

The surfactant system preferably consists mainly of the surfactants and water along with such traces of sodium sulfate as inevitably present as an impurity in the anionic surfactant. However, it is possible to use smaller amounts of non-surface-active electrolytes to modify the viscosity and / or phase structure of the formulation. It is generally preferred that such electrolytes be present in amounts of less than 10%, preferably less than 5%, usually less than 2%, e.g. B. less than 1%, based on the total weight of the surfactant system. The presence of organic solvents is not preferred.

Preferably, the liquid detergent composition according to the invention additionally contains suspended solid particles of a builder substance.

The alkylbenzenesulfonate usually has an average of 10 to 14 aliphatic carbon atoms, e.g. 12, and is preferably a linear alkyl benzene sulfonate. Particularly preferred are alkylbenzenesulfonates containing a wide range of different homologues and isomers.

For use as low-foaming agent is preferable that an anionic surfactant at least one C _14-22 mono- and / or dialkyl phosphate ester in a proportion of up to 50%, eg. From 2 to 40%, preferably from 5 to 30%, especially from 10 to 20%, of the total weight of anionic surfactant present.

The anionic surfactant may additionally or alternatively contain other sulfonated and / or sulfated surfactants and / or carboxylates. For example, the anionic surfactant may consist of a mixture of alkylbenzenesulfonate with 5 to 100%, preferably 10 to 50%, eg 15 to 30%, of a C ₈ -M (preferably C ₁₀ -U) alkyl sulfate, based on the Total weight of alkylbenzenesulfonate. If a low-temperature effect is important and little foaming is needed, the preparation preferably contains from 5 to 150%, preferably from 20 to 120%,

z. From 50 to 110% of a C ₈ -C ₀ (preferably C _{16, 18} ) alkyl polyalkylene sulphate, based on the weight of alkyl benzene sulphonate.

The alkylpolyalkylene oxysulfate preferably contains an average of 1 to 10, e.g. 1.5 to 5, parts by mole of ethylene oxide. Other anionic surfactants that may be present include olefin sulfonates, paraffin sulfonates, fatty acid sulfonates, sulfosuccinates, sulfosuccinamates, and soaps. The counterion of the anionic surfactant may be sodium, lithium, potassium, ammonium, lower alkyl ammonium or mono, di or tri alkanol ammonium or a mixture of such ions.

The nonionic surfactant is preferably an ethoxylated alcohol, but may alternatively be an ethoxylated carboxylic acid, alkylamine, alkanolamide, alkylphenol or an ester such as ethoxylated glyceryl ester, sorbitol ester, phosphate ester or phosphonate ester.

The alkyl groups of the nonionic surfactant Mit may be straight chain and primary, but preferably comprise at least some branched alkyl groups. It is often found that the greater the amount of branched chain alkyl groups and the amount of branching, the more effective the detergent properties of the product

The alkyl groups of the nonionic surfactant have an average of 8 to 20, preferably 10 to 18, carbon atoms. For example, ethoxylated Ce, 5-, z. B. C ₈ -I ₁ - or C ₁₂ - ₁₃ branched chain alcohols especially preferable in terms of detergency, but ethoxylated C _te _ie-linear alcohols give a superior foam inhibition. At wash conditions at lower temperatures CE_ are preferably ₁₆ alkyl groups.

The number of ethylene oxide groups is selected according to the length of the alkyl chain to achieve the desired HLB value. Typically, 1 to 12, z. B. 2 to 8, ethylene oxide groups. It is possible to replace one or more of the ethylonoxide groups with propylene oxide. The HLB value of the nonionic surfactant is preferably from 2 to 12, e.g. B. 3 to 10, especially 3.5 to 8.

Ethoxylates of starting materials are preferred which contain at least 20% or preferably at least 30%, in particular at least 50%, e.g. B. contain at least 60%, branched-chain alcohols.

The nonionic surfactant may contain an amount of free Cg_2 ₂ alcohol. This is particularly preferred in poorly foaming preparations. The latter typically contain C _14-22 fatty alcohols, for example in amounts of up to 100 wt .-% of the total anionic surfactant. High-foaming, low-temperature formulations may contain minor amounts of non-ethoxylated fatty alcohols, as supplied to fatty alcohol ethoxylate. The latter are usually C ₈ - to C ₁₆ -, for example C ₉ ^ ₁₁ -AlkOhOIe. It does not exclude the presence of polyethylene glycol in the nonionic surfactant.

Any fatty alcohol or polyethylene glycol may be included in the total amount of ethoxylated nonionic surfactant when the HLB value of the latter is estimated or relative amounts of nonionic surfactant are defined. In the case of ethoxylated fatty alcohols, for the purposes of the present invention, the HLB value may be taken as one fifth of the weight percent of ethylene oxide by weight of the nonionic surfactant.

The total amount of surfactant is 6 to 25% of the liquid of the total weight of the detergent formulation. For low foaming applications, the total amount of surfactant is preferably less than 20%, e.g. Less than 14%, and most preferably 6 to 12%, based on the weight of the liquid urethane preparation. However, for use at low temperatures and when low foaming is not required, a higher amount of total surfactant may also be preferred, e.g. more than 18%, in particular 20 to 25%, based on the total weight of the liquid detergent preparation. The detergent composition according to the invention contains an electrolyte in an amount sufficient to provide a completely sedimenting spherulitic preparation. The term "electrolyte" is used hereinafter for water-soluble compounds which are dissolved in the preparation and ionize in solution and capable of salting out the surfactants from the micellar solution to form a spherulitic preparation, but the agent itself is not a surface-active agent The electrolyte may preferably consist of one of the water-soluble builders or it may be a dissolved part of a slightly soluble builder Examples of suitable electrolytes are therefore citrates, orthophosphates, nitrilotriacetates, condensed phosphates such as pyrophosphates, tripolyphosphates ortotraphosphates, soluble phosphate glasses such as hexametaphosphates, Carbonates, silicates, phosphonates such as acetodiphosphonates, aminotris (methylenephosphonates), ethylenediaminetetrakis (methylenephosphonates), diethylenetriaminepentakis- (methylenephosphonates) and higher homologs of the same series, and ethylenediamine tetra acetate.

It is possible to use as a electrolyte, or a part thereof, a buffer such as a borate, or less preferably a non-functional salt such as a chloride, bromide, iodide, nitrate or the like. Organic electrolytes such as formate or acetate may also be present. Sulfate is usually present in small amounts as an impurity of the anionic surfactant, but may give rise to undesirable crystallization when present in amounts greater than about 3%. It is therefore preferred to avoid the use of higher concentrations of sulphate. The cationic portion of the electrolyte is preferably an alkali metal, e.g. Lithium, potassium or more, sodium. The total dissolved electrolyte concentration is preferably greater than 1%, typically 2 to 12%, depending on the concentration of the surfactant and the total amount of nonionic to anionic detergents. Higher concentrations of surfactant and / or higher levels of nonionic surfactant require lower concentrations of electrolyte to form non-separating spherulitic formulations. If the concentration of the surfactant and / or the amount of the nonionic surfactant is sufficiently high, any extraneous amounts of sodium sulfate may be sufficient to form a stable spherulitic formulation without the addition of extra electrolyte.

The builder is preferably sodium tripolyphosphate and is preferably present in excess of the solubility amount, in the form of suspended solid particles. Alternatively or additionally, the preparation may contain zeolites and / or solid particles of any of the builders mentioned above in the discussion of the electrolytes.

The poorly foaming preparations according to the invention containing phosphate esters prevent excessive foaming, but do not completely suppress foaming on washing, which visibly indicates that the detergent is present and effective. There is little or no foaming in the rinse water.

It is possible, but less preferred, to add other antifoaming agents such as ctt-u-fatty alkanolamides and / or hydrocarbons in addition to or instead of the phosphate ester. However, it is preferred not to use silicones as anti-foaming agents, although it is possible to achieve effective foam suppression according to the invention with reduced proportions of silicone anti-foaming agent compared to the commonly used agents. Smaller amounts of silicone can be added as protectants if it is desired to incorporate enzymes into the formulation, e.g. according to the European patent application 87301489.2.

Detergent preparations according to the invention may contain the usual minor ingredients. Preferably, these anti-redeposition agents, such as sodium carboxymethylcellulose, in conventional amounts comprise an optical brightener and perfumes and / or dyes. The compositions may contain suspended particles of fabric softening agents such as bentonite or synthetic clays, or they may generally contain any of the other minor ingredients, builders and electrolytes listed in the aforementioned British Patent Application 2153380, as well as substantially the same amounts ,

A particularly preferred liquid detergent formulation for low foaming applications comprises: water; 4 to 10%, preferably 5 to 8% of the C, ₂ -u-linear alkylbenzenesulfonate, 0.5 to 4%, preferably 1 to 3% of a C ₁₀ -H-alkyl sulfate, 0.5 to 4%, preferably 1 to 3%, of an ethoxylated alcohol, this alcohol containing 10 to 14, preferably 11 to 13 carbon atoms and the ethoxylated alcohol contains on average 1 to 5, preferably 2 to 4, ethyleneoxy group per molecule, and 20 to 30%, preferably 24 to 27% Sodium tripolyphosphate, all amounts are by weight based on the total weight of the preparation. The above-mentioned preferred formulation normally contains common amounts of soil suspending agents such as carboxymethyl cellulose, optical brighteners and perfumes. Preferably, it contains small amounts of 0.1 to 2% each of sodium silicate, an alkanolamine such as triethanolamine and / or phosphonate. Optionally, it may contain mixtures of antifoams, such as silicone and / or phosphate esters, fabric softeners, such as concreteite, enzymes, such as proteases and / or lipases, preferably dispersed in a soil medium, such as silicone, and preservatives, such as formaldehyde.

Another type of preferred formulation is one which does not require low sudsing, but the low temperature detergency is an important consideration. These preparations include water, 6 to 12, z. B. 7 to 10%, sodium linear C, ^ ₁₄ alkylbenzenesulfonate; but preferably 6 to 12, z. B. 7 to 10% sodium C ₁₄ -2o (preferably C _ie _ ₁₈ ) alkylpolyethylenoxysulfat with an average of 1 to 5, z. B. 2 to 4 ethyleneoxy groups per molecule; 1 to 8%, preferably 2 to 7% Cg-he (preferably C ₉ -Ii) -alcohol ethoxylate with an average of 1 to 5.5, z. B. 2 to 5 ethylene oxide groups per molecule, and 5 bsi 30%, preferably 19 to 26%, sodium tripolyphosphate. The preparation preferably contains the usual minor ingredients, such as suspending agents for dirt, optical brighteners and perfumes in conventional amounts.

Car course description

The invention is further illustrated by the following examples wherein in the examples the ingredients are in terms of weight percentages based on the total formulation given in the following tables, the remainder being water in each case. In each case, the surfactants were e.g. B. such components as shown in the tables below and comprising the Cie -ie-alcohol in the case of Examples 1 to 18, wherein these substances are mixed together with sufficient water until a pourable turbid mixture is formed, the active concentrations between 30 and 50Gew .-% has. In each case, the samples are centrifuged at 20000 g for 90 minutes to determine the optimum concentrations, no separation being observed.

The obtainable pourable, non-separating, aqueous Sphärolithlschen or lamellar preparations are storable.

The aqueous active mixtures may also be perfumed and / or combined with the appropriate amount of carboxymethylcellulose and / or optical brighteners and / or phosphonate, adjusting the concentration if desired.

Finally, the active concentrate was mixed with the builder (sodium tripolyphosphate and / or zeolite), as well as sufficient water to obtain the desired final formulation.

Each of Examples 1 to 18 gave a stable, non-sedimenting, spherulitic formulation having foam properties making it suitable for use with front wall fill-in washers and gave good wash performance with both natural and synthetic fibers.

The formulations gave moderate controlled foaming during the wash cycle and little or no foaming during the rinse cycle.

Examples 19-25 gave all non-sodimizing spherulitic formulations with good low temperature wash behavior.

Table 1

Example no. 1 5.0 2 4.8 3 5.5 4 5.4 5 5.5 6 5.8 7 5.5 8th 5.5 9 5.0 10 Sodium Cio-M-linear · alkylbenzenesulfonut 2.0 1.9 3.2 2.9 3.0 3.3 4.0 4.0 1.0 5.0 Ci ₂ -Is-AlkOhOl- 3 mol-ethoxylate 0.8 1.9 2.2 2.0 2.0 2.2 2.0 2.0 1.0 2.0 mixed mono- and di-Cie-18-alkylphasphate 0.8 1.0 1.0 C, e_ie alcohol 30.0 23.8 28.1 24.4 25.0 27.2 20.0 20.0 31.0 1.0 Sodium tripolyphosphate 4.8 2.4 7.3 7.3 30.0 Zeolite A 0.15 0.19 0.23 0.20 0.20 0.20 0.20 0.20 0.15 optical brightener 0.1 0.1 0.11 0.1 0.1 0.1 0.1 0.1 0.15 Sodium carboxymethylcellulose 0.5 0.48 0.56 0.5 0.5 0.5 0.5 1.0 0.5 • Sodium ethylenediamine tetrakis (methanophosphonate) 0.35 0.38 0.45 0.4 0.4 0.4 0.4 0.4 0.35 0.5 Perfume ^, 35 Table 2 11 12th 13 14 15 16 17 18 Example no. 6.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Sodium C, o-u-linear alkyl benzene sulfonate 2.0 1.0 1.5 C, ₂ .ie alcohol 3 mol ethoxylate 1.0 1.5 1.0 1.5 Nonylphenol-9 9 mole ethoxylate 1.0 Nonylphenol-12 mole ethoxylate 2.0 1.0 C, 2, ₈ -alcohol-8 mole ethoxylate 1.0 2.0 2.0 2.0 2.0 2.0 1.7 1.7 mixed mono- and di-C ₁ -18-alkyl phosphate 1.0 Ctt- _I8 alcohol

Example no. 11 0.15 0.25 12 13 14 15 16 17 18. • Sodium tripolyphosphate 27.0 0.1 1.5 28.0 30.0 28.0 28.0 28.0 25.0 25.0 ZeotithA 0.5 4.7 4.7 optical brightener 0.35 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Sodium carboxymethylcellulose 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Sodium ethylenediamine tetrakis (methanophosphonate) 19 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Perfume 6.0 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Table 3 1.5 Example no. 20 21 22 23 24 25 Sodium Cto-M linear alkylbenzoisulfonate 2.0 8.96 8.98 7.96 6.99 9.0 7.0 Triethanolamine lauryl sulfate Sodium lauryl-3-methylethoxysulfate 8.95 8.96 7.98 6.98 C ₁₂ -I ₃ -A. ^v , ool-3-methyl ethoxylate C ₉ - ,, - Alcohol ^ .Bmol ethoxylate Sodium tripolyphosphate 25,9 2.05 2.08 2.04 3 3 Cg-ii-alcohol-enol-ethoxylate Sodium silicate (NaO = SiO ₂ = 2.5: 1) 2.23 2.22 2.20 CfM, -alcohol-6-methyl-ethoxylate Sodium methylenediamine tetrakis (methanophosphate) 2.08 19.86 19.9 19.9 19.9 25 25

sodium carboxymethyl

cellulose 0.1 0.1 0.1 0.1 0.1 0.1 0.1

"TINOPAL-LMS-X optical brightener 0.15 0.1 0.1 0.1 0.1 0.1 0.1 .TINOPAL-CBS-X optical brightener 0.05 formaldehyde 0.05 .ALKALASE "3.5SL Type WB Protease dispersed in silicone 0.2 1.98 2 2 1.99 potassium carbonate 0.35 0.29 0.29 0.27 0.3 0.3 Perfume 0.15-0.3 S132 antifoam agent 0.2

Claims (17)

A liquid detergent preparation characterized in that it comprises water, sufficient amounts of an active mixture of (a) at least 50% by weight, based on the total weight of surface active agents present, of an anionic surfactant containing at least 20% by weight and (b) at least 2% by weight, based on the total weight of surfactants present, of an alkoxylated nonionic surfactant having an HLB value below 12, as well as sufficient water to provide a non-reactive surfactant separating, pourable, spherulitic or G phase preparation, to provide a total surfactant concentration of from 5 to 25% by weight of the formulation, as well as sufficient dissolved amounts, to provide the non-sedimenting spherulitic surfactant Preparation consists. 2. Liquid detergent mixture according to claim 1, characterized in that it contains suspended solid particles of a builder substance. 3. Preparation according to claim 1 and 2, characterized in that the alkylbenzenesulfonate is a linear C ₁₂ -i4-alkylbenzenesulfonate. 4. Preparation according to claim 1 to 3, characterized in that the anionic surface-active agent contains up to 50 wt .-%, based on the total weight of the anionic surfactants present, of a C ₁₄ _ ₂ 2 mono- and / or dialkyl phosphate ester. 5. A preparation according to claim 4, characterized in that the alkyl phosphate ester is present in an amount of from 2 to 40% by weight, based on the total weight of anionic surface active agent present. 6. A composition according to claim 1 to 5, characterized in that the anionic surfactant contains 5 to 100 wt .-% of a C ^ o-alkyl sulfate, based on the weight of alkylbenzenesulfonate. 7. A preparation according to claim 6, characterized in that the amount by weight of alkyl sulfate to 30%, based on the weight of alkylbenzenesulfonate is. Composition according to any one of Claims 1 to 7, characterized in that the anionic surfactant contains from 5 to 150% by weight of alkylpolyalkyleneoxysulphate, relative to the weight of alkylbenzenesulphonate. 9. A preparation according to claim 8, characterized in that the Alkylpolyalkylenoxysulfat is a C ₁₆ -i8-alkyl-1.5 to 5 moles polyethylenoxysulfat. 10. A preparation according to any one of claims 8 and 9, characterized in that the amount of alkylpolyalkylene oxysulfate 50 to 110 wt .-%, based on the weight of alkylbenzenesulfonate. 11. A preparation according to any one of claims 1 to 10, characterized in that the anionic surfactant is an ethoxylated alcohol. 12. Preparation according to claims 1 to 11, characterized in that it contains suspended solid particles of sodium tripolyphosphate and / or zeolite. 13. A preparation according to claims 1 to 12, characterized in that the total amount of surface-active agent, based on the weight, 6 to 12Gew .-%, based on the total weight of the preparation is. 14. A preparation according to claim 13, characterized in that it contains: Water, 4 to 10% of sodium linear cio-i4-alkylbenzenesulfonate, 0.5 to 4% of a C ₁₀ _i ₄ -alkylsulfate salt, 0.5 to 4% of a C ₁ ^ ₁₄ -AIky 1-1 to 5 Moi ethoxylate , and 20 to 25% sodium tripolyphosphate, all percentages based on the total weight of the formulation. 15. A composition according to claim 14, characterized in that the alkyl sulfate is a triethanolamine salt. 16. The preparation according to claim 1 to 15, characterized in that it additionally contains up to 2% sodium silicate and a sodium phosphonate and up to 1% of a dirt-suspending agent and an optical brightener. 17. A preparation according to claims 1 to 12, characterized in that it contains 18 to 25 wt .-% total amount of surface-active agent, based on the total weight of the preparation.