WO2023172859A1 - Procédés de fabrication de mélanges de tensioactifs concentrés - Google Patents

Procédés de fabrication de mélanges de tensioactifs concentrés Download PDF

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WO2023172859A1
WO2023172859A1 PCT/US2023/063757 US2023063757W WO2023172859A1 WO 2023172859 A1 WO2023172859 A1 WO 2023172859A1 US 2023063757 W US2023063757 W US 2023063757W WO 2023172859 A1 WO2023172859 A1 WO 2023172859A1
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WIPO (PCT)
Prior art keywords
surfactant
alkyl
alkyl alcohol
blend
concentrated
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PCT/US2023/063757
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English (en)
Inventor
Karl Ghislain Braeckman
Christopher Stephen JONES
Robby Renilde Francois Keuleers
Scott Edward Stephans
Rocco TARCHINI
Saima Tariq
Diederik Emiel Omer VANHOUTTE
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The Procter & Gamble Company
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Priority claimed from EP22202167.7A external-priority patent/EP4249578A1/fr
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Publication of WO2023172859A1 publication Critical patent/WO2023172859A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • the present invention relates to processes for making concentrated surfactant blends, in particular, concentrated surfactant blends for use in making liquid detergent compositions, especially liquid hand dishwashing cleaning compositions.
  • Liquid hand dishwashing detergent compositions are typically high sudsing and provide long-lasting suds, in addition to good grease removal, in order to provide a high level of consumer satisfaction.
  • such detergent compositions comprise alkyl sulfated anionic surfactants as they provide both high, long-lasting suds during use, and good grease removal.
  • Alkyl sulfated anionic surfactants include non-alkoxylated alkyl sulfate surfactants and alkoxylated alkyl sulfate surfactants such as ethoxylated alkyl sulfate surfactants.
  • Liquid hand dishwashing detergent compositions typically include co-surfactants as part of the surfactant system to further boost the cleaning and sudsing performance.
  • co-surfactants can include amphoteric surfactants such as amine oxide surfactants, zwitterionic surfactants such as betaine surfactants, and mixtures thereof.
  • the liquid dishwashing detergent composition should also have a high viscosity.
  • alkyl sulfated anionic surfactants are made by processes involving a sulfation step, followed by a neutralisation step.
  • SO3 sulfur trioxide
  • Such processes are typically carried out using a film reactor, such as an annular falling film reactor, or a multi-tube film reactor, such as the “Ballestra” reactor.
  • the SO3 is typically first diluted with air.
  • air/SO3 sulfation processes are direct processes in which SO3 gas is diluted with very dry air and reacted directly with the alkyl alcohol feedstock. The reaction of gaseous SO3 with the alkyl alcohol is rapid and stoichiometric.
  • sulfamic acid can be used in the sulfation step in order to form the ammonium salt.
  • Sulfamic acid is a mild and specific sulfating reagent suitable for making ammonium neutralized alcohol ethoxylates.
  • An advantage of sulfamic acid is that it selectively sulfates alcohol groups and will not sulfonate aromatic rings. Therefore, it is particularly suited for sulfation of alkyl phenol ethoxylates, in order to prevent formation of mixed sulfate-sulfonate compounds.
  • An advantage of using sulfamic acid as a reagent is that the neutralised form of the sulfate surfactant is produced.
  • sulfamic acid is an expensive reagent. Moreover, when using sulfamic acid, one can only make the ammonium neutralized salt of the alkyl sulfate surfactant. This limits the application of the surfactants made using this sulfating reagent since the pH of compositions comprising such ammonium salts of alkyl sulfate surfactant has to be less than 8 in order to avoid an ammonia smell from the detergent composition.
  • ion-exchange processes can be used to replace the ammonium ions with sodium or other ions. However, such ion exchange processes are expensive and typically not cost effective for applications such as household detergent compositions. Moreover, such processes result in low surfactant concentrations in the resultant blends of typically less than 30%, resulting in limiting their application to low active detergent compositions and higher transport costs for the blends.
  • Chlorosulfuric acid can also be used to produce alkyl sulfates and alkyl ether sulfates. While substantially cheaper than sulfamic acid, chlorosulfuric acid is still substantially more expensive than other reagents. In addition, additional equipment and complexity are added to the process by using such reagents, especially since as the reaction moves to completion, hydrochloric acid (HC1) is released. This acid must be scrubbed or otherwise recovered.
  • alkyl sulfate surfactants For most commercial processes used to make alkyl sulfate surfactants, such as the air/SO3 processes and processes using chlorosulfuric acid, the acid form of the alkyl sulfate surfactant is formed. However, such acid forms of the alkyl sulfate surfactant are not stable and have to be neutralised shortly after the sulfation step, since hydrolysis back to the alkyl alcohol and the starting acid is rapid at a pH of below 7.
  • Sodium hydroxide is the most commonly neutralising agent used in the neutralising step. However, other neutralising agents such as potassium hydroxide, ammonia, mono-ethanolamine, di-ethanolamine, andtri-ethanolamine, amongst others, can be used.
  • alkyl sulfate containing surfactant blends are used to make detergent compositions having a pH of from 7.0 to 9.0.
  • the pH of the detergent composition has to be “trimmed” using an acid, such as citric acid or HC1.
  • an acid such as citric acid or HC1.
  • high levels of salts are typically present in the composition, which cause both viscosity and phase stability challenges, especially at low temperatures. Therefore, more organic solvent or structurants must be added in order to provide the desired low temperature stability and viscosity profile. Since high salt levels and high solvent levels can affect the solubility of other actives, this also makes formulation of the finished liquid detergent composition more complex. High salt levels also make the detergent composition harder to dissolve, leading to greater dissatisfaction from users
  • the alkyl alcohol Prior to sulfation, can be alkoxylated, especially ethoxylated.
  • the resultant alkyl alkoxylated sulfate surfactants provide improved low temperature stability for the resultant liquid detergent composition, while also providing the desired level of grease cleaning and sudsing performance.
  • 1,4-di oxanes can be produced.
  • Tight control of processing conditions and feedstock material compositions is typically needed, both during alkoxylation especially ethoxylation and sulfation steps, so that the amount of 1,4-di oxane by-product within alkoxylated especially ethoxylated alkyl sulfates can be minimised. Even if the 1,4-di oxane by-product level is kept to a minimum in the freshly formed surfactant blend, for many blends formed from prior art processes, the level of 1,4-di oxane by-product increases over time. The formation of 1,4-di oxanes has been found to be higher when concentrated alkyl ethoxylated sulfate blends are stored at higher pH.
  • US4477372A, US4476044A, and US4476045A relate to high active content surfactant wherein the anionic portion of the surfactant is neutralized with a secondary or tertiary amine containing at least three carbon atoms attached to the nitrogen atom of the amine, at least one alcoholic hydroxy group therein and such that the amine is alpha or beta substituted with respect to the nitrogen atom products.
  • WO9418160A relates to a process for producing high active alkyl sulfate solutions comprising the steps of adding and mixing an alkyl sulfuric acid having a chain length of C12-C18, with an organic amine to produce a neutralized product having substantially no water.
  • EP2964741 A relates to a method of preparing a substantially anhydrous composition of alkyl (ethoxy) sulfate neutralized with an organic amine base, the said composition being suitable for use as a surfactant in an ecodose.
  • WO201472840A relates to a process for preparing high- concentration, flowable aqueous fatty alkyl sulfate solution, said process comprises (i) ethoxylation of fatty alcohol with very low of about 0.3 to about 0.8 moles of ethylene oxide, and (ii) sulfating the ethoxylated fatty alcohol with specific reaction conditions, and (iii) neutralizing the sulfation product with an aqueous base, the obtained fatty alkyl sulfate solution contains at least 65% by weight of mixture of fatty alkyl sulfates and fatty alkyl ether sulfates in a weight ratio in the range from about 80:20 to about 50:50 wherein the average number of moles of ethylene oxide (EO) of the mixture is between 0.3 to 0.8; less than 3 ppm of dioxane; and water, and wherein the solution does not contain any antimicrobial or preservatives and is homogeneous, flowable and pumpable at
  • WO9738972A relates to sulfation methods for producing longer chain length alkyl sulfate and/or alkyl alkoxylated sulfate surfactant compositions, the method utilising the presence of a significant amount of mid-chain branched alcohol and/or polyoxyalkylene alcohol in the sulfation reaction to significantly reduce the reaction temperature, thereby improving product quality and saving energy.
  • W09404640A relates to a concentrated aqueous surfactant solution comprising alkyl ether sulfate and alkaline earth metal, preferably magnesium, the composition is a stable liquid which is suitable for making into cleaning products, especially dish washing liquids, the concentrated surfactant solution can be prepared by partial neutralisation of the acid precursor with the hydroxide or oxide of the alkaline earth metal, followed by a further neutralisation with the hydroxide of an alkali metal or ammonium.
  • WO9105764A relates to the sulfatisation of ethoxylised alkanols obtained by the reaction of ethylene oxide with alcohols with 8 to 22 C atoms in the presence of a hydrotalcite catalyst provides alkyl polyethoxy ether sulfates distinguished by a low dioxane content and extremely good coagulability using ordinary electrolytes.
  • US20170158625A relates to a process for preparing an alcohol ether sulfate which comprises: (a) sulfating an alkoxylated alcohol; and (b) neutralizing the sulfated product of step (a) in the presence of a base and a co-solvent having a flash point of at least 60° C.
  • GB977281A relates to surface active sulfates of alkyl ether alcohols, wherein the ether-alcohol may be made by (a) the reaction of olefins with ethylene glycol, (b) the reaction of olefins with ethylene halohydrins, followed by hydrolysis of the halogen-containing products, or (c) the reaction of secondary or tertiary alcohols with ethylene oxide, and wherein the products are all sulfated with chlorosulfonic acid.
  • EP3919594A1 relates to a liquid detergent composition suitable for washing dishes, fitting both in-sink as well as direct application habits, which provides reduced smearing when used in direct application dishwashing methods, while having good suds mileage especially under in-sink application habit, and good viscosity
  • the liquid detergent composition comprising a surfactant system, which comprises an alkyl sulfate anionic surfactant comprising C13 alkyl sulfate anionic surfactant, the C 13 alkyl sulfate anionic surfactant comprising a specific fraction of 2-branched C13 alkyl sulfate anionic surfactant, with a specific distribution of the 2-branching.
  • the present invention relates to a process for making a concentrated surfactant blend, wherein the concentrated surfactant blend comprises alkyl sulfated anionic surfactant and a buffering surfactant selected from the group consisting of amphoteric surfactant, zwitterionic surfactant, and mixtures thereof, wherein the process comprises the following steps: providing an alkyl alcohol stream comprising at least one alkyl alcohol; a sulfation step, during which the at least one alkyl alcohol in the alkyl alcohol stream is sulfated to form an alkyl sulfuric acid stream comprising at least one alkyl sulfuric acid; providing a neutralising stream comprising at least one neutralising agent; a neutralisation step, during which the alkyl sulfuric acid stream and the neutralising stream are combined, in order to neutralise the alkyl sulfuric acid; wherein the buffering surfactant is added before or during the neutralising step, the buffering surfactant is added at a level to provide the resultant concentrated surfactant blend with a
  • the present invention further relates to a concentrated surfactant blend
  • a concentrated surfactant blend comprising: from 30 % to 70 % by weight of the concentrated surfactant blend of alkyl sulfated anionic surfactant, wherein the alkyl sulfated anionic surfactant has an average degree of alkoxylation of less than 0.5; from 1.0 % to 25 % by weight of the concentrated surfactant blend of a buffering surfactant selected from the group consisting of: amphoteric surfactant, zwitterionic surfactant, and mixtures thereof; and wherein the concentrated surfactant blend has a reserve alkalinity of greater than 0.02, when measured as a 10% by weight solution of the concentrated surfactant blend in demineralized water at 20°C, using the method as described herein; and the resultant concentrated surfactant blend has a pH of from 7.1 to 10, when measured as a 10% by weight solution of the concentrated surfactant blend in demineralized water at 20°C.
  • the concentrated surfactant blend can be kept at a lower pH. Furthermore, when formulating such concentrated surfactant blends into detergent compositions, less acid has to be added in order to reach the desired pH. As such, the resultant liquid detergent composition comprises less salt, and is hence more phase stable, especially at lower temperatures, without the need for additional organic solvents. In addition, the desired viscosity can be achieved with little or no organic solvent and/or added structurants.
  • the lower salt content in the finished product composition has also been found to facilitate finished product dissolution, resulting in a faster onset of suds creation during washing accordingly. Furthermore, since the concentrated surfactant blend can be kept at a lower pH, the formation of 1,4-di oxanes is reduced or eliminated, both during making and during storage.
  • salt-based buffer systems can limit pH drift of the concentrated surfactant blend, they introduce additional salts into the final detergent composition, which has a detrimental effect on both low temperature stability and viscosity.
  • the buffering surfactants of use herein provide detersive and sudsing benefit in addition to buffering, while not having a detrimental effect on composition viscosity and physical product stability.
  • compositions of the present invention can comprise, consist of, and consist essentially of the essential elements and limitations of the invention described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein.
  • the term "dishware” as used herein includes cookware and tableware made from, by nonlimiting examples, ceramic, china, metal, glass, plastic (e.g., polyethylene, polypropylene, polystyrene, etc.) and wood.
  • greyware or “greasy” as used herein means materials comprising at least in part (z.e., at least 0.5 wt% by weight of the grease in the material) saturated and unsaturated fats and oils, preferably oils and fats derived from animal sources such as beef, pig and/or chicken.
  • pill soils as used herein means inorganic and especially organic, solid soil particles, especially food particles, such as for non-limiting examples: finely divided elemental carbon, baked grease particle, and meat particles.
  • Sudsing profile refers to the properties of a cleaning composition relating to suds character during the dishwashing process.
  • the term "sudsing profile" of a cleaning composition includes initial suds volume generated upon dissolving and agitation, typically manual agitation, of the cleaning composition in the aqueous washing solution, and the retention of the suds during the dishwashing process.
  • hand dishwashing cleaning compositions characterized as having "good sudsing profile” tend to have high initial suds volume and/or sustained suds volume, particularly during a substantial portion of or for the entire manual dishwashing process. This is important as the consumer uses high suds as an indicator that enough cleaning composition has been dosed.
  • the consumer also uses the sustained suds volume as an indicator that enough active cleaning ingredients (e.g., surfactants) are present, even towards the end of the dishwashing process.
  • active cleaning ingredients e.g., surfactants
  • the consumer usually renews the washing solution when the sudsing subsides.
  • a low sudsing cleaning composition will tend to be replaced by the consumer more frequently than is necessary because of the low sudsing level.
  • test methods that are disclosed in the Test Methods Section of the present application must be used to determine the respective values of the parameters of Applicants' inventions as described and claimed herein.
  • the present process is used to make a concentrated surfactant blend.
  • the concentrated surfactant blend comprises alkyl sulfated anionic surfactant and a buffering surfactant selected from the group consisting of: amphoteric surfactant, zwitterionic surfactant, and mixtures thereof.
  • the process comprises the following steps: a) providing an alkyl alcohol stream comprising at least one alkyl alcohol; b) a sulfation step, during which the at least one alkyl alcohol in the alkyl alcohol stream is sulfated to form an alkyl sulfuric acid stream comprising at least one alkyl sulfuric acid; c) providing a neutralising stream comprising at least one neutralising agent; d) a neutralisation step, during which the alkyl sulfuric acid stream and the neutralising stream are combined, in order to neutralise the alkyl sulfuric acid; wherein the buffering surfactant is added before or during the neutralising step.
  • the buffering surfactant is added at a level to provide the resultant concentrated surfactant blend with a reserve alkalinity of greater than 0.02 when measured as a 10% by weight solution of the concentrated surfactant blend in demineralized water at 20°C, using the method as described herein, with the resultant concentrated surfactant blend having a pH of from 7.1 to 10, when measured as a 10% by weight solution of the concentrated surfactant blend in demineralized water at 20°C.
  • the buffering capacity is the ability to neutralize the pH and the resistance to change in it due to the small acidic or basic inputs or discharges.
  • the buffering capacity is the ability to neutralize the pH and the resistance to change in it due to the small acidic or basic inputs or discharges.
  • Reserve alkalinity is a measure often used industrially to indicate the amount of alkaline components present in the product. For some compositions, such as the concentrated surfactant blends disclosed herein, it is more important to know the reserve alkalinity of the blend rather than the buffer capacity, because the reserve alkalinity provides a measure of the capacity of the blend to neutralise any acid that is present or formed in-situ, and hence maintain an alkaline pH.
  • the processes described herein comprise a step whereby an alkyl alcohol stream is provided.
  • the alkyl alcohol stream comprises at least one alkyl alcohol.
  • the alkyl alcohol stream as such can comprise one alkyl alcohol or alternatively a blend of alkyl alcohols.
  • the mol average alkyl chain length of the alkyl alcohol or of the blend of alkyl alcohols can be from 8 to 18, preferably from 10 to 14, more preferably from 12 to 14, most preferably from 12 to 13 carbon atoms, in order to provide a combination of improved sudsing and grease removal and enhanced speed of cleaning from the resultant alkyl sulfate surfactant.
  • the alkyl chain of the alkyl alcohol or of the blend of alkyl alcohols can have a mol fraction of C12 and C13 chains of at least 50%, preferably at least 65%, more preferably at least 80%, most preferably at least 90%. Suds mileage is particularly improved, especially in the presence of greasy soils, when the C13/C12 mol ratio of the alkyl chain in the alkyl alcohol or in the blend of alkyl alcohols used to make the alkyl sulfate surfactant is at least 57/43, preferably from 60/40 to 90/10, more preferably from 60/40 to 80/20, most preferably from 60/40 to 70/30, while not compromising suds mileage in the presence of particulate soils.
  • the relative molar amounts of C13 and C12 alkyl chains in the alkyl alcohol or in the blend of alkyl alcohols can be derived from the carbon chain length distribution in the alkyl chain of the alkyl alcohol.
  • the carbon chain length distribution of the alkyl chains of the alkyl alcohols can be obtained from the technical data sheets from the suppliers for the constituent alkyl alcohol.
  • the chain length distribution and average molecular weight of the alkyl alcohols, used to make the alkyl sulfated anionic surfactant can also be determined by methods known in the art. Such methods include capillary gas chromatography with flame ionisation detection on medium polar capillary column, using hexane as the solvent.
  • the alkyl alcohol or blends of alkyl alcohol can be alkoxylated or free of alkoxylation. Where it is desired that the resultant concentrated surfactant blend comprises alkyl alkoxylated sulfate, the at least one alkyl alcohol in the alkyl alcohol stream is preferably alkoxylated before the sulfation step.
  • the alkyl alcohol can be a blend of alkyl alcohols which are first blended together and then jointly alkoxylated to provide the desired average degree of alkoxylation.
  • one or more of alcohols can first be alkoxylated, and then the alkoxylated alcohols or alcohol blends can be mixed together to achieve the desired average degree of alkoxylation. In the first case, a monomodal distribution of the alkoxylation is typically achieved, while in the second case, the alkoxylation distribution is typically multi-modal.
  • the alkyl alcohol can have an average degree of alkoxylation of less than 3.5, preferably from 0.3 to 2.0, more preferably from 0.5 to 0.9, in order for the resultant alkyl sulfated anionic surfactant to improve low temperature physical stability and improve suds mileage of the compositions of the present invention.
  • the average degree of alkoxylation (especially ethoxylation) of the starting alkyl alcohol is preferably less than 0.5, preferably less than 0.1, and more preferably the starting alkyl alcohol is free of alkoxylation, since the resultant alkyl sulfate anionic surfactant provide improved grease cleaning.
  • ethoxylation is preferred.
  • the average degree of alkoxylation is the mol average degree of alkoxylation (i.e., mol average alkoxylation degree) of all the alkyl alcohol.
  • mol average alkoxylation degree the mols of non-alkoxylated alkyl alcohols are included:
  • Mol average alkoxylation degree (xl * alkoxylation degree of alkyl alcohol 1 + x2 * alkoxylation degree of alkyl alcohol 2 + .7) / (xl + x2 + . . . .) wherein xl, x2, . . . are the number of moles of each alkyl (or alkoxy) alcohol of the mixture and alkoxylation degree is the number of alkoxy groups in each alkyl alcohol.
  • alkyl alkoxy alcohols for use in making the alkyl sulfate surfactant are alkyl ethoxy alcohols
  • the performance can be affected by the width of the alkoxylation distribution of the resultant alkoxylated alkyl sulfate anionic surfactant, including grease cleaning, sudsing, low temperature stability and viscosity of the finished product.
  • the alkoxylation distribution including its broadness can be varied through the selection of catalyst and process conditions when making the alkoxylated alkyl alcohol.
  • alkoxylation such as ethoxylation
  • ethoxylation of the alkyl alcohol
  • the amount of 1,4-di oxane by-product within alkoxylated especially ethoxylated alkyl sulfates can be reduced.
  • a further reduction of 1,4-di oxane by-product can be achieved by subsequent stripping, distillation, evaporation, centrifugation, microwave irradiation, molecular sieving or catalytic or enzymatic degradation steps.
  • 1,4-di oxane level control within detergent formulations has also been described in the art through addition of 1,4-di oxane inhibitors to 1,4-di oxane comprising formulations, such as 5,6-dihydro-3-(4-morpholinyl)-l-[4-(2-oxo-l-piperidinyl)-phenyl]-2-(l-H)-pyridone, 3-a- hydroxy-7-oxo stereoisomer-mixtures of cholinic acid, 3-(N- methyl amino)-L-alanine, and mixtures thereof.
  • 1,4-di oxane inhibitors such as 5,6-dihydro-3-(4-morpholinyl)-l-[4-(2-oxo-l-piperidinyl)-phenyl]-2-(l-H)-pyridone, 3-a- hydroxy-7-oxo stereoisomer-mixtures of cholinic acid, 3-(N-
  • the alkyl alcohol has a weight average degree of branching of from 15% to 50%, preferably from 20% to 40%.
  • the use of such branched alkyl alcohols can result in improved low temperature stability for compositions comprising the resultant alkyl sulfate surfactant, as well as providing the desired grease cleaning performance.
  • the resultant alkyl sulfate surfactants have been found to provide liquid detergent compositions with improved product stability, even at low temperatures, and provide higher finished product viscosities, without compromising on suds mileage and grease cleaning. Furthermore, by limiting the average degree of alkoxylation (especially ethoxylation) of the starting alkyl alcohol to less than 0.5, preferably less than 0.1, and more preferably being free of alkoxylation, the resultant liquid detergent composition can have a reduced viscosensitivity with variations in the starting alcohol used to make the alkyl sulfate surfactant.
  • compositions require less solvent in order to achieve good physical stability at low temperatures.
  • Higher surfactant branching also provides faster initial suds generation, but typically less suds mileage.
  • the weight average branching, described herein, has been found to improve low temperature stability, initial foam generation and suds longevity in liquid detergent compositions comprising alkyl sulfate surfactants formed from such alkyl alcohols.
  • the branched alkyl alcohol used to make the alkyl sulfate surfactant can comprise C2-branched alkyl alcohol and non-C2-branched alkyl alcohol.
  • the weight ratio of non-C2- branched alkyl alcohol to C2-branched alkyl alcohol can be greater than 0.5, preferably from 1.0:1 to 5: 1, more preferably from 2: 1 to 4: 1.
  • C2-branched means the alkyl branching is a single alkyl branching on the alkyl chain of the alkyl alcohol and is positioned on the C2 position, as measured counting carbon atoms from the hydroxyl group for non-alkoxylated alkyl alcohol, or counting from the alkoxy-group furthest from the hydroxyl group for alkoxylated alkyl alcohols.
  • Non-C2 branching means the alkyl chain comprises branching at multiple carbon positions along the alkyl chain backbone, or a single branching group present on a branching position on the alkyl chain other than the C2 position.
  • the non-C2 branched alkyl alcohol can comprise less than 30%, preferably less than 20%, more preferably less than 10% by weight of the non-C2 branched alkyl alcohol of Cl -branched alkyl alcohol, most preferably the non-C2 branched alkyl alcohol is free of Cl -branched alkyl alcohol.
  • the non-C2 branched alkyl alcohol can comprise at least 50%, preferably from 60 to 90%, more preferably from 70 to 80% by weight of the non-C2 branched alkyl alcohol of isomers comprising a single branching at a branching position greater than the 2-position. That is, more than 2 carbons atoms away from the hydrophilic headgroup, as defined above.
  • the non-C2 branched alkyl alcohol can comprise from 5% to 30%, preferably from 7% to 20%, more preferably from 10% to 15% by weight of the non-C2 branched alkyl alcohol of multi branched isomers.
  • the non-C2 branched alkyl alcohol can comprise from 5% to 30%, preferably from 7% to 20%, more preferably from 10% to 15% by weight of non-C2 branched alkyl alcohol of cyclic isomers.
  • the acyclic branching groups can be selected from Cl to C5 alkyl groups, and mixtures thereof.
  • the weight average degree of branching for an alkyl alcohol mixture can be calculated using the following formula:
  • Weight average degree of branching [(xl * wt% branched alkyl alcohol 1 in alcohol 1 + x2 * wt% branched alkyl alcohol 2 in alcohol 2 + .%) / (xl + x2 + .7)] * 100 wherein xl, x2, ... are the weight in grams of each alkyl alcohol in the total alkyl alcohol mixture of the alkyl alcohols which were used as starting material before (alkoxylation and) sulfation to produce the alkyl (alkoxy) sulfate surfactant. In the weight average degree of branching calculation, the weight of the alkyl alcohol which is not branched is included.
  • the weight average degree of branching and the distribution of branching can typically be obtained from the technical data sheet for the surfactant or constituent alkyl alcohol.
  • the branching can also be determined through analytical methods known in the art, including capillary gas chromatography with flame ionisation detection on medium polar capillary column, using hexane as the solvent.
  • the weight average degree of branching and the distribution of branching is based on the starting alkyl alcohol used to produce the alkyl sulfated anionic surfactant.
  • Suitable examples of commercially available alkyl alcohols include, those derived from alcohols sold under the Neodol® brand-name by Shell, or the Lial®, Isalchem®, and Safol® brand-names by Sasol, or some of the natural alcohols produced by The Procter & Gamble Chemicals company.
  • the alcohols (and alkoxylated alcohols) can be blended in order to achieve the desired mol fraction of C12 and C13 chains and the desired C13/C12 ratio, based on the relative fractions of C13 and C12 within the starting alcohols (as well as the desired degree of alkoxylation), as obtained from the technical data sheets from the suppliers or from analysis using methods known in the art.
  • the alkyl alcohol can comprise alkyl chains which are essentially linear or even fully linear, which are blended with the branched alcohol to achieve the desired degree of branching.
  • Preferred sources of naturally derived alkyl chains include palm kernel and coconut derived alkyl chains, with palm kernel derived alkyl chains being more preferred.
  • the naturally derived alkyl chain can be fractionated in order to provide the desired average alkyl chain length, as well as to adjust the alkyl chain length distribution.
  • the C12 to C14 fraction is often referred to as the mid cut fraction within the naturally derived alkyl chains.
  • essentially linear alkyl chains can be synthetically derived using the Ziegler process, or a derivative thereof, a method for producing fatty alcohols from ethylene using an organoaluminium compound. The reaction produces linear primary alcohols with an even numbered carbon chain. Again, the C12-C14 alkyl fraction is preferred and can be fractionated out of the total Ziegler alcohol.
  • the alkyl alcohol stream comprising the at least one alkyl alcohol is sulfated to form an alkyl sulfuric acid stream comprising at least one alkyl sulfuric acid.
  • Sulfation involves forming a carbon-oxygen-sulfur bond.
  • the resultant alkyl sulfate in acid form (alkyl sulfuric acid) is not hydrolytically stable. Unless neutralized, it decomposes to form sulfuric acid and other chemicals.
  • SO3 sulfur trioxide
  • SO3 is an aggressive electrophilic reagent that rapidly reacts with any organic compound containing an electron donor group. The resultant reaction is highly exothermic. Effective cooling of the reaction mass is essential because high temperatures promote side reactions that produce undesirable by-products. Also, precise control of the molar ratio of SO3 to alkyl alcohol is essential because any excess SO3, due to its reactive nature, contributes to side reactions and by-product formation. Therefore, commercial scale sulfation reactions require special equipment and instrumentation that allows tight control of the mole ratio of SO3 to alkyl alcohol and rapid removal of the heat of reaction.
  • the problem of SO3 reactivity has typically been solved by diluting and/or complexing the SO3 to moderate the rate of reaction.
  • Commercial diluting or complexing agents include ammonia (sulfamic acid), hydrochloric acid (chlorosulfuric acid), and dry air (air/SO, film sulfation). Control of the ratio of SO3 to alkyl alcohol can be used to achieve improved product quality with use of any of these reagents.
  • Air/SCE film sulfation processes are typically carried out using a film reactor, such as an annular falling film reactor, such as a “Chemithon” reactor, or a multi-tube film reactor, such as the “Ballestra” reactor.
  • a film reactor such as an annular falling film reactor, such as a “Chemithon” reactor, or a multi-tube film reactor, such as the “Ballestra” reactor.
  • the SO3 is first diluted with dry air.
  • Such air/SCh sulfation processes are direct processes in which SO3 gas is diluted with very dry air and reacted directly with the alkyl alcohol feedstock.
  • the reaction of gaseous SO3 with the alkyl alcohol is rapid and stoichiometric.
  • Such processes are complicated by the possibility of side reactions, However, with tight process control, very high purity alkyl sulfate surfactants can be achieved.
  • the SO3 can be provided by burning molten sulfur in an excess of oxygen to form SO2, which is then catalytically oxidised to SO3, for instance, at a temperature of from 400 °C to 470 °C. Conversion of sulfur to SO2 is typically at least 95%, preferably at least 99%, more preferably at least >99.9% complete.
  • the oxygen can be supplied by air which has been pre-dried to remove the major part of water by condensation and subsequently drying with a desiccant until the air has a maximum dewpoint of -60°C, preferably ⁇ -70°C.
  • the SCh/air flow is cooled in an indirect air cooler, prior to converting the SO2 to SO3 through a catalytic oxidation.
  • Catalytic oxidation is typically done using at least one, preferably from 3 to 4 catalytic beds.
  • An example of such a catalytic converter includes a converter tower filled with 4 packed beds of V2O5 catalyst on a silica carrier.
  • an intermediate cooling of the resulting process gas is executed between the various beds through indirect air coolers, such as vertical air cooled shell and tube heat exchangers.
  • the gas stream at this point in the process is cooled to at least 60°C, but most preferably the gas stream is cooled to a temperature of from 30 to 55 °C.
  • the sulfation step is typically carried out in a liquid-gas interface reactor, preferably a falling film reactor.
  • Suitable falling film reactors include annulargap falling film (“Chemithon”) reactors, (multi)tubular (“Ballestra”) reactors, and the like.
  • the alkyl alcohol or blend of alkyl alcohols is converted through reaction with the SO3 within the falling film reactor into alkyl sulfuric acid. Considering the exothermic nature of the sulfonation reaction, consequent cooling is again required after which the air/gas is separated from the liquid stream. Ideally the reaction mixture is maintained at the outlet of the reactor at a temperature of from 15 °C to 50 °C, preferably from 30 °C and 40°C.
  • the air/gas can be separated from the liquid using a liquid separator. Where the separation does not remove sufficient gas from the liquid mixture, an extra degassing step can be done, for instance, by using a “Fryma” spinning disc deaerator.
  • the exhaust gas typically comprises small amounts of non-converted SO2, non-reacted SO3 and some entrained organic acid.
  • the organic aerosol and fine SO3/H2SO4 droplets are typically separated from the exhaust gas flow in an electrostatic precipitator, and the gaseous SO2 gasses are typically washed from the process air in a scrubber using a dilute caustic solution.
  • the alkyl alcohol stream fed into the sulfation reaction preferably comprises less than 0.1%, preferably less than 0.05%, more preferably is free of water.
  • a sulfation reaction typically results in a conversion of at least 90%, preferably at least 95%, more preferably at least 97% by weight of the starting alkyl alcohol.
  • the sulfuric acid presence in the liquid stream after sulfation is typically less than 1%, preferably less than 0.75%, more preferably less than 0.5% by weight of the total liquid stream.
  • a neutralising stream comprising at least one neutralising agent is provided.
  • the neutralising agent can be added at a level to provide the resultant concentrated surfactant blend with a pH of from 7.1 to 10, preferably from 7.3 to 9.5, more preferably from 7.5 to 9.0, measured as a 10% by weight solution of the concentrated surfactant blend in demineralized water, at 20°C.
  • Too low a pH can lead to re-hydrolysis of the alkyl sulfated anionic surfactant, while too high a pH typically complicates conversion of the concentrated surfactant blend into a finished detergent product composition, such as requiring a significant amount of acid to trim back the pH to the targeted finished product pH.
  • too high a pH can result in the generation of 1,4- dioxanes over time, as well as higher amounts of neutralizing agent being added, increasing the salt level in the concentrated surfactant blend accordingly.
  • Concentrated surfactant blends which comprise high salt levels are more challenging to formulate into detergent compositions, and result in a reduced low temperature stability as well as increased viscosity upon initial dissolution with water, slowing down product dissolution accordingly.
  • the neutralising agent is an alkali. Further neutralising agent can be added after the neutralisation step in order to adjust the pH to the desired level. Suitable alkali can be selected from the group consisting of sodium hydroxide potassium hydroxide, ammonia, monoethanolamine, di-ethanolamine, tri-ethanolamine, and mixtures thereof, with sodium hydroxide being most preferred. Alternatively, or in addition, other alkalis can be added as part of the neutralisation step. Particularly suitable other alkalis are alkalis that can be added to the resultant liquid detergent composition to improve performance. In particular, amines, especially cyclic polyamine having amine functionalities that helps cleaning, as described later.
  • the neutralisation step should be completed in less than 10 minutes, preferably less than 5 minutes and most preferably less than 2 minutes, after the sulfation step has been completed.
  • the neutralisation can take place in any suitable means, including in a batch reactor or by combining the alkyl sulfuric acid stream and neutralising stream using a high shear mixer.
  • a loop reactor can be used.
  • a loop reactor is a continuous tube or pipe, typically stainless steel, which connects the outlet of a recirculation pump to its inlet. Reactants are fed into the loop where the neutralisation occurs, and the at least partially neutralised mixture is withdrawn from the loop.
  • a loop reactor typically comprises a circulation pump, a homogenizer or high shear mixer, and a heat exchanger, due to the exothermic nature of the neutralisation reaction. Efficient mixing of the alkyl sulfuric acid stream and the neutralising stream results in instantaneous reaction and avoids undesired degradation reactions in isolated spots and pH drift occurring during the neutralisation step.
  • high shear mixers are typically used considering the highly viscous nature of the resulting paste, especially at low shear rates.
  • a heat exchanger such as a plate and frame heat exchanger, can be used to continuously cool the mixture to achieve a temperature of less than 70°C, preferably less than 60°C and most preferably in a range of 20 to 40°C for the alkyl sulfate stream after neutralisation.
  • Organic solvents can be added either to control the viscosity during the neutralisation step or to improve homogenisation.
  • Suitable organic solvents include C1-C4 alcohols, particularly ethanol. Such organic solvents can be added as a separate stream during the neutralisation step, or as part of the alkyl alcohol stream, or as part of the neutralisation stream. Water can be added as a separate stream during the neutralisation step, or as part of the neutralisation stream.
  • Water can be added at a level such that the resultant concentrated surfactant blend comprises water at a level of from 20% to 50%, preferably from 25% to 45%, more preferably from 30% to 40% by weight of the concentrated surfactant blend.
  • the water level can be measured using any suitable means, such as via Karl Fisher Titration,
  • the neutralisation stream can comprise water at a level of from 35% to 80%, preferably from 45% to 75%, more preferably from 55% to 65% by weight of the neutralisation stream.
  • the buffering surfactant is preferably added during the neutralisation step to ensure that the resulting mixture reaches the desired pH quickly so as to avoid the aforementioned hydrolysis.
  • the neutralising stream can comprise other optional ingredients, such as nonionic surfactant, polymers, and peroxides, such as those described later, and mixtures thereof.
  • the resulting neutralized surfactant paste can be transported through a transfer pump into a storage tank.
  • the buffering surfactant is preferably added during the neutralization step, either as a separate buffer stream, but is preferably added as part of the neutralisation stream. Alternatively, the buffering surfactant can be added before the neutralisation step.
  • the alkyl sulfuric acid and the buffering surfactant can be combined in a weight ratio of the alkyl sulfuric acid to the buffering surfactant of from 10: 1 to 1 : 1, preferably from 8: 1 to 2: 1, more preferably from 6: 1 to 3 : 1.
  • the buffering surfactant reduces the pH variation and pH drift when small amounts of acid are added or formed, for instance, through hydrolysis of the alkyl sulfate surfactant, or even from absorption of carbon dioxide from the air.
  • the resultant concentrated surfactant blend can be stored at lower pH, resulting in less formation of 1,4-di oxanes and less salt being present in detergent compositions comprising the concentrated surfactant blend.
  • the buffering surfactant is an amphoteric surfactant, zwitterionic surfactant, or mixtures thereof.
  • Suitable buffering surfactants can be selected from the group consisting of: amine oxide surfactant, betaine surfactant, and mixtures thereof, preferably amine oxide surfactant, more preferably Cl 0-16 dimethyl amine oxide surfactant. Cl 2- 14 dimethyl amine oxide (lauryl dimethyl amine oxide) is particularly preferred.
  • Such buffering surfactants also contribute to the performance of the resultant liquid hand dishwashing detergent.
  • the buffering surfactant results in the concentrated surfactant blends, formed by the processes described herein, having reduced viscosity, especially when amine oxide surfactant is used as the buffering surfactant.
  • the buffering surfactant can be added at a level such that the resultant concentrated surfactant blend comprises the buffering surfactant at a level of from 1.0% to 25% preferably from 5.0% to 20%, more preferably from 10% to 15% by weight of the concentrated surfactant blend.
  • Suitable amine oxide surfactants can be linear or branched, though linear are preferred. Suitable linear amine oxides are typically water-soluble, and characterized by the formula R1 - N(R2)(R3) O wherein R1 is a C8-18 alkyl, and the R2 and R3 moi eties are selected from the group consisting of Cl -3 alkyl groups, Cl -3 hydroxyalkyl groups, and mixtures thereof. For instance, R2 and R3 can be selected from the group consisting of: methyl, ethyl, propyl, isopropyl, 2- hydroxethyl, 2-hydroxypropyl and 3 -hydroxypropyl, and mixtures thereof, though methyl is preferred for one or both of R2 and R3.
  • the linear amine oxide surfactants in particular may include linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
  • the amine oxide surfactant is selected from the group consisting of: alkyl dimethyl amine oxide, alkyl amido propyl dimethyl amine oxide, and mixtures thereof.
  • Alkyl dimethyl amine oxides are particularly preferred, such as C8-18 alkyl dimethyl amine oxides, or Cl 0-16 alkyl dimethyl amine oxides (such as coco dimethyl amine oxide).
  • Suitable alkyl dimethyl amine oxides include CIO alkyl dimethyl amine oxide surfactant, Cl 0-12 alkyl dimethyl amine oxide surfactant, C12-C14 alkyl dimethyl amine oxide surfactant, and mixtures thereof.
  • C12-C14 alkyl dimethyl amine oxide, Cl 2- 14 alkyl amido propyl amine oxide, and mixtures thereof are particularly preferred.
  • amine oxide surfactants include mid-branched amine oxide surfactants.
  • mid-branched means that the amine oxide has one alkyl moiety having nl carbon atoms with one alkyl branch on the alkyl moiety having n2 carbon atoms. The alkyl branch is located on the a carbon from the nitrogen on the alkyl moiety. This type of branching for the amine oxide is also known in the art as an internal amine oxide.
  • the total sum of nl and n2 can be from 10 to 24 carbon atoms, preferably from 12 to 20, and more preferably from 10 to 16.
  • the number of carbon atoms for the one alkyl moiety (nl) is preferably the same or similar to the number of carbon atoms as the one alkyl branch (n2) such that the one alkyl moiety and the one alkyl branch are symmetric.
  • symmetric means that
  • the amine oxide further comprises two moi eties, independently selected from a Cl -3 alkyl, a Cl -3 hydroxyalkyl group, or a polyethylene oxide group containing an average of from about 1 to about 3 ethylene oxide groups.
  • the two moi eties are selected from a Cl -3 alkyl, more preferably both are selected as Cl alkyl.
  • the amine oxide surfactant can be a mixture of amine oxides comprising a mixture of low-cut amine oxide and mid-cut amine oxide.
  • the amine oxide of the composition of the invention can then comprises: a) from about 10% to about 45% by weight of the amine oxide of low-cut amine oxide of formula R1R2R3AO wherein R1 and R2 are independently selected from hydrogen, C1-C4 alkyls or mixtures thereof, and R3 is selected from CIO alkyls and mixtures thereof; and b) from 55% to 90% by weight of the amine oxide of mid-cut amine oxide of formula R4R5R6AO wherein R4 and R5 are independently selected from hydrogen, C1-C4 alkyls or mixtures thereof, and R6 is selected from C12-C16 alkyls or mixtures thereof
  • R3 is n-decyl, with preferably both R1 and R2 being methyl.
  • R4 and R5 are preferably both methyl.
  • the amine oxide comprises less than about 5%, more preferably less than 3%, by weight of the amine oxide of an amine oxide of formula R7R8R9AO wherein R7 and R8 are selected from hydrogen, C1-C4 alkyls and mixtures thereof and wherein R9 is selected from C8 alkyls and mixtures thereof.
  • R7R8R9AO Limiting the amount of amine oxides of formula R7R8R9AO improves both physical stability and suds mileage.
  • Suitable zwitterionic surfactants include betaine surfactants.
  • betaine surfactants includes alkyl betaines, alkylamidobetaine, amidazoliniumbetaine, sulfobetaine (INCI Sultaines) as well as the phosphobetaine, and preferably meets formula (I):
  • R1 is selected from the group consisting of: a saturated or unsaturated C6-22 alkyl residue, preferably C8-18 alkyl residue, more preferably a saturated Cl 0-16 alkyl residue, most preferably a saturated Cl 2- 14 alkyl residue;
  • X is selected from the group consisting of: NH, NR4 wherein R4 is a Cl -4 alkyl residue, O, and S, n is an integer from 1 to 10, preferably 2 to 5, more preferably 3, x is 0 or 1, preferably 1,
  • R2 and R3 are independently selected from the group consisting of: a Cl-4 alkyl residue, hydroxy substituted such as a hydroxy ethyl, and mixtures thereof, preferably both R2 and R3 are methyl, m is an integer from 1 to 4, preferably 1, 2 or 3, y is 0 or 1, and
  • Y is selected from the group consisting of: COO, SO3, OPO(OR5)O or P(O)(OR5)O, wherein R5 is H or a Cl-4 alkyl residue.
  • Preferred betaines are the alkyl betaines of formula (la), the alkyl amido propyl betaine of formula (lb), the sulfobetaine of formula (Ic) and the amido sulfobetaine of formula (Id): R 1 -N + (CH 3 ) 2 -CH 2 COO- (la)
  • Suitable betaines can be selected from the group consisting or [designated in accordance with INCI]: capryl/capramidopropyl betaine, cetyl betaine, cetyl amidopropyl betaine, cocamidoethyl betaine, cocamidopropyl betaine, cocobetaines, decyl betaine, decyl amidopropyl betaine, hydrogenated tallow betaine / amidopropyl betaine, isostearamidopropyl betaine, lauramidopropyl betaine, lauryl betaine, myristyl amidopropyl betaine, myristyl betaine, oleamidopropyl betaine, oleyl betaine, palmamidopropyl betaine, palmitamidopropyl betaine, palm-kernelamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, tallowamidopropyl betaine, tallow betaine
  • Preferred betaines are selected from the group consisting of: cocamidopropyl betaine, cocobetaines, lauramidopropyl betaine, lauryl betaine, myristyl amidopropyl betaine, myristyl betaine, and mixtures thereof.
  • Cocamidopropyl betaine is particularly preferred.
  • the at least one alkyl sulfuric acid and the buffering surfactant can be combined in a weight ratio of from 10: 1 to 1 : 1, preferably from 8: 1 to 2: 1, more preferably from 6: 1 to 3: 1.
  • the unreacted alkyl alcohol and/or alkoxylated alcohol level is preferably below 3%, more preferably below 2.5%, and most preferably below 2% by weight of the starting alkyl sulfuric acid at the start of the neutralisation step.
  • the amount of unreacted alkyl (alkoxylated) alcohol can be determined by GC analysis (after neutralisation of the alkyl sulfuric acid).
  • the buffering surfactant can be added in a stream which further comprises peroxide, especially where amine oxide is used as a buffering surfactant.
  • the peroxide can be present such that the stream comprising the buffering surfactant has a residual peroxide level of from 5.0 ppm to 300 ppm, preferably from 40 ppm to 80 ppm for every one part by weight of buffering surfactant. It is believed that the presence of peroxide further limits the formation and growth of 1,4-di oxane within the concentrated surfactant blend formed by the present process, when the concentrated surfactant blend comprises ethoxylated alkyl sulfate surfactant.
  • adjunct ingredients as described below can also be added prior to, during or after neutralisation, for instance, to simplify making of the final liquid detergent composition.
  • Other optional ingredients include water, organic solvents, pH modifier, further surfactants, polymers, amines, preservatives, and mixtures thereof.
  • Suitable further surfactants include further anionic surfactants, nonionic surfactants, and mixtures thereof.
  • the resultant concentrated surfactant blend comprises: from 30 wt% to 70 wt%, preferably from 40 wt% to 60 wt%, more preferably from 45 wt% to 55 wt% by weight of the resultant concentrated surfactant blend of the alkyl sulfated anionic surfactant, and from 1.0 wt% to 25 wt%, preferably from 5.0 wt% to 20 wt%, more preferably from 10 wt% to 15 wt% by weight of the resultant concentrated surfactant blend of the buffering surfactant.
  • the concentrated surfactant blend comprises alkyl sulfated anionic surfactant, wherein the alkyl sulfated anionic surfactant has an average degree of alkoxylation of less than 0.5, preferably less than 0.1, more preferably is free of alkoxylation.
  • the alkoxylation preferably is ethoxylation.
  • the buffering surfactant buffers the pH of the concentrated surfactant blend without requiring additional salts to be introduced into the blend.
  • the concentrated surfactant blend resists changes in pH due to the addition or formation of an acid (or base).
  • the resultant buffering reduces the risk of hydrolysis of the alkyl sulfate surfactant due to lowering pH, for example, upon ageing in contact with air, lowering the alkyl sulfate concentration but also resulting in the formation of by-products which cause browning of the concentrated surfactant blend (such as HSOf).
  • Buffers for a given application must be effective at the desired pH, and must also provide sufficient buffer capacity to maintain the desired pH as needed.
  • the resultant concentrated surfactant blend formed by the processes described herein, preferably have a buffer region of from a pH of 7.0 to 7.8.
  • a measure of the efficacy of the buffering system is provided by the reserve alkalinity.
  • the reserve alkalinity is essentially the ability of the composition to neutralise acidic residues that are formed in the composition, such as by the hydrolysis of the alkyl sulfate surfactant.
  • the buffering surfactant is added at a level to provide the resultant concentrated surfactant blend with a reserve alkalinity of greater than 0.02, preferably from 0.04 to 0.50, more preferably from 0.06 to 0.30 when measured as a 10% by weight solution of the concentrated surfactant blend in demineralized water at 20°C, using the method described herein.
  • the alkyl sulfated anionic surfactant and the buffering surfactant can be present in the concentrated surfactant blend in a weight ratio of from 10: 1 to 1 : 1, preferably from 8: 1 to 2: 1, more preferably from 6: 1 to 3 : 1.
  • the present process utilising the buffering surfactant, enables a lower pH for the concentrated surfactant blend.
  • lower levels of 1,4-di oxane are present in the concentrated surfactant blend.
  • the resultant alkyl sulfate containing concentrated surfactant blends exhibit lower rates of increase in the 1,4-dioxane by-product level upon ageing.
  • the dioxane level in the concentrated surfactant blends formed by the process of the present invention can be less than 40ppm, preferably less than 30, most preferably less than 15ppm.
  • the concentrated surfactant blend can comprise further surfactants.
  • Suitable further surfactants include further anionic surfactants such as sulfonate anionic surfactants such as HLAS, or sulfosuccinate anionic surfactants.
  • the amount of such further anionic surfactants is kept low. In more preferred processes, no further anionic surfactant is added. Therefore, the concentrated surfactant blend can comprise at least 70%, preferably at least 85%, more preferably 100% by weight of the anionic surfactant of the alkyl sulfated anionic surfactant.
  • the concentrated surfactant blend is preferably free of fatty acid or salt thereof, since such fatty acids impede the generation of suds.
  • Suitable further surfactants include nonionic surfactants.
  • the concentrated surfactant blend can further comprise a nonionic surfactant.
  • Suitable nonionic surfactants include alkoxylated alcohol nonionic surfactants, alkyl polyglucoside nonionic surfactants, and mixtures thereof.
  • the concentrated surfactant blend can comprise from 1% to 25%, preferably from 1.25% to 20%, more preferably from 1.5% to 15%, most preferably from 1.5% to 5%, by weight of the total surfactant within the concentrated surfactant blend, of an alkoxylated alcohol non-ionic surfactant.
  • the alkoxylated alcohol non-ionic surfactant is a linear or branched, primary or secondary alkyl alkoxylated non-ionic surfactant, preferably an alkyl ethoxylated non-ionic surfactant, preferably comprising on average from 9 to 15, preferably from 10 to 14 carbon atoms in its alkyl chain and on average from 5 to 12, preferably from 6 to 10, most preferably from 7 to 8, units of ethylene oxide per mole of alcohol.
  • the concentrated surfactant blend can comprise alkyl polyglucoside ("APG") surfactant.
  • APG alkyl polyglucoside
  • the addition of alkyl polyglucoside surfactants has been found to improve sudsing beyond that of comparative nonionic surfactants such as alkyl ethoxylated nonionic surfactants.
  • the alkyl polyglucoside can be present in the concentrated surfactant blend at a level of from 0.5% to 20%, preferably from 0.75% to 15%, more preferably from 1% to 10%, most preferably from 1% to 5% by weight of the total surfactant within the concentrated surfactant blend.
  • the alkyl polyglucoside surfactant is a C8-C16 alkyl polyglucoside surfactant, preferably a C8-C14 alkyl polyglucoside surfactant.
  • the alkyl polyglucoside preferably has an average degree of polymerization of between 0.1 and 3, more preferably between 0.5 and 2.5, even more preferably between 1 and 2.
  • the alkyl polyglucoside surfactant has an average alkyl carbon chain length between 10 and 16, preferably between 10 and 14, most preferably between 12 and 14, with an average degree of polymerization of between 0.5 and 2.5 preferably between 1 and 2, most preferably between 1.2 and 1.6.
  • C8-C16 alkyl polyglucosides are commercially available from several suppliers (e.g., Simusol® surfactants from Seppic Corporation; and Glucopon® 600 CSUP, Glucopon® 650 EC, Glucopon® 600 CSUP/MB, and Glucopon® 650 EC/MB, from BASF Corporation).
  • the resultant concentrated surfactant blend can have a pH of from 7.1 to 10, preferably from 7.3 to 9.5, more preferably from 7.5 to 9.0, when measured as a 10% by weight solution of the concentrated surfactant blend in demineralized water at 20 °C. Too low a pH can lead to rehydrolysis of the alkyl sulfate, while too high a pH typically complicates conversion of the concentrated surfactant blend into a finished detergent product composition, such as requiring a significant amount of acid to trim back the pH to the targeted finished product pH.
  • Concentrated surfactant blends which comprise high salt levels are more challenging to formulate into detergent compositions, and result in a reduced low temperature stability as well as increased viscosity upon initial dissolution with water, slowing down product dissolution.
  • the concentrated surfactant blend can be Newtonian or non-Newtonian, preferably Newtonian.
  • the surfactant blend can have a viscosity of from 5,000 mPa-s to 25,000 mPa-s, preferably from 7,500 mPa-s to 20,000 mPa-s, most preferably from 10,000 mPa-s to 15,000 mPa-s, measured at a shear rate of 10 s' 1 and a temperature of 20° C.
  • the concentrated surfactant blend can have a flow index of from 0.1 to 1.0, preferably from 0.2 to 0.5, more preferably from 0.2 to 0.4.
  • the concentrated surfactant blend can have a yield stress of from 5.0 Pa to 30 Pa, preferably from 10 Pa to 25 Pa, more preferably from 15 Pa to 20 Pa. The aforementioned flow index and yield stress result in improved processibility of the concentrated surfactant blend.
  • the melting point of the concentrated surfactant blend is preferably less than 20 °C, more preferably less than 15 °C, most preferably less than 10 °C so that the concentrated surfactant blend can be stored at ambient temperatures and not require heating in order to process into a detergent composition.
  • the melting point can be measured using Differential Scanning Calorimetry” (DSC).
  • the concentrated surfactant blend can have a density in the range from 500 kg/m 3 to 1,500 kg/m 3 , preferably from 750 kg/m 3 to 1,250 kg/m 3 , more preferably from 1,000 kg/m 3 to 1,100 kg/m 3 , measured at a temperature of 20 °C.
  • the density can be measured using any suitable means, such as using a pycnometer.
  • Liquid hand dishwashing composition
  • the concentrated surfactant blends, as described herein can be used to make liquid detergent compositions, especially liquid hand dishwashing detergent composition.
  • ishware and “dish” as used herein includes cookware and tableware made from, by non-limiting examples, ceramic, china, metal, glass, plastic (e.g., polyethylene, polypropylene, polystyrene, etc.) and wood.
  • plastic e.g., polyethylene, polypropylene, polystyrene, etc.
  • the cleaning composition is a liquid cleaning composition, preferably a liquid hand dishwashing cleaning composition, and hence is in liquid form.
  • the liquid cleaning composition is preferably an aqueous cleaning composition.
  • the composition can comprise from 50% to 85%, preferably from 50% to 75%, by weight of the total composition of water.
  • the liquid cleaning composition has a pH greater than 6.0, or a pH of from 6.0 to 12.0, preferably from 7.0 to 11.0, more preferably from 8.0 to 10.0, measured as a 10% aqueous solution in demineralized water at 20 degrees °C.
  • the reserve alkalinity can be from 0.1 to 1.0, more preferably from 0.1 to 0.5.
  • Reserve alkalinity is herein expressed as grams of NaOH/100 ml of composition required to titrate product from a pH 7.0 to the pH of the finished composition. This pH and reserve alkalinity further contribute to the cleaning of tough food soils.
  • the liquid cleaning composition of the present invention can be Newtonian or nonNewtonian, preferably Newtonian.
  • the composition has a viscosity of from 10 mPa-s to 10,000 mPa-s, preferably from 100 mPa-s to 5,000 mPa-s, more preferably from 300 mPa-s to 2,000 mPa-s, or most preferably from 500 mPa-s to 1,500 mPa-s, alternatively combinations thereof.
  • the viscosity is measured at 20°C with a Brookfield RT Viscometer using spindle 31 with the RPM of the viscometer adjusted to achieve a torque of between 40% and 60%.
  • the liquid cleaning composition can comprise the concentrated surfactant blend and optionally additional surfactant, such that the composition comprises from 5.0% to 50%, preferably from 6.0% to 40%, most preferably from 15% to 35%, by weight of the total composition of a surfactant system.
  • the liquid hand dishwashing detergent composition comprises anionic surfactant that is comprised in the concentrated surfactant blend used to make the detergent composition.
  • the liquid hand dishwashing detergent composition does not comprise any further anionic surfactant.
  • the liquid hand dishwashing detergent composition comprises a co-surfactant which comprises or consists of the buffering surfactant comprised in the concentrated surfactant blend used to make the detergent composition. Further co-surfactant can be added, in addition to the cosurfactant comprised in the concentrated surfactant blend.
  • the liquid hand dishwashing detergent composition can comprise nonionic surfactant. Suitable nonionic surfactants include alkoxylated alcohol nonionic surfactants, alkyl polyglucoside nonionic surfactants, and mixtures thereof, as described earlier. Such nonionic surfactant can be added as part of the concentrated surfactant blend used to make the detergent composition, or can be added separately and in addition to the concentrated surfactant blend, or both.
  • composition can comprise further ingredients such as those selected from: amphiphilic alkoxylated polyalkyleneimines, cyclic polyamines, triblock copolymers, inorganic mono-, di- or trivalent salts, hydrotropes, organic solvents, other adjunct ingredients such as those described herein, and mixtures thereof.
  • Such ingredients can be added as part of the surfactant blend, or separately added, in addition to the surfactant blend.
  • composition of the present invention may further comprise from 0.05% to 2%, preferably from 0.07% to 1% by weight of the total composition of an amphiphilic polymer.
  • Suitable amphiphilic polymers can be selected from the group consisting of: amphiphilic alkoxylated polyalkyleneimine and mixtures thereof. The amphiphilic alkoxylated polyalkyleneimine polymer has been found to improve grease removal.
  • a preferred amphiphilic alkoxylated polyethyleneimine polymer has the general structure of formula (I): wherein the polyethyleneimine backbone has a weight average molecular weight of 600, n of formula (I) has an average of 10, m of formula (I) has an average of 7 and R of formula (I) is selected from hydrogen, a C1-C4 alkyl and mixtures thereof, preferably hydrogen.
  • the degree of permanent quaternization of formula (I) may be from 0% to 22% of the polyethyleneimine backbone nitrogen atoms.
  • the molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer preferably is between 10,000 and 15,000 Da.
  • the amphiphilic alkoxylated polyethyleneimine polymer has the general structure of formula (I) but wherein the polyethyleneimine backbone has a weight average molecular weight of 600 Da, n of Formula (I) has an average of 24, m of Formula (I) has an average of 16 and R of Formula (I) is selected from hydrogen, a C1-C4 alkyl and mixtures thereof, preferably hydrogen.
  • the degree of permanent quaternization of Formula (I) may be from 0% to 22% of the polyethyleneimine backbone nitrogen atoms and is preferably 0%.
  • the molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer preferably is between 25,000 and 30,000, most preferably 28,000 Da.
  • amphiphilic alkoxylated polyethyleneimine polymers can be made by the methods described in more detail in PCT Publication No. WO 2007/135645.
  • the composition can comprise a cyclic polyamine having amine functionalities that helps cleaning.
  • the composition of the invention preferably comprises from 0.1% to 3%, more preferably from 0.2% to 2%, and especially from 0.5% to 1%, by weight of the composition, of the cyclic polyamine.
  • the cyclic polyamine has at least two primary amine functionalities.
  • the primary amines can be in any position in the cyclic amine but it has been found that in terms of grease cleaning, better performance is obtained when the primary amines are in positions 1,3. It has also been found that cyclic amines in which one of the substituents is -CH3 and the rest are H provided for improved grease cleaning performance.
  • the most preferred cyclic polyamine for use with the cleaning composition of the present invention are cyclic polyamine selected from the group consisting of: 2- m ethylcyclohexane- 1,3 -diamine, 4-methylcyclohexane-l,3-diamine and mixtures thereof. These specific cyclic polyamines work to improve suds and grease cleaning profile through-out the dishwashing process when formulated together with the surfactant system of the composition of the present invention.
  • Suitable cyclic polyamines can be supplied by BASF, under the Baxxodur tradename, with Baxxodur ECX-210 being particularly preferred.
  • the composition can further comprise magnesium sulfate at a level of from 0.001 % to 2.0 %, preferably from 0.005 % to 1.0 %, more preferably from 0.01 % to 0.5 % by weight of the composition.
  • the composition of the invention can comprise a triblock copolymer.
  • the triblock copolymers can be present at a level of from 0.1% to 10%, preferably from 0.5% to 7.5%, more preferably from 1% to 5%, by weight of the total composition.
  • Suitable triblock copolymers include alkylene oxide triblock co-polymers, defined as a triblock co-polymer having alkylene oxide moieties according to Formula (I): (EO)x(PO)y(EO)x, wherein EO represents ethylene oxide, and each x represents the number of EO units within the EO block.
  • Each x can independently be on average of from 5 to 50, preferably from 10 to 40, more preferably from 10 to 30.
  • x is the same for both EO blocks, wherein the "same" means that the x between the two EO blocks varies within a maximum 2 units, preferably within a maximum of 1 unit, more preferably both x's are the same number of units.
  • PO represents propylene oxide
  • y represents the number of PO units in the PO block. Each y can on average be from between 28 to 60, preferably from 30 to 55, more preferably from 30 to 48.
  • the triblock co-polymer has a ratio of y to each x of from 3 : 1 to 2: 1.
  • the triblock co-polymer preferably has a ratio of y to the average x of 2 EO blocks of from 3: 1 to 2: 1.
  • the triblock co-polymer has an average weight percentage of total EO of between 30% and 50% by weight of the tri-block co-polymer.
  • the triblock co-polymer has an average weight percentage of total PO of between 50% and 70% by weight of the triblock co-polymer. It is understood that the average total weight % of EO and PO for the triblock co-polymer adds up to 100%.
  • the triblock co-polymer can have an average molecular weight of between 2060 and 7880, preferably between 2620 and 6710, more preferably between 2620 and 5430, most preferably between 2800 and 4700. Average molecular weight is determined using a 1H NMR spectroscopy (see Thermo scientific application note No. AN52907).
  • Triblock co-polymers have the basic structure ABA, wherein A and B are different homopolymeric and/or monomeric units.
  • A is ethylene oxide (EO) and B is propylene oxide (PO).
  • EO ethylene oxide
  • PO propylene oxide
  • block copolymers is synonymous with this definition of "block polymers”.
  • Triblock co-polymers according to Formula (I) with the specific EO/POZEO arrangement and respective homopolymeric lengths have been found to enhance suds mileage performance of the liquid hand dishwashing detergent composition in the presence of greasy soils and/or suds consistency throughout dilution in the wash process.
  • Suitable EO-PO-EO triblock co-polymers are commercially available from BASF such as Pluronic® PE series, and from the Dow Chemical Company such as TergitolTM L series. Particularly preferred triblock co-polymer from BASF are sold under the tradenames Pluronic® PE6400 (MW ca 2900, ca 40wt% EO) and Pluronic® PE 9400 (MW ca 4600, 40 wt% EO). Particularly preferred triblock co-polymer from the Dow Chemical Company is sold under the tradename TergitolTM L64 (MW ca 2700, ca 40 wt% EO).
  • Preferred triblock co-polymers are readily biodegradable under aerobic conditions.
  • composition of the present invention may further comprise at least one active selected from the group consisting of: salt, hydrotrope, organic solvent, and mixtures thereof.
  • composition of the present invention may comprise from 0.05% to 2%, preferably from 0.1% to 1.5%, or more preferably from 0.5% to 1%, by weight of the total composition of a salt, preferably a monovalent or divalent inorganic salt, or a mixture thereof, more preferably selected from: sodium chloride, sodium sulfate, and mixtures thereof.
  • a salt preferably a monovalent or divalent inorganic salt, or a mixture thereof, more preferably selected from: sodium chloride, sodium sulfate, and mixtures thereof.
  • sodium chloride is most preferred.
  • composition of the present invention may comprise from 0.1% to 10%, or preferably from 0.5% to 10%, or more preferably from 1% to 10% by weight of the total composition of a hydrotrope or a mixture thereof, preferably sodium cumene sulfonate.
  • the composition can comprise from 0.1% to 10%, or preferably from 0.5% to 10%, or more preferably from 1% to 10% by weight of the total composition of an organic solvent.
  • Suitable organic solvents include organic solvents selected from the group consisting of: alcohols, glycols, glycol ethers, and mixtures thereof, preferably alcohols, glycols, and mixtures thereof. Ethanol is the preferred alcohol.
  • Polyalkyleneglycols, especially polypropyleneglycol (PPG), are the preferred glycol.
  • the polypropyleneglycol can have a molecular weight of from 400 to 3000, preferably from 600 to 1500, more preferably from 700 to 1300.
  • the polypropyleneglycol is preferably poly- 1 ,2-propyleneglycol .
  • the cleaning composition may optionally comprise a number of other adjunct ingredients such as builders (preferably citrate), further chelants, conditioning polymers, other cleaning polymers, surface modifying polymers, structurants, emollients, humectants, skin rejuvenating actives, enzymes, carboxylic acids, scrubbing particles, perfumes, malodor control agents, pigments, dyes, opacifiers, pearlescent particles, inorganic cations such as alkaline earth metals such as Ca/Mg-ions, antibacterial agents, preservatives, antioxidants, viscosity adjusters (e.g., salt such as NaCl, and other mono-, di- and trivalent salts) and pH adjusters and buffering means (e.g. carboxylic acids such as citric acid, HC1, NaOH, KOH, alkanolamines, carbonates such as sodium carbonates, bicarbonates, sesquicarbonates, and alike).
  • adjunct ingredients such as builders (preferably citrate), further chelants, conditioning polymers, other cleaning
  • the composition comprises from 0.01% to 2.0%, preferably from 0.05% to 1.5%, or more preferably from 0.1% to 1.0%, by weight of alkaline earth metal ions, with magnesium and/or calcium ions being particularly preferred.
  • Low levels of transition metal ions can also be present in the liquid detergent composition, such as up to 1.0%, or up to 0.5% by weight of the composition.
  • the hand dishwashing detergent composition can be packaged in a container, typically plastic containers.
  • Suitable containers comprise an orifice.
  • the container comprises a cap, with the orifice typically comprised on the cap.
  • the cap can comprise a spout, with the orifice at the exit of the spout.
  • the spout can have a length of from 0.5 mm to 10 mm.
  • the orifice can have an open cross-sectional surface area at the exit of from 3 mm 2 to 20 mm 2 , preferably from 3.8 mm 2 to 12 mm 2 , more preferably from 5 mm 2 to 10 mm 2 , wherein the container further comprises the composition according to the invention.
  • the cross-sectional surface area is measured perpendicular to the liquid exit from the container (that is, perpendicular to the liquid flow during dispensing).
  • the container can typically comprise from 200 ml to 5,000 ml, preferably from 350 ml to 2000 ml, more preferably from 400 ml to 1,000 ml of the liquid hand dishwashing detergent composition.
  • the hand dishwashing detergent composition can be packaged in an inverted container.
  • inverted containers typically comprise a cap at the bottom of the container, the cap comprising either a closure or a self-sealing valve, or a combination thereof.
  • the cap preferably comprises a self-sealing valve.
  • Suitable self-sealing valves include slit-valves.
  • the self-sealing valve defines a dispensing orifice that is reactably openable when the pressure on the valve interior side exceeds the pressure on the valve exterior side.
  • the bottom dispensing container can comprise an impact resistance system, such as that described in WO2019108293A1.
  • the resultant liquid detergent compositions can be used for manually washing. Suitable methods can comprise the steps of delivering such a liquid detergent composition to a volume of water to form a wash solution and immersing the dishware in the solution.
  • the dishware is be cleaned with the composition in the presence of water.
  • the dishware can be rinsed.
  • rinsed it is meant herein contacting the dishware cleaned with the process according to the present invention with substantial quantities of appropriate solvent, typically water.
  • substantial quantities it is meant usually about 1 to about 20 L, or under running water.
  • the composition herein can be applied in its diluted form.
  • Soiled dishware are contacted with an effective amount, typically from about 0.5 mL to about 20 mL (per about 25 dishes being treated), preferably from about 3 mL to about 10 mL, of the cleaning composition, preferably in liquid form, of the present invention diluted in water.
  • the actual amount of cleaning composition used will be based on the judgment of the user and will typically depend upon factors such as the particular product formulation of the cleaning composition, including the concentration of active ingredients in the cleaning composition, the number of soiled dishes to be cleaned, the degree of soiling on the dishes, and the like.
  • a cleaning composition of the invention is combined with from about 2,000 mL to about 20,000 mL, more typically from about 5,000 mL to about 15,000 mL of water in a sink.
  • the soiled dishware is immersed in the sink containing the diluted cleaning compositions then obtained, before contacting the soiled surface of the dishware with a cloth, sponge, or similar cleaning implement.
  • the cloth, sponge, or similar cleaning implement may be immersed in the cleaning composition and water mixture prior to being contacted with the dishware, and is typically contacted with the dishware for a period of time ranged from about 1 to about 10 seconds, although the actual time will vary with each application and user.
  • the contacting of cloth, sponge, or similar cleaning implement to the dishware is accompanied by a concurrent scrubbing of the dishware.
  • the composition is applied in its neat form to the dish to be treated.
  • in its neat form it is meant herein that said composition is applied directly onto the surface to be treated, or onto a cleaning device or implement such as a brush, a sponge, a nonwoven material, or a woven material, without undergoing any significant dilution by the user (immediately) prior to application. Application using a sponge is preferred.
  • "In its neat form” also includes slight dilutions, for instance, arising from the presence of water on the cleaning device, or the addition of water by the consumer to remove the remaining quantities of the composition from a bottle.
  • the composition in its neat form includes mixtures having the composition and water at ratios ranging from 50:50 to 100:0, preferably 70:30 to 100:0, more preferably 80:20 to 100:0, even more preferably 90: 10 to 100:0 depending on the user habits and the cleaning task.
  • the pH is measured as a 10% aqueous solution in demineralized water at 20 °C, using a pH meter, such as an Orion Model 720A with an Ag/AgCl electrode (for example an Orion sure flow Electrode model 9172BN), calibrated using standardized pH 7 and pH 10 buffers.
  • a pH meter such as an Orion Model 720A with an Ag/AgCl electrode (for example an Orion sure flow Electrode model 9172BN), calibrated using standardized pH 7 and pH 10 buffers.
  • Reserve alkalinity is defined as the grams of NaOH per 100 g of composition required to titrate the test composition at pH 7.0 to come to the test composition pH.
  • the reserve alkalinity for a solution is determined in the following manner.
  • the reserve alkalinity is measured at a 10% solution of the concentrated surfactant blend in deionized water at 20°C.
  • 50g of the concentrated surfactant blend is diluted to 10% with deionized water and mixed for 5 minutes until fully homogenized.
  • 100g of the 10% solution is then titrated using an automated titrator, such as the Omnis sample robot and Omnis titrator, supplied by Metrohm, using 0.1 N hydrochloric acid (HC1) and pH meter (as above), until an endpoint of pH 4 is achieved or the maximum titration amount of the titrator is reached (25 ml for the titrator above).
  • the volume of the titrant required to reach a pH of 7.0 is recorded, or if the maximum titration amount is reached, the final pH and volume of titrant is recorded.
  • the reserve alkalinity is calculated as follows:
  • the final pH is recorded and the reserve alkalinity to this pH is calculated.
  • the reserve alkalinity to pH 7.0 can then be estimated through linear extrapolation to pH 7.0 of the obtained “pH versus volume titrant” titration curves between an added titrant volume of 20ml and 25 ml.
  • the rheology profile is measured using a "TA instruments DHR1" rheometer, using a cone and plate geometry with a flat steel Peltier plate and a 40 mm diameter, 2.008° cone (TA instruments, serial number: SN999393).
  • the viscosity measurement procedure includes a conditioning step and a sweep step at 20 °C.
  • the conditioning step takes place at 20°C and consists of 10 seconds at zero shear, followed by pre-shearing for 10 seconds at 10 s' 1 , followed by 30 seconds at zero shear in order for the sample to equilibrate.
  • An upwards shear rate sweep is conducted from a shear rate of from 0.1s' 1 to 100s' 1 , in increments of 10 points per decade, each incremental step is executed by the rheometer automatically after stabilisation of the measurement. Unless otherwise stated, the viscosity is measured at shear rate of 10 s' 1 and a temperature of 20 °C.
  • the rheology profile is measured using a "TA instruments DHR1" rheometer, using a cone and plate geometry with a flat steel Peltier plate and a 40 mm diameter, 2.008° cone (TA instruments, serial number: SN999393).
  • the viscosity measurement procedure includes a conditioning step and a sweep step at 20 °C.
  • the conditioning step takes place at 20°C and consists of 10 seconds at zero shear, followed by pre-shearing for 10 seconds at 10 s' 1 , followed by 30 seconds at zero shear in order for the sample to equilibrate.
  • An upwards shear rate sweep is conducted from a shear rate of from 0.1s' 1 to 100s' 1 , in increments of 10 points per decade, each incremental step is executed by the rheometer automatically after stabilisation of the measurement.
  • T TO + K y 11 , where “T” is the shear stress, “TO” is the yield stress, and is y the shear rate. “K” is the consistency index, and “n” is the flow index.
  • the rheology variation with temperature is measured using a "TA instruments DHR1" rheometer, using a cone and plate geometry with a flat steel Peltier plate and a 40 mm diameter, 2.026° cone (TA instruments, serial number: SN999393), at a shear rate of 10s' 1 and a temperature sweep of from 60°C down to 5°C using a temperature ramp of 2°C/min, after a 100 second equilibration step at a shear rate of 10s' 1 at 60°C.
  • the viscosity of a detergent composition is measured at 20°C with a Brookfield RT Viscometer using spindle 31 with the RPM of the viscometer adjusted to achieve a torque of between 40% and 60%.
  • the initial foamability of a composition is assessed using a KRUSS DFA100 Dynamic Foam Analyzer.
  • the detergent composition is diluted to 50% in water having a hardness of 2.67 mmol/1 equivalent of CaCCE at 22 °C. 50 ml of the diluted solution is dosed using a syringe into a standard glass column (CY4501) fitted onto the Quick Fit Unit for agitation (SH4512), equipped with the standard agitator blade (SR4501). The initial solution height is recorded.
  • the solution is then agitated for 5 seconds at 5000 RPM. 20 seconds after agitation has stopped, the total sample height is recorded (foam + liquid solution). To calculate the height of the foam, the initial solution height is distracted from the total height measured.
  • test composition is dispensed through a plastic pipette at a flow rate of 0.67 mL/ sec at a height of 37 cm above the bottom surface of a sink (dimension: 300 mm diameter and 288 mm height) into water streams having a water hardness of 0.36 mmol/L equivalence of calcium carbonate (2.0 gpg), 1.25 mmol/L equivalence of calcium carbonate (7.0 gpg), and 2.67 mmol/L equivalence of calcium carbonate (15 gpg) and water temperature of 35°C, that is filling up the sink to 4 L at a constant pressure of 4 bar.
  • a fixed amount (6 mL) of a soil with the defined composition below is immediately injected into the middle of the sink.
  • the resultant solution is mixed with a metal blade (10 cm x 5 cm) positioned in the middle of the sink at the air liquid interface under an angle of 45° rotating at 85 RPM for 20 revolutions.
  • Steps 3-5 are repeated until the measured total suds volume reaches a level of 400 cm 3 or less.
  • the amount of added soil that is needed to get to the 400 cm 3 level is considered as the suds mileage for the test composition.
  • test composition is tested 4 times per testing condition (i.e., water temperature, composition concentration, water hardness, soil type).
  • the average suds mileage is calculated as the average of the 4 replicates for each sample for a defined test condition.
  • the Suds Mileage Index is calculated by comparing the average mileage of a test composition sample versus a reference composition sample. The calculation is as follows:
  • the neutralising stream was an aqueous solution of sodium hydroxide and C12-C14 dimethyl amine oxide (as the buffering surfactant), at the levels given in table 1.
  • the neutralising stream was an aqueous solution of sodium hydroxide, with no buffering surfactant added.
  • the blend of example 1 (of the invention) comprised branched alkyl sulfuric acid having a weight average degree of branching of 50% and amine oxide buffering surfactant at a ratio of 4.4: 1.
  • the blend of comparative example A was similar to example 1 but comprised a weight average degree of branching of 55% (above that required by the present invention).
  • the blend of comparative example B was similar to example 1, except that a linear alkyl sulfuric acid was used.
  • Comparative blend examples D to E used the same alkyl sulfuric acid as inventive example 1 and comparative examples A and B, respectively but did not comprise buffering surfactant. As such, a higher level of sodium hydroxide was needed to ensure the pH was sufficiently high to achieve a robust reserve alkalinity (to avoid re-hydrolysis of the alkyl sulfuric acid).
  • Table 1 levels of actives present during the neutralisation step for the inventive concentrated surfactant blends.
  • Comparative 1 50% branched C12-C13 alkyl sulfate, produced from SafolTM 23 alcohol, aFischer-Tropsh derived alcohol, supplied by Sasol
  • compositions of the present invention comprising the buffering surfactant, had a higher reserve alkalinity and hence greater robustness against rehydrolysis of the alkyl sulfuric acid, even though less alkali (sodium hydroxide) was used.
  • alkali sodium hydroxide
  • the lower amounts of alkali resulted in less salt being present in the concentrated surfactant blend, resulting in a more stable and pourable viscosity.
  • the concentrated surfactant blends of the present invention comprising the buffering surfactant, have a more readily processible viscosity profile, in contrast to the comparative compositions which do not comprise the buffering surfactant.
  • the small difference in surfactant level between the inventive and comparative examples does not give rise to the sharp difference in viscosity that has been measured.
  • the concentrated surfactant blends of comparative compositions C and D had a viscosity that was an almost solid gel, such that the viscosity was not even measurable.
  • Adding water to these compositions in order to arrive at the same active level as inventive compositions 1 and comparative compositions A and B resulted in composition C entering the gel phase and composition D remaining in the highly viscous gel-phase, with the viscosity being not measurable for both.
  • Example 2 is a further example of the present invention, and examples F to H are further comparative examples (having a degree of branching outside the present invention) using different ratios of anionic surfactant to buffering surfactant.
  • Table 2 levels of actives present during the neutralisation step for the different concentrated surfactant blends.
  • the surfactant blend of comparative example B was remade (comparative example H) and formulated into a detergent composition (comparative detergent example B).
  • Comparative detergent example A was formulated using a commercial concentrated alkyl sulfate blend not comprising a buffering surfactant (Tensopol® S30LSHPH, commercially available from KLK Oleo). Tensopol® S30LSHPH is a 30% active sodium lauryl sulfate in liquid form, having a high pH (greater than pH 11.0).
  • the pH of detergent composition B was adjusted (using sodium hydroxide) to arrive at a pH of 9.2.
  • the pH of comparative detergent composition A was adjusted (using citric acid) to arrive at the same pH of 9.2.
  • the resultant compositions are given below in table 3.
  • the amine oxide level given for detergent composition B includes a part added with the concentrated surfactant blend of comparative example H, and a part that was subsequently added when making the composition. Since it is not known how much alkali was present in the Tensopol® S30LSHPH starting material for detergent composition A, this is marked as “unknown”.
  • detergent composition B made using comparative surfactant blend H which was made using the process of the invention but using alcohol having linear alkyl chains
  • detergent composition A comparative and made using a different process
  • compositions produced from concentrated surfactant blends made using the process of the present invention are more readily dispersed - even though they comprise the same level of active ingredients and had essentially the same starting viscosity.
  • comparative detergent composition B was made using a comparative surfactant blend having a degree of branching above that required in the present invention (55%)
  • the improvement in viscosity upon dilution can be interpolated for surfactant blends made with the present process, using alkyl alcohol having the degree of branching required for the present invention.
  • the foamability of comparative detergent composition B and comparative detergent composition A were assessed. The foamability was measured for the two compositions following the foamability test method described herein. The amount of foam generated was summarized in table 4.
  • compositions produced from the concentrated surfactant blends made using the present process albite comprising anionic surfactant having a degree of branching above that required by the present invention
  • albite comprising anionic surfactant having a degree of branching above that required by the present invention
  • the above comparative detergent composition B was made using a comparative surfactant blend having a degree of branching above that required in the present invention (55%)
  • the improvement in foamability can be extrapolated to surfactant blends made with the present process, using alkyl alcohol having the degree of branching required for the present invention.
  • the surfactant blend of comparative example H (made with the present process, but using an alkyl alcohol having a weight average degree of branching of 55%, see table 3 above) was formulated to form comparative detergent composition C.
  • Comparative detergent example D was formulated using the same commercial concentrated alkyl sulfate blend as used to make comparative detergent composition A (Tensopol®S30LSHPH, commercially available from KLK Oleo). In both cases, the pH was adjusted to pH 9.2.
  • the resultant detergent compositions are given in table 6 below.
  • compositions produced with the process of the invention but using alkyl alcohol having a weight average degree of branching of 55% (detergent composition C) are more readily foaming than equivalent detergent compositions made using surfactant blends formed from traditional processes - even though they comprise the same level of active ingredients, and have improved freeze-thaw recovery, without negatively impacting foam mileage in the presence of greasy soils.
  • detergent composition C was made using a comparative surfactant blend having a degree of branching above that required in the present invention (55%)
  • the improvement in low temperature stability can be interpolated for surfactant blends made with the present process, using alkyl alcohol having the degree of branching required for the present invention.
  • Alcohol blend 1 had a degree of branching of 42.1%.
  • Alcohol blend A had a higher degree of branching of 62.5% (again primarily C2 branching), while alcohol blend B had a higher degree of branching of 86.6%.
  • Alcohol blends 1 (of use in the invention) and A and B were primarily branched at the C2 position.
  • All the blends comprised the same C13 branched (non-ethoxylated) alcohol, C13 branched ethoxylated (to degree 3.0) alcohol and Cl 2- 14 linear (non-ethoxylated) alcohol, mixed together at different ratios to achieve an average degree of ethoxylation of 0.6 and the desired degree of branching.
  • the sulfation step was done on a pilot plant scale using SO3 gas to sulfate the material in a falling film reactor.
  • C12-C14 dimethyl amine oxide was added as the buffering surfactant during the neutralisation step, to provide a weight ratio of the alkyl sulfuric acid to the buffering surfactant of 4.4: 1.
  • the sulfation reaction completion rate was measured for each alcohol blend.
  • Table 7 Alkyl chain distribution of starting C13 alcohols, and resultant completion rate for the sulfation reaction. by weight of starting C13 alcohol, the remainder being linear alcohol

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Abstract

Le besoin pour un tensioactif anionique alkylsulfaté contenant un mélange de tensioactifs concentrés qui ne nécessite pas un pH élevé pour être stable à l'hydrolyse et peut ainsi être utilisé pour former des compositions de détergent qui ne contiennent pas de niveaux élevés de sels ou ne nécessitent pas l'ajout de niveaux élevés de solvants organiques ou de structurants afin d'être stables, et qui présente le profil de viscosité, de dissolution et de moussage souhaités, est satisfait par un procédé par lequel un tensioactif tampon est ajouté avant ou pendant l'étape de neutralisation du flux d'acide sulfurique alkylé pour former le tensioactif anionique alkylsulfaté.
PCT/US2023/063757 2022-03-07 2023-03-06 Procédés de fabrication de mélanges de tensioactifs concentrés WO2023172859A1 (fr)

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