FI85380C - Homogeneous, concentrated, liquid detergent composition comprising a system of three surfactants - Google Patents

Abstract

Homogeneous concentrated liquid detergent compositions with a ternary surfactant system are disclosed. The ternary system contains two anionic surfactants, an alkyl (aryl) - sulfonate and a succinate, and a nonionic surfactant. The compositions exhibit a pH in the neutral to mildly alkaline domain. Preferred compositions additionally contain low level of oleic acid.

Description

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This invention relates to a homogeneous, concentrated, aqueous, liquid detergent combination containing less than 50% by weight of water, a ternary anionic nonionic surfactant system and a homogeneous, concentrated, liquid detergent composition comprising a system of three surfactants. if desired, conventional additives.

The ternary surfactant system comprises mostly an anionic surfactant represented by a binary mixture of an alkyl (aryl) sulfonated surfactant and an alk (en) yl succinate in a weight ratio of 3: 1 to 1: 4, and non- ionic surfactant component.

The combinations of the invention show excellent and highly desirable washing performance, can be easily prepared, and further show excellent stability over extended storage times.

Homogeneous, concentrated, high performance liquid detergents are well known in the art and have found commercial use. Such combinations may comprise a ternary active system, namely synthetic anionic sulfonates or sulfates in combination with nonionic ethoxylates and soaps.

Such prior combinations are difficult to process, especially due to alkalinity. Previously concentrated liquid detergents are sensitive in this respect to phase separation under conditions from neutral to slightly basic. As a result of the criticality of such a matrix, it is quite difficult to modify the matrix with respect to power increase, taking into account certain staining / cleaning situations. In terms of washing performance, it is known that concentrated liquid combinations known in the art, 35 although they show excellent cleaning performance,

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for most of the fibers, can be advantageously improved in terms of the washing performance of the cellulosic fiber compared to the power obtained from the use of granular detergents containing polyphosphate containing oxygen bleach.

5 The prior art for concentrated, homogeneous liquid heavy duty detergent combinations is diverse. For example, U.S. Patent No. 4,285,841 discloses non-active concentrated, homogeneous liquid combinations containing a combination of anionic, synthetic surfactants and fatty acids. The preparation of such combinations containing less than 50% water requires the use of substantial amounts of solvents and compatible substances, and even under these conditions limited stability remains, especially with low levels of non-anionic fatty acids, especially saturated species, and possible electrolytes such as organic active ingredients. in terms of quantities.

The succinate ingredient is well known in the detergent industry and has been presented in combination with all kinds of detergent implementations, especially granular combinations. Although succinates of this kind have been recommended for use in liquid combinations, it is well known that formulation difficulties arise substantially from their use in such combinations, especially in the presence of low amounts of water and substantial amounts of nonionic substances.

DE-A-1 768 851 discloses the use of specific succinate derivatives as a soap additive. These combinations contain mainly anionic surfactants and further substantial amounts of water in combination with hydrotropes.

DE-A-1 956 671 discloses binary liquid preparations containing substantial amounts of alk (en) yl succinates in combination with nonionic surfactants.

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DE-A-3 013 904 deals with alkaline detergent combinations, liquid or solid, containing a partially neutralized succinic acid derivative, which is apparently used due to its foaming properties.

EP-A-0 017 951 relates to the use of alk (en) yl-formic acid salts or monoesters thereof with polyhydric alcohols to make perfumes hydrotropic in liquid detergent combinations containing large amounts of electrolytes.

The main object of the present invention is to prepare a homogeneous, concentrated liquid detergent combination having excellent performance properties compared to those obtainable from polyphosphate-structured granular de-15 tangent combinations containing oxygen bleach.

It is a further object of this invention to provide homogeneous, highly concentrated liquid detergent compositions containing substantial amounts of a ternary surfactant system based on anionic sulfonates and succinates in combination with nonionic ethoxylates and containing less than 50% water. .

It is a further object of the present invention to define highly concentrated, storage-stable liquid detergent combinations having excellent laundry cleaning properties at pH conditions from neutral to slightly basic.

This invention relates to homogeneous, concentrated liquid detergent compositions having less than about 50% water and containing a ternary surfactant system. In particular, these combinations are characterized in that a) the ternary surfactant system represents 35 to 75% by weight of the combination; 4,35380 b) the anionic surfactant component is present in an amount of 50 to 90% by weight of the ternary surfactant system and is represented by a binary mixture of: 1) an alkyl (aryl) sulfonated surfactant; and 2) alk (en) yl succinate of formula

R-CH-CH-COOH

10 COOH

wherein R 1 is an alk (en) yl group having 10 to 20 carbon atoms, R 2 is hydrogen or C 1-4 alkyl; the weight ratio of sulfonate to succinate is between 3: 1 and 1: 4; and c) the nonionic surfactant component corresponds to 50-10% of the ternary surfactant system; the pH of said combination measured as a 1% solution at 20 ° C is between about 7 and about 9; 20 and that the combination further contains 1-8% by weight

CjQ.jg fatty acid, preferably oleic acid.

The combinations of this invention can be characterized as highly concentrated, homogeneous liquid detergent combinations containing a ternary pin-25 active system and having a pH ranging from neutral to slightly basic.

The essential parameters describing the invention will be described in more detail later.

Unless otherwise indicated, percentages are by weight of 30 combinations.

The anionic surfactant component comprises 50-90% of the ternary surfactant system and is represented by a binary combination of: 1) an alkyl (aryl) sulfonated surfactant; and 5 ^ 5380 2) alk (en) yl succinate of formula? *

R-CH-CH-COOH

5 COOH

wherein Rx is an alk (en) yl group having 10 to 20 carbon atoms, and R2 is hydrogen or C1-4 alkyl; and the weight ratio of sulfosuccinate to succinate is between 3: 1 and 1: 4.

The anionic sulfonate surfactant can be represented by any of the alkyl (aryl) sulfonated surfactants known to be suitable for use in liquid detergent combinations and in fact widely used in commercial detergent implementations.

Such anionic synthetic sulfonates may be represented by the general formula R 1 -C 2 M, wherein R 1 represents a hydrocarbon moiety selected from the group consisting of straight or branched chain alkyl groups containing from about 8 to about 24 carbon atoms and alkylphenyl groups containing from about 10 to about 24 carbon atoms. about 18 carbon atoms in the alkyl group. M is a salt-forming cation typically selected from the group consisting of sodium, potassium, magnesium, ammonium, monoalkylammonium, dialkanolammonium, trialkanolammonium, and mixtures thereof.

The preferred synthetic anionic surfactant sulfonate is a water-soluble salt of alkylbenzenesulfonic acid containing from about 10 to about 18 carbon atoms in the alkyl group, and the most preferred species has from 12 to 30 carbon atoms in the alkyl chain.

Alk (en) yl succinate has the formula referred to above, wherein R 2 is either a saturated or unsaturated group having 10 to 20 carbon atoms, preferably an unsaturated derivative having 12 to 16 carbon atoms in the alkenyl solution. R 2 may be hydrogen or C 1-4 alkyl, with hydrogen being preferred.

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The terms "succinate" and "succinic acid" are used alternatively. Suitable succinic acid salts include sodium, potassium, lithium, ammonium, mono-, di- and tri-alkanolamine salts and mixtures thereof.

Preferred succinic acid derivatives for use herein include 2-dodecenylsuccinic acid, 2-tetra-decenylsuccinic acid, 2-hexadecenylsuccinic acid, decylsuccinic acid, dodecylsuccinic acid and tetradeic succinic acid, their tetradeic succinic acid. The alkyl or alkenyl chain attached to Meri-10 resin acid can be either straight or branched. Straight chain alk (en) yl moieties are preferred.

The weight ratio of sulfonate to succinate surfactant in the binary mixture is between 3: 1 and 1: 4, preferably between 2: 1 and 1: 2.

The ternary surfactant system generally represents 35 to 75% of the combination. The anionic surfactant component is determined in salt form.

The nonionic surfactant component contains 20 hydrophobic organic groups condensed with a hydrophilic portion of ethylene oxide. All known ethoxylated nonionic surfactants known to be suitable for use in detergents can be used in the combinations of this invention. Preferred nonionic species are polyethoxylates derived from primary and secondary aliphatic alcohols having from 8 to 24 carbon atoms and having an HLB (hydrophilic-lipophilic equilibrium) of between about 8 and 15. These preferred ethoxylates often contain from 2 to about 14 moles of ethylene oxide per mole of hydrophobic moiety. The hydrocarbyl chain (hydrophobic moiety) can be represented by linear or branched fatty alcohols.

A preferred class of nonionic ethoxylates is represented by the condensation product of a fatty alcohol having 12 to 35 carbon atoms and about 4 to 10 moles of ethylene oxide per mole.

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7 * 5380 liters of fatty alcohol. Suitable ethoxylates in this class include: the condensation product of C12-15 oxo alcohols and 7 moles of ethoxide per mole of alcohol; Condensation product of C13-15 oxoalcohols and 5 moles of ethylene oxide; a condensation product of narrow 5 C14-15 oxo alcohols and 7 or 9 moles of ethylene oxide per mole of fatty (oxo) alcohol; a condensation product of narrow C12-13 fatty (oxo) alcohols and 6.5 moles of ethylene oxide per mole of fatty alcohol; and condensation products of C10-14 co-fatty alcohol with a degree of ethoxylation (10 moles EO / mole fatty alcohol) between 5-8.

Fatty oxoalcohols, although predominantly linear, may have a certain degree of branching, especially short chain, such as methyl branching, depending on the processing conditions and the raw material olefins. A degree of branching of 15 to 50% by weight is often observed with commercial oxoalcohols.

Preferred nonionic ethoxylated components can also be represented by a mixture of two separately ethoxylated nonionic surfactants with different degrees of ethoxylation. For example, a nonionic ethoxylate can be represented by mixtures of first an ethoxylated surfactant containing 3 to 7 moles of ethylene oxide per mole of hydrophobic moiety and a second ethoxylated species of 8 to 14 moles of ethylene oxide per mole of hydrophobic moiety. The preferred nonionic ethoxylated mixture contains a lower ethoxylate which is a condensation product of a C12.15 oxo alcohol having a branching of up to 50% by weight and about 3-7 moles of ethylene oxide per mole of fatty oxo alcohol, and 30 higher ethoxylate, which is the condensation product of a C16-19 oxo alcohol having more than 50% by weight of branching and about 8-14 moles of ethylene oxide per mole of branched oxoalcohol.

The nonionic surfactant component comprises 50 to 10%, preferably 15 to 40% of the ternary surfactant system.

8 * 5380 The combinations presented herein contain less than 50%, usually 15-40% water.

The combinations according to the invention are further characterized in that their pH, measured as a 1% aqueous solution at 20 ° C, is between about 7 and about 9. This pH range indicates that the anionic surfactant component, i. the binary mixture of sulfonate and succinate, especially succinate, is substantially completely (i.e., greater than 90%) neutralized in the desired combination.

In addition to the essential ingredients described above, the combinations presented herein often contain a series of possible ingredients that are used in conventional amounts because of their known functionality.

Examples of such potential constituents may include fatty acids, saturated and / or unsaturated, and the like, soaps, synthetic anionic surfactants other than sulfonates (non-sulfonate anionics), water-insoluble solvents, enzymes, enzyme stabilizers, polyacids, foam regulators, brighteners, perfumes, dyes, antioxidants, bactericides, corrosion inhibitors, fabric softeners, phase regulators, etc.

Suitable saturated or unsaturated fatty acids have 10 to 18 carbon atoms in the alkyl chain.

Preferred are unsaturated species having 14 to 18 carbon atoms in the alkyl chain, most preferably oleic acid. Corresponding soaps are used in an amount of up to 10%, preferably 1 to 8% of the combination; fatty acids / soaps, among other things, act as foam modifiers / regulators.

Synthetic non-sulfonate-anionic agents can also be used in combinations in relatively small amounts, e.g., in amounts not exceeding 25% of the ternary surfactant system. Examples of suitable non-sulfonate anionic agents include salts of sulfated fatty acids having 12 to 20 carbon atoms in the alcohol chain.

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Water-insoluble solvents such as terpenes, phthalic acid esters and liquid paraffins, generally less than 5%, may also be used.

Detergent enzymes generally help and increase the removal of specific stains. Suitable enzymes include proteases, amylases, lipases, glucose oxidases, cellulase or mixtures thereof. Proteases and amylases are preferred in the concentrated liquid combinations of the invention. They are often used in an amount of about 0.01 to about 10 1%.

All generally known enzyme stabilization systems can be used in these combinations in amounts determined by the art. Examples of suitable stabilizing systems are short-chain C 1-4 carboxylic acid, in particular formic acid, together with low amounts of calcium and boric acid and their water-soluble salts, optionally together with polyols.

Another preferred possible ingredient is polyacid or a mixture of polyacids; about 0.05 to about 2%. Suitable poly-acids are those having a pK value of at least 5. Preferred polyacid species for use herein are organophosphonic acids, especially alkylene-polyamino-polyalkylenephosphonic acid and diethylenetriamine pentamethylenephosphonic acid or their salts.

Non-fatty acid detergent foam regulators can also be used. Preferred species include alkylated polysiloxanes, such as dimethylpolysiloxane, often referred to as silicone. Silicones are often used in less than 0.5%, most preferably 0.01 to 0.2%.

The compounds disclosed herein may also contain known antioxidants for their known use; often radical scavengers, in amounts reported in the art, i.e., 0.01 to 0.25% of the total combination. These antioxidants are often added together with unsaturated organic acids. Although many suitable antioxidants are known and are available for this purpose, 2,6-ditertier-butyl-p-cresol, more commonly known as butylated hydroxytoluene, is particularly suitable for use in the combinations disclosed herein. (BHT), and tertiary butyl 4-hydroxyanisole. Other suitable antioxidants include 4,4-thiobis (6-tert-butyl-m-cresol) and 2-methyl-4,6-dinonylphenol.

Dirt-removing polymers can also be added to these combinations. Suitable species of such releasable polymers are described in U.S. Patent 4,702,857.

A further potential ingredient for these combinations is a phase regulator. This component together with water can form a solvent matrix for concentrated liquid combinations as required. Suitable classes of substances include aliphatic alcohols having 2 to 6 carbon atoms and 1 to 3 hydroxyl groups, and ethers of diethyl glycol and lower aliphatic monoalcohols having 1 to 4 carbon atoms. Specific examples of phase regulators include ethanol; n-propanol; isopropanol; butanol; 1.2-20 propanediol; 1,3-propanediol and monomethyl, ethyl, propyl and monobutyl esters of diethylene glycol.

The invention is illustrated by the following examples.

Example 1

According to the invention, a liquid detergent composition is prepared by mixing the ingredients listed below in the proportions shown.

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Ingredient ___ palno-% dodecylbenzene sulfonic acid 10.0

C 1-10 oxoalcohol condensed with 7 moles of ethylene oxide per mole of 5 fatty alcohols 11.5 2-dodecyl succinic acid 15.0

Cjj.H-alcohol silylate triethanolamine salt 4.0 oleic acid 4.0 triethanolamine neutralizing agents 5.0 sodium hydroxide) to obtain a pH of 7.6 6.0 ethanol 7.0 water 32.0 various smaller ingredients are added to 100

The above combination is compared to ARIEI, a granular tripolyphosphate-based detergent containing oxygen bleach.

The tests are performed in a horizontal drum washing machine with a program of 20 to 60 ° C. Comparative efficiencies are measured on cotton strips stained with various types of artificial stains, including bleach-sensitive dirt, enzyme-sensitive dirt, particulate dirt, and greasy dirt. It is found that the combination of the present invention provides a textile cleaning performance comparable to that obtained with ARIEL® on all types of stains.

It was also found that the liquid combination of Example 1 remained homogeneous and stable after storage for at least two weeks at temperatures ranging from 4 ° C to 50 ° C, and also after several freeze / sun cycles.

The following examples illustrate other embodiments of this invention.

The abbreviations for the individual components of the examples have the following meanings:

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C12HLAS linear dodecylbenzenesulfonic acid C16HLAS linear hexadecylbenzenesulfonic acid C20AS sodium salt of eicosene α-sulfonate 5 TEA CnAS triethanolamine coconut (C12-14) alcohol sulfate

Cx.yEO is the Cx_y alcohol ethoxylated with n moles of ethylene oxide

Cx_yEOnS sodium salt of sulfated Cx_yEOn 10 DSA 2-dodecenylsuccinic acid HDSA dodecylsuccinic acid TSA 2-tetradecenylsuccinic acid propyl-30-phthalate With 30 moles of ethylene oxide 13 8 5 380

eXAMPLES

II III IV V VI VII VIII IX x XI XII XIII

(percentage by weight) C12HLAS 8,5 15 10 - 11 10 6 8 11 14 8 C16HLAS 12,5 C20ES 12 C16-18R011 7 C13-15K07 11,5 6 15 12 12 12 10 C13-15E05 13 11 14 C13-15E04 7 7 6 C16-18E02S 5 DSA 15 15 12.5 15 15 15 10 15 8 15 HDSA 7 TSA 17 TEA CnAS 443 3 4 C12-14FA 5 5 oleic acid 4,544 8 3 34 citric acid 0.9 1.0 0.2 1, 0 0.2 1.0 0.2 1.0 0.2 1.0 1.0 0.5 DETPMP 0.8 0.9 0.9 0.6 0.9 0.6 0.9 0.6 0.9 0.9 0.9 0.8; - TPG-EO 0,5 0,5 ethanol 88 6 58 10 6 685 10 8 ‘TEA 55 4565 4 44558

To neutralize NaOH components to pH 7.5 to 7.8: water 30 38 36 32 39 35 32 31 35 39 33 30 -:: other substances, e.g.

brightener, enzyme, up to 100% aesthetic pH (1% solution) 7.9 7.9 7.7 7.9 7.5 8.0 7.9 7.9 7.7 7.9 7.9 5 7.7

Claims (5)

14 d 5 380 A homogeneous, concentrated, aqueous, liquid detergent combination comprising less than 50% by weight of water, a ternary anionic nonionic surfactant system and, if desired, conventional additives, characterized in that a) the ternary surfactant system represents 35 to 75 % by weight of the combination; B) the anionic surfactant component is present in an amount of 50 to 90% by weight of the ternary surfactant system and corresponds to a binary mixture of: 1. an alkyl (aryl) sulfonated surfactant; and 2) an alk (en) yl succinate of the formula R 1 -CH-CH-COOH COOH 20 wherein R 1 is an alk (en) yl group having 10 to 20 C atoms, R 2 is hydrogen or C 1-4 alkyl; the weight ratio of sulfonate to succinate is between 3: 1 and 1: 4; and 'c) the nonionic surfactant component corresponds to 50-10% of the ternary surfactant system; the pH of said combination measured as a 1% solution at 20 ° C is between about 7 and about 9; and that the combination further contains 1-8% by weight C10-18 fatty acid, preferably oleic acid. Combination according to Claim 1, characterized in that the alkyl (aryl) sulfonate is an alkylbenzenesulfonate salt having 10 to 18 carbon atoms in the alkyl group and the salt-forming cation is 35 sodium, potassium, magnesium, ammonium, monoalkanolammonium. nium, dialkanolammonium, trialkanolammonium or a mixture thereof. A combination according to claim 1, characterized in that the alk (en) yl succinate is selected from the group consisting of 2-dodecenylsuccinic acid, 2-tetradecenylsuccinic acid, 2-hexadecenylsuccinic acid, decylsuccinic acid, dodecylsuccinic acid and dodecylsuccinic acid and A combination according to claim 1, characterized in that it further contains 0.01 to 0.25% by weight of an antioxidant. 16: <5 5 S O