EP3156475B1 - Liquid cleaning concentrate - Google Patents

Liquid cleaning concentrate Download PDF

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Publication number
EP3156475B1
EP3156475B1 EP15190193.1A EP15190193A EP3156475B1 EP 3156475 B1 EP3156475 B1 EP 3156475B1 EP 15190193 A EP15190193 A EP 15190193A EP 3156475 B1 EP3156475 B1 EP 3156475B1
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EP
European Patent Office
Prior art keywords
weight
metal hydroxide
detergent concentrate
dispersing agent
suspension
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EP15190193.1A
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German (de)
French (fr)
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EP3156475A1 (en
EP3156475B2 (en
Inventor
Hans Georg Hagleitner
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Individual
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Individual
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Application filed by Individual filed Critical Individual
Priority to ES15190193.1T priority Critical patent/ES2685655T3/en
Priority to FIEP15190193.1T priority patent/FI3156475T4/en
Priority to SI201530378T priority patent/SI3156475T1/en
Priority to TR2018/12405T priority patent/TR201812405T4/en
Priority to HUE15190193A priority patent/HUE038978T2/en
Priority to EP15190193.1A priority patent/EP3156475B2/en
Priority to PL15190193T priority patent/PL3156475T3/en
Priority to PT15190193T priority patent/PT3156475T/en
Priority to RS20181018A priority patent/RS57613B1/en
Priority to BR112018007204-4A priority patent/BR112018007204B1/en
Priority to CN201680060556.7A priority patent/CN108350398B/en
Priority to EA201890976A priority patent/EA201890976A1/en
Priority to AU2016336915A priority patent/AU2016336915B2/en
Priority to PCT/EP2016/074744 priority patent/WO2017064266A1/en
Priority to US15/768,770 priority patent/US20180305643A1/en
Priority to CA3001652A priority patent/CA3001652C/en
Priority to MX2018004608A priority patent/MX2018004608A/en
Publication of EP3156475A1 publication Critical patent/EP3156475A1/en
Priority to CL2018000964A priority patent/CL2018000964A1/en
Priority to SA518391361A priority patent/SA518391361B1/en
Priority to CONC2018/0004021A priority patent/CO2018004021A2/en
Priority to IL258739A priority patent/IL258739B/en
Publication of EP3156475B1 publication Critical patent/EP3156475B1/en
Application granted granted Critical
Priority to HRP20181256TT priority patent/HRP20181256T1/en
Priority to US18/200,401 priority patent/US20230313071A1/en
Publication of EP3156475B2 publication Critical patent/EP3156475B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/06—Hydroxides
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/36—Organic compounds containing phosphorus

Definitions

  • the invention relates to a liquid cleaning concentrate comprising at least one alkali metal hydroxide.
  • the invention further relates to a process for the preparation of a liquid cleaning concentrate comprising alkali metal hydroxide.
  • alkaline detergents are preferably used.
  • Liquid detergents based on hydroxides and complexing agents are known from the prior art and have advantages over powdered formulations. On the one hand there is no dust and on the other hand, the handling is easier when dosing with pumps.
  • Liquid cleaning concentrates comprising alkali metal hydroxide are, for example, in DE 199 06 660 A1 described, with a water content of 53- 80 wt .-% is called.
  • a high water content in liquid cleaning concentrates is detrimental to the stability of the concentrate and significantly increases the required volume of cleaning concentrate, which is accompanied by additional containers.
  • highly concentrated cleaning concentrates with a low volume are preferred for storage and transport as well as for environmental reasons.
  • Non-aqueous liquid cleaning concentrates as in EP 1 181 346 described are a strategy; however, such compositions are associated with lower detergency or handling of hazardous or environmentally hazardous chemicals.
  • WO 96/27653 A1 discloses a paste-form detergent having a viscosity of over 15,000 mPa * s, which can not flow out of a container without the action of shearing forces.
  • Cleaning concentrates are dosed industrially with dosing machines and automatically with water to the desired final concentration in the ready-to-use detergent diluted.
  • peristaltic pumps for metering the cleaning concentrate are used, these peristaltic pumps can dose only liquid cleaning concentrates. Creamy or pasty cleaning concentrates are not suitable for use in automatic dosing machines due to their high viscosity - in the worst case, the peristaltic pump or dosing machine becomes clogged and destroyed.
  • Object of the present invention is therefore to provide a highly concentrated, but still liquid cleaning concentrate based on alkali metal hydroxide, which can be dosed and diluted with a dosing.
  • this suspension has a viscosity of at most 6500 mPa ⁇ s, measured on the basis of ISO 2555: 1989 at 20 ° C at a speed of 5 rpm.
  • the measurement may e.g. done with a Brookfield viscometer.
  • suspensions described herein are stable suspensions.
  • the cleaning concentrate has no further ingredients.
  • the present invention has therefore also set itself the task of providing a method for producing a stable suspension.
  • “adding a portion” means that only a part and not the entire amount of the respective ingredient is added to the respective step.
  • a stable suspension is possible - ie a suspension that does not segregate in the storage or use and in which there is no precipitate formation or in which no solid settles.
  • This is the first time the production of a stable suspension comprising large amounts of alkali metal hydroxide possible, and it is - in contrast to the cream-shaped Composition according to DE 100 02 710 A1 - A liquid, ie pumpable and metered cleaning concentrate produced.
  • a cleaning agent is a ready-to-use preparation for cleaning and is a mixture of a cleaning concentrate with water.
  • the cleaning agent is preferably a ready-to-use preparation for cleaning dishes.
  • a cleaning concentrate is a composition in which the ingredients - with the exception of the diluent water - are in a more concentrated form than in the ready-to-use detergent.
  • a stable suspension is understood here to mean a suspension which does not segregate during storage and use and in which no precipitate formation occurs.
  • the stability can be measured, for example, by measuring the viscosity and density, which may change only insignificantly over time.
  • the stability can also be determined by climate change test or storage over a defined period of time and subsequent optical control (separation into two or more phases).
  • One way of measuring is to check whether the viscosity and density after 30 days of storage, ie without stirring or moving the suspension at 20 ° C by sedimentation by less than 5%.
  • alkali metal hydroxide is meant the hydroxides of at least one alkali metal. It may therefore also be a mixture of several alkali metal hydroxides. Preference is given to using sodium hydroxide (NaOH) and potassium hydroxide (KOH).
  • a dispersant is an additive which improves the optimal mixing of at least two immiscible substances. Dispersants also aim at an improved cleaning performance of the cleaning agent. Dispersants may also be understood as meaning a mixture of two or more dispersants. A dispersant in the cleaner also helps to reduce old deposits.
  • a complexing agent or chelating agent is an additive which forms chelate complexes with metal ions. This undesirable properties of certain metal ions are masked. In the purification process, especially divalent metal ions are undesirable, especially alkaline earth metal ions such as Ca 2+ and Mg 2+ . Therefore, the complexing agents are preferably those which form complexes with alkaline earth metal ions.
  • Surfactants are substances which reduce the surface tension of a liquid or the interfacial tension between two phases and thus promote the formation of dispersions. They can also act as solubilizers. There may also be a mixture of two or more surfactants.
  • fatty alcohol ethoxylates show particularly good cleaning performance.
  • Defoamers may be selected, for example, from the group of paraffin oils, silicone oils or mixtures thereof.
  • An example of a possible paraffin oil is white oil, techn. (Fa. Bussetti); an example of silicone oil is silicone oil 100 (Bussetti).
  • the content of antifoaming agent may, for example, be 0 to 5% by weight.
  • Thickeners may be selected, for example, from the group of 1,2,3-propanetriol, propan-2-ol, xanthan gum (eg Keltrol types, Fa. CP Kelco).
  • the content of thickener may be for example 0 to 5 wt .-%.
  • Purification enhancers may be, for example, substances which have a basic action, ie have a pH-increasing effect, and may be, for example, monoethanolamine or triethanolamine.
  • Other cleaning enhancers include polymers or alkaline compounds such as Mirapol SURF S (a mixture based on Na 2 CO 3 , Rhodia), Polyquart Ampho 149 (BASF).
  • the content of cleaning enhancer may be, for example, 0 to 5% by weight.
  • Suspending agents may be selected, for example, from the group polyvinyl alcohol or polyvinylpyrrolidone.
  • the content of suspending agent may be, for example, 0 to 2% by weight.
  • no suspending agent is provided because it has been shown that increasing amounts of suspending agent cause segregation and sedimentation.
  • Threshold substances are compounds that prevent or at least greatly retard the formation of precipitates at very low (substoichiometric) concentrations. In a supersaturated solution, the formation of an insoluble precipitate is prevented by swelling substances block the surface of the first forming microcrystals by adsorption, so that no larger crystals can form by addition.
  • suitable swelling substances in the cleaning industry are compounds from the group of low molecular weight phosphonates and higher molecular weight complexing agents (eg polycarboxylates).
  • a particularly suitable threshold substance was Hydrodis WP 40 with the main constituent of an oligomeric phosphonic acid. Although it is known that many threshold active substances have solubility problems in aqueous solutions with high calcium concentrations (called calcium sensitivity), no Ca-sensitive zone was found when adding oligomeric phosphonic acid in the form of Hydrodis WP 40. The addition of Hydrodis WP 40 favors that the cleaning concentrate remains stable and has very good calcium binding capacity and good cleaning performance.
  • the content of the threshold substance is preferably from 2 to 5% by weight.
  • a mixture of a first and a second complexing agent is provided.
  • a first complexing agent may e.g. be selected from the group of aminocarboxylic acids and a second complexing agent from the group of aminophosphonic acids.
  • step a) a mixture of an aqueous solution of the first complexing agent (such as an aminocarboxylic acid, more preferably methylglycinediacetic acid or a salt thereof), and an aqueous solution of a second complexing agent (such as an aminophosphonic acid, more preferably diethylenetriaminepentamethylenephosphonic acid or a salt thereof).
  • the first complexing agent such as an aminocarboxylic acid, more preferably methylglycinediacetic acid or a salt thereof
  • a second complexing agent such as an aminophosphonic acid, more preferably diethylenetriaminepentamethylenephosphonic acid or a salt thereof.
  • step b) auxiliaries can be added.
  • Step d) Addition of a portion of alkali metal hydroxide as aqueous solution:
  • step d) a first addition of alkali metal hydroxide takes place with stirring, namely as an aqueous solution. Based on the total amount of alkali metal hydroxide, preferably less than half, more preferably less than one third, of the final amount of alkali metal hydroxide is added in this step.
  • Suitable aqueous solutions are preferably those of NaOH or KOH in question, wherein it makes no difference whether a NaOH solution or a KOH solution is used or whether each a NaOH solution and a KOH solution are added separately or whether a NaOH / KOH mixture is added. All combinations of these are also possible.
  • step e a surfactant is added with stirring.
  • step f) a further portion of alkali metal hydroxide is added as a solid.
  • the addition preferably takes place by stirring in NaOH and / or KOH pellets.
  • step g the addition of a further portion of dispersant, which is added with stirring.
  • step h) the still missing amount of alkali metal hydroxide is added slowly with stirring, wherein at least a part, preferably all the still missing amount of alkali metal hydroxide, is added as a solid.
  • the addition preferably takes place by stirring in NaOH and / or KOH pellets.
  • the aqueous phase may no longer reach a temperature above 40 ° C.
  • steps d) to h) must be carried out at temperatures ranging between 15 ° C and at most 40 ° C in order to achieve a stable suspension with the above-mentioned properties.
  • temperatures ranging between 15 ° C and at most 40 ° C there was no influence of the temperature on the stability and viscosity of the suspension.
  • the solubility of NaOH and / or KOH increases.
  • no stable, metered suspension could be achieved because the cleaning concentrate had a pasty consistency after cooling.
  • the suspension produced according to the invention irreversibly thickened on heating to temperatures above 60 ° C after cooling, which is due to the adverse effect on the suspension.
  • the temperature control may e.g. can be achieved by cooling (for example with a cooling sleeve) or by correspondingly slow process control.
  • step d) it is e.g. It is helpful to add a ready-to-use solution of alkali metal hydroxide to avoid any significant increase in temperature.
  • an active external cooling e.g., cooling collar
  • an active external cooling e.g., cooling collar
  • a stirrer for example an anchor stirrer, may be provided.
  • a disperser is additionally provided in order to accelerate the suspension formation.
  • KOH is more expensive compared to NaOH.
  • the cleaning performance of a pure KOH solution for dishwashing is (slightly) worse than the cleaning performance of a pure NaOH solution.
  • KOH is known to be more reactive with CO 2 from the air than NaOH and carbonates are formed in the solution ("crusting").
  • pure KOH has a stronger exotherm in the dissolution process (enthalpy of enthalpy - 57.1 kJ / mol) compared to NaOH (enthalpy of dissolution - 44.5 kJ / mol), which would fundamentally discourage the skilled artisan from using KOH when a low Temperature in the aqueous phase is observed.
  • composition of the liquid cleaning concentrate which is a suspension
  • the following could be found:
  • Dishwashing detergents show the best cleaning performance at high alkali metal hydroxide concentrations.
  • an admixture of up to 46 wt .-% alkali metal hydroxide was possible, with a stable suspension was achieved, the viscosity of which maintained the above range.
  • NaOH 22 to 46% by weight
  • KOH 22 to 46% by weight
  • mixtures thereof NaOH: 25 to 46% by weight-x% by weight; KOH: x % By weight
  • the highest stability of the suspension was achieved with a mixture of NaOH and KOH in which the content of KOH is between 5 and 10% by weight.
  • a particularly good cleaning action of the cleaning agent was achieved if at least one dispersant and at least one complexing agent are present in the cleaning concentrate.
  • the dispersant comprises a polymeric dispersant.
  • a preferred cleaning concentrate comprises from 1 to 10% by weight of polymeric dispersant.
  • the complexing agent has an organic amino function, preferably selected from the group comprising aminocarboxylic acids, aminophosphonic acids or a combination thereof. In this way, a liquid cleaning concentrate could be generated particularly advantageous.
  • the polymeric dispersant is a polycarboxylic acid, preferably polyacrylic acid or a derivative thereof.
  • the proportion of surfactants must not be too high because of the foam behavior and the stability, as well as for cost and environmental reasons. Preference is given to 2 wt .-%, more preferably 0.5 to 1.5 wt .-% are used. As such, known surfactants for dishwashing detergents can be used. In one embodiment, however, it has proved to be advantageous if the surfactant is a nonionic surfactant, preferably a fatty alcohol alkoxylate or a derivative thereof. A particularly suitable surfactant is fatty alcohol alkoxylate 8 (Plurafac LF 400, BASF).
  • auxiliaries 0 to 5% by weight of auxiliaries:
  • the excipients can be made to the comments from above.
  • Monoethanolamine is particularly preferably added.
  • the water content is preferably 28 to 39 wt .-%, wherein concentrations below 28 wt .-% no longer had the desired viscosities. Although concentrations above 39% by weight can be produced as a suspension, the advantage over a solution is then no longer very great.
  • the liquid cleaning concentrate is free of ethanol, glycerol and other short-chain alcohols (C 1 to C 5 alcohols), since it has been shown that such alcohols increase the viscosity, ie act as a thickener. It has also been found that introduction of NaOH solutions into alcohols, polyols or glycerol with the addition of solid NaOH leads to uncontrollable curing and inhomogeneous thickening.
  • the cleaning concentrate has no further constituents than those mentioned above.
  • the above-described liquid cleaning concentrate is a stable suspension and has a viscosity such that it can be pumped and thus metered in a metering system. Therefore, it is preferably provided that the viscosity of the cleaning concentrate has a maximum of 6500 mPa ⁇ s, measured on the basis of ISO 2555: 1989 at 20 ° C at a speed of 5 rpm.
  • Example 1 Inventive Example ⁇ / b> ingredient Proportion of raw material 1 [% by weight] Proportion of ingredient 2 [wt .-%] function step Alanine N, N-carboxymethyl trisodium salt 3) in aqueous solution (40% by weight) 27.0 10.8 K a) Aminophosphonic acid salt 4) in aqueous solution (42% by weight) 10.0 4.2 K Monoethanolamine 2.2 2.2 H b) Polymeric phosphonic acid 5) ; Hydrochloric acid; in aqueous solution (60% by weight) 5.0 3.0 K c) Sodium hydroxide solution (50% by weight) 22.3 11.15 XOH d) Isotridecanol ethoxylate 6) 1.5 1.5 T e) potassium hydroxide 10.0 10.0 XOH f) Polyacrylic acid
  • the total content of water is 36.5 wt .-%. During the manufacturing process, cooling took place so that the maximum temperature of 35 ° C was not exceeded.
  • the viscosity of the suspension was: Viscosity (mPa ⁇ s): 4500 mPa ⁇ s, measured in accordance with ISO 2555: 1989 at 20 ° C and 5 rpm ⁇ b>
  • Example 2 Inventive Example ⁇ / b> ingredient Proportion of raw material 1 [% by weight] Content of ingredient 2 [% by weight] function step Alanine N, N-carboxymethyl trisodium salt 3) in aqueous solution (40% by weight) 27.0 10.8 K a) Aminophosphonic acid salt 4) in aqueous solution (42% by weight) 10.0 4.2 K Monoethanolamine 2.2 2.2 H b) Polymeric phosphonic acid 5) ; Hydrochloric acid; in aqueous solution (60% by weight) 5.0 3.0 K c) Sodium hydroxide solution (50% by weight
  • the total water content is 37.4 wt .-%. During the manufacturing process, cooling took place so that the maximum temperature of 35 ° C was not exceeded.
  • the viscosity of the suspension was: Viscosity (mPa ⁇ s) 6000 mPa ⁇ s, measured in accordance with ISO 2555: 1989 at 20 ° C and 5 rpm ⁇ b>
  • Example 3 Inventive Example ⁇ / b> ingredient Proportion of raw material 1 [% by weight] Content of ingredient 2 [% by weight] function step Alanine N, N-carboxymethyl-trisodiumsalz 3) in aqueous solution (40 wt .-%) 27.0 10.8 K a) Aminophosphonic acid salt 4) in aqueous solution (42% by weight) 10.0 4.2 K Monoethanolamine 2.2 2.2 H b) Polymeric phosphonic acid 5) ; Hydrochloric acid; in aqueous solution (60% by weight) 5.0 3.0 K c) Sodium hydrox
  • the total water content is 37.4 wt .-%. During the manufacturing process, cooling took place so that the maximum temperature of 35 ° C was not exceeded.
  • the viscosity of the suspension was: Viscosity (mPa ⁇ s) 3800 mPa ⁇ s, 20 ° C measured on the basis of ISO 2555: 1989 at 20 ° C and 5 rpm ⁇ b> Comparative Example 1: ⁇ / b> ingredient Proportion of raw material 1 [% by weight] Content of ingredient 2 [% by weight] function step water 35.0 - LM 1 Polymeric phosphonic acid in aqueous solution (50% by weight) 3 10.0 5.0 K 2 glycerin 5.0 5.0 K 3 potassium hydroxide 10.0 10.0 XOH 4 Polyacrylic acid, sodium salt 4 20.0 20.0 K 5 sodium hydroxide 20.0 20.0 XOH 6 total 100.0 60.0 1) Ingredient including water 2) Pure ingredient (free of water) 3) Hydrodis ADW 3814 / N 4) Sokalan PA 25
  • the preparation is free of surfactants.
  • the recipe proved to be too viscous in the production without temperature control. With temperature control in the production process (maximum temperature of 35 ° C), the viscosity of the suspension was still in the range 6500 mPa ⁇ s. The complete absence of surfactants, however, proved to be negative for the viscosity. An addition of 0.5% by weight showed a reduction in viscosity and increase in stability.
  • a reduction of the water content in water-based cleaning concentrates usually leads to an increase in the viscosity.
  • DE 100 02 710 A1 is described a cream-shaped cleaning concentrate with a water content of 32.5%.
  • the property as a cream or paste is, however, unfavorable for use in dosing machines due to the high viscosity.
  • Such a cleaning agent could not be dosed with a peristaltic pump in the dosing unit.
  • a cleaning concentrate prepared by the process according to the invention has the cream or paste-like cleaning agents according to DE 100 02 710 A1 two differences: first, in DE 100 02 710 A1 a homogeneous mixture without particles, ie no suspension produced. Second, the cleaning concentrate of DE 100 02 710 A1 a significantly higher viscosity, resulting in the poor dosability.
  • Table 1 below shows a cleaning concentrate according to the invention and the cleaning concentrate according to DE 100 02 710 A1 compared.
  • Table 1 Comparison of the viscosity of cleaning concentrates: Composition Example 1 Example of DE 100 02 710 A1 Viscosity (mPa ⁇ s) * 2671 +/- 35 20,000 to 90,000 (Suspension) (Creamy paste) *) Measuring conditions as in DE 100 02 710 A1 : Brookfield viscometer based on ISO 2555: 1989.
  • Example 1 Viscosity, mPa ⁇ s Measurement 1 2651 Measurement 2 2711 Measurement 3 2651
  • Example 3 The composition according to Example 3 was additionally prepared under different conditions, ie at different temperatures. The addition steps d) to h) were carried out in such a way that a temperature of 40 ° C. was not exceeded in the aqueous phase (see Table 2).
  • Table 2 Comparison of the viscosity - composition according to Example 3. Results: Viscosity (mPa ⁇ s) at 5 rpm, 20 ° C * Sample 1 2184 Sample 2 6360 Sample 3 2400 Sample 4 3030 *) Measurement conditions: Brookfield viscometer in accordance with ISO 2555: 1989th

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Description

Die Erfindung betrifft ein flüssiges Reinigungskonzentrat, umfassend zumindest ein Alkalimetallhydroxid. Die Erfindung betrifft weiters ein Verfahren zur Herstellung eines flüssigen Reinigungskonzentrats, umfassend Alkalimetallhydroxid.The invention relates to a liquid cleaning concentrate comprising at least one alkali metal hydroxide. The invention further relates to a process for the preparation of a liquid cleaning concentrate comprising alkali metal hydroxide.

Stand der TechnikState of the art

Zur Reinigung von Geschirr, insbesondere zur Entfernung von dem Geschirr anhaftenden Schmutz, werden bevorzugt alkalische Reinigungsmittel eingesetzt.For cleaning dishes, especially for removing dirt adhering to the dishes, alkaline detergents are preferably used.

Flüssige Reinigungsmittel auf der Basis von Hydroxiden und Komplexbildnern sind aus dem Stand der Technik bekannt und haben gegenüber pulverförmigen Formulierungen Vorteile. Einerseits kommt es zu keiner Staubentwicklung und andererseits ist die Handhabung bei der Dosierung mit Pumpen erleichtert.Liquid detergents based on hydroxides and complexing agents are known from the prior art and have advantages over powdered formulations. On the one hand there is no dust and on the other hand, the handling is easier when dosing with pumps.

Flüssige Reinigungskonzentrate umfassend Alkalimetallhydroxid sind z.B. in DE 199 06 660 A1 beschrieben, wobei ein Wasseranteil von 53 - 80 Gew.-% genannt wird. Ein so hoher Wassergehalt in flüssigen Reinigungskonzentraten ist allerdings nachteilig für die Stabilität des Konzentrats und erhöht das erforderliche Volumen an Reinigungskonzentrat erheblich, was mit zusätzlichen Gebinden einhergeht. Gerade im gewerblichen Bereich werden hochkonzentrierte Reinigungskonzentrate mit geringem Volumen für Lagerung und Transport sowie aus Umweltschutzgründen bevorzugt.Liquid cleaning concentrates comprising alkali metal hydroxide are, for example, in DE 199 06 660 A1 described, with a water content of 53- 80 wt .-% is called. However, such a high water content in liquid cleaning concentrates is detrimental to the stability of the concentrate and significantly increases the required volume of cleaning concentrate, which is accompanied by additional containers. Particularly in the commercial sector, highly concentrated cleaning concentrates with a low volume are preferred for storage and transport as well as for environmental reasons.

Um dem nachteiligen hohen Wassergehalt entgegenzuwirken, werden im Stand der Technik verschiedene Strategien verfolgt. Nichtwässrige flüssige Reinigungskonzentrate wie in EP 1 181 346 beschrieben sind eine Strategie; solche Zusammensetzungen sind aber mit geringerem Reinigungsvermögen oder dem Hantieren mit gesundheitsbedenklichen oder umweltbedenklichen Chemikalien verbunden.In order to counteract the disadvantageous high water content, various strategies are pursued in the prior art. Non-aqueous liquid cleaning concentrates as in EP 1 181 346 described are a strategy; however, such compositions are associated with lower detergency or handling of hazardous or environmentally hazardous chemicals.

Ein anderer Ansatz ist die Reduktion des Wasseranteils in wässrigen Reinigungskonzentraten, der allerdings zu einer Steigerung der Viskosität führt. In DE 100 02 710 A1 ist z.B. ein cremeförmiges Reinigungskonzentrat mit einem Wasseranteil von 32,5% beschrieben.Another approach is the reduction of the water content in aqueous cleaning concentrates, which, however, leads to an increase in the viscosity. In DE 100 02 710 A1 For example, a cream-type cleaning concentrate with a water content of 32.5% is described.

WO 96/27653 A1 offenbart ein pastenförmiges Reinigungsmittel mit einer Viskosität von über 15 000 mPa*s, welches ohne vorherige Einwirkung von Scherkräften nicht aus einem Behälter ausfließen kann. WO 96/27653 A1 discloses a paste-form detergent having a viscosity of over 15,000 mPa * s, which can not flow out of a container without the action of shearing forces.

Reinigungskonzentrate werden industriell mit Dosierautomaten dosiert und automatisch mit Wasser auf die gewünschte Endkonzentration im gebrauchsfertigen Reinigungsmittel verdünnt. In solchen Dosierautomaten kommen meist Schlauchquetschpumpen zur Dosierung des Reinigungskonzentrats zum Einsatz, wobei diese Schlauchquetschpumpen nur flüssige Reinigungskonzentrate dosieren können. Cremeförmige bzw. pastöse Reinigungskonzentrate eignen sich aufgrund der hohen Viskosität für den Einsatz in Dosierautomaten nicht - im schlimmsten Fall kommt es zur Verstopfung und Zerstörung der Schlauchquetschpumpe oder des Dosierautomaten.Cleaning concentrates are dosed industrially with dosing machines and automatically with water to the desired final concentration in the ready-to-use detergent diluted. In such metering usually peristaltic pumps for metering the cleaning concentrate are used, these peristaltic pumps can dose only liquid cleaning concentrates. Creamy or pasty cleaning concentrates are not suitable for use in automatic dosing machines due to their high viscosity - in the worst case, the peristaltic pump or dosing machine becomes clogged and destroyed.

Aufgabe der vorliegenden Erfindung ist es daher, ein hochkonzentriertes, aber dennoch flüssiges Reinigungskonzentrat auf Alkalimetallhydroxid-Basis bereitzustellen, welches mit einem Dosierautomaten dosiert und verdünnt werden kann.Object of the present invention is therefore to provide a highly concentrated, but still liquid cleaning concentrate based on alkali metal hydroxide, which can be dosed and diluted with a dosing.

Kurzbeschreibung der ErfindungBrief description of the invention

Gelöst wird diese Aufgabe durch ein flüssiges Reinigungskonzentrat, umfassend

  1. (i) 22 bis 46 Gew.-% Alkalimetallhydroxid,
  2. (ii) 5 bis 50 Gew.-% Dispergiermittel, Komplexbildner oder eine Kombination daraus,
  3. (iii) 0 bis 5 Gew.-% Tensid,
  4. (iv) 0 bis 5 Gew.-% Hilfsstoffe, und
  5. (v) 28 bis 39 Gew.-% Wasser,
wobei das Reinigungskonzentrat eine Suspension ist.This object is achieved by a liquid cleaning concentrate comprising
  1. (i) from 22 to 46% by weight of alkali metal hydroxide,
  2. (ii) 5 to 50% by weight of dispersant, complexing agent or a combination thereof,
  3. (iii) 0 to 5% by weight of surfactant,
  4. (iv) 0 to 5% by weight of adjuvants, and
  5. (v) 28 to 39% by weight of water,
wherein the cleaning concentrate is a suspension.

Bevorzugt ist vorgesehen, dass diese Suspension eine Viskosität von maximal 6500 mPa·s aufweist, gemessen in Anlehnung an ISO 2555:1989 bei 20°C bei einer Umdrehungszahl von 5 rpm.It is preferably provided that this suspension has a viscosity of at most 6500 mPa · s, measured on the basis of ISO 2555: 1989 at 20 ° C at a speed of 5 rpm.

Die Messung kann z.B. mit einem Brookfield-Viskosimeter erfolgen.The measurement may e.g. done with a Brookfield viscometer.

Bei den hierin beschriebenen Suspensionen handelt es sich um stabile Suspensionen.The suspensions described herein are stable suspensions.

Es hat sich im Rahmen der Erfindung herausgestellt, dass die Verringerung des Wasseranteils und die damit normalerweise gekoppelte Erhöhung der Viskosität vermieden werden kann, wenn das Reinigungskonzentrat in Form einer Suspension hergestellt wird.It has been found in the context of the invention that the reduction of the water content and the thus normally coupled increase in viscosity can be avoided if the cleaning concentrate is prepared in the form of a suspension.

Bevorzugt ist vorgesehen, dass das Reinigungskonzentrat keine weiteren Inhaltsstoffe aufweist.It is preferably provided that the cleaning concentrate has no further ingredients.

Allerdings ist die Herstellung einer stabilen Suspension, welche eine hohe Konzentration an Alkalimetallhydroxid in einer geringen Menge Wasser aufweist, mit herkömmlichen Verfahren zur Herstellung von Suspensionen nicht möglich. Mit bekannten Herstellungsverfahren für Suspensionen nach Stand der Technik lassen sich keine stabilen Alkalimetallhydroxid-Suspensionen herstellen und soweit (nicht-stabile) Suspensionen herstellbar sind, weisen diese eine so hohe Viskosität auf, dass eine Dosierung unmöglich ist.However, the preparation of a stable suspension having a high concentration of alkali metal hydroxide in a small amount of water is conventional Process for the preparation of suspensions not possible. It is not possible to prepare stable alkali metal hydroxide suspensions with known preparation processes for suspensions according to the prior art and to the extent that (non-stable) suspensions can be prepared, they have such high viscosity that metering is impossible.

Die vorliegende Erfindung hat es sich daher auch zur Aufgabe gestellt, ein Verfahren zur Herstellung einer stabilen Suspension bereitzustellen.The present invention has therefore also set itself the task of providing a method for producing a stable suspension.

Die Aufgabe wird durch ein Verfahren zur Herstellung einer Suspension, umfassend

  1. (i) 22 bis 46 Gew.-% Alkalimetallhydroxid,
  2. (ii) 5 bis 50 Gew.-% Dispergiermittel, Komplexbildner oder eine Kombination daraus,
  3. (iii) 0 bis 5 Gew.-% Tensid,
  4. (iv) 0 bis 5 Gew.-% Hilfsstoffe und
  5. (v) 28 bis 39 Gew.-% Wasser, gelöst, wobei das Verfahren die Schritte umfasst:
    1. a) Bereitstellen einer Portion Dispergiermittel, Komplexbildner oder einer Kombination daraus in wässriger Phase,
    2. b) gegebenenfalls Zugabe von Hilfsstoffen,
    3. c) im Falle der Zugabe von Hilfsstoffen, anschließende Zugabe einer weiteren Portion Dispergiermittel,
    4. d) Zugabe einer Portion Alkalimetallhydroxid als wässrige Lösung,
    5. e) gegebenenfalls Zugabe eines Tensids,
    6. f) Zugabe einer weiteren Portion Alkalimethallhydroxid,
    7. g) Zugabe eines Dispergiermittels,
    8. h) Zugabe einer weiteren Portion Alkalimethallhydroxid,
wobei die Zugabeschritte unter Rühren erfolgen und zumindest die Zugabeschritte d) bis h) derart erfolgen, dass in der wässrigen Phase eine Temperatur von maximal 40°C, vorzugsweise maximal 35°C eingehalten wird.The object is achieved by a process for producing a suspension
  1. (i) from 22 to 46% by weight of alkali metal hydroxide,
  2. (ii) 5 to 50% by weight of dispersant, complexing agent or a combination thereof,
  3. (iii) 0 to 5% by weight of surfactant,
  4. (iv) 0 to 5% by weight of adjuvants and
  5. (v) 28 to 39% by weight of water, dissolved, the process comprising the steps of:
    1. a) providing a portion of dispersing agent, complexing agent or a combination thereof in the aqueous phase,
    2. b) optionally adding auxiliaries,
    3. c) in the case of the addition of auxiliaries, subsequent addition of a further portion of dispersant,
    4. d) adding a portion of alkali metal hydroxide as an aqueous solution,
    5. e) optionally adding a surfactant,
    6. f) adding a further portion of alkali metal hydroxide,
    7. g) adding a dispersant,
    8. h) adding a further portion of alkali metal hydroxide,
wherein the addition steps are carried out with stirring and at least the addition steps d) to h) carried out such that in the aqueous phase, a temperature of at most 40 ° C, preferably at most 35 ° C is maintained.

Dabei bedeutet "Zugabe einer Portion", dass nur ein Teil und nicht die gesamte Menge des jeweiligen Inhaltsstoffs beim jeweiligen Schritt zugegeben wird.In this case, "adding a portion" means that only a part and not the entire amount of the respective ingredient is added to the respective step.

Mit einem solchen Verfahren ist die Herstellung einer stabilen Suspension möglich - d.h. einer Suspension, die sich in der Lagerung bzw. Anwendung nicht entmischt und bei der es zu keiner Niederschlagsbildung kommt bzw. bei der sich kein Feststoff absetzt. Damit ist erstmals die Herstellung einer stabilen Suspension, umfassend große Mengen an Alkalimetallhydroxid möglich, und es ist - im Unterschied zur cremeförmigen Zusammensetzung gemäß DE 100 02 710 A1 - ein flüssiges, d.h. pump- und dosierbares Reinigungskonzentrat herstellbar.With such a method, the production of a stable suspension is possible - ie a suspension that does not segregate in the storage or use and in which there is no precipitate formation or in which no solid settles. This is the first time the production of a stable suspension comprising large amounts of alkali metal hydroxide possible, and it is - in contrast to the cream-shaped Composition according to DE 100 02 710 A1 - A liquid, ie pumpable and metered cleaning concentrate produced.

Begriffe:terms:

Im Rahmen dieser Erfindung werden die in der Anmeldung genannten Begriffe wie folgt verstanden:
Ein Reinigungsmittel stellt eine gebrauchsfertige Zubereitung für die Reinigung dar und ist eine Mischung aus einem Reinigungskonzentrat mit Wasser. Bevorzugt handelt es sich bei dem Reinigungsmittel um eine gebrauchsfertige Zubereitung für die Reinigung von Geschirr.In the context of this invention, the terms mentioned in the application are understood as follows:
A cleaning agent is a ready-to-use preparation for cleaning and is a mixture of a cleaning concentrate with water. The cleaning agent is preferably a ready-to-use preparation for cleaning dishes.

Ein Reinigungskonzentrat ist eine Zusammensetzung, in der die Inhaltsstoffe - mit Ausnahme des Verdünnungsmittels Wasser - in höher konzentrierter Form vorliegen als im gebrauchsfertigen Reinigungsmittel.A cleaning concentrate is a composition in which the ingredients - with the exception of the diluent water - are in a more concentrated form than in the ready-to-use detergent.

Unter einer stabilen Suspension wird hierin eine Suspension verstanden, die sich in der Lagerung und Anwendung nicht entmischt und bei der es zu keiner Niederschlagsbildung kommt. Die Stabilität kann beispielsweise durch die Messung der Viskosität und Dichte gemessen werden, die sich zeitlich nur unwesentlich ändern dürfen. Die Stabilität kann auch durch Klimawechseltest bzw. Lagerung über einen definierten Zeitraum und anschließender optischer Kontrolle (Trennung in zwei oder mehrere Phasen) ermittelt werden. Eine Möglichkeit der Messung besteht darin zu überprüfen, ob sich die Viskosität und Dichte nach 30 Tagen Lagerung, d.h. ohne Rühren oder Bewegen der Suspension, bei 20°C durch Sedimentation um weniger als 5 % ändern.A stable suspension is understood here to mean a suspension which does not segregate during storage and use and in which no precipitate formation occurs. The stability can be measured, for example, by measuring the viscosity and density, which may change only insignificantly over time. The stability can also be determined by climate change test or storage over a defined period of time and subsequent optical control (separation into two or more phases). One way of measuring is to check whether the viscosity and density after 30 days of storage, ie without stirring or moving the suspension at 20 ° C by sedimentation by less than 5%.

Unter Alkalimetallhydroxid werden die Hydroxide zumindest eines Alkalimetalls verstanden. Es kann sich daher auch um ein Gemisch aus mehreren Alkalimetallhydroxiden handeln. Bevorzugt kommen Natriumhydroxid (NaOH) und Kaliumhydroxid (KOH) zum Einsatz.By alkali metal hydroxide is meant the hydroxides of at least one alkali metal. It may therefore also be a mixture of several alkali metal hydroxides. Preference is given to using sodium hydroxide (NaOH) and potassium hydroxide (KOH).

Ein Dispergiermittel ist ein Zusatzstoff, welcher die optimale Durchmischung von mindestens zwei eigentlich nicht mischbaren Substanzen verbessert. Dispergiermittel zielen dabei auch auf eine verbesserte Reinigungsleistung des Reinigungsmittels ab. Unter Dispergiermittel kann auch ein Gemisch aus zwei oder mehreren Dispergiermitteln verstanden werden. Ein Dispergiermittel im Reinigungsmittel hilft überdies dabei, alte Ablagerungen abzubauen.A dispersant is an additive which improves the optimal mixing of at least two immiscible substances. Dispersants also aim at an improved cleaning performance of the cleaning agent. Dispersants may also be understood as meaning a mixture of two or more dispersants. A dispersant in the cleaner also helps to reduce old deposits.

Ein Komplexbildner oder Chelatbildner ist ein Zusatzstoff, welcher mit Metallionen Chelatkomplexe bildet. Dabei werden unerwünschte Eigenschaften bestimmter Metallionen maskiert. Beim Reinigungsvorgang sind insbesondere zweiwertige Metallionen unerwünscht, besonders Erdalkalimetallionen wie Ca2+ und Mg2+. Daher sind die Komplexbildner bevorzugt solche, welche Komplexe mit Erdalkalimetallionen bilden.A complexing agent or chelating agent is an additive which forms chelate complexes with metal ions. This undesirable properties of certain metal ions are masked. In the purification process, especially divalent metal ions are undesirable, especially alkaline earth metal ions such as Ca 2+ and Mg 2+ . Therefore, the complexing agents are preferably those which form complexes with alkaline earth metal ions.

In Reinigungsmitteln agieren manche Komplexbildner aber auch als Dispergiermittel und umgekehrt.In detergents, some complexing agents also act as dispersants and vice versa.

Tenside sind Substanzen, welche die Oberflächenspannung einer Flüssigkeit oder die Grenzflächenspannung zwischen zwei Phasen vermindern und so die Bildung von Dispersionen unterstützen. Sie können auch als Lösungsvermittler wirken. Es kann auch eine Mischung aus zwei oder mehreren Tensiden vorliegen. Surfactants are substances which reduce the surface tension of a liquid or the interfacial tension between two phases and thus promote the formation of dispersions. They can also act as solubilizers. There may also be a mixture of two or more surfactants.

In Reinigungsmitteln haben sie die Aufgabe, die Überführung von dem Geschirr anhaftenden Fett- und Schmutzpartikeln in die wässrige Phase zu begünstigen. Diese können z.B. ausgewählt sein aus der Gruppe der Alkylbenzolsulfonate, Alkylpolyglycoside, Esterquats, Fettalkoholethoxylate, Fettalkoholsulfate und Fettalkoholethersulfate oder Mischungen daraus, wobei Fettalkoholethoxylate besonders gute Reinigungsleistungen zeigen.In cleaning agents they have the task to promote the transfer of the adhering fat and dirt particles in the aqueous phase. These may e.g. be selected from the group of alkylbenzenesulfonates, alkylpolyglycosides, esterquats, fatty alcohol ethoxylates, fatty alcohol sulfates and fatty alcohol ether sulfates or mixtures thereof, wherein fatty alcohol ethoxylates show particularly good cleaning performance.

Hilfsstoffe umfassen Verbindungen, die in der fertigen Zubereitung des Reinigungsmittels dessen Anwendung erleichtern oder dessen Reinigungswirkung verstärken können. Hilfsstoffe können aber auch Verbindungen umfassen, welche die Suspensionsbildung begünstigen. Typische Hilfsmittel sind z.B.

  • Entschäumer, d.h. Stoffe, welche die Bildung von unerwünschten Schäumen beim Rühren des Reinigungsmittels verringern,
  • Verdickungsmittel, die die Viskosität des Reinigungsmittels erhöhen,
  • Reinigungsverstärker, die die Reinigungswirkung von Alkalimetallhydroxiden verstärken,
  • Schwellensubstanzen,
  • Suspendiermittel oder aber auch
  • Duftstoffe,
um nur einige Beispiele zu nennen. Adjuvants include compounds which may facilitate its use or enhance its detergency in the final detergent formulation. However, adjuvants may also include compounds that promote suspension formation. Typical aids are eg
  • Defoamers, ie substances which reduce the formation of undesirable foams during the stirring of the cleaning agent,
  • Thickeners that increase the viscosity of the detergent,
  • Cleaning enhancers that enhance the cleaning action of alkali metal hydroxides,
  • Threshold substances
  • Suspending agent or else
  • Fragrances,
to name just a few examples.

Entschäumer können z.B. ausgewählt sein aus der Gruppe Paraffinöle, Silikonöle oder Mischungen daraus. Ein Beispiel für ein mögliches Paraffinöl ist Weißöl, techn. (Fa. Bussetti); ein Beispiel für Silikonöl ist Silikonöl 100 (Fa. Bussetti). Der Gehalt an Entschäumer kann beispielsweise 0 bis 5 Gew.-% betragen. Defoamers may be selected, for example, from the group of paraffin oils, silicone oils or mixtures thereof. An example of a possible paraffin oil is white oil, techn. (Fa. Bussetti); an example of silicone oil is silicone oil 100 (Bussetti). The content of antifoaming agent may, for example, be 0 to 5% by weight.

Verdickungsmittel können z.B. ausgewählt sein aus der Gruppe 1,2,3-Propantriol, Propan-2-ol, Xanthan Gum (z.B. Keltrol-Typen, Fa. CP Kelco). Der Gehalt an Verdickungsmittel kann beispielsweise 0 bis 5 Gew.-% betragen. Thickeners may be selected, for example, from the group of 1,2,3-propanetriol, propan-2-ol, xanthan gum (eg Keltrol types, Fa. CP Kelco). The content of thickener may be for example 0 to 5 wt .-%.

Reinigungsverstärker können z.B. Stoffe sein, welche eine basische Wirkung haben, d.h. pH-Wert erhöhend wirken, und sie können z.B. Monoethanolamin oder Triethanolamin sein. Andere Reinigungsverstärker umfassen Polymere oder alkalische Verbindungen, wie z.B. Mirapol SURF S (ein Gemisch auf Na2CO3-Basis; Fa. Rhodia), Polyquart Ampho 149 (Fa. BASF). Der Gehalt an Reinigungsverstärker kann beispielsweise 0 bis 5 Gew.-% betragen. Purification enhancers may be, for example, substances which have a basic action, ie have a pH-increasing effect, and may be, for example, monoethanolamine or triethanolamine. Other cleaning enhancers include polymers or alkaline compounds such as Mirapol SURF S (a mixture based on Na 2 CO 3 , Rhodia), Polyquart Ampho 149 (BASF). The content of cleaning enhancer may be, for example, 0 to 5% by weight.

Suspendiermittel können z.B. ausgewählt sein aus der Gruppe Polyvinylalkohol oder Polyvinylpyrrolidon. Der Gehalt an Suspendiermittel kann beispielsweise 0 bis 2 Gew.-% betragen. Bevorzugt ist kein Suspendiermittel vorgesehen, da sich gezeigt hat, dass es bei steigenden Mengen an Suspendiermittel zur Entmischung und Bodensatzbildung kommt. Suspending agents may be selected, for example, from the group polyvinyl alcohol or polyvinylpyrrolidone. The content of suspending agent may be, for example, 0 to 2% by weight. Preferably, no suspending agent is provided because it has been shown that increasing amounts of suspending agent cause segregation and sedimentation.

Schwellensubstanzen sind Verbindungen, die bei sehr niedrigen (unterstöchiometrischen) Konzentrationen die Bildung von Niederschlägen verhindern oder zumindest stark verzögern. In einer übersättigten Lösung wird die Bildung eines unlöslichen Niederschlages verhindert, indem Schwellensubstanzen die Oberfläche der sich zuerst bildenden Mikrokristalle durch Adsorption blockieren, sodass sich keine größeren Kristalle durch Anlagerung bilden können. Als Schwellensubstanzen sind in der Reinigungsindustrie z.B. Verbindungen aus der Gruppe der niedermolekularen Phosphonate und der höhermolekularen Komplexbildner (z. B. Polycarboxylate) bekannt. Threshold substances are compounds that prevent or at least greatly retard the formation of precipitates at very low (substoichiometric) concentrations. In a supersaturated solution, the formation of an insoluble precipitate is prevented by swelling substances block the surface of the first forming microcrystals by adsorption, so that no larger crystals can form by addition. Examples of suitable swelling substances in the cleaning industry are compounds from the group of low molecular weight phosphonates and higher molecular weight complexing agents (eg polycarboxylates).

Eine besonders geeignete Schwellensubstanz war Hydrodis WP 40 mit dem Hauptbestandteil einer oligomeren Phosphonsäure. Obwohl an sich bekannt ist, dass viele schwellenaktive Substanzen Löslichkeitsprobleme in wässrigen Lösungen mit hohen Kalziumkonzentrationen (Calcium Sensitivity genannt) aufweisen, zeigte sich beim Zusatz von oligomerer Phosphonsäure in Form von Hydrodis WP 40 keine Ca-sensitive Zone. Der Zusatz von Hydrodis WP 40 begünstigt, dass das Reinigungskonzentrat stabil bleibt und sehr gutes Calciumbindevermögen sowie gute Reinigungsleistung aufweist. Der Gehalt an Schwellensubstanz beträgt bevorzugt 2 bis 5 Gew.-%.A particularly suitable threshold substance was Hydrodis WP 40 with the main constituent of an oligomeric phosphonic acid. Although it is known that many threshold active substances have solubility problems in aqueous solutions with high calcium concentrations (called calcium sensitivity), no Ca-sensitive zone was found when adding oligomeric phosphonic acid in the form of Hydrodis WP 40. The addition of Hydrodis WP 40 favors that the cleaning concentrate remains stable and has very good calcium binding capacity and good cleaning performance. The content of the threshold substance is preferably from 2 to 5% by weight.

Ausführliche Beschreibung der ErfindungDetailed description of the invention

Nachfolgend werden weitere Vorteile und Details der Erfindung erläutert. Die Ausführungen beziehen sich auf das flüssige Reinigungskonzentrat und das Herstellungsverfahren für die Suspension gleichermaßen. Aus Erwägungen für das bessere Verständnis wird das Herstellungsverfahren allerdings zuerst genauer dargelegt.Hereinafter, further advantages and details of the invention will be explained. The statements relate to the liquid cleaning concentrate and the production process for the suspension alike. However, for reasons of better understanding, the manufacturing process is first set out in more detail.

Schritt a) Bereitstellen einer Portion Dispergiermittel, Komplexbildner oder einer Kombination daraus in wässriger Lösung:Step a) Provision of a Portion of Dispersant, Complexing Agent or a Combination thereof in Aqueous Solution:

Zunächst wird eine Lösung von Dispergiermittel, Komplexbildner oder einer Kombination daraus in Wasser bereitgestellt.First, a solution of dispersant, complexing agent or a combination thereof in water is provided.

Bevorzugt wird eine Mischung aus einem ersten und einem zweiten Komplexbildner bereitgestellt.Preferably, a mixture of a first and a second complexing agent is provided.

Ein erster Komplexbildner kann z.B. aus der Gruppe der Aminocarbonsäuren und ein zweiter Komplexbildner aus der Gruppe der Aminophosphonsäuren ausgewählt sein.A first complexing agent may e.g. be selected from the group of aminocarboxylic acids and a second complexing agent from the group of aminophosphonic acids.

In einer Ausführungsvariante kann in Schritt a) eine Mischung einer wässrigen Lösung des ersten Komplexbildners (wie z.B. einer Aminocarbonsäure, noch bevorzugter von Methylglycindiessigsäure oder eines Salzes davon), und einer wässrigen Lösung eines zweiten Komplexbildners (wie z.B. einer Aminophosphonsäure, noch bevorzugter von Diethylentriaminpentamethylenphosphonsäure oder eines Salzes davon), bereitgestellt werden.In one embodiment, in step a), a mixture of an aqueous solution of the first complexing agent (such as an aminocarboxylic acid, more preferably methylglycinediacetic acid or a salt thereof), and an aqueous solution of a second complexing agent (such as an aminophosphonic acid, more preferably diethylenetriaminepentamethylenephosphonic acid or a salt thereof).

Schritt b) Gegebenenfalls Zugabe von Hilfsstoffen:Step b) If appropriate, addition of auxiliaries:

In Schritt b) können Hilfsstoffe beigemengt werden.In step b) auxiliaries can be added.

Schritt c) Zugabe einer weiteren Portion Dispergiermittel:Step c) Addition of another portion of dispersant:

Wenn es zu einer Zugabe von Hilfsstoffen kommt, ist es vorteilhaft, in einem nachfolgenden Schritt eine weitere Portion Dispergiermittel zuzugeben. Die Zugabe von Hilfsstoffen und die anschließende Zugabe von Dispergiermittel führen zu einer stabileren Suspension.If it comes to an addition of excipients, it is advantageous to add in a subsequent step, a further portion of dispersant. The addition of auxiliaries and the subsequent addition of dispersant lead to a more stable suspension.

Schritt d) Zugabe einer Portion Alkalimetallhydroxid als wässrige Lösung:Step d) Addition of a portion of alkali metal hydroxide as aqueous solution:

In Schritt d) erfolgt unter Rühren eine erste Zugabe von Alkalimetallhydroxid und zwar als wässrige Lösung. Bezogen auf die Gesamtmenge an Alkalimetallhydroxid wird in diesem Schritt bevorzugt weniger als die Hälfte, besonders bevorzugt weniger als ein Drittel der endgültigen Menge an Alkalimetallhydroxid zugesetzt.In step d), a first addition of alkali metal hydroxide takes place with stirring, namely as an aqueous solution. Based on the total amount of alkali metal hydroxide, preferably less than half, more preferably less than one third, of the final amount of alkali metal hydroxide is added in this step.

Als wässrige Lösungen kommen bevorzugt solche von NaOH oder KOH in Frage, wobei es keinen Unterschied macht, ob eine NaOH-Lösung oder eine KOH-Lösung eingesetzt wird oder ob je eine NaOH-Lösung und eine KOH-Lösung getrennt voneinander zugesetzt werden oder ob eine NaOH/KOH-Mischung zugesetzt wird. Sämtliche Kombinationen daraus sind auch möglich.Suitable aqueous solutions are preferably those of NaOH or KOH in question, wherein it makes no difference whether a NaOH solution or a KOH solution is used or whether each a NaOH solution and a KOH solution are added separately or whether a NaOH / KOH mixture is added. All combinations of these are also possible.

Schritt e) Zugabe eines Tensids:Step e) Addition of a surfactant:

In Schritt e) wird ein Tensid unter Rühren zugesetzt.In step e) a surfactant is added with stirring.

Schritt f) Zugabe einer weiteren Portion Alkalimetallhydroxid:Step f) Addition of another portion of alkali metal hydroxide:

In Schritt f) wird eine weitere Portion Alkalimetallhydroxid als Feststoff zugesetzt. Vorzugsweise erfolgt die Zugabe durch Einrühren von NaOH- und/oder KOH-Pellets.In step f), a further portion of alkali metal hydroxide is added as a solid. The addition preferably takes place by stirring in NaOH and / or KOH pellets.

Schritt g) Zugabe einer weiteren Portion Dispergiermittel:Step g) Addition of another portion of dispersant:

In Schritt g) erfolgt die Zugabe einer weiteren Portion Dispergiermittel, welches unter Rühren eingetragen wird.In step g), the addition of a further portion of dispersant, which is added with stirring.

Schritt h) Zugabe einer weiteren Portion Alkalimetallhydroxid:Step h) Addition of another portion of alkali metal hydroxide:

In Schritt h) wird die noch fehlende Menge an Alkalimetallhydroxid langsam unter Rühren zugesetzt, wobei zumindest ein Teil, vorzugsweise die gesamte noch fehlende Menge Alkalimetallhydroxid, als Feststoff zugesetzt wird. Vorzugsweise erfolgt die Zugabe durch Einrühren von NaOH- und/oder KOH-Pellets.In step h), the still missing amount of alkali metal hydroxide is added slowly with stirring, wherein at least a part, preferably all the still missing amount of alkali metal hydroxide, is added as a solid. The addition preferably takes place by stirring in NaOH and / or KOH pellets.

Temperatur maximal 40°C, vorzugsweise maximal 35°C für die Zugabeschritte d) bis h):Temperature maximum 40 ° C, preferably maximum 35 ° C for the addition steps d) to h):

Ab Schritt d) darf die wässrige Phase keine Temperatur mehr erreichen, die über 40°C liegt. Die Erfinder haben herausgefunden, dass die Schritte d) bis h) bei Temperaturen durchgeführt werden müssen, die im Bereich zwischen 15°C und maximal 40°C liegen, um eine stabile Suspension mit den oben genannten Eigenschaften zu erreichen. Im Temperaturbereich 15 bis 35°C zeigte sich kein Einfluss der Temperatur auf die Stabilität und Viskosität der Suspension. Bei steigenden Temperaturen steigt die Löslichkeit von NaOH und/oder KOH zunehmend an. Allerdings konnte, wenn die Temperaturen bei der Zugabe über 40°C lagen, keine stabile, dosierbare Suspension mehr erzielt werden, da das Reinigungskonzentrat nach dem Abkühlen eine pastöse Konsistenz aufwies.From step d), the aqueous phase may no longer reach a temperature above 40 ° C. The inventors have found that steps d) to h) must be carried out at temperatures ranging between 15 ° C and at most 40 ° C in order to achieve a stable suspension with the above-mentioned properties. In the temperature range 15 to 35 ° C, there was no influence of the temperature on the stability and viscosity of the suspension. As the temperature increases, the solubility of NaOH and / or KOH increases. However, if the temperatures were above 40 ° C in the addition, no stable, metered suspension could be achieved because the cleaning concentrate had a pasty consistency after cooling.

Des weiteren hat sich herausgestellt, dass die erfindungsgemäß hergestellte Suspension beim Erwärmen auf Temperaturen über 60°C nach Abkühlen irreversibel eindickte, was auf die nachteilige Beeinträchtigung der Suspension zurückzuführen ist.Furthermore, it has been found that the suspension produced according to the invention irreversibly thickened on heating to temperatures above 60 ° C after cooling, which is due to the adverse effect on the suspension.

Die Temperaturkontrolle kann z.B. durch Kühlen (beispielsweise mit einer Kühlmanschette) oder durch entsprechend langsame Prozessführung erzielt werden. In Schritt d) ist es z.B. hilfreich, bereits eine fertige Lösung von Alkalimetallhydroxid beizumengen, damit es zu keinem nennenswerten Temperaturanstieg kommt.The temperature control may e.g. can be achieved by cooling (for example with a cooling sleeve) or by correspondingly slow process control. In step d) it is e.g. It is helpful to add a ready-to-use solution of alkali metal hydroxide to avoid any significant increase in temperature.

Bevorzugt ist eine aktive, externe Kühlung (z.B. Kühlmanschette) vorgesehen.Preferably, an active external cooling (e.g., cooling collar) is provided.

Zur Herstellung der Suspension kann ein Rührer, beispielsweise ein Ankerrührer, vorgesehen sein.To prepare the suspension, a stirrer, for example an anchor stirrer, may be provided.

In einer Ausführungsvariante wird zusätzlich ein Dispergierer bereitgestellt, um die Suspensionsbildung zu beschleunigen.In one embodiment, a disperser is additionally provided in order to accelerate the suspension formation.

Eine überraschende Erkenntnis der Erfinder war, dass es aus zwei Gründen vorteilhaft ist, der Zusammensetzung zumindest teilweise KOH als Alkalimetallhydroxid beizumengen. Grundsätzlich gibt der Fachmann NaOH aus verschiedenen Gründen den Vorzug gegenüber KOH:
KOH ist im Vergleich zu NaOH teurer. Darüber hinaus ist die Reinigungsleistung einer reinen KOH-Lösung für die Geschirrreinigung (geringfügig) schlechter als die Reinigungsleistung einer reinen NaOH-Lösung. Außerdem ist KOH bekannt dafür, dass es mit CO2 aus der Luft stärker reagiert als NaOH und Carbonate in der Lösung gebildet werden ("Krustenbildung"). Schließlich weist reines KOH eine stärkere Exothermie beim Lösevorgang auf (Löseenthalpie - 57,1 kJ/mol) im Vergleich zu NaOH (Löseenthalpie - 44,5 kJ/mol), was den Fachmann grundsätzlich davor abschrecken würde, KOH zu verwenden, wenn eine niedrige Temperatur in der wässrigen Phase einzuhalten ist.A surprising discovery of the inventors was that for two reasons it is advantageous to at least partially incorporate KOH as the alkali metal hydroxide in the composition. Basically, the expert NaOH for several reasons, the preference over KOH:
KOH is more expensive compared to NaOH. In addition, the cleaning performance of a pure KOH solution for dishwashing is (slightly) worse than the cleaning performance of a pure NaOH solution. In addition, KOH is known to be more reactive with CO 2 from the air than NaOH and carbonates are formed in the solution ("crusting"). Finally, pure KOH has a stronger exotherm in the dissolution process (enthalpy of enthalpy - 57.1 kJ / mol) compared to NaOH (enthalpy of dissolution - 44.5 kJ / mol), which would fundamentally discourage the skilled artisan from using KOH when a low Temperature in the aqueous phase is observed.

Im Rahmen der vorliegenden Erfindung haben die Erfinder allerdings herausgefunden, dass die CO2-Aufnahme bei der Beimengung von KOH zu verringerter Krustenbildung führt als beim reinen Einsatz von NaOH. Die Bildung von Krusten ist unerwünscht, da die Förderung der Suspension über eine Sauglanze zur Pumpe erfolgt und Krusten die Sauglanze verstopfen können. Deshalb ist die Anwesenheit von KOH bevorzugt.In the context of the present invention, however, the inventors have found that the CO 2 uptake in the addition of KOH results in reduced crust formation than in the pure use of NaOH. The formation of crusts is undesirable because the promotion of the suspension via a suction lance to the pump and crusts can clog the suction lance. Therefore, the presence of KOH is preferred.

Trotz grundsätzlich höherer Exothermie bei der KOH-Auflösung zeigte sich, dass bei der Zugabe von KOH-Pellets in Schritt f) der spontane Temperaturanstieg geringer war als bei der Zugabe von NaOH-Pellets, sodass der Prozess leichter kontrolliert werden kann.Despite basically higher exothermicity in KOH dissolution, it was found that when KOH pellets were added in step f), the spontaneous temperature rise was lower than with the addition of NaOH pellets, so that the process is easier to control.

Hinsichtlich der Zusammensetzung des flüssigen Reinigungskonzentrats, welches eine Suspension ist, konnte noch folgendes herausgefunden werden:With regard to the composition of the liquid cleaning concentrate, which is a suspension, the following could be found:

i) 22 bis 46 Gew.-% Alkalimetallhydroxid:i) from 22 to 46% by weight of alkali metal hydroxide:

Geschirrreiniger zeigen die beste Reinigungsleistung bei hohen Alkalimetallhydroxidkonzentrationen. Für die gegenständliche Erfindung war eine Beimengung von bis zu 46 Gew.-% Alkalimetallhydroxid möglich, mit der eine stabile Suspension erzielbar war, deren Viskosität den oben genannten Bereich einhielt.Dishwashing detergents show the best cleaning performance at high alkali metal hydroxide concentrations. For the subject invention, an admixture of up to 46 wt .-% alkali metal hydroxide was possible, with a stable suspension was achieved, the viscosity of which maintained the above range.

Aus den zuvor genannten Gründen sind NaOH (22 bis 46 Gew.-%), KOH (22 bis 46 Gew.-%) oder Mischungen davon (NaOH: 25 bis 46 Gew.-% - x Gew.-%; KOH: x Gew.-%), bevorzugt.For the reasons mentioned above, NaOH (22 to 46% by weight), KOH (22 to 46% by weight) or mixtures thereof (NaOH: 25 to 46% by weight-x% by weight; KOH: x % By weight), preferably.

Die höchste Stabilität der Suspension wurde mit einer Mischung aus NaOH und KOH erzielt, bei der der Gehalt an KOH zwischen 5 und 10 Gew.-% beträgt.The highest stability of the suspension was achieved with a mixture of NaOH and KOH in which the content of KOH is between 5 and 10% by weight.

ii) 5 bis 50 Gew.-% Dispergiermittel, Komplexbildner oder eine Kombination daraus:ii) 5 to 50% by weight of dispersant, complexing agent or a combination thereof:

Eine besonders gute Reinigungswirkung des Reinigungsmittels wurde erzielt, wenn im Reinigungskonzentrat mindestens ein Dispergiermittel und mindestens ein Komplexbildner vorhanden sind. Besonders bevorzugt umfasst das Dispergiermittel ein polymeres Dispergiermittel. Ein bevorzugtes Reinigungskonzentrat umfasst 1 bis 10 Gew.-% polymeres Dispergiermittel.A particularly good cleaning action of the cleaning agent was achieved if at least one dispersant and at least one complexing agent are present in the cleaning concentrate. Most preferably, the dispersant comprises a polymeric dispersant. A preferred cleaning concentrate comprises from 1 to 10% by weight of polymeric dispersant.

In einer bevorzugten Ausführungsvariante hat es sich als vorteilhaft erwiesen, wenn der Komplexbildner eine organische Aminofunktion aufweist, bevorzugt ausgewählt ist aus der Gruppe umfassend Aminocarbonsäuren, Aminophosphonsäuren oder einer Kombinationen davon. Auf diese Weise konnte besonders vorteilhaft ein flüssiges Reinigungskonzentrat erzeugt werden.In a preferred embodiment, it has proved to be advantageous if the complexing agent has an organic amino function, preferably selected from the group comprising aminocarboxylic acids, aminophosphonic acids or a combination thereof. In this way, a liquid cleaning concentrate could be generated particularly advantageous.

Es erwies sich als vorteilhaft, wenn das polymere Dispergiermittel eine Polycarbonsäure ist, bevorzugt Polyacrylsäure oder ein Derivat davon.It has proved to be advantageous if the polymeric dispersant is a polycarboxylic acid, preferably polyacrylic acid or a derivative thereof.

iii) 0 bis 5 Gew.-% Tensid:iii) 0 to 5% by weight of surfactant:

Der Anteil von Tensiden darf aufgrund des Schaumverhaltens und der Stabilität, sowie aus Kosten- und Umweltgründen nicht zu hoch sein. Bevorzugt kommen bis 2 Gew.-%, besonders bevorzugt 0,5 bis 1,5 Gew.-% zum Einsatz. An sich können bekannte Tenside für Geschirrreiniger eingesetzt werden. In einer Ausführungsvariante hat es sich aber als vorteilhaft erwiesen, wenn das Tensid ein nicht-ionisches Tensid darstellt, bevorzugt ein Fettalkoholalkoxylat oder ein Derivat davon. Als besonders geeignetes Tensid hat sich Fettalkoholalkoxylat 8 (Plurafac LF 400, Fa. BASF) gezeigt.The proportion of surfactants must not be too high because of the foam behavior and the stability, as well as for cost and environmental reasons. Preference is given to 2 wt .-%, more preferably 0.5 to 1.5 wt .-% are used. As such, known surfactants for dishwashing detergents can be used. In one embodiment, however, it has proved to be advantageous if the surfactant is a nonionic surfactant, preferably a fatty alcohol alkoxylate or a derivative thereof. A particularly suitable surfactant is fatty alcohol alkoxylate 8 (Plurafac LF 400, BASF).

iv) 0 bis 5 Gew.-% Hilfsstoffe:iv) 0 to 5% by weight of auxiliaries:

Zu den Hilfsstoffen kann auf die Ausführungen von oben verwiesen werden. Bevorzugt werden zwischen 1 und 3 Gew.-% Hilfsstoff zugesetzt. Besonders bevorzugt wird dabei Monoethanolamin zugegeben.For the excipients can be made to the comments from above. Preferably, between 1 and 3 wt .-% adjuvant is added. Monoethanolamine is particularly preferably added.

v) 28 bis 39 Gew.-% Wasser:v) 28 to 39% by weight of water:

Der Wassergehalt beträgt bevorzugt 28 bis 39 Gew.-%, wobei Konzentrationen unter 28 Gew.-% nicht mehr die gewünschten Viskositäten aufwiesen. Konzentrationen über 39 Gew.-% sind zwar als Suspension erzeugbar, der Vorteil gegenüber einer Lösung ist dann allerdings nicht mehr sehr groß.The water content is preferably 28 to 39 wt .-%, wherein concentrations below 28 wt .-% no longer had the desired viscosities. Although concentrations above 39% by weight can be produced as a suspension, the advantage over a solution is then no longer very great.

In einer Ausführungsvariante ist vorgesehen, dass das flüssige Reinigungskonzentrat frei von Ethanol, Glycerol und anderen kurzkettigen Alkoholen (C1-bis C5-Alkohole) ist, da sich gezeigt hat, dass solche Alkohole die Viskosität erhöhen, d.h. als Verdickungsmittel wirken. Es hat sich auch gezeigt, dass ein Einbringen von NaOH-Lösungen in Alkohole, Polyole oder Glycerol unter Zusatz von festem NaOH zu einem unkontrollierbaren Aushärten und einer inhomogenen Verdickung führt.In one embodiment, it is provided that the liquid cleaning concentrate is free of ethanol, glycerol and other short-chain alcohols (C 1 to C 5 alcohols), since it has been shown that such alcohols increase the viscosity, ie act as a thickener. It has also been found that introduction of NaOH solutions into alcohols, polyols or glycerol with the addition of solid NaOH leads to uncontrollable curing and inhomogeneous thickening.

In einer bevorzugten Ausführungsvariante weist das Reinigungskonzentrat keine weiteren Bestandteile als die oben genannten auf.In a preferred embodiment, the cleaning concentrate has no further constituents than those mentioned above.

Experimentelle Ergebnisse und Ausführungsbeispiel:Experimental Results and Embodiment:

Das oben dargestellte flüssige Reinigungskonzentrat ist eine stabile Suspension und weist eine Viskosität auf, so dass es in einer Dosieranlage pumpbar und damit dosierbar ist. Daher ist bevorzugt vorgesehen, dass die Viskosität des Reinigungskonzentrats maximal 6500 mPa·s, gemessen in Anlehnung an ISO 2555:1989 bei 20°C bei einer Drehzahl von 5 rpm aufweist.The above-described liquid cleaning concentrate is a stable suspension and has a viscosity such that it can be pumped and thus metered in a metering system. Therefore, it is preferably provided that the viscosity of the cleaning concentrate has a maximum of 6500 mPa · s, measured on the basis of ISO 2555: 1989 at 20 ° C at a speed of 5 rpm.

BeispieleExamples

Nachfolgend werden beispielhaft Rezepturen sowie Herstellungsverfahren für erfindungsgemäße Reinigungskonzentrate, sowie deren rheologische Eigenschaften gezeigt und nicht-erfindungsgemäßen Vergleichsbeispielen gegenübergestellt. Beispiel 1: Erfindungsgemäßes Beispiel Inhaltsstoff Anteil Rohstoff1 [Gew.-%] Anteil Inhaltsstoff2 [Gew.-%] Funktion Schritt Alanin N,N-Carboxymethyl-trisodiumsalz 3) in wässriger Lösung (40 Gew.-%) 27,0 10,8 K a) Aminophosphonsäuresalz 4) in wässriger Lösung (42 Gew.-%) 10,0 4,2 K Monoethanolamin 2,2 2,2 H b) Polymere Phosphonsäure 5); Salzsäure; in wässriger Lösung (60 Gew.-%) 5,0 3,0 K c) Natronlauge (50 Gew.-%) 22,3 11,15 XOH d) Isotridecanolethoxylat 6) 1,5 1,5 T e) Kaliumhydroxid 10,0 10,0 XOH f) Polyacrylsäure 9), Natriumsalz (in wässriger Lösung, 55 Gew.-%) 3,0 1,65 K g) Natriumhydroxid 19,0 19,0 XOH h) Gesamt 100 63,5 1) Inhaltsstoff inklusive Wasser
2) Reiner Inhaltsstoff (frei von Wasser)
3) Trilon M fl.,
4) Dequest 2066
5) Hydrodis WP 40
6) Lutensol TO 7
9) Sokalan PA 30 CL (wässrige Lösung).
K Komplexbildner/Dispergiermittel
H Hilfsstoff
T Tensid
XOH Alkalimetallhydroxid
Schritt Verfahrens schritt nach Anspruch 10 In the following, exemplary formulations and production processes for cleaning concentrates according to the invention, as well as their rheological properties are shown and non-inventive comparative examples are compared. <b> Example 1: Inventive Example </ b> ingredient Proportion of raw material 1 [% by weight] Proportion of ingredient 2 [wt .-%] function step Alanine N, N-carboxymethyl trisodium salt 3) in aqueous solution (40% by weight) 27.0 10.8 K a) Aminophosphonic acid salt 4) in aqueous solution (42% by weight) 10.0 4.2 K Monoethanolamine 2.2 2.2 H b) Polymeric phosphonic acid 5) ; Hydrochloric acid; in aqueous solution (60% by weight) 5.0 3.0 K c) Sodium hydroxide solution (50% by weight) 22.3 11.15 XOH d) Isotridecanol ethoxylate 6) 1.5 1.5 T e) potassium hydroxide 10.0 10.0 XOH f) Polyacrylic acid 9) , sodium salt (in aqueous solution, 55% by weight) 3.0 1.65 K G) sodium hydroxide 19.0 19.0 XOH H) total 100 63.5 1) Ingredient including water
2) Pure ingredient (free of water)
3) Trilon M fl.,
4) Dequest 2066
5) HYDRODIS WP 40
6) Lutensol TO 7
9) Sokalan PA 30 CL (aqueous solution).
K complexing agent / dispersant
H adjuvant
T surfactant
XOH alkali metal hydroxide
Step method step according to claim 10

Der Gesamtgehalt an Wasser beträgt 36,5 Gew.-%. Beim Herstellungsprozess erfolgte eine Kühlung, sodass die maximale Temperatur 35°C nicht überschritten wurde. Die Viskosität der Suspension betrug: Viskosität (mPa·s): 4500 mPa·s, gemessen in Anlehnung an ISO 2555:1989 bei 20°C und 5 rpm Beispiel 2: Erfindungsgemäßes Beispiel Inhaltsstoff Anteil Rohstoff1 [Gew.-%] Anteil Inhaltsstoff2 [Gew.-%] Funktion Schritt Alanin N,N-Carboxymethyl-trisodiumsalz 3) in wässriger Lösung (40 Gew.-%) 27,0 10,8 K a) Aminophosphonsäuresalz 4) in wässriger Lösung (42 Gew.-%) 10,0 4,2 K Monoethanolamin 2,2 2,2 H b) Polymere Phosphonsäure 5); Salzsäure; in wässriger Lösung (60 Gew.-%) 5,0 3,0 K c) Natronlauge (50 Gew.-%) 22,3 11,15 XOH d) Isotridecanolethoxylat 6) 0,5 0,5 T e) Kaliumhydroxid 8,0 8,0 XOH f) Polyacrylsäure 9), Natriumsalz (in wässriger Lösung, 55 Gew.-%) 5,0 2,75 K g) Gemisch auf Basis von Natriumcarbonat 8); ohne Phosphate 1,0 1,0 H g) Natriumhydroxid 19,0 19,0 XOH h) Gesamt 100 62,6 1) Inhaltsstoff inklusive Wasser
2) Reiner Inhaltsstoff (frei von Wasser)
3) Trilon M fl.,
4) Dequest 2066
5) Hydrodis WP 40
6) Lutensol TO 7
7) Sokalan PA 25 CL gran.
8) Mirapol Surf S
9) Sokalan PA 30 CL (wässrige Lsg.)
K Komplexbildner/Dispergiermittel
H Hilfsstoff
T Tensid
XOH Alkalimetallhydroxid The total content of water is 36.5 wt .-%. During the manufacturing process, cooling took place so that the maximum temperature of 35 ° C was not exceeded. The viscosity of the suspension was: Viscosity (mPa · s): 4500 mPa · s, measured in accordance with ISO 2555: 1989 at 20 ° C and 5 rpm <b> Example 2: Inventive Example </ b> ingredient Proportion of raw material 1 [% by weight] Content of ingredient 2 [% by weight] function step Alanine N, N-carboxymethyl trisodium salt 3) in aqueous solution (40% by weight) 27.0 10.8 K a) Aminophosphonic acid salt 4) in aqueous solution (42% by weight) 10.0 4.2 K Monoethanolamine 2.2 2.2 H b) Polymeric phosphonic acid 5) ; Hydrochloric acid; in aqueous solution (60% by weight) 5.0 3.0 K c) Sodium hydroxide solution (50% by weight) 22.3 11.15 XOH d) Isotridecanol ethoxylate 6) 0.5 0.5 T e) potassium hydroxide 8.0 8.0 XOH f) Polyacrylic acid 9) , sodium salt (in aqueous solution, 55% by weight) 5.0 2.75 K G) Mixture based on sodium carbonate 8) ; without phosphates 1.0 1.0 H G) sodium hydroxide 19.0 19.0 XOH H) total 100 62.6 1) ingredient including water
2) Pure ingredient (free of water)
3) Trilon M fl.,
4) Dequest 2066
5) Hydrodis WP 40
6) Lutensol TO 7
7) Sokalan PA 25 CL gran.
8) Mirapol Surf S
9) Sokalan PA 30 CL (aqueous solution)
K complexing agent / dispersant
H adjuvant
T surfactant
XOH alkali metal hydroxide

Der Gesamtwassergehalt beträgt 37,4 Gew.-%. Beim Herstellungsprozess erfolgte eine Kühlung, sodass die maximale Temperatur 35°C nicht überschritten wurde. Die Viskosität der Suspension betrug: Viskosität (mPa·s) 6000 mPa·s, gemessen in Anlehnung an ISO 2555:1989 bei 20°C und 5 rpm Beispiel 3: Erfindungsgemäßes Beispiel Inhaltsstoff Anteil Rohstoff1 [Gew.-%] Anteil Inhaltsstoff2 [Gew.-%] Funktion Schritt Alanin N,N-Carboxymethyl-trisodiumsalz 3) in wässriger Lösung (40 Gew.-%) 27,0 10,8 K a) Aminophosphonsäuresalz 4) in wässriger Lösung (42 Gew.-%) 10,0 4,2 K Monoethanolamin 2,2 2,2 H b) Polymere Phosphonsäure 5); Salzsäure; in wässriger Lösung (60 Gew.-%) 5,0 3,0 K c) Natronlauge (50 Gew.-%) 22,3 11,15 XOH d) Isotridecanolethoxylat 6) 1,5 1,5 T e) Kaliumhydroxid 8,0 8 XOH f) Polyacrylsäure 9), Natriumsalz (in wässriger Lösung, 55 Gew.-%) 5,0 2,75 K g) Natriumhydroxid 19,0 19,0 XOH h) Gesamt 100 62,6 1) Inhaltsstoff inklusive Wasser
2) Reiner Inhaltsstoff (frei von Wasser)
3) Trilon M fl.,
4) Dequest 2066
5) Hydrodis WP 40
6) Lutensol TO 7
9) Sokalan PA 30 wässrige Lösung
8) Mirapol Surf S
K Komplexbildner
H Hilfsstoff
T Tensid
XOH Alkalimetallhydroxid The total water content is 37.4 wt .-%. During the manufacturing process, cooling took place so that the maximum temperature of 35 ° C was not exceeded. The viscosity of the suspension was: Viscosity (mPa · s) 6000 mPa · s, measured in accordance with ISO 2555: 1989 at 20 ° C and 5 rpm <b> Example 3: Inventive Example </ b> ingredient Proportion of raw material 1 [% by weight] Content of ingredient 2 [% by weight] function step Alanine N, N-carboxymethyl-trisodiumsalz 3) in aqueous solution (40 wt .-%) 27.0 10.8 K a) Aminophosphonic acid salt 4) in aqueous solution (42% by weight) 10.0 4.2 K Monoethanolamine 2.2 2.2 H b) Polymeric phosphonic acid 5) ; Hydrochloric acid; in aqueous solution (60% by weight) 5.0 3.0 K c) Sodium hydroxide solution (50% by weight) 22.3 11.15 XOH d) Isotridecanol ethoxylate 6) 1.5 1.5 T e) potassium hydroxide 8.0 8th XOH f) Polyacrylic acid 9) , sodium salt (in aqueous solution, 55% by weight) 5.0 2.75 K G) sodium hydroxide 19.0 19.0 XOH H) total 100 62.6 1) Ingredient including water
2) Pure ingredient (free of water)
3) Trilon M fl.,
4) Dequest 2066
5) Hydrodis WP 40
6) Lutensol TO 7
9) Sokalan PA 30 aqueous solution
8) Mirapol Surf S
K complexing agent
H adjuvant
T surfactant
XOH alkali metal hydroxide

Der Gesamtwassergehalt beträgt 37,4 Gew.-%. Beim Herstellungsprozess erfolgte eine Kühlung, sodass die maximale Temperatur 35°C nicht überschritten wurde. Die Viskosität der Suspension betrug: Viskosität (mPa·s) 3800 mPa·s, 20°C gemessen in Anlehnung an ISO 2555:1989 bei 20°C und 5 rpm Vergleichsbeispiel 1: Inhaltsstoff Anteil Rohstoff1 [Gew.-%] Anteil Inhaltsstoff2 [Gew.-%] Funktion Schritt Wasser 35,0 - LM 1 Polymere Phosphonsäure in wässriger Lösung (50 Gew.-%)3 10,0 5,0 K 2 Glycerin 5,0 5,0 K 3 Kaliumhydroxid 10,0 10,0 XOH 4 Polyacrylsäure, Natriumsalz4 20,0 20,0 K 5 Natriumhydroxid 20,0 20,0 XOH 6 Gesamt 100,0 60,0 1) Inhaltsstoff inklusive Wasser
2) Reiner Inhaltsstoff (frei von Wasser)
3) Hydrodis ADW 3814/N
4) Sokalan PA 25 CL gran.
K Komplexbildner
LM Lösungsmittel
XOH Alkalimetallhydroxid Der Gesamtgehalt an Wasser beträgt 40,0 Gew.-%.The total water content is 37.4 wt .-%. During the manufacturing process, cooling took place so that the maximum temperature of 35 ° C was not exceeded. The viscosity of the suspension was: Viscosity (mPa · s) 3800 mPa · s, 20 ° C measured on the basis of ISO 2555: 1989 at 20 ° C and 5 rpm <b> Comparative Example 1: </ b> ingredient Proportion of raw material 1 [% by weight] Content of ingredient 2 [% by weight] function step water 35.0 - LM 1 Polymeric phosphonic acid in aqueous solution (50% by weight) 3 10.0 5.0 K 2 glycerin 5.0 5.0 K 3 potassium hydroxide 10.0 10.0 XOH 4 Polyacrylic acid, sodium salt 4 20.0 20.0 K 5 sodium hydroxide 20.0 20.0 XOH 6 total 100.0 60.0 1) Ingredient including water
2) Pure ingredient (free of water)
3) Hydrodis ADW 3814 / N
4) Sokalan PA 25 CL gran.
K complexing agent
LM solvent
XOH alkali metal hydroxide The total content of water is 40.0 wt .-%.

Beim Herstellen des Konzentrats von Vergleichsbeispiel 1 war keine Temperaturkontrolle vorgesehen. Beim Herstellungsprozess trat eine maximale Temperatur von 75°C auf. Bereits unmittelbar nach der Herstellung war das Konzentrat hochviskos; nach 24 Stunden war die Zusammensetzung gelartig. Das Vorhandensein von Glycerin dürfte sich für die Stabilität der Viskosität als negativ erweisen. Vergleichsbeispiel 2: Inhaltsstoff Anteil Rohstoff1 [Gew.-%] Anteil Inhaltsstoff2 [Gew.-%] Funktion Schritt Alanin N,N-Carboxymethyl-trisodiumsalz 3) in wässriger Lösung (40 Gew.-%) 27,7 11,1 K a) Aminophosphonsäuresalz 4) in wässriger Lösung (42 Gew.-%) 10 4,2 K Monoethanolamin 2,2 2,2 H b) Polymere Phosphonsäure 5); Salzsäure; in wässriger Lösung (60 Gew.-%) 5 3 K c) Natronlauge (50 Gew.-%) 22 11,0 XOH d) Gemisch auf Basis von Natriumcarbonat 6); ohne Phosphate 0,8 0,8 H e) Kaliumhydroxid 7,5 7,5 XOH f) Polyacrylsäure 7), Natriumsalz 5,8 5,8 K g) Natriumhydroxid 19 19,0 XOH h) Gesamt 100 64,6 1) Inhaltsstoff inklusive Wasser
2) Reiner Inhaltsstoff (frei von Wasser)
3) Trilon M fl.,
4) Dequest 2066
5) Hydrodis WP 40
6) Mirapol Surf S
7) Sokalan PA 25 CL gran.
K Komplexbildner
H Hilfsstoff
XOH Alkalimetallhydroxid Gesamtgehalt Wasser: 35,4 Gew.-%.When preparing the concentrate of Comparative Example 1, no temperature control was provided. During the manufacturing process, a maximum temperature of 75 ° C occurred. Immediately after production, the concentrate was highly viscous; after 24 hours, the composition was gelatinous. The presence of glycerol should prove negative for viscosity stability. <b> Comparative Example 2: </ b> ingredient Proportion of raw material 1 [% by weight] Content of ingredient 2 [% by weight] function step Alanine N, N-carboxymethyl-trisodiumsalz 3) in aqueous solution (40 wt .-%) 27.7 11.1 K a) Aminophosphonic acid salt 4) in aqueous solution (42% by weight) 10 4.2 K Monoethanolamine 2.2 2.2 H b) Polymeric phosphonic acid 5) ; Hydrochloric acid; in aqueous solution (60% by weight) 5 3 K c) Sodium hydroxide solution (50% by weight) 22 11.0 XOH d) Mixture based on sodium carbonate 6) ; without phosphates 0.8 0.8 H e) potassium hydroxide 7.5 7.5 XOH f) Polyacrylic acid 7) , sodium salt 5.8 5.8 K G) sodium hydroxide 19 19.0 XOH H) total 100 64.6 1) Ingredient including water
2) Pure ingredient (free of water)
3) Trilon M fl.,
4) Dequest 2066
5) Hydrodis WP 40
6) Mirapol Surf S
7) Sokalan PA 25 CL gran.
K complexing agent
H adjuvant
XOH alkali metal hydroxide Total content of water: 35.4% by weight.

Die Zubereitung ist frei von Tensiden. Die Rezeptur erwies sich ohne Temperaturkontrolle bei der Herstellung als zu viskos. Mit Temperaturkontrolle beim Herstellungsverfahren (max. Temperatur von 35°C) war die Viskosität der Suspension noch im Bereich 6500 mPa·s. Das vollständige Fehlen von Tensiden erwies sich für die Viskosität allerdings als negativ. Eine Beimengung von 0,5 Gew.-% zeigte eine Verringerung der Viskosität und Erhöhung der Stabilität.The preparation is free of surfactants. The recipe proved to be too viscous in the production without temperature control. With temperature control in the production process (maximum temperature of 35 ° C), the viscosity of the suspension was still in the range 6500 mPa · s. The complete absence of surfactants, however, proved to be negative for the viscosity. An addition of 0.5% by weight showed a reduction in viscosity and increase in stability.

Eine Reduktion des Wassergehalts in Reinigungskonzentraten auf Wasserbasis führt meist zu einer Steigerung der Viskosität. In DE 100 02 710 A1 ist ein cremeförmiges Reinigungskonzentrat mit einem Wasseranteil von 32,5% beschrieben. Die Eigenschaft als Creme oder Paste ist allerdings auf Grund der hohen Viskosität für den Einsatz in Dosierautomaten ungünstig. Ein solches Reinigungsmittel konnte mit einer Schlauchquetschpumpe in der Dosiereinheit nicht dosiert werden.A reduction of the water content in water-based cleaning concentrates usually leads to an increase in the viscosity. In DE 100 02 710 A1 is described a cream-shaped cleaning concentrate with a water content of 32.5%. The property as a cream or paste is, however, unfavorable for use in dosing machines due to the high viscosity. Such a cleaning agent could not be dosed with a peristaltic pump in the dosing unit.

Ein nach dem erfindungsgemäßen Verfahren hergestelltes Reinigungskonzentrat weist zu den creme- oder pastenförmigen Reinigungsmitteln gemäß DE 100 02 710 A1 zwei Unterschiede auf: Erstens wird in DE 100 02 710 A1 eine homogene Mischung ohne Partikel, d.h. keine Suspension hergestellt. Zweitens weist das Reinigungskonzentrat von DE 100 02 710 A1 eine erheblich höhere Viskosität auf, was in der schlechten Dosierbarkeit resultiert.A cleaning concentrate prepared by the process according to the invention has the cream or paste-like cleaning agents according to DE 100 02 710 A1 two differences: first, in DE 100 02 710 A1 a homogeneous mixture without particles, ie no suspension produced. Second, the cleaning concentrate of DE 100 02 710 A1 a significantly higher viscosity, resulting in the poor dosability.

In der nachfolgenden Tabelle 1 sind ein erfindungsgemäßes Reinigungskonzentrat und das Reinigungskonzentrat gemäß DE 100 02 710 A1 gegenübergestellt. Tabelle 1: Vergleich der Viskosität von Reinigungskonzentraten: Zusammensetzung Beispiel 1 Beispiel von DE 100 02 710 A1 Viskosität (mPa·s)* 2671 +/-35 20 000 bis 90 000 (Suspension) (Cremeförmige Paste) *) Messbedingungen wie in DE 100 02 710 A1 : Brookfield Viskosimeter in Anlehnung an ISO 2555:1989.Table 1 below shows a cleaning concentrate according to the invention and the cleaning concentrate according to DE 100 02 710 A1 compared. Table 1: Comparison of the viscosity of cleaning concentrates: Composition Example 1 Example of DE 100 02 710 A1 Viscosity (mPa · s) * 2671 +/- 35 20,000 to 90,000 (Suspension) (Creamy paste) *) Measuring conditions as in DE 100 02 710 A1 : Brookfield viscometer based on ISO 2555: 1989.

Die Einzelmessergebnisse für Beispiel 1 lauteten: Ergebnis Beispiel 1 Viskosität, mPa· s Messung 1 2651 Messung 2 2711 Messung 3 2651 The individual measurement results for Example 1 were: Result Example 1 Viscosity, mPa · s Measurement 1 2651 Measurement 2 2711 Measurement 3 2651

Die Zusammensetzung gemäß Beispiel 3 wurde zusätzlich unter unterschiedlichen Bedingungen, d.h. bei unterschiedlichen Temperaturen hergestellt. Die Zugabeschritte d) bis h) erfolgten so, dass in der wässrigen Phase eine Temperatur von bei 40°C nicht überschritten wurde (siehe Tabelle 2). Tabelle 2: Vergleich der Viskosität - Zusammensetzung gemäß Beispiel 3. Ergebnisse: Viskosität (mPa·s) bei 5 rpm, 20°C* Probe 1 2184 Probe 2 6360 Probe 3 2400 Probe 4 3030 *) Messbedingungen: Brookfield Viskosimeter in Anlehnung an ISO 2555:1989. The composition according to Example 3 was additionally prepared under different conditions, ie at different temperatures. The addition steps d) to h) were carried out in such a way that a temperature of 40 ° C. was not exceeded in the aqueous phase (see Table 2). Table 2: Comparison of the viscosity - composition according to Example 3. Results: Viscosity (mPa · s) at 5 rpm, 20 ° C * Sample 1 2184 Sample 2 6360 Sample 3 2400 Sample 4 3030 *) Measurement conditions: Brookfield viscometer in accordance with ISO 2555: 1989th

Bei den Proben 1, 3 und 4 trat eine maximale Temperatur von 35 °C auf, bei Probe 2 trat kurzfristig eine Temperatur von 40°C auf. Die Messwerte korrelieren mit der maximal aufgetretenen Temperatur, d.h. bei Probe 1 traten die niedrigsten Temperaturen auf, bei Probe 2 die höchsten.For samples 1, 3 and 4, a maximum temperature of 35 ° C occurred in sample 2, a short-term temperature of 40 ° C occurred. The measurements correlate with the maximum occurring temperature, i. Sample 1 had the lowest temperatures, and Sample 2 the highest.

Claims (10)

  1. A detergent concentrate comprising
    (i) 22 to 46 % by weight alkaline metal hydroxide,
    (ii) 5 to 50 % by weight dispersing agent, chelating agent or a combination thereof,
    (iii) 0 to 5 % by weight tenside,
    (iv) 0 to 5 % by weight excipients and
    (v) 28 to 39 % by weight water,
    wherein the detergent concentrate is a suspension.
  2. A detergent concentrate according to claim 1, characterized by a viscosity of the suspension of at the most 6500 mPa·s, measured according to ISO 2555:1989 at 20°C at a rotational speed of 5 rpm.
  3. A detergent concentrate according to claim 1 or 2, characterized in that the alkaline metal hydroxide is sodium hydroxide, potassium hydroxide or a mixture thereof.
  4. A detergent concentrate according to claim 3, characterized by
    - 20 to 41 % by weight sodium hydroxide and
    - 5 to 10 % by weight potassium hydroxide.
  5. A detergent concentrate according to any of claims 1 to 4, characterized in that the dispersing agent comprises at least a chelating agent and polymeric dispersing agent.
  6. A liquid detergent concentrate according to claim 5, characterized by
    - 5 to 49 % by weight chelating agent and
    - 1 to 10 % by weight polymeric dispersing agent.
  7. A liquid detergent concentrate according to claim 5 or 6, characterized in that the chelating agent has an organic amino function, preferably selected from the group including amino carboxylic acids, amino phosphonic acids or combinations thereof.
  8. A liquid detergent concentrate according to claim 4 to 7, characterized in that the polymeric dispersing agent is a polycarboxylic acid, preferably a polyacrylic acid or a derivative thereof.
  9. A liquid detergent concentrate according to claim 1 to 8, characterized in that the excipient is monoethanol amine.
  10. A method for producing a suspension, comprising
    (i) 22 to 46 % by weight alkaline metal hydroxide,
    (ii) 5 to 50 % by weight dispersing agent, chelating agent or a combination thereof,
    (iii) 0 to 5 % by weight tenside,
    (iv) 0 to 5 % by weight excipients and
    (v) 28 to 39 % by weight water,
    wherein the method comprises the following steps:
    a) providing a portion of a dispersing agent, chelating agent or a combination thereof in an aqueous solution,
    b) optionally adding excipients,
    c) in the case of the addition of excipients, subsequently adding a further portion of a dispersing agent,
    d) adding a portion of an alkaline metal hydroxide as an aqueous solution,
    e) optionally adding a tenside,
    f) adding a portion of an alkaline metal hydroxide as a solid,
    g) adding a dispersing agent,
    h) adding a further portion of an alkaline metal hydroxide,
    wherein the steps of adding are carried out while stirring and wherein at least the addition steps d) to h) are carried out such that in the aqueous phase there is maintained a temperature of at the most 40 °C, preferably at the most 35 °C.
EP15190193.1A 2015-10-16 2015-10-16 Liquid cleaning concentrate Active EP3156475B2 (en)

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ES15190193.1T ES2685655T3 (en) 2015-10-16 2015-10-16 Liquid cleaning concentrate
FIEP15190193.1T FI3156475T4 (en) 2015-10-16 2015-10-16 Liquid cleaning concentrate
SI201530378T SI3156475T1 (en) 2015-10-16 2015-10-16 Liquid cleaning concentrate
TR2018/12405T TR201812405T4 (en) 2015-10-16 2015-10-16 Liquid detergent concentrate.
HUE15190193A HUE038978T2 (en) 2015-10-16 2015-10-16 Liquid cleaning concentrate
EP15190193.1A EP3156475B2 (en) 2015-10-16 2015-10-16 Liquid cleaning concentrate
PL15190193T PL3156475T3 (en) 2015-10-16 2015-10-16 Liquid cleaning concentrate
PT15190193T PT3156475T (en) 2015-10-16 2015-10-16 Liquid cleaning concentrate
RS20181018A RS57613B1 (en) 2015-10-16 2015-10-16 Liquid cleaning concentrate
EA201890976A EA201890976A1 (en) 2015-10-16 2016-10-14 LIQUID WASHING CONCENTRATE
MX2018004608A MX2018004608A (en) 2015-10-16 2016-10-14 Liquid cleaning concentrate.
CN201680060556.7A CN108350398B (en) 2015-10-16 2016-10-14 Liquid detergent concentrate
BR112018007204-4A BR112018007204B1 (en) 2015-10-16 2016-10-14 LIQUID CLEANING CONCENTRATE, AND PROCESS FOR PRODUCTION OF A SUSPENSION
AU2016336915A AU2016336915B2 (en) 2015-10-16 2016-10-14 Liquid cleaning concentrate
PCT/EP2016/074744 WO2017064266A1 (en) 2015-10-16 2016-10-14 Liquid cleaning concentrate
US15/768,770 US20180305643A1 (en) 2015-10-16 2016-10-14 Liquid cleaning concentrate
CA3001652A CA3001652C (en) 2015-10-16 2016-10-14 Liquid detergent concentrate
CL2018000964A CL2018000964A1 (en) 2015-10-16 2018-04-13 Concentrated liquid detergent
SA518391361A SA518391361B1 (en) 2015-10-16 2018-04-15 Liquid Detergent Concentrate
IL258739A IL258739B (en) 2015-10-16 2018-04-16 Liquid cleaning concentrate
CONC2018/0004021A CO2018004021A2 (en) 2015-10-16 2018-04-16 Concentrated liquid cleaner
HRP20181256TT HRP20181256T1 (en) 2015-10-16 2018-08-06 Liquid cleaning concentrate
US18/200,401 US20230313071A1 (en) 2015-10-16 2023-05-22 Liquid detergent concentrate

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