Aqueous compositions, their manufacture and use

Abstract

Aqueous compositions with a pH value in the range of from 3.0 to 10.0, determined at 20°C, comprising (A) at least one alkyl polyglycoside of the general formula (I), (G)u-OR1 (I) R1 is selected from branched C6-C18-alkyl, u is in the range of from 1.1 to 4, and G is selected from monosaccharides with 4 to 6 carbon atoms, (B) at least one surfactant selected from sulfates of branched C10-C20-alkanols, and (C) at least one surfactant selected from sulfates from ethoxylated branched C10-C20-alkanols.

Description

[0001] Aqueous Compositions, their Manufacture and Use

[0002] The present invention is directed towards aqueous compositions with a pH value in the range of from 3.0 to 10.0 comprising

[0003] (A) at least one alkyl polyglycoside of the general formula (I),

[0004] (G)u-OR1(I)

[0005] R1is selected from branched Ce-Cis-alkyl, u is in the range of from 1.1 to 4, and

[0006] G is selected from monosaccharides with 4 to 6 carbon atoms,

[0007] (B) at least one surfactant selected from sulfates of branched C -C2o-alkanols, and

[0008] (C) at least one surfactant selected from sulfates from ethoxylated branched C -C2o-alkanols.

[0009] Formulations for hard surface cleanings are still the field of developmental and research work. Improvement of the efficiency of current formulations is still of interest, since either more hard surfaces can be cleaned with the same amount of formulation, or less active matter needs to be used, and the environment can be spared sewage water containing a higher amount of surfactant. In addition, a reduction of fuel and fossil based raw materials is highly desired. Many of the bio-based surfactants, however, are based on palm oil (more precisely, “palm kernel oil”).

[0010] WO 2024 / 002922 discloses a liquid laundry formulation comprising several ingredients like alkyl polyglycosides and alkyl ether sulfates that are bio-based, preferably based on palm kernel oil.

[0011] US 2009 / 036345 discloses alkyl polyglycosides and their use in light-duty liquid dishwash compositions.

[0012] The circumstances of the generation of palm kernel oil, however, creates concerns as well, such as burning down the rain forest with undesired consequences such as climate change, rain forest reduction and extinction of exotic animals. Palm kernel oil based surfactants, however, appear to be indispensable due to the excellent foaming behaviour, see, e.g., C. Genova et al., J. Surfactants Det 2003, 6, 371 and to their advanced soil emulsification properties. In many hard surface cleaning applications such as manual dishwashing, foaming is usually assigned to good cleaning behaviour by end users. Hard surfaces in this context are surfaces that do not show an impact obvious to the naked eye, such as compression when pressed manually. Examples of hard surfaces are stone, ceramics, china, glassware, metals and alloys such as steel, stainless steel, silver, iron, nickel, but also polymers (“plastics”) such as melamine resin, polyurethanes, polystyrene, nylon (polyamide) polypropylene, said plastics having a sufficient thickness, for example one mm or more. Examples of dishware are plates, bowls, glass, cutlery, pots, pans, and tools like fish slices and ladles. Examples of hard surfaces outside dishware are tiles, e.g., floor tiles and wall tiles such as in a kitchen or bathroom, additionally toilet bowls, bathtubs, sinks and the like.

[0013] Aliphatic alcohols based on palm kernel oil are usually non-branched, thus, straight-chain aliphatic or straight-chain olefinic alcohols. For the foaming behaviour, especially anionic surfactants and non-ionic surfactants play an important role. Significant amounts of palm kernel oil are thus used to manufacture sodium lauryl ether sulfate (“LES”) and linear alcohol ethoxylates.

[0014] It was an objective to provide a detergent composition for hard surface cleaning and especially for manual dishwashing that displays a foaming behaviour like a palm kernel oil-based anionic and non-ionic surfactants.

[0015] Accordingly, the aqueous compositions as defined at the outset have been found, hereinafter also referred to as inventive (aqueous) compositions or (aqueous) compositions according to the present invention. Inventive compositions have a pH value in the range of from 3.0 to 10.0, preferably from 3.5 to 9.5 and more preferably from 6.5 to 9.5, the pH value being determined at 20°C.

[0016] Inventive compositions are aqueous compositions. This means that they are liquid or gel-type at ambient temperature, that is 15 to 25°C, preferably liquid.

[0017] As solvent, inventive compositions contain mainly water, for example at least 50 vol-% with respect to solvent, preferably at least 80 vol-%. The term solvent includes the water.

[0018] In one embodiment of the present invention, inventive compositions may comprise solvents other than water, for example ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec.- butanol, ethylene glycol, propylene glycol, 1,3-propane diol, butane diol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, and phenoxyethanol, preferred are ethanol, isopropanol or propylene glycol.

[0019] In one embodiment of the present invention, inventive compositions comprise 0.5 to 12 % by weight of organic solvent, referring to the total respective composition. In another embodiment, inventive compositions do not contain solvents other than water.

[0020] Inventive compositions contain

[0021] (A) at least one alkyl polyglycoside of the general formula (I), hereinafter also referred to as component (A) or surfactant (A) or simply as (A),

[0022] (G)u-OR1(I)

[0023] R1is selected from branched Ce-Cis-alkyl, u is in the range of from 1.1 to 4, and

[0024] G is selected from monosaccharides with 4 to 6 carbon atoms,

[0025] (B) at least one surfactant selected from sulfates of branched C -C2o-alkanols, hereinafter also referred to as component (B) or surfactant (B) or simply as (B), and

[0026] (C) at least one surfactant selected from sulfates from ethoxylated branched C -C2o-alkanols, hereinafter also referred to as component (C) or surfactant (C) or simply as (C).

[0027] Sometimes, branched alkanols and branched alkenols contain minor amounts of straight-chain alkanol as an impurity. Preferably, inventive compositions comprise less than in total 10% by weight of anionic or non-ionic surfactants with linear Ce-Cis-alkyl groups, percentages referring to the total amount of anionic and non-ionic surfactants in such inventive compositions.

[0028] Alkenols in the context of the present invention refer to one or more C=C double bods per organic moiety, the substitution pattern corresponding to (Z)-substitution.

[0029] More preferably, inventive compositions comprise less than 20% by weight of surfactants other than anionic and non-ionic surfactants that are based on non-branched alkanols or nonbranched alkenols. Surfactants other than anionic and non-ionic surfactants as cationic or zwitterionic surfactants. Components (A), (B) and (C) are described in more detail below.

[0030] Component (A) refers to one or more alkyl polyglycosides of the general formula (I),

[0031] (G)u-OR1(I)

[0032] Wherein

[0033] R1is selected from branched Ce-Cis-alkyl, with one or more branchings, for example two or three. Preferably, a branching is in the 2-position, thus derived from a Guerbet alcohol, or the Ce-Cis-alkyl is iso-alkyl. Examples are iso-hexyl, 2-methylpentyl, iso-heptyl, 2-ethylhexyl, isoheptyl, iso-octyl, isononyl, iso-decyl, 2-(n-propyl)heptyl (“2-propylheptyl”), 2-isopropyl-heptyl, 2- isopropyl-5-methylhexyl, 2-n-propyl-6-methylhexyl, combinations of at least two of 2- propylheptyl, 2-isopropyl-heptyl, 2-isopropyl-5-methylhexyl, and 2-n-propyl-6-methylhexyl, 2-n- butyloctyl, is-dodecyl, iso-myristyl, iso-pentadecyl, iso-hexadecyl, iso-octadecyl.

[0034] Another preferred example is 3-ethyl 8-methyl decyl.

[0035] The variable u is the degree of polymerization and is in the range of from 1.1 to 4, preferred are 1.1 to 2 and in particularly preferred are 1.2 to 1.8. In the context of the present invention, the variable u refers to average values, and u is not necessarily a whole number. In a specific molecule only whole groups of G can occur. It is preferred to determine u by High Temperature Gas Chromatography (HTGC).

[0036] G is selected from monosaccharides with 4 to 6 carbon atoms, preferably from glucose and xylose and even more preferably, G is glucose.

[0037] In a more preferred embodiment, component (A) is selected from branched C8-Ci4-alkyl polyglucosides such as compounds of general average formula (1.1). wherein: R3is Ci-Ce-alkyl, straight-chain or branched, in particular ethyl, n-propyl, isopropyl, n-butyl and iso-butyl,

[0038] R4is -(CH2)2-R3, straight-chain or branched, wherein R3is defined as above.

[0039] G is defined as above, more preferably glucose, or glucose with up to 10 mole-% of xylose. u is in the range of from 1.1 to 4, preferred are 1.1 to 2 and in particularly preferred are 1.2 to 1.8, u being an average number, vide supra.

[0040] In a preferred embodiment, R1in formula (I) is selected from 2-ethyl hexyl and 2-propylheptyl and 3-ethyl-8-methyl decyl.

[0041] In one embodiment of the present invention, component (A) has a colour number (Hazen) in the range of from 10 to 1 ,000, preferably in the range of from 50 to 800 and more preferably in the range of from 100 to 500.

[0042] The Hazen colour number can be determined according to DIN EN ISO 6271-1 or 6271-2.

[0043] Component (B) is selected from least one surfactant selected from sulfates of branched C10-C20- alkanols. Sulfates are preferably partially or more preferably fully neutralized with alkali, preferably with potassium and more preferably with sodium.

[0044] Said branched C -C2o-alkanol may have one or more branches per alkyl chain, preferred is one branching. Preferably, said alcohol is an iso-alkanol with an uneven number of carbon atoms, for example iso-undecyl, iso-tridecyl, iso-pentadecyl, or iso-heptadecanol. Iso-tridecanol may contain one or more isomers as impurities, for example 2-tridecanol, 3-tridecanol, 4-tridecanol or others.

[0045] Component (C) is at least one surfactant selected from sulfates from ethoxylated branched C10- C2o-alkanols, preferably with an even number of carbon atoms per molecule. Preferred are Guerbet alcohols such as, but not limited to 2-ethylhexyl, 2-propylheptyl, 2-butyl octyl, and mixtures of isomers such as 2-isopropyl-heptyl, 2-isopropyl-5-methylhexyl, 2-n-propyl-6- methylhexyl, and combinations of at least two of 2-propylheptyl, 2-isopropyl-heptyl, 2-isopropyl- 5-methylhexyl, and 2-n-propyl-6-methylhexyl. In other embodiments, iso-alkyl groups are comprised in component (C).

[0046] Guerbet alcohols as base for component (C) are preferred. Component (C) may bear 1 to 10, preferably 2 to 7 ethoxy groups.

[0047] In one embodiment of the present invention, component (C) is selected from compounds according to general formula (II)

[0048] R2-O-(EO)y-SO3M (II) wherein

[0049] R2is selected from branched C -Cis-alkyl, especially 2-propylheptyl,

[0050] EO is ethylene oxide, CH2-CH2-O, and the variable y is selected from 1 to 7, preferably 2 to 6, and

[0051] M is alkali metal selected from Na and K, especially Na.

[0052] In one embodiment of the present invention, surfactants (B) and (C) are comprised in a weight ratio of from 5: 1 to 15: 1.

[0053] In one embodiment of the present invention, the total solids content of inventive formulations is in the range of from 5 to 40% by weight, preferably 10 to 39% by weight, more preferably 20 to 38% by weight. The solids content is preferably determined by evaporating the volatiles at 115°C at ambient pressure.

[0054] Inventive compositions may contain further ingredients such as fragrance, perfumes, dyestuff and the like.

[0055] In one embodiment of the present invention, inventive compositions comprise in the range of from 0.5 to 10% by weight of component (A), preferably 4 to 7% by weight, in the range of from 5 to 30% by weight of component (B), preferably 15 to 30% by weight, in the range of from 0.5 to 10% by weight of component (C), preferably 2 to 5 % by weight, percentages referring to the total weight of the respective inventive composition.

[0056] In a special embodiment of the present invention, inventive compositions comprise in the range of from 0.5 to 10% by weight of component (A) with G = glucose, 1.2 < u < 1.5, R1is 3-ethyl-8-methyl decyl, and preferably, 4 to 7% by weight in the range of from 5 to 30% by weight of component (B) selected from 2-propyl, preferably 15 to 30% by weight, in the range of from 0.5 to 10% by weight of component (C) according to formula (11.1), preferably 2 to 5 % by weight, percentages referring to the total weight of the respective inventive composition.

[0057] R2 1-O-(EO)yi-SO3Na (11.1)

[0058] R2 1is 2-propylheptyl, y1 is 4 or 5.

[0059] In one embodiment of the present invention, inventive compositions may contain a complexing agent, for example for water hardness removal. Examples of complexing agents are EDTA, NTA, and STPP (sodium tripolyphosphate) but such ingredients raise ecological concerns. Further examples are citric acid, methyl glycine N,N-diacetate (“MGDA”), ethylendiamine tetraacetic acid (“EDTA”), iminodisuccininic acid (“IDS”), diethylene triamine pentaacetic acid (“DTPA”), and glutamic acid N,N-diacetate (“GLDA”).

[0060] In one embodiment of the present invention, inventive compositions comprise

[0061] (D) an alkali metal salt of citric acid or MGDA or GLDA or EDTA or IDS or DTPA, preferably a sodium salt, more preferably a sodium salt of citric acid or MGDA.

[0062] Depending on the pH value, mono-or di- or trialkali metal salts are comprised, or in the case of GLDA and EDTA the tetraalkali salt, especially the mono- or disodium salt of citric acid or MGDA.

[0063] In one embodiment of the present invention, inventive compositions comprise 0.01 to 0.5 % alkali metal salt (D) of citric acid or MGDA or GLDA or EDTA or IDS or DTPA, preferably a sodium salt, more preferably a sodium salt of citric acid or MGDA.

[0064] In one embodiment of the present invention, inventive compositions comprise (E) at least one zwitterionic surfactant, hereinafter also referred to as component (E) or surfactant (E) or simply (E). Zwitterionic surfactants are sometimes also referred to as amphoteric surfactants.

[0065] Zwitterionic surfactants (E) bear a positive and a negative charge in the same molecule under use conditions. Preferred examples of zwitterionic surfactants are so-called betaine-surfactants. Many examples of betaine-surfactants bear one quaternized nitrogen atom and one carboxylic acid group per molecule. An example of amphoteric surfactants is lauramidopropyl betaine, for example generated as cocamidopropyl betaine or babussu amidopropyl betaine.

[0066] Further examples of zwitterionic surfactants are amine oxide surfactants (E) are compounds of the general formula (III)

[0067] R5R6R7N^O (III) wherein R5, R6and R7are selected independently from each other of aliphatic, cycloaliphatic or C2-C4-alkylene groups, for example C -C2o-alkylamido moieties. Preferably, R5is selected from Cs-C2o-alkyl or C2-C4-alkylene C -C2o-alkylamido and R6and R7are both methyl.

[0068] A particularly preferred example is lauryl dimethyl aminoxide, sometimes also called lauramine oxide. A further particularly preferred example is cocamidylpropyl dimethylaminoxide, sometimes also called cocamidopropylamine oxide.

[0069] Another class of amphoteric surfactants (E) are sultaines (sulfobetaines), for example fatty alkyl hydroxysultaines.

[0070] In one embodiment of the present invention, inventive compositions exhibit a dynamic viscosity at 23°C in the range of from 500 to 2200 mPa s (Brookfield viscosimeter, spindel No. 2, 50 rpm).

[0071] In one embodiment of the present invention, inventive compositions may contain one or more adjunct ingredients. Examples of adjunct ingredients are special effect polymers, enzymes, for example proteases, lipases, cellulases, hemicellulases. Other examples of adjunct ingredients are hydrotropes dyestuffs and fragrances. Examples of dyestuffs are Acid Blue 9, Acid Yellow 3, Acid Yellow 23, Acid Yellow 73, Pigment Yellow 101 , Acid Green 1 , Solvent Green 7, and Acid Green 25. Other examples of adjunct ingredients are rheology modifiers, for example thickeners, or NaCI. Other examples of adjunct ingredients are biocides, for example 1 ,2- benzisothiazolin-3-one (“BIT”) (commercially available as Proxel® grades from Avecia Lim.) or alkali metal salts thereof; other suitable biocides are 2-methyl-2H-isothiazol-3-one (“MIT”) and 5- chloro-2-methyl-2H-isothiazol-3-one (“CIT”), also 2-bromo-2-nitropropane-1 ,3-diol, benzalkonium chlorides and 4,4‘-dichloro-2-hydroxydiphenyl ether. Other examples of adjunct ingredients are stabilizers, such as UV absorbants, for example benzophenone, sodium benzotriazolyl butylphenol sulfonate and ESQ like Tris(tetramethylhydroxypiperidinol)citrate. Other types of stabilizers are antioxidants such as, but not limited to tocopherol BHT, phenolic antioxidants such as pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), and non-phenolic antioxidants such as didodecyl 3,3'-thiodipropionate. Sodium benzoate may serve as hydrotrope.

[0072] Examples of special effect polymers are alkoxylated polyethylenimines. Other examples are polyacrylates, copolymers of acrylic acid, and polyoxymers.

[0073] Another class of adjunct ingredients is re-fattening agents, for example squalene and cetyl palmitate.

[0074] Another adjunct ingredient is sodium chloride.

[0075] A further aspect of the present invention is directed towards a process for making inventive compositions, hereinafter also referred to as inventive process. In order to perform the inventive process, components (A) to (C) and, optionally, at least one of component (D) and (E) are mixed in the presence of water in one or more steps. The order of addition is not critical.

[0076] In one embodiment of the present invention, the inventive process comprises the additional step of adjusting the pH value to 3.0 to 10.0 with citric acid or its sodium salt, with the trisodium salt of MGDA, with a sodium salt of GLDA, IDS, EDTA, DTPA, or with NaOH. Citric acid, the trisodium salt of citric acid, the trisodium salt of MGDA and the tetrasodium salt of GLDA are preferred.

[0077] In one embodiment of the present invention the inventive process is carried out at a temperature in the range of from 10°C to 50°C, preferably at ambient temperature which is in the range of from 15 to 25°C.

[0078] The mixing step can be performed by shaking, or preferably by stirring. In order to avoid strong foaming, gentle stirring is preferred. In laboratory trials, magnetic stirring is preferred. In one embodiment of the present invention, one or more adjunct ingredients is added during the inventive process.

[0079] Another aspect of the present invention is related to the use of inventive compositions as or for the manufacture of manual dishwashing compositions. Manual dishwashing is sometimes also referred to as hand dishwash. In order to make a manual dishwashing composition, inventive compositions may be diluted with water, or at least one more adjunct ingredient is added. Another aspect of the present invention is a process for cleaning dishware with the help of an inventive composition, hereinafter also referred to as inventive cleaning process.

[0080] Cleaning dishware with the help of an inventive composition may be performed by mixing a shot of an inventive composition with water, thus creating a dishwashing liquor, and contacting soiled dishware with dishwashing liquor. The temperature of the dishwashing liquor is preferably in the range of from 20 to 50°C, preferably 40 to 45°C. Cleaning may be supported with a brush or a sponge or a cloth. It is advantageous to rinse the cleaned dishware with water before allowing to dry or removing wetness with a tea towel or a dishcloth.

[0081] In the inventive cleaning process, a high efficiency can be detected, for example measured with the plate test, and a high amount of foam is generated during manufacture of the respective dishwashing liquor.

[0082] The present invention is further illustrated with the help of working examples.

[0083] The following ingredients were used:

[0084] (A.1): G = glucose, u = 1.35, R1is 3-ethyl-8-methyl decyl

[0085] (A.2): G = glucose, u = 1.5, R1is C9 / C11 iso-alkyl c-(A.3): G = glucose, u = 1.3, instead of R1an n-Cs-alkyl / n-Cw-alkyl mixture

[0086] (B.1): (CH3)2CH(CH2)io-OS03Na c-(B.2): n-Ci2H25-OSO3Na

[0087] (C.1): 2-propylheptyl, y = 4, M is sodium c-(C.2): n-Ci2H25-O(EO)3-OSO3Na

[0088] (D.1): citric acid

[0089] (D.2): MGDA-Na3(trisodium salt of MGDA)

[0090] (E.1): “lauramine N-oxide” - N,N,N-dimethyl-n-lauryl- N-oxide

[0091] (E.2): OOC-CH2-N(CH3)2-(CH2)3-CO-NH-n-CnH23c-(F.1): n-Ci8-alkyl-G-(EO)8o-H General protocol: in a glass beaker, the above ingredients were mixed at ambient temperature in accordance with Table 1. Compositions containing c-(A.3) or c-(B.2) or c-(C.2) are comparative compositions. The resulting mixtures were each adjusted with water to 100 g. Inventive compositions IC-1 to IC-4 as well as comparative compositions Comp-C-5 and Comp-C6 were obtained as clear liquids.

[0092] The following tests were performed: (general protocol according to ASTM D4009-92, Method A Soil B): a wash liquor was produced in a sink by adding a shot (4 grams) of the respective inventive - or comparative - composition to tab water with a temperature of 42°C.

[0093] Soil B consists of 50% flour, 48% Crisco, and 2% oleic acid.

[0094] To each plate, 6 grams of soil B were applied. The soiled plates were cleaned manually. The number of plates was determined until the foam had broken. The results in Table 1 are average values from 4 experiments.

[0095] Table 1 : contents of inventive and comparative compositions All quantities in g active ingredient per 100 g

[0096] The dynamic viscosity q was determined with a Brookfield LV viscosimeter, spindle SC4-31 , at 25°C unless indicated otherwise.

Claims

Patent claims1. Aqueous composition with a pH value in the range of from 3.0 to 10.0, determined at20°C, comprising(A) at least one alkyl polyglycoside of the general formula (I),(G)u-OR1(I)R1is selected from branched Ce-Cis-alkyl, u is in the range of from 1.1 to 4, andG is selected from monosaccharides with 4 to 6 carbon atoms,(B) at least one surfactant selected from sulfates of branched C -C2o-alkanols, and(C) at least one surfactant selected from sulfates from ethoxylated branched C10-C20- alkanols.

2. Aqueous composition according to claim 1 wherein said composition additionally contains(D) an alkali metal salt of citric acid or MGDA or GLDA.

3. Aqueous composition according to claim 1 or 2 having a total solids content in the range of from 5 to 40% by weight.

4. Aqueous composition according to any of the preceding claims wherein surfactants (B) and (C) are comprised in a weight ratio of from 5: 1 to 15: 1.

5. Aqueous composition according to any of the preceding claims wherein R1is selected from 2-ethylhexyl and 2-propylheptyl.

6. Aqueous composition according to any of the preceding claims wherein surfactant (C) is selected from compounds according to general formula (II)R2-O-(EO)y-SO3M (II) whereinR2is selected from branched C -Cis-alkyl,EG is ethylene oxide, CH2-CH2-O, y is in the range of from 1 to 7,M is alkali metal selected from Na and K.

7. Aqueous composition according to any of the preceding claims comprising less than 10% by weight of surfactants with linear Ce-Cis-alkyl groups, percentages referring to the total amount of anionic and non-ionic surfactants.

8. Aqueous composition according to any of the preceding claims comprising (E) at least one zwitterionic surfactant.

9. Aqueous composition according to any of the preceding claims wherein compound (A) is a compound according to general formula (1.1)R3is Ci-Ce-alkyl, straight-chain or branched,R4is -(CH2)2-R3,10. Process for making an aqueous composition according to any of the claims 1 to 9. wherein components (A) to (C) and, optionally, at least one of component (D) and (E) are mixed in the presence of water in one or more steps.

11. Process according to claim 10 comprising the additional step of adjusting the pH value to 3.0 to 10.0 with citric acid or its sodium salt, with the trisodium salt of MGDA, with a sodium salt of GLDA, IDS, EDTA, DTPA, or with NaOH.

12. Use of a composition according to claims 1 to 9 as or for the manufacture of manual dishwashing composition.

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