[go: up one dir, main page]

WO2017013161A1 - Produit pour lave-vaisselle multiphase à noyau tensioactif - Google Patents

Produit pour lave-vaisselle multiphase à noyau tensioactif Download PDF

Info

Publication number
WO2017013161A1
WO2017013161A1 PCT/EP2016/067265 EP2016067265W WO2017013161A1 WO 2017013161 A1 WO2017013161 A1 WO 2017013161A1 EP 2016067265 W EP2016067265 W EP 2016067265W WO 2017013161 A1 WO2017013161 A1 WO 2017013161A1
Authority
WO
WIPO (PCT)
Prior art keywords
phase
dishwashing detergent
acid
nonionic surfactants
branched
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2016/067265
Other languages
German (de)
English (en)
Inventor
Inga Kerstin Vockenroth
David MATULLA
Oliver Kurth
Volker Blank
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=56464213&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2017013161(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL16741024T priority Critical patent/PL3325591T3/pl
Priority to EP16741024.0A priority patent/EP3325591B1/fr
Publication of WO2017013161A1 publication Critical patent/WO2017013161A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • a multi-phase dishwashing detergent comprising a surfactant core
  • the present invention relates to a solid, multi-phase dishwashing detergent comprising at least two phases and the use of such a dishwashing detergent and a method for cleaning dishes using such a dishwashing detergent.
  • Dishwasher sump / filter Dishwasher sump / filter.
  • Powder phases in particular consisting of Geschirr mecanictabs, do not meet the aesthetic requirements of customers.
  • Surfactant melt in the form of a surfactant core which is inserted into a core well of a pressed powder dishwashing tablet, results in a visually appealing tablet.
  • the present invention is directed to a dishwashing detergent comprising at least a first solid, compacted phase and at least one second phase, characterized in that the at least one second phase is a surfactant melt comprising 10-100 wt%, preferably 20-100%, more preferably 50-100 wt% surfactant (s), preferably nonionic surfactant (s) ).
  • the present invention is directed to the use of a dishwashing detergent according to the invention for machine dishwashing.
  • the present invention is directed to a method for machine cleaning of dishes, characterized in that in at least one method step, a dishwashing agent according to the invention is applied.
  • a dishwashing detergent is to be understood as meaning all agents which are suitable for washing or cleaning hard surfaces, in particular crockery.
  • Other suitable ingredients are described in detail below.
  • At least one refers to 1 or more, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.
  • the dishwashing agent according to the invention comprises at least two phases, wherein the first phase is solid and compacted and the second phase is a surfactant melt.
  • the term "melt” refers to a composition liquefied under the influence of elevated temperatures (for example> 50 ° C. or> 60 ° C.), which solidifies again on cooling to room temperature and forms a solid form.
  • a phase in the sense of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous.
  • a phase is different from another phase by different features, for example, ingredients, physical properties, appearance, etc.
  • different phases can be visually distinguished.
  • the at least one first phase is clearly distinguishable from the at least one second phase. If the washing or cleaning agent according to the invention has more than one first phase, then these can likewise be distinguished from one another by the naked eye, because they can be found, for example, in the
  • Coloring differ from each other.
  • a visual differentiation of the phases for example due to a color or transparency difference is possible.
  • Phases in the sense of the present invention are thus self-contained areas that can be optically distinguished from the consumer by the naked eye.
  • the individual phases may have different properties in use, such as the rate at which the phase dissolves in water and thus the rate and order of release of the ingredients contained in the respective phase.
  • the phases are typically spatially separated. This can be done in various embodiments such that when one or both of the phases are liquid phases, the liquid phase is separate from the other phase in a separate, sealed area, for example the chamber of a pouch.
  • Such Kon Stammionsformen are known in the art.
  • solid agents i. Means in which both phases
  • the two phases are also made up spatially separated from each other, for example in the form of a multi-chamber pouches, each of the phases is present in a separate chamber.
  • the two phases may be arranged directly adjacent to each other spatially in such a way that the phases are formulated separately and contact each other, but can not mix.
  • the dishwashing detergent according to the invention comprises at least two different phases. Both the at least one first phase and the at least one second phase are described below. In the event that the dishwashing detergent according to the invention has more than two phases, each further phase corresponds in each case either to the at least one first phase, as defined herein, or to the at least one second phase, as defined herein. In this case, the compositions of the respectively corresponding phases may differ to the extent permitted by the respective definitions given below of both the at least one first phase and the at least one second phase. For example, it may be a three-phase dishwashing detergent that has two phases the first phase as defined herein and having a phase corresponding to the second phase as defined herein.
  • the at least one second phase of the dishwashing agent is a surfactant melt which is from 10 to 100% by weight, preferably
  • surfactant 20-100 wt .-%, more preferably 50-100 wt .-% of surfactant (s), in particular
  • surfactant melt nonionic surfactant (s).
  • surfactant melt phase surfactant melt phase
  • Nonionic surfactants which can be used in this at least one surfactant melt phase are all nonionic surfactants known to the person skilled in the art. In preferred
  • nonionic surfactants from the group of alkoxylated alcohols.
  • a class of preferably usable nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants as constituent of the surfactant melt are accordingly alkoxylated (preferably ethoxylated or ethoxylated and propoxylated) fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain ,
  • Non-end-capped, poly (oxyalkylated) nonionic surfactants according to the formula R 0 [CH 2 CH 2 O] x H are preferred in this context, where R is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably 4 to 22 carbon atoms Carbon atoms, and x stands for values between 1 and 80, preferably for values between 15 and 50 and in particular for values between 25 and 50. Very particular preference is given to fatty alcohol ethoxylates in which R is a linear or branched C 12-20 alkyl radical, in particular a linear or branched C 16-18 alkyl radical.
  • end-capped, poly (oxyalkylated) nonionic surfactants of the surfactant melt phase in amounts of 5-100, preferably from 5-50 wt .-%, preferably 10-30 wt .-%, based on the
  • the above-described non-end-capped, poly (oxyalkylated) nonionic surfactants of the surfactant melt phase are combined with another surfactant from the group of end-capped, poly (oxyalkylated) nonionic surfactants.
  • Hydrocarbon radicals having 2 to 30 carbon atoms, preferably 4 to 22
  • Carbon atoms further having linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals R 2 having 1 to 30 carbon atoms, wherein x stands for values between 1 and 80, preferably for values between 15 and 50 and in particular for values between 25 and 50 , Very particularly preferred are
  • R is a linear or branched C 12-20 alkyl radical, in particular a linear or branched C 16-18 alkyl radical
  • / or R 2 is a linear or branched C 6-22 alkyl radical, in particular a linear or branched C 8- 10 alkyl radical.
  • the end-capped, poly (oxyalkylated) nonionic surfactants of the surfactant melt phase described above are used in amounts of 5-60% by weight, preferably 40-60% by weight, based on the surfactant melt phase.
  • the mass ratio between the end capped nonionic surfactants described above and the non end capped nonionic surfactants in the surfactant melt phase is from 20: 1 to 1: 5, preferably from 10: 1 to 1: 1. In particularly preferred embodiments, the ratio is 3 : 1 to 2: 1.
  • nonionic surfactants used in the surfactant melt phase have a melting point above room temperature.
  • the surfactant melt phase may contain other ingredients.
  • such ingredients include, for example, polyethylene glycols (PEG).
  • PEG polyethylene glycols
  • the at least one first phase of the dishwashing agent according to the invention is a solid, compacted phase, typically a pressed powder phase.
  • This at least one first phase of the dishwashing agent according to the invention usually contains at least one surfactant, preferably at least one nonionic surfactant. Suitable surfactants are described below.
  • Suitable nonionic surfactants of the first phase are, for example, alkyl glycosides of the general formula RO (G) x in which R corresponds to a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1, 2 to 1, 4.
  • nonionic surfactants that can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants in the first phase of the dishwashing detergent are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • low-foaming nonionic surfactants are preferably used in the first phase, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.
  • the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols.
  • a class of useful nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants are accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • Preferably used surfactants come from the groups of ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as
  • Polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are characterized by good foam control.
  • Suitable nonionic surfactants are those which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -Chta, -CH 2 CH 3, -CH 2 CH 2 -CH 3, CH (CH 3) 2 and the indices w, x, y, z independently represent integers from 1 to 6.
  • nonionic surfactants having a C9-alkyl group with 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units, followed by 1 to 4
  • Preferred nonionic surfactants here are those of the general formula
  • R is -CH (OH) CH 2 O- (AO) w- (A'0) x- (A "0) y - (A '" 0) z R 2 in which
  • R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical
  • R 2 is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A, ⁇ ', A "and A'" independently of one another are radicals from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 - CH (CH 3 ) -CH 2 -, - CH 2 -CH (CH 2 -CH 3 ),
  • w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
  • Hydrocarbon radicals having 2 to 30 carbon atoms, preferably 4 to 22
  • Carbon atoms furthermore a linear or branched, saturated or
  • x stands for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
  • surfactants of the formula R 0 [CH 2 CH (CH 3) O] x [CH 2 CH 2 O] yCH 2 CH (OH) R 2 in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear one or branched
  • Hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15 stands.
  • nonionic surfactants include, for example, the C2-26 fatty alcohol (PO) i- (EO) is-4o-2-hydroxyalkyl ethers, in particular the coco fatty alcohol (PO) i (EO) 22-2-hydroxydecyl ethers , Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH 2 CH 2 O] x [CH 2 CH (R 3 ) O] y CH 2 CH (OH) R 2 in which R and R 2 independently of one another are linear or branched , saturated or single or multiple
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] jOR 2 where R and R 2 are linear or branched , saturated or unsaturated, aliphatic or aromatic
  • Hydrocarbon radicals having 1 to 30 carbon atoms R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is Values between 1 and 30, k and j represent values between 1 and 12, preferably between 1 and 5.
  • k and j represent values between 1 and 12, preferably between 1 and 5.
  • R and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22
  • Carbon atoms, with radicals having 8 to 18 carbon atoms are particularly preferred.
  • R 3 is H, -Chta or -CH 2 CH 3 particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x> 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • R 1 RO [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 simplified.
  • R 1 R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R and R 2 Have 9 to 14 carbon atoms, R 3 is H and x assumes values of 6 to 15.
  • nonionic surfactants of the general formula R -CH (OH) CH 2 O- (AO) w -R 2 have proved to be particularly effective, in which
  • R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A is a radical from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH (CH 3 ), preferably CH 2 CH 2 , and
  • w stands for values between 1 and 120, preferably 10 to 80, in particular 15 to 50.
  • nonionic surfactants include, for example, the C4-22 fatty alcohol (EO) io-so-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o 8o-2-hydroxyalkyl ethers.
  • Degradation levels of nonionic surfactants represent statistical averages which may be an integer or a fractional number for a particular product. Due to the
  • Herste II method exist commercial products of the formulas mentioned mostly not from an individual representative, but from mixtures, which may result in both the C chain lengths and for the Ethoxyl michsgrade or degrees of alkoxylation averages and resulting broken numbers.
  • nonionic surfactants can not only be used as
  • dishwashing compositions described herein which comprise in the at least one first phase at least one surfactant, preferably a nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, contain the surfactant in various aspects
  • Embodiments in an amount based on the total weight of the composition of at least 2% by weight, preferably at least 5% by weight.
  • the amounts used per application may be in the range of 0.5-10 g / job, preferably in the range of 0.5-5 g / job.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which are solid at room temperature.
  • the first phase may also contain the surfactants described above in connection with the second phase, in particular the described optionally end-group-capped fatty alcohol ethoxylates.
  • the first phase of the dishwashing detergent according to the invention may also contain surfactants from the group of anionic, cationic and amphoteric surfactants.
  • Suitable anionic surfactants in dishwashing detergents are all anionic surfactants. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule.
  • Suitable anionic surfactants are preferably present in the form of the sodium, potassium and ammonium as well as mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group, but also zinc, manganese (II), magnesium, calcium or Mixtures of these can serve as counterions.
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and
  • Ethercarbon yarn having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.
  • cationic and / or amphoteric surfactants such as betaines or quaternary ammonium compounds.
  • the dishwashing detergent in the at least one first phase may contain further ingredients which further improve the performance and / or aesthetic properties of the dishwashing detergent.
  • the dishwashing detergent in various embodiments contains at least one or preferably several substances from the group of builders, polymers, bleaching agents, bleach activators,
  • Bleaching catalysts enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, glass corrosion inhibitors, foam inhibitors, dyes, additives for improving the drainage and drying behavior, disintegrants, preservatives, pH adjusters, fragrances and perfume carriers.
  • builders such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builders, may be advantageous.
  • phosphates including polyphosphates
  • the agent in this embodiment preferably contains less than 5% by weight, more preferably less than 3% by weight, in particular less than 1% by weight of phosphate (s).
  • the agent in this embodiment is completely phosphate-free, ie the agents contain less than 0.1% by weight of phosphate (s).
  • the builders include in particular carbonates, citrates, phosphonates,
  • Total weight of compositions according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight.
  • Suitable organic builders according to the invention are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean carboxylic acids which have more than one, in particular two to eight, acid functions, preferably two to six, in particular two, three, four or five
  • Preferred polycarboxylic acids are thus dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids.
  • the polycarboxylic acids may carry further functional groups, such as hydroxyl or amino groups.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and
  • Glucaric acid aminocarboxylic acids, especially aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as nitrilotriacetic acid (NTA), glutamine-N, N-diacetic acid (also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA),
  • NTA nitrilotriacetic acid
  • glutamine-N glutamine-N
  • N-diacetic acid also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA
  • Methylglycinediacetic acid (MGDA)) and their derivatives and mixtures thereof.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures thereof.
  • polymeric polycarboxylates organic polymers having a multiplicity of (in particular greater than 10) carboxylate functions in the
  • Macromolecule Polyaspartates, polyacetals and dextrins.
  • the free acids also typically have the property of an acidifying component and can therefore, if desired, also be used to adjust a lower acidity pH value serve.
  • an acidifying component can therefore, if desired, also be used to adjust a lower acidity pH value serve.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • Particularly preferred cleaning agents according to the invention in particular dishwashing agents, preferably automatic dishwasher detergents, contain one or more salts of citric acid, ie citrates, as one of their essential builders. These are preferably in a proportion of 2 to 40 wt .-%, in particular from 5 to 30 wt .-%, particularly from 7 to 28 wt .-%, particularly preferably 10 to 25 wt .-%, most preferably 15 to Contain 20 wt .-%, each based on the total weight of the composition.
  • dishwashing detergents preferably automatic dishwashing detergents
  • dishwashing detergents are characterized in that they comprise at least two builders from the group of silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, the weight fraction of these builders, based on the total weight of the inventive detergent, preferably 5 to 70 wt .-%, preferably 15 to 60 wt .-% and in particular 20 to 50 wt .-% is.
  • the combination of two or more builders from the above-mentioned group has proven to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents.
  • one or more other builders may additionally be present.
  • Preferred cleaning agents in particular dishwashing agents, preferably mechanical
  • Dishwashing detergents are characterized by a builder combination of citrate and carbonate and / or bicarbonate.
  • a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular from 10 to 35% by weight, very particularly preferably from 15 to 30% by weight. and the amount of citrate is preferably from 5 to 35 wt .-%, in particular 10 to 25 wt .-%, most preferably 15 to 20 wt .-%, each based on the total amount of the cleaning agent, wherein the total amount of these two Builders preferably 20 to 65% by weight, in particular 25 to 60 wt .-%, preferably 30 to 50 wt .-%, is. In addition, one or more further builders may additionally be included.
  • the detergents according to the invention in particular dishwashing detergents, preferably automatic dishwashing detergents, may in particular contain phosphonates as further builder.
  • the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
  • the hydroxyalkane phosphonates the 1-hydroxyethane-1, 1-diphosphonate (HEDP) is of particular importance.
  • Aminoalkanphosphonate are preferably
  • Ethylenediamine tetramethylene phosphonate Ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs in question.
  • Phosphonates are preferably present in compositions according to the invention in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.5 to 8% by weight, very particularly preferably from 2.5 to 7.5% by weight, in each case based on the
  • citrate particularly preferred is the combined use of citrate, (hydrogen) carbonate and phosphonate. These can be used in the above quantities. In particular, in this combination amounts of, in each case based on the total weight of the composition, 10 to 25 wt .-% citrate, 10 to 30 wt .-% carbonate (or bicarbonate), and 2.5 to 7.5 wt .-%
  • dishwashing agents preferably automatic dishwashing detergents
  • dishwashing agents are characterized in that they contain citrate and
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid diacetate
  • ASDA aspartic diacetic acid
  • HEIDA Hydroxyethyliminodiacetate
  • IDS iminodisuccinate
  • EDDS ethylenediamine disuccinate
  • a particularly preferred combination is, for example, citrate, (hydrogen) carbonate and MGDA and optionally phosphonate.
  • the percentage by weight of the further phosphorus-free builder, in particular of the MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25% by weight.
  • Particularly preferred is the use of MGDA or GLDA, in particular MGDA, as granules.
  • MGDA granules which contain as little water as possible and / or a lower hygroscopicity compared to the non-granulated powder
  • organic builders polymeric polycarboxylates are also suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid,
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • the content of the cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwashing agents, of (homo) polymeric polycarboxylates is preferably 0.5 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight.
  • Cleaning agents according to the invention can be used as builder also crystalline layered silicates of general formula NaMSix02x + i ⁇ y H2O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1, 9 to 4, with particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferably delayed in dissolution and
  • the content of silicates is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight ,
  • the washing or cleaning agents according to the invention may furthermore comprise alkali metal hydroxides.
  • alkali carriers are preferably present only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably in the detergents or cleaners and in particular in the second phases 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the washing or cleaning agent used.
  • Alternative cleaning agents according to the invention are free of alkali metal hydroxides.
  • the at least one first phase of the dishwashing detergent described herein may further contain various polymers.
  • homopolymers of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids can be used according to the invention.
  • unsaturated carboxylic acids ⁇ , ⁇ -ethylenically unsaturated carboxylic acids
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid,
  • Methylenmalonic acid sorbic acid, cinnamic acid or mixtures thereof.
  • acrylic acid very particular preference is given to acrylic acid.
  • the homopolymer is therefore a polyacrylic acid.
  • the carboxylic acid groups may be wholly or partially in neutralized form, i. in that the acidic carbon atom of the carboxylic acid group in some or all of the carboxylic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or completely neutralized polymers is preferred according to the invention.
  • the molecular weight of the homopolymers used can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred dishwashing detergents are characterized in that the homopolymers, in particular the polyacrylic acids, have molar masses M n of from 1000 to 20 000 g / mol. Because of their superior solubility can be This group in turn, the short-chain polyacrylates, the molecular weights of 1 100 to 10,000 g / mol, and more preferably from 1200 to 5000 g / mol, preferably be.
  • the agents further comprise at least one sulfopolymer.
  • the polymers which can be used in this context are, in particular, copolymers which may have two, three, four or more different monomer units, where at least one monomer unit carries a sulfonic acid group.
  • Preferred copolymers contain, in addition to sulfonic acid-containing (s) monomer (s) at least one monomer from the group of unsaturated carboxylic acids.
  • unsaturated carboxylic acid As the unsaturated carboxylic acid (s), the above-described unsaturated carboxylic acids are / are used with particular preference. Acrylic acid is very particularly preferred.
  • R 5 (R 6 ) C C (R 7 ) -X-SO 3 H in which R 5 to R 7, independently of one another, is -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with alkyl or alkenyl radicals substituted by -NH 2 , -OH or -COOH, or by -COOH or -COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1 propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2 - Propenl-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salts
  • the acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic and / or carboxylic acid group in some or all acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • the monomer distribution of the copolymers preferably used in the case of copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably in each case from 5 to 95% by weight, with the proportion of
  • Sulfonic acid group-containing monomers 50 to 90 wt .-% and the proportion of
  • the copolymers may contain other monomers, particularly unsaturated carboxylic acid ester group-containing monomers.
  • Particularly preferred unsaturated carboxylic acid esters are alkyl esters of monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid,
  • Crotonic acid a-phenyl-acrylic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • C1-8-alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate,
  • the molecular weight of the copolymers used can be varied in order to adapt the properties of the polymers to the desired use.
  • Preferred dishwashing detergents are characterized in that the copolymers have molecular weights M n of 2000 to 200,000 g / mol, preferably from 4000 to 25,000 g / mol and in particular from 5000 to 15,000 g / mol.
  • the above-described homopolymers and copolymers may each be used in amounts of from 0.5 to 10% by weight, preferably from 1 to 5% by weight, based on the total weight of the composition. Absolute amounts are typically in the range of 0.1 to 2 g / job, preferably in the range of 0.2 to 1.0 g / job.
  • the mass ratio of the polymers to each other, i. Homopolymer to copolymer is in various embodiments, 5: 1 to 1: 5, preferably 2: 1 to 1: 2.
  • the dishwashing agents may alternatively or additionally contain other polymers.
  • Suitable polymers include, in particular, the cleaning-active amphoteric, zwitterionic or cationic polymers, for example the rinse aid polymers and / or polymers which act as softeners.
  • Preferred usable amphoteric polymers are from the group of
  • Alkylacrylamide / acrylic acid copolymers the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers , the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.
  • Further usable zwitterionic polymers are from the group of acrylamidoalkyl trialkyl ammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the Methacroylethylbetain / methacrylate copolymers.
  • Applicable cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and
  • Methacrylic acid and its esters and amides the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, the vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, the quaternized polyvinyl alcohols or among the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 indicated polymers.
  • amphoteric, zwitterionic or cationic polymers are present in prefabricated form.
  • Coating compositions preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;
  • Support materials from the group of washing or cleaning-active substances particularly preferably from the group of builders (builders) or cobuilders.
  • dishwashing agents according to the invention in the first phase preferably contain one or more enzyme (s).
  • enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof.
  • These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents, which are preferably used accordingly.
  • Detergents according to the invention preferably contain enzymes in total amounts of from 1 ⁇ 10 -6 % by weight to 5% by weight, based on active protein.
  • the protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens, from ⁇ . stearothermophilus, from Aspergillus niger and A. oryzae and the improved for use in detergents developments of the aforementioned amylases. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention.
  • lipases or cutinases in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, those originally from Humicola lanuginosa
  • Thermomyces lanuginosus available, or further developed lipases, especially those with the amino acid exchange in positions D96L, T213R and / or N233R, most preferably all of the exchanges D96L, T213R and N233R.
  • enzymes can be used which are termed hemicellulases
  • mannanases xanthan lyases
  • pectin lyases pectinases
  • pectin esterases pectate lyases
  • xyloglucanases xylanases
  • pullulanases and ⁇ -glucanases.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • oxidases oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • organic, more preferably aromatic, enzyme-interacting compounds to enhance the activity of the respective oxidoreductases (enhancers) or to react at greatly varying redox potentials between the oxidizing enzymes and the
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for the first and / or second phase, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • a preferably natural polymer or in the form of capsules for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying poly
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and
  • detergents which, based in each case on their total weight, are from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.5 to 8% by weight, of the respective enzyme preparations contain.
  • the dishwashing detergent may further contain one or more enzyme stabilizer (s).
  • enzyme stabilizers include boron-containing compounds such as boric acid or boronic acids, and their salts and esters, polyols such as glycerol or 1, 2-ethylene glycol, sugars, sugar alcohols, lactic acid or antioxidants.
  • Dishwashing agents according to the invention contain in a preferred embodiment as further constituent at least one zinc salt as glass corrosion inhibitor.
  • the zinc salt may be an inorganic or organic zinc salt.
  • the zinc salt to be used according to the invention preferably has a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and especially above 5 g / l (all solubilities at 20 ° C water temperature).
  • the inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
  • the organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group Zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
  • zinc acetate is used as the zinc salt.
  • the zinc salt is preferably present in the detergent according to the invention in an amount of from 0.01% by weight to 5% by weight, more preferably in an amount of from 0.05% by weight to 3% by weight, in particular in an amount of 0, 1 wt .-% to 2 wt .-%, based on the
  • Salts especially the zinc salts
  • Polyethyleneimines such as those available under the name Lupasol® (BASF), preferably in an amount of 0 to 5 wt .-%, in particular 0.01 to 2 wt .-%, as
  • the at least one first phase of the dishwashing agent may further comprise a bleaching agent, in particular an oxygen bleaching agent and optionally a bleach activator and / or bleach catalyst. These are, if available, only included in the first phase.
  • Dishwashing agents according to the invention contain as preferred bleaching agents
  • Other useful bleaching agents are, for example
  • Peroxypyrophosphates citrate perhydrates and H2O2-yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or
  • Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Because of its good bleaching performance, sodium percarbonate is particularly preferred. A particularly preferred oxygen bleach is sodium percarbonate.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.
  • the bleach catalysts are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe-Cu and Ru ammine complexes are also known
  • Bleach catalysts usable With particular preference complexes of manganese in the oxidation state II, III, IV or IV are used, preferably one or more
  • ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN ) and / or 2-methyl-1, 4,7-triazacyclononane (Me / TACN).
  • bleach catalyst s
  • the pH of the dishwashing detergent can be adjusted by means of customary pH regulators, the pH value being chosen as a function of the desired intended use.
  • the pH is in a range of 5.5 to 1 1,
  • the pH adjusting agents are acids and / or alkalis, preferably alkalis.
  • Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.
  • mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the
  • Alkali metal hydroxides of which potassium hydroxide and especially sodium hydroxide is preferred.
  • volatile alkali for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule.
  • the alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
  • the inventive composition for adjusting and / or stabilizing the pH, the inventive
  • Dishwashing agents also contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%. Preference is given to buffer substances which are at the same time Complexing agents or even chelating agents (chelators, INCI chelating agents) are.
  • buffer substances are the citric acid or the citrates, in particular the sodium and potassium conduction rates, for example trisodium citrate 2H.sub.2O and tripotassium citrate.RTM.
  • perfume oils or perfumes within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • preservatives may be contained in the dishwashing detergent according to the invention. Suitable examples are preservatives from the groups of alcohols, aldehydes, antimicrobial acids and / or their salts, carboxylic acid esters, acid amides, phenols,
  • Phenol derivatives diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1, 2 Dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides.
  • Preferred antimicrobial active ingredients are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, Thymol, 2-benzyl-4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) N- (3,4-dichlorophenyl) urea, N, N '- (1, 10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis - (4-chlorophenyl) -3,12-diimino-2,4,1,1,1,3
  • particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.
  • disintegration aids so-called tablet disintegrants
  • tablet disintegrants or disintegrants excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients.
  • Desintegration aids may preferably be used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
  • the dishwashing detergent according to the invention consists of at least two phases, wherein the first phase is solid and compacted and the second phase consists of a surfactant melt.
  • the first phase is first prepared by methods known in the art in the form of a pressed powder phase. After preparation, the first phase preferably has a depression or the like, into which the second phase can be introduced as surfactant melt.
  • the melting temperature of the surfactant melt depends on the melting points of the particular components used. Subsequently, the liquid surfactant melt is hot in the designated well of the first solid phase of
  • the second phase hot liquid surfactant melt may also be preformed in any other suitable form as desired to be subsequently adhered to a designated and suitable location on the surface of the solid first phase.
  • a suitable location on the surface of the first solid phase may, for example, be a suitable depression or depression.
  • the cured surfactant melt has more attractive optical properties compared to pressed powder phases.
  • the dishwashing agents described herein are preferably prefabricated into dosage units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a total weight of between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
  • the volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher.
  • the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.
  • the weight ratio of the first, preferably compacted phase to the second phase (surfactant melt phase) is preferably 20: 1 to 1: 1, preferably 15: 1 to 5: 1, in particular 12: 1 to 7: 1, for example 10: 1 to 8: 1.
  • the automatic dishwashing agents in particular the prefabricated metering units, have a water-soluble coating, with particular preference.
  • the water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends.
  • the wrapper may be formed of one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.
  • the water soluble package may have one or more chambers.
  • the agent may be contained in one or more chambers, if any, of the water soluble envelope.
  • the amount of agent preferably corresponds to the full or half dose needed for a rinse.
  • the water-soluble coating be polyvinyl alcohol or a
  • Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
  • Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose
  • Molecular weight in the range of 5,000 to 1,000,000 gmol, preferably from 20,000 to 500,000 gmol 1 , more preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol 1 .
  • polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
  • polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a polymer selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath is selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath
  • (Meth) acrylic acid-containing (co) polymers polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added.
  • a preferred additional polymer is polylactic acids.
  • Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
  • polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters.
  • Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
  • the film material contains further additives.
  • the film material may include, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol,
  • Additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, detackifiers, or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900.
  • Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
  • the multi-phase dishwashing detergent is closely enveloped by a water-soluble film
  • the water-soluble film which is preferably used in the narrow enclosure, particularly preferably comprises polyvinyl alcohol, as described above, wherein as starting thickness preferably a thickness of 10 .mu.m to 100 .mu.m, in particular from 12 .mu.m to 60 .mu.m, particularly preferably from 15 .mu.m to 50 ⁇ , especially from 20 ⁇ to 40 ⁇ , in particular from 22 ⁇ to 35 ⁇ is used.
  • a disposable portion of the washing or cleaning agent is wrapped in each case.
  • the coating rests close to its surface at any point of the tablets.
  • the envelope is even under tension, which is not absolutely necessary.
  • This tightness of the wrapper is conducive to disintegration: on first contact with water, the wrapper will pass a small amount of water at some point At first she does not need to solve herself at all. At this point, the disintegrant contained in the tablet begins to swell. This leads to the wrapping now due to the
  • volume increase of the tablet abruptly ruptures and releases the tablet. If the wrapper is not tight, the mechanism described here will not work as the tablet can swell without bursting the wrapper. In this case, the use of a swellable disintegrating agent is superior to a gas-developing system, since its explosive effect in each case leads to a rupture of the casing. At a
  • Gas evolving system may "deflate" the explosive effect by venting the gas from a leakage of the enclosure.
  • Preferred detergent or cleaning agent portions according to the invention are characterized in that the distance between the disposable portion and water-soluble coating over the entire surface is 0.1 to 1000 ⁇ , preferably 0.5 to 500 ⁇ , particularly preferably 1 to 250 ⁇ and in particular 2.5 to 100 ⁇ , is.
  • the film wrapping is first laid loosely around a washing or cleaning agent portion and welded and then shrunk onto it, so that a close contact between the film package and the detergent concentrate is given.
  • washing or cleaning agent disposable portions according to the invention are characterized in that the wrapping is a film packaging shrunk onto the latter.
  • this wrapping can be done by placing a water-soluble lower film on a conveyor chain or a mold (s) tool, then one or more detergent or cleaning agent portion (s) are placed on the lower film; then a water-soluble upper film is placed on the washing or cleaning agent portion (s) on the lower film and this is then fixed on the lower film, including the washing or cleaning agent portion (s),
  • this step can also be done by a single-stranded film, which is then placed around the disposable portions as a tube. This is followed by sealing and optional cutting of the films. Subsequently, then the shrinking of the film by the use of hot air or infrared radiation, optionally with pressing done.
  • Table 1 Frame formulation of the cleaning agents according to the invention (base tablets without surfactant-melting core), in particular dishwashing detergent, preferably automatic dishwashing detergent;
  • Active substance based on the total weight of the composition:
  • Table 2 Frame formulation of the surfactant melt core according to the invention for combination with cleaning agents, in particular dishwashing agents, preferably automatic dishwasher detergents according to Table 1; Unless indicated otherwise, the following information relates to% by weight of active substance, based on the total weight of the core: % By weight preferred
  • the invention likewise relates to a method, in particular a machine dishwashing method, in which a washing or cleaning center according to the invention is used in at least one step of the method.
  • the subject matter of the present application is therefore furthermore a process for the cleaning of dishes in a dishwashing machine, in which the agent according to the invention is passed through the passage of a
  • Dishwasher is metered into the interior of a dishwasher before the main wash cycle or in the course of the main wash cycle.
  • the metering or the entry of the agent according to the invention in the interior of the dishwasher can be done manually, but preferably the means by means of the metering chamber in the interior of the
  • Example 1 Preparation of a tablet with a surfactant melt core
  • the enamel body consists for example of 10-50% PEG (average Mr 1000 to 8000 g / mol), 5-60% fatty alcohol ethoxylate endcap, preferably C8-C10 endcap, 5-50% fatty alcohol ethoxylate with 10-80 EO, preferably 25-50 EO.
  • the components are mixed at temperatures> 50 ° C and poured hot into the well of a dishwasher tab (preferably according to the base tablet, Table 3).
  • the mass will be in the Cured well. Preforming and subsequent gluing of such a melt is also conceivable.
  • Surfactant melt core This serves to build up fat on the filter.
  • the amount of fat in the filter is determined gravimetrically.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne un produit pour lave-vaisselle solide multiphase, comportant au moins deux phases, ainsi que l'utilisation d'un tel produit pour lave-vaisselle, et un procédé de nettoyage de vaisselle utilisant un tel produit. La première phase du produit pour lave-vaisselle est une phase solide compacte. La seconde phase est une matière fondue tensioactive comportant 10 à 100% de tensioactifs, de préférence de tensioactifs non ioniques.
PCT/EP2016/067265 2015-07-23 2016-07-20 Produit pour lave-vaisselle multiphase à noyau tensioactif Ceased WO2017013161A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL16741024T PL3325591T3 (pl) 2015-07-23 2016-07-20 Wielofazowy środek do mycia naczyń obejmujący rdzeń środka powierzchniowo czynnego
EP16741024.0A EP3325591B1 (fr) 2015-07-23 2016-07-20 Produit pour lave-vaisselle multiphase à noyau tensioactif

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102015213939.5 2015-07-23
DE102015213939.5A DE102015213939A1 (de) 2015-07-23 2015-07-23 Mehrphasiges Geschirrspülmittel umfassend einen Tensid-Kern

Publications (1)

Publication Number Publication Date
WO2017013161A1 true WO2017013161A1 (fr) 2017-01-26

Family

ID=56464213

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/067265 Ceased WO2017013161A1 (fr) 2015-07-23 2016-07-20 Produit pour lave-vaisselle multiphase à noyau tensioactif

Country Status (4)

Country Link
EP (1) EP3325591B1 (fr)
DE (1) DE102015213939A1 (fr)
PL (1) PL3325591T3 (fr)
WO (1) WO2017013161A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11518961B2 (en) 2019-09-27 2022-12-06 Ecolab Usa Inc. Concentrated 2 in 1 dishmachine detergent and rinse aid
US11932830B2 (en) 2017-11-14 2024-03-19 Ecolab Usa Inc. Solid controlled release caustic detergent compositions
WO2025131436A1 (fr) * 2023-12-18 2025-06-26 Henkel Ag & Co. Kgaa Procédé de production de détergents ou de produits de nettoyage

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018212208A1 (de) 2018-07-23 2020-01-23 Henkel Ag & Co. Kgaa Mehrphasiger Reinigungsmittelpouch

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19961367A1 (de) * 1999-12-17 2001-07-05 Henkel Kgaa Preßverfahren für mehrphasige Formkörper
EP1669438A1 (fr) * 2004-12-08 2006-06-14 Unilever N.V. Comprimé détergent
EP1746151A1 (fr) * 2005-07-20 2007-01-24 Unilever N.V. Pastilles de composition détergente
EP1845153A1 (fr) * 2006-04-12 2007-10-17 Unilever N.V. Tablettes détergentes
EP2071018A1 (fr) * 2007-12-06 2009-06-17 Dalli-Werke GmbH & Co. KG Pastille de détergent avec une partie non comprimée
EP2392639A1 (fr) * 2010-06-04 2011-12-07 Dalli-Werke GmbH & Co. KG Mélange d'un agent tensioactif avec un composé solide pour améliorer la performance de rinçage de détergents pour le lavage automatique de la vaisselle

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5877134A (en) 1996-09-11 1999-03-02 The Procter & Gamble Company Low foaming automatic dishwashing compositions
GB2340842A (en) 1998-08-28 2000-03-01 Procter & Gamble Detergent tablet
ATE303431T1 (de) 2001-03-05 2005-09-15 Unilever Nv Wasch- oder reinigungsmittel
DE10223266C1 (de) 2002-05-24 2003-11-20 Henkel Kgaa Verwendung Einspülkammer-dosierbare Tabletten-Portionen
DE10245260A1 (de) 2002-09-27 2004-04-15 Henkel Kgaa Verfahren zur Herstellung umhüllter Wasch- oder Reinigungsmittel-Portionen
EP1642961A1 (fr) 2004-10-01 2006-04-05 Unilever N.V. Comprimés détergents

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19961367A1 (de) * 1999-12-17 2001-07-05 Henkel Kgaa Preßverfahren für mehrphasige Formkörper
EP1669438A1 (fr) * 2004-12-08 2006-06-14 Unilever N.V. Comprimé détergent
EP1746151A1 (fr) * 2005-07-20 2007-01-24 Unilever N.V. Pastilles de composition détergente
EP1845153A1 (fr) * 2006-04-12 2007-10-17 Unilever N.V. Tablettes détergentes
EP2071018A1 (fr) * 2007-12-06 2009-06-17 Dalli-Werke GmbH & Co. KG Pastille de détergent avec une partie non comprimée
EP2392639A1 (fr) * 2010-06-04 2011-12-07 Dalli-Werke GmbH & Co. KG Mélange d'un agent tensioactif avec un composé solide pour améliorer la performance de rinçage de détergents pour le lavage automatique de la vaisselle

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11932830B2 (en) 2017-11-14 2024-03-19 Ecolab Usa Inc. Solid controlled release caustic detergent compositions
US11518961B2 (en) 2019-09-27 2022-12-06 Ecolab Usa Inc. Concentrated 2 in 1 dishmachine detergent and rinse aid
US11905493B2 (en) 2019-09-27 2024-02-20 Ecolab Usa Inc. Concentrated 2 in 1 dishmachine detergent and rinse aid
US12338414B2 (en) 2019-09-27 2025-06-24 Ecolab Usa Inc. Concentrated 2 in 1 dishmachine detergent and rinse aid
WO2025131436A1 (fr) * 2023-12-18 2025-06-26 Henkel Ag & Co. Kgaa Procédé de production de détergents ou de produits de nettoyage

Also Published As

Publication number Publication date
EP3325591B1 (fr) 2020-09-02
DE102015213939A1 (de) 2017-01-26
EP3325591A1 (fr) 2018-05-30
PL3325591T3 (pl) 2021-03-08

Similar Documents

Publication Publication Date Title
EP2220205B1 (fr) Produit de nettoyage
EP3325596B1 (fr) Lessive lave-vaisselle contenant des agents de blanchiment et des polymères
EP3325592B1 (fr) Utilisation d'une combinaison d'un agent complexant et d'un tensioactif pour améliorer l'efficacité de rinçage
EP3574074A1 (fr) Dose de détergent comprenant au moins deux phases
WO2016062784A1 (fr) Détergent pour lave-vaisselle contenant des complexes métalliques
EP3599274B1 (fr) Poche d'agent de nettoyage multiphase
EP2225357A1 (fr) Détergents
EP3102658B2 (fr) Détergents polyphasiques préportionnés
EP3325597B1 (fr) Lessive lave-vaisselle contenant des agents de blanchiment et des enzymes
EP3325591B1 (fr) Produit pour lave-vaisselle multiphase à noyau tensioactif
EP3431575B1 (fr) Détergent pour lave-vaisselle comportant un citrate dihydraté et anhydre
EP4008764A1 (fr) Nettoyage amélioré au moyen du carbonate d'hydrogène dans le détergent de lavage en machine
EP3574075B1 (fr) Corps moulé et son procédé de fabrication
EP3502224A1 (fr) Détergent pour lave-vaisselle à performance de nettoyage améliorée, procédé reposant sur l'utilisation dudit détergent ainsi que l'utilisation dudit détergeant
EP4067469A1 (fr) Détergent
DE102017212348A1 (de) Verwendung eines Reinigungsmittels enthaltend Aminocarbonsäuren und Sulfopolymere zur Belagsinhibierung
WO2022207590A1 (fr) Agents de lavage ou de nettoyage
EP4314224A1 (fr) Agents de lavage ou de nettoyage
EP3842511A1 (fr) Tensioactif non ionique permettant d'améliorer l'efficacité de rinçage en lavage de vaisselle automatique
EP3502220A1 (fr) Détergent pour lave-vaisselle à performance de rinçage et de nettoyage améliorée, procédé reposant sur l'utilisation dudit détergent ainsi que l'utilisation dudit détergent
WO2018138122A1 (fr) Tensioactifs en capsules ayant un point de trouble optimisé

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16741024

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE