DK167155B1 - CONCENTRATED, HOMOGENEOUS, WATERFUL, LIQUID DETERGENT COMPOSITION - 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

in DK 167155 B1

The invention relates to concentrated, homogeneous, aqueous liquid detergent compositions containing less than 50% by weight of water, a ternary anionic / nonionic surfactant system and, if desired, conventional additives. The ternary surfactant system contains a major amount of an anionic surfactant which is constituted by a binary mixture of an alkyl (aryl) sulfonated surfactant and an alk (s) ylsuccinate in a weight ratio of sulfonate to succinate. ranging from 3: 1 to 1: 4 as well as a nonionic surfactant.

10

The compositions of the invention exhibit excellent and highly desirable detergent action, are easy to prepare, and further exhibit excellent stability during prolonged storage.

Homogeneous, concentrated, high-performance liquid detergents are well known in the art and have found commercial use. Such compositions may comprise a ternary active system, namely: synthetic, anionic sulfonates or sulfates in combination with nonionic ethoxylates and soaps. These prior art compositions are difficult to manufacture, especially in dependence on alkalinity.

The previously known concentrated liquid detergents are prone to phase separation under neutral and mildly alkaline conditions. As a further consequence of such critical conditions for the matrix, it is rather difficult to modify the matrix to increase the effect with respect to certain staining / purification situations. From a detergent point of view, it is known that although concentrated liquid compositions in the art exhibit excellent purity to the majority of fibers, it would be desirable if they could be improved with respect to the purification of cellulose fibers when compared to the effect of which are obtainable using oxygen-containing, polyphosphate-formed granular detergents.

The prior art relating to concentrated, homogeneous, high-performance liquid detergent compositions is extensive and diverse. For example, U.S. Patent No. 4,285,841 discloses builder-free, concentrated, homogeneous, liquid compositions containing a combination of anionic, synthetic, surfactant, nonionic, surfactant and fatty acids. The preparation of such compositions containing less than 50% water requires the use of substantial amounts of solvents and / or compatibility enhancers, and even under these circumstances, there remains boundary stability, especially in terms of the extent and type of the nonionic compounds, fatty acids, especially saturated species, and any electrolytes, as well as low levels of organic builders.

Succinate content is well known in the field of detergent and has been described in connection with all kinds of detergent embodiments, mostly granular compositions. Although such succinates have been recommended for use in liquid compositions, it is well known that significant formulation difficulties will be encountered in their use in these compositions, especially in the presence of low levels of water and significant amounts of nonionic substances. .

German Patent No. 1,768,851 relates to the use of specific succinate derivatives as foam enhancers. These compositions contain only anionic surfactants as well as substantial amounts of water in combination with additional hydrotropes.

German Patent No. 1,956,671 describes binary liquid preparations containing substantial amounts of alk (en) ylsuccinates in combination with nonionic surfactants. German Publication No. 3,013,904 relates to alkaline, solid or liquid detergent compositions containing a partially neutralized succinic anhydride derivative which appears to be used because of its foaming properties.

European Patent Application No. 17,951 relates to the use of alk (en) yl succinic salts or monoesters thereof with polyhydric alcohols to make perfumes hydrotropic in liquid detergent compositions containing large amounts of electrolytes.

35

Further, from EP Publication No. 28,850, there are known aqueous liquid-based detergent compositions comprising a nonionic detergent material, a water-soluble builder salt, a monoalkyl or alkenyl succinate, wherein the alkyl or carbonyl group contains 7-12 0.5-3% by weight of alkyl-benzenesulphonate, wherein the alkyl group contains 10-15 carbon atoms. The content of the small amount of all benzene sulphonate cooler is intended to improve the storage stability of the detergent composition at low temperatures. In addition to the low content of all cool benzenesulphonate, no appreciable amounts of anionic detergents are used in compositions.

Finally, GB Publication No. 2,049,723 is known, inter alia,

10 liquid detergent compositions containing from 3 to 50% by weight of partially neutralized succinic derivative of the formula: R - CH - CH 2 C00X C00Y 15 wherein R represents a saturated or unsaturated hydrocarbon group having 3 to 18 carbon atoms and X and Y independently each represent hydrogen, alkali metal, ammonium or alkanolamine. The compositions to be used in particular as detergents are stated to have 20 good foaming and cleansing properties while being mild to the skin, unlike anionic surfactants which are said to be hard on the skin and make it rough, and non-ionic surfactants, which are skin-friendly but deficient in foaming and cleansing properties.

Contrary to the prior art, the present invention relates to highly concentrated, homogeneous, aqueous, liquid detergent compositions having a substantial content of a ternary surfactant system based on anionic sulfonates and succinates in combination with a nonionic surfactant component. , which compositions are storage stable and have excellent detergent properties under neutral to mildly alkaline pH conditions.

The homogeneous, concentrated, aqueous liquid detergent compositions of the invention contain less than 50% water and a ternary surfactant system and, if desired, usual additives which are characterized by: a) the ternary surfactant system constituting b) that the anionic surfactant constitutes from 50 to 90% by weight of the ternary surfactant system and is made up of a binary mixture of: 1) an all cooling (aryl) sulfonated surfactant; 2) an alk (yl) ylsuccinate of the formula: 10 * 2

R - CH - CH - COOH

COOH

represents an alk (one) yl radical having from 10 to 20 C atoms, and represents hydrogen or C1-C6 alkyl, wherein the weight ratio of sulphonate to succinate is in the range 20 from 3: 1 to 1: 4, and c) that the nonionic surfactant constitutes from 50% to 10% of the ternary surfactant system, which composition has a pH as measured in a 1% solution at 20 ° C is in the range of approx. 7 to approx. 9th

Thus, the present invention can be realized as highly concentrated, homogeneous liquid detergent compositions containing a ternary surfactant system and having a pH in the neutral to mildly alkaline range.

The essential parameters characterizing the invention are described in more detail below.

35 Unless otherwise indicated, the "percentages" represent "weight percent" of the composition.

The anionic surfactant constitutes from 50% to 90% of the ternary surfactant system and is constituted by a binary combination of: 1) an alkyl (aryl) sulfonated surfactant, and 5 2) an alk ( one) ylsuccinate of the formula: I2

R - CH - CH - COOH

10 I

COOH

wherein R 1 represents an alk (yl) yl radical having from 10 to 20 C atoms and R 2 represents hydrogen or C 1 -C 6 alkyl, wherein the weight ratio of sulfonate to succinate is in the range of 3: 1 to 1: 4.

The anionic surfactant sulfonate may be any alkyl (aryl) sulfonated surfactant which is known to be suitable for use in liquid detergent compositions and has actually been widely used in commercial detergent embodiments.

These anionic synthetic sulfonates may be represented by the general formula R 1 O 2 M, wherein R 1 represents a hydrocarbon moiety selected from the group consisting of straight or branched alkyl radicals having from about 1 8 to approx. 24 carbon atoms and all cool phenyl radicals with from approx. 10 to approx. 18 carbon atoms in the alkyl group. M is a salt-forming cation typically selected from the group consisting of sodium, potassium, magnesium, ammonium, monoalkanolammonium, di-all canonammonium, tri-alkanonolammonium and mixtures thereof.

A preferred synthetic, anionic surfactant sulfonate is a water-soluble salt of an alkyl benzene sulphonic acid containing from about 35%. 10 to approx. 18 carbon atoms in the alkyl group, the most preferred species for use herein having from 12 to 16 carbon atoms in the alkyl chain.

The alk (en) ylsuccinate has the above formula, wherein R 1 is either a saturated or unsaturated radical having from 10 to 20 carbon atoms, preferably an unsaturated derivative having from 12 to 16 carbon atoms in alkenyl part one. Rg may be hydrogen or Cj-C ^ alkyl, although hydrogen is preferred. The terms "succinate" and "succinic acid" are used synonymously. Suitable succinic salts include sodium, potassium, lithium, ammonium, mono-, di- and trialkanolamine salts and mixtures thereof.

Preferred succinic derivatives for use in the present invention include 2-dodecenyl succinic acid, 2-tetradecenyl-1 ° succinic acid, 2-hexadecenyl succinic acid, decyl succinic acid, dodecyl succinic acid and tetradecyl succinic acid, and the water-soluble salts thereof. The all cooling or alkenyl chains attached to the succinic acid can be either straight or branched. Straight-chain alk (one) wool parts are preferred.

The weight ratio of sulphonate to surfactant succinate in the binary mixture ranges from 3: 1 to 1: 4, preferably from 2: 1 to 1: 2.

The ternary surfactant system usually constitutes from 35% to 20% of the composition. The anionic surfactant is indicated in its salt form.

The nonionic surfactant component contains a hydrophobic organic radical which is condensed with a hydrophilic ethylene oxide moiety.

All ethoxylated, nonionic surfactants known to be useful for use in detergents can be used in the compositions of the present invention. Preferred nonionic species for use in the present invention are polyethoxylates derived from primary and secondary aliphatic alcohols having from 8 to 24 carbon atoms and an HLB (hydrophilic-lipophilic balance) in the range of about 8. to 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) may be linear or branched fatty carbon.

35

A preferred class of non-ionic ethoxylates is the condensation product of a fatty alcohol having from 12 to 15 carbon atoms and from ca. 4 to 10 moles of ethylene oxide per mole of fatty alcohol. Suitable species of this ethoxy class include: the condensation product of C C-C ^ 7 oxoalcohols and 7 moles of ethylene oxide per mole of alcohol; the condensation product of C13-C15 oxoalcohols and 5 moles of ethylene oxide; the condensation product of a narrow fraction of C14 "C15 oxo alcohols and 7 or 9 moles of ethylene oxide per mole of fat (oxo) alcohol; the condensation product of a narrow fraction of C12 C13 fat (oxo) all alcohol and 6.5 moles of ethylene oxide per mole of fatty alcohol and the condensation product of a C10'C14 coconut fatty alcohol having an ethoxylation degree (mol EO / mol of fatty alcohol) in the range of 5 to 8. Although the fatty oxal alcohols are essentially linear, depending on the process conditions and the definitions of the raw material, they may have some degree of branching, preferably short-chain branching, such as methyl branching. A branching range in the range of 15% to 50% (wt.%) is often found in commercial oxoalcohols.

Preferred nonionic ethoxylated components may also be represented by a mixture of 2 separately ethoxylated nonionic surfactants of varying degrees of ethoxylation. For example, the nonionic ethoxylate may be represented by mixtures of a first ethoxylated surfactant containing from 3 to 20 7 moles of ethylene oxide per mole of hydrophobic moiety, and another of a second ethoxylated species containing from 8 to 14 moles of ethylene oxide per mole of hydrophobic moiety. A preferred non-ionic ethoxylated mixture contains a lower ethoxylate which is the condensation product of a C 12 15 oxoalcohol with (* OP 50% (wt.%) Branching) and from about 3 to 7 moles of ethylene oxide per mole of fatty oxal alcohol, and a higher ethoxylate, which is the condensation product of a C16 "C19 oxo alcohol having more than 50% (wt.%) branching and from about 8 to 14 moles of ethylene oxide per mole of branched oxoalcohol.

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

The compositions of this invention contain less than 50%, preferably from 15% to 40%, water.

The compositions described are further characterized in that their pH value, measured in a 1% aqueous solution at 20 ° C, is in the range of approx. 7 to approx. 9. This pH range implies that the anionic surfactant component, i.e. the binary mixture of sulphonate and succinate, and especially the succinate, is substantially completely (i.e., more than 90%) neutralized in the composition described as present.

5

In addition to the essential ingredients described above, the compositions herein often contain a variety of optional ingredients which are used because of their known function in conventional quantities.

10

Examples of such optional ingredients may include saturated and / or unsaturated fatty acids and the corresponding soaps, synthetic, anionic, surfactants different from sulfonates (non-sulfonate anionic agents), water-insoluble solvents, enzymes, enzyme stabilizers, polyacids, foaming agents. , detergents, perfumes, dyes, antioxidants, bactericides, corrosion inhibitors, fabric softeners, phase regulators and the like.

. 20 Suitable fatty acids, saturated or unsaturated, have from 10 to 18 carbon atoms in each cooling chain. Unsaturated species having from 14 to 18 carbon atoms in the entire chain, most preferably oleic acid, are preferred. The corresponding soaps can also be used. The optional fatty acids / soaps are used up to approx. 10%, preferably from 1% to 8% 25 (of the composition). The fatty acids / soaps, among other agents, act as foam modifiers / regulators.

Synthetic, non-sulfonate, anionic agents can also be used in the composition in relatively small amounts, e.g. in amounts not exceeding 25% of the ternary surfactant system. Examples of suitable non-sulfonate, anionic agents include the salts of sulphated fatty carbon are from 12 to 20 carbon atoms in all the carbon chain.

Water-insoluble solvents such as terpenes, phthalic acid esters and liquid paraffins can also be used to an extent generally below 5%.

Detergent enzymes help and generally promote the removal of specific stains. Suitable enzymes may be represented by proteases, amylases, lipases, glucose oxidases, cellulases or mixtures thereof. Proteases and amylases are preferred in the liquid concentrated compositions described herein. They are often used to a degree of approx. 0.01% to approx. 1%.

All commonly known enzyme stabilization systems can be used in the compositions of the present invention in the relative amounts known in the art. Examples of suitable stabilization systems 10 include short-chain C 1 -C 4 carbolyxy acid, especially formic acid in combination with a low calcium level, boric acid and its water-soluble salts, optionally in combination with polyols.

Another preferred optional ingredient is a polyacid or a mixture of polyacids in a relative amount of from 0.05% to approx. 2%. Suitable polyacid species for use in the present invention are those having a pK value of at least 5. Preferred polyacid species for use in the present invention are represented by organophosphonic acids, especially alkylene polyamine polyalkylene-2-phosphonic acids such as ethylenediaminetetramethylene phosphonic acid and diethylenetriamine pentamethylene

Non-fatty acid detergent foam regulators can also be used. Preferred species include alkylated polysiloxanes, such as dimethyl polysiloxane, also referred to as silicone. The silicones are often used in a relative amount not exceeding 0.5%, most preferably between 0.01% and 0.2%.

The compositions herein may also contain antioxidants due to their known beneficial effect, often radical scavengers, to the extent customary in the art, i.e. 0.01% to 0.25% (referring to the total composition). These antioxidants are often introduced together with unsaturated organic acids. Although many suitable antioxidants are well known and obtainable for this purpose, they are subsequently preferred for use in the compositions herein: 2,6-ditertiarybutyl-β-cresol, more commonly known as butylated hydroxytoluene, BHT and 2-tertiary-butyl 4-hydroxananisol. Other suitable antioxidants are: 4,4'-thiobis (6-butyl-m-cresol) and 2-methyl-4,6-dinonylphenol.

Dirt-releasing polymers can also be incorporated into the compositions herein. Suitable species of such loosening polymers are described in the specification of US Patent No. 4,702,857 and incorporated herein by reference.

A phase regulator is an additional optional ingredient in the compositions herein. This component, together with water 10, may constitute the solvent matrix of the concentrated liquid compositions described. Suitable ingredient classes include lower aliphatic alcohols having from 2 to 6 carbon atoms and from 1 to 3 hydroxyl groups, ethers of diethylene glycol and lower aliphatic monoalcohols having from 1 to 4 carbon atoms. Specific examples of phase control agents are: ethanol, n-propanol, isopropanol, butanol, 1,2-propanediol, 1,3-propanediol, monomethyl, ethyl, propyl and monobutyl ethers of di ethylene glycol.

The invention described is illustrated and illustrated by the following examples.

Example 1

A liquid detergent composition of the present invention is prepared by mixing the ingredients listed below in the conditions specified.

Ingredient Weight percent 30 Dodecylbenzenesulfonate acid 10 C10 "C15 -oxoal carbon condensed with 7 moles of ethyl enoxide per mole of fatty carbon 11.5 2-dodecenyl succinic acid 15 C12'C14 all carbon sulphate-free ethanol amine salt 4 35 Oleic acid 4 11 DK 167155 B1

Ingredient Weight percent

Tri ethanolamine neutralizers to 5 $ 5 Sodium hydroxide to obtain a pH of 7.6 6

Ethanol 7

Water 32

Other - Minor Ingredients Balance to 100 The above composition was compared for detergent performance with ARIEL, a granular tripolyphosphate coated detergent containing oxygen bleach. The test was carried out in a horizontal drum washer in a program up to 60 ° C. Comparative test results were determined using 15 cotton strips sprinkled with various types of artificial dirt, including, among others, drug builder-sensitive dirt, enzyme-sensitive dirt, particulate dirt and grease-oily dirt. It has been found that the composition of the invention provides a textile cleansing effect against all types of debris which is comparable to the effect obtained with ARIEL.

It was also found that the liquid composition of Example 1 remained homogeneous and stable after more than 2 weeks of storage at a temperature ranging from 4 ° C to 50 ° C and even after being exposed to several times. freezing and thawing.

The following examples further illustrate embodiments of the present invention. In the examples, the abbreviations for the 30 individual ingredients have the following meaning:

CjgHLAS linear dodecylbenzene sulfonic acid

CjgHLAS linear hexadecylbenzene sulphonic acid C £ qAS sodium salt of eicose-a-sulfonate 35 TEA CnAS triethanolamine coconut (C12-C14) alcohol sulphate C E0 C "alcohol ethoxylated with n moles of ethylene oxide x-y n x-y

Cx_yE0nS sodium salt of sulphated Cx_yE0n DSA 2-dodecenyl succinic acid HDSA docecyl succinic acid TSA 2-tetradecenyl succinic acid 12 DK 167155 B1 ^ 12-14 30 moles of ethylene oxide.

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Claims (9)

A homogeneous, concentrated, aqueous, liquid detergent composition containing less than 50% by weight of water, a ternary anionic / nonionic surfactant system and, if desired, usual additives, characterized by: (a) the ternary surfactant; b) that the anionic surfactant constitutes from 50 to 90% by weight of the ternary surfactant system and is a binary mixture of: 1. an alkyl (aryl) sulfonated, surfactant, 2. an alk (s) ylsuccinate of the formula: wherein R 1 represents an alk (y) yl radical having from 10 to 20 C atoms and R 2 represents hydrogen or C C) all cooling in which the weight ratio of sulphonate to succinate ranges from 3: 1 to 1: 4, and c) that the nonionic surfactant constitutes from 50 fra to 10% of the ternary surfactant system which composition has a pH as measured in a 1% solution at 20 ° C is in the range of approx. 7 to approx. 9. 35 Composition according to claim 1, characterized in that all the alkyl (aryl) sulfonate is an alkyl of benzenesulfonate salt having from 10 to 18 carbon atoms in the alkyl group, the salt-forming cation being sodium, potassium, magnesium, ammonium, monoalkanol, ammonium, di alkanolammonium, DK 167155 B1 tri alkanolammonium or mixtures thereof. Composition according to claim 1, characterized in that the alk (en) ylsuccinate is selected from the group consisting of 2-dodecenyl succinic acid, 2-tetradecenyl succinic acid, 2-hexadecenyl succinic acid, decyl succinic acid, dodecyl succinic acid and tetradecyl succinic acid as well as water soluble acid. » Composition according to claim 3, characterized in that the alk (en) yl group is straight-chain and that the weight ratio of the surfactant sulfonate to the surfactant succinate is in the range from 2: 1 to 1: 2. Composition according to claim 3, characterized in that the nonionic surfactant constitutes from 15 to 40% by weight 15% of the ternary surfactant system. Composition according to claim 1, characterized in that it contains from 15 to 40% by weight of water. Composition according to claim 1, characterized in that it further contains from 1 to 8% by weight of one (qo / 1S fatty acid). Composition according to claim 7, characterized in that it further contains from 0.01 to 0.25% by weight of an antioxidant. Composition according to claim 8, characterized in that the fatty acid is oleic acid. 30 35