EP2929002A1 - Produits de nettoyage liquides, pauvres en eau à exempts d'eau - Google Patents

Produits de nettoyage liquides, pauvres en eau à exempts d'eau

Info

Publication number
EP2929002A1
EP2929002A1 EP13732544.5A EP13732544A EP2929002A1 EP 2929002 A1 EP2929002 A1 EP 2929002A1 EP 13732544 A EP13732544 A EP 13732544A EP 2929002 A1 EP2929002 A1 EP 2929002A1
Authority
EP
European Patent Office
Prior art keywords
water
cleaning agent
detergent
acid
potassium
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.)
Withdrawn
Application number
EP13732544.5A
Other languages
German (de)
English (en)
Inventor
Konstantin Benda
Thomas Eiting
Nina Mussmann
Volker Blank
Noelle Wrubbel
Thorsten Bastigkeit
Peter Schmiedel
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
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2929002A1 publication Critical patent/EP2929002A1/fr
Withdrawn legal-status Critical Current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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2048—Dihydric alcohols branched
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • 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
    • C11D3/43—Solvents

Definitions

  • the present invention relates to liquid, phosphate-containing, low-water to anhydrous detergents, in particular automatic dishwashing detergents which comprise at least one phosphate-containing builder component and at least one polyhydric alcohol, a process for their preparation and their use.
  • Hard surface cleaners such as dishwashing detergents
  • dishwashing detergents are available to the consumer in a variety of forms.
  • traditional solid agents are gaining increasingly increasingly flowable and especially liquid to gel detergent in importance.
  • the consumer particularly appreciates the rapid solubility and the associated rapid availability of the ingredients in the cleaning liquor, especially in short-dishwashing programs and at low temperatures.
  • compositions in which in particular the water content is reduced compared to conventional compositions, increases.
  • compositions whose water content is as low as possible, for example less than 20% by weight, are particularly desirable.
  • organic solvents in particular polyhydric alcohols, are therefore used instead of water.
  • 1,2-propylene glycol and glycerol and mixtures thereof have proved to be advantageous.
  • a matrix of these solvents is only able to absorb sufficient quantities of rinse aid surfactant to a limited extent, which may adversely affect the rinse performance of the product.
  • Known formulations usually contain a large part of the ingredients in the form of sodium salts.
  • the European patent EP 131 1654 B1 describes the preparation of aqueous liquid compositions with water contents of 20 to 50 wt .-%, wherein for improved solubility of the ingredients sodium salts are exchanged for potassium salts, so that the molar ratio of the potassium ions to the sodium ions in the total composition between 0.55: 1 and 20 : 1 is.
  • sodium salts are first dissolved in water, preferably even the entire amount of sodium salts, while in a further step, the potassium salts and in particular potassium tripolyphosphate are added.
  • the rinsing performance of low-water to anhydrous, phosphate-containing, liquid detergent compositions containing less than 25 wt .-%, preferably less than 20 wt .-% water, sodium and potassium ions and glycerol or a mixture of glycerol and 1 , 2-propylene glycol, especially on the substrates glass and porcelain, can be optimized for the same amount of rinse aid by choosing a suitable ratio of glycerol to 1, 2-propylene glycol. It has also been found that the rinse performance can be further optimized by varying the ratios of sodium ions to potassium ions.
  • the invention is directed to a liquid, phosphate-containing, water-poor to anhydrous detergent containing at least one phosphate-containing builder component, preferably a polyphosphate, sodium and potassium ions and at least one polyhydric alcohol selected from glycerol and mixtures of glycerol and 1, Contains 2-propylene glycol and has a water content less than 25 wt .-%, characterized in that the mass ratio of glycerol to 1, 2-propylene glycol 1: 1 or greater, preferably 2: 1 or greater and the mass ratio of potassium to sodium ions in the detergent is either (1) 2: 1 or more or (2) 1, 5: 1 or less.
  • low in water means that the composition thus characterized contains less than 25% by weight of water, preferably less than 20% by weight of water. -% water, 1 to 15 wt .-% water, 5-15 wt .-% water or 10 to less than 20 wt .-% water.
  • composition contains less than 5% by weight, more preferably less than 3% by weight, preferably less than 1% by weight of water.
  • the water content as defined herein refers to the water content determined by Karl Fischer titration.
  • "Liquid” as used herein with respect to the cleaning agent of the present invention includes all flowable compositions and, in particular, also encompasses gels and pasty compositions.
  • At least one means 1 or more, for example, 1, 2, 3, 4, 5, or more.
  • the water activity is a w , which is a measure of freely available water in a material and is defined as the quotient of the water vapor pressure over a material to the water vapor pressure over pure water at room temperature (23 ° C), at most 0.6 and preferably 0.3 to 0.6.
  • the polyhydric alcohols present in the detergents according to the invention make it possible to incorporate other constituents into the detergent formulation even if the amount of water is small, in particular if the amount of water is limited to 20% by weight.
  • the total amount of polyhydric alcohol or mixtures of alcohols used in detergents according to the invention is preferably at least 20% by weight, in particular at least 25% by weight, more preferably at least 28% by weight, especially at least 30% by weight.
  • Preferred quantitative ranges are in this case from 20 to 50% by weight, in particular from 25 to 45% by weight, in particular from 28 to 40% by weight.
  • the polyhydric alcohol is selected from glycerol and mixtures of glycerol with 1,2-propylene glycol.
  • Glycerol is used in inventive compositions preferably in an amount of 1 to 50 wt .-%, in particular in an amount of 10 to 45 wt .-%, particularly preferably in an amount of 20 to 40 wt .-%.
  • glycerol is preferably used in an amount of 0, 1 to 50 wt .-%, in particular in an amount of 15 to 45 wt .-%, particularly preferably in an amount of 20 to 40 wt .-%.
  • the 1, 2-propylene glycol is in this case preferably in an amount of 1 to 20 wt .-%, in particular in an amount of 5 to 15 wt .-%, more preferably in an amount of 8 to 14 wt .-%, in some Embodiments used to 12 wt .-%, each based on the total mass of the cleaning agent, wherein the total amount of glycerol and 1, 2-propylene glycol preferably at least 20 wt .-%, in particular at least 25 wt .-%, especially at least 30 wt .-%, particularly preferably 25 to 45 wt .-%, in particular 30 to 42 wt .-%, especially 35 to 40 wt .-% in each case based on the total mass of the cleaning agent is.
  • the cleaning agents are characterized in that the mass ratio of glycerol to 1,2-propylene glycol is greater than 2: 1, preferably greater than 3: 1, more preferably greater than 4: 1, most preferably 5: 1 until 1: 0.
  • the detergent further contains potassium and sodium ions, the mass ratio of potassium to sodium ions in the detergent being either 2: 1 or more or 1.5: 1 or less, preferably 3: 1 or more or 1: 1 or less. Alternatively, the mass ratio of potassium to sodium ions in the detergent is chosen not to fall in the range of 1.5: 1 to 2: 1, preferably not in the range of 1.1: 1 to 2.9: 1 ,
  • the mass ratio of potassium to sodium ions in the detergent is either (1) 3: 1 to 85: 1, preferably 4: 1 to 30: 1, more preferably about 5: 1; or (2) 1, 5: 1 to 0.25: 1, preferably 1, 25: 1 to 0.5: 1, more preferably about 1: 1 to 0.7: 1.
  • the sodium and potassium ions can originate from the various ingredients of the cleaning agent, in particular the builder components and anionic surfactants, but also from all other optionally contained constituents, in particular those which are described below.
  • the cleaning agents according to the invention are preferably a dishwasher detergent, in particular a machine dishwashing detergent.
  • the cleaning agent may be in a water-insoluble, water-soluble or water-dispersible packaging.
  • the cleaning agent according to the invention is preferably contained in a water-soluble packaging.
  • the water-soluble packaging in particular allows a one-time portioning of the cleaning agent.
  • the invention therefore also relates to kits which contain the cleaning agent in such a water-soluble package in the form of a bag.
  • the cleaning agent can be made up so that disposable portions are each packed separately.
  • a further subject of the present invention is also a machine dishwashing process in which a cleaning agent according to the invention or a cleaning agent according to the invention is used in a water-soluble packaging.
  • the invention also relates to the use of the cleaning agent according to the invention or of the cleaning agent according to the invention in a water-soluble packaging as dishwashing detergent, in particular automatic dishwashing detergent.
  • dishwashing detergents which are commercially available as a rule contain as builders phosphates in the form of polyphosphates.
  • Polyphosphates which can be used according to the invention are, for example, tripolyphosphates, pyrophosphates and metaphosphates and, in particular, their sodium or potassium salts. Preference is given to using tripolyphosphates.
  • tripolyphosphates (or else triphosphates) which can be used according to the invention are condensation products of ortho-phosphoric acid (H 3 PO 4 ) with the empirical formula P 3 O 10 5 " , which are usually used in the form of their salts, preferably the alkali metal or alkaline earth metal, more preferably in the form of their alkali metal salts
  • Tripolyphosphate salts are generally hygroscopic, white, odorless, noncombustible solids which are readily soluble in water
  • the potassium salt of tripolyphosphate (K 5 P 3 Oi 0 ) or a mixture of the potassium salt of tripolyphosphate and the sodium salt of tripolyphosphate is particularly preferred (Na 5 P 3 O 0) is used, the mass ratio between potassium and sodium ions is selected such that the mass ratio of potassium to sodium ions in the final detergent product either.
  • the proportion by weight of the polyphosphates, in particular the tripolyphosphate, in the total weight of the cleaning agent according to the invention is preferably 0.1 to 30 wt .-%, in particular from 1 to 28 wt .-%, particularly preferably from 5 to 25 wt .-%, more preferably from 10 to 23 wt .-%.
  • the cleaning agents preferably comprise one or more skeletons) (builder / cobuilder) in addition to the at least one phosphate-containing builder component.
  • the proportion by weight of these additional builders differing from the at least one phosphate-containing builder component in the total weight of the compositions according to the invention is preferably from 0.1 to 10% by weight and in particular from 2 to 7% by weight.
  • These builders which differ from the at least one phosphate-containing builder component, include in particular carbonates, citrates, phosphonates, MGDA (methylglycinediacetic acid) or its salts, GLDA (glutamic acid-N, N-diacetic acid) or its salts, EDDS (ethylenediamine-N, N '). -Dibernsteinklare) o- their salts, organic cobuilders and silicates.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. This fabric classes are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • the free acids also typically have the property of an acidifying component and thus also serve for setting a lower and milder pH of cleaning agents.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • Particularly preferred cleaning agents contain citrates, for example sodium or potassium citrate, as one of their essential builders, which differ from the at least one phosphate-containing builder component.
  • the citrate may be a source of the potassium and / or sodium ions contained in the detergent.
  • Detergents containing from 1 to 10% by weight, preferably from 2 to 5% by weight, of citrate are preferred according to the invention.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • 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 cleaning agents may contain, in particular, phosphonates as further builder other than the at least one phosphate-containing builder component.
  • the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance.
  • aminoalkanephosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • Phosphonates are contained in the compositions preferably in amounts of 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the cleaning agent.
  • the detergent can be used as further crystalline of the at least one phosphate-containing builder component different builder layered silicates of general formula NaMSi x 0 2x + i ⁇ y H 2 0 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.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus 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 preferably delayed release and have secondary washing properties.
  • the content of silicates is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
  • Particularly preferred cleaning agents are silicate-free.
  • the cleaning agents of the invention may further contain a sulfopolymer.
  • the proportion by weight of the sulfopolymer in the total weight of the cleaning agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1, 0 to 15 wt .-%, in particular from 4 to 14 wt .-%, especially from 6 to 12 wt .-%.
  • the sulfopolymer is typically employed in the form of an aqueous solution wherein the aqueous solutions typically contain from 20 to 70 weight percent, more preferably from 30 to 50 weight percent, preferably from about 35 to 40 weight percent sulfopolymer (s).
  • the sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
  • the copolymers may have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain, in addition to sulfonic acid-containing monomers, at least one monomer selected from the group consisting of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • unsaturated dicarboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • unsaturated dicarboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇
  • 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, methythyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3 -Sulfopropylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or
  • the sulfonic acid groups may be wholly or partly in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions.
  • metal ions preferably alkali metal ions and especially sodium ions.
  • partially or fully neutralized sulfonic acid group-containing copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol 1 , preferably from 4000 to 25,000 gmol 1 and in particular from 5000 to 15,000 gmol "1 .
  • the copolymers in addition to the carboxyl group-containing monomer and the monomer containing sulfonic acid groups, furthermore comprise at least one nonionic, preferably hydrophobic monomer.
  • the use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
  • Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.
  • nonionic monomers are preferably monomers of the general formula
  • R (R 2 ) C C (R 3 ) -XR 4 used, in which R to R 3 are independently -H, -CH 3 or -C 2 H 5 , X is an optional spacer group selected is from -CH 2 -, -C (0) 0- and -C (0) -NH-, and R 4 is a straight or branched chain saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4- Trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1, 3,5-dimethylhexene-1, 4,4-dimehtylhexane-1, ethylcyclohexyne, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene
  • the monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing monomer 60 to 80 wt .-%, the monomers are in this case preferably selected from the aforementioned.
  • the cleaning agents may comprise alkali metal hydroxides.
  • These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0, 1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the cleaning agent used.
  • Alternative cleaning agents according to the invention are free of alkali metal hydroxides.
  • the cleaning agents according to the invention preferably also contain at least one nonionic surfactant.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.
  • the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols.
  • nonionic surfactants which have a melting point above room temperature.
  • Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred .
  • Preferably used surfactants come from the groups of alkoxylated nonionic surfactants, in particular the 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 also characterized by good foam control.
  • nonionic surfactants have been low-foaming nonionic surfactants 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 .
  • 2 is 4-alkyl or alkenyl; each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of integers from 1 to 6 are available.
  • nonionic surfactants are particularly preferred that have a C thylenoxidtechniken 9 .i 5 alkyl radical having 1 to 4 E, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
  • Preferred nonionic surfactants here are those of the general formula R -CH (OH) CH 2 O-
  • R stands for a straight-chain or branched, saturated or mono- or polyunsaturated C6 -24 alkyl or alkenyl group
  • 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.
  • nonionic surfactants of the general formula R - CH (OH) CH 2 O- (AO) w - (AO) x - (A "O) y - (A '" O) z -R 2 , hereinafter also referred to as "hydroxymix ether"
  • the cleaning performance of the preparations according to the invention can be significantly improved Both in comparison to surfactant-free system as well as compared to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
  • surfactants of the formula R 0 [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 Cl-1 (OI-l) R 2 , in which R is a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x represents values between 0.5 and 1, 5 and y represents a value of at least 15.
  • nonionic surfactants include, for example, the C 2 -26 fatty alcohol (PO) i (EO) i 5 . 4o-2-hydroxyalkyl ethers, in particular also the C 8 -io-fatty alcohol (PO) i- (EO) 2 2-2-hydroxydecyl ethers.
  • R and R 2 are independent each represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms
  • R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ) 2 , but preferably -CH 3
  • 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 ] j OR 2 in which R and R 2 R 1 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different.
  • 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 being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are 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.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 0 [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 simplified.
  • R, 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) wR 2 have proven to be particularly effective, in which
  • R stands for a straight-chain or branched, saturated or mono- or polyunsaturated C6 -24 alkyl or alkenyl group
  • 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 20 to 40
  • nonionic surfactants include, for example, the C 4 . 22 fatty alcohol (EO) i 0 -8o-2-hydroxyalkyl ethers, in particular also the C 8 -i 2 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4 . 22 fatty alcohol (EO) 40 -8o-2-hydroxyalkyl ethers.
  • Preferred liquid cleaning agents are characterized in that the cleaning agent contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant in the total weight of the cleaning agent preferably 0, 1 to 10 wt .-%, preferably 0 , 5 to 8.0 wt .-% and in particular 1, 0 to 4.0 wt .-% is.
  • the pH of the cleaning agent can be adjusted by means of customary pH regulators, the pH value being selected depending on the desired application.
  • the pH is in a range of 5.5 to 10.5, preferably 5.5 to 9.5, more preferably 7 to 9, especially greater than 7, especially in the range 7.5 to 8.5
  • 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.
  • Suitable bases 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 alkanolamine is preferably contained in agents according to the invention in an amount of from 0.5 to 10% by weight, in particular in an amount of from 1 to 6% by weight.
  • the composition according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of from 0.001 to 5% by weight. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelating agents, INCI chelating agents).
  • buffers are citric acid or citrates, in particular the sodium and Kaliumeitrate, for example, tri- sodium citrate 2H 2 0 and H 2 tripotassium 0th
  • the agents according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of anionic, cationic and amphoteric surfactants, bleaches, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances , Bitter substances, and antimicrobial agents.
  • at least one further constituent preferably selected from the group consisting of anionic, cationic and amphoteric surfactants, bleaches, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances , Bitter substances, and antimicrobial agents.
  • Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates.
  • the anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form of their corresponding acid, eg Dodecylbenzenesulfonic.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R “ 1 ) (R lv ) (R v ) N + CH 2 COO " , in which R '"is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R IV and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 8 alkyl dimethylcarboxymethylbetain and Cn-Ci7-Alkylamidopropyl-dimethylcarboxymethylbetain.
  • Suitable cationic surfactants are i.a. the quaternary ammonium compounds of the formula
  • R VI (R VI ) (R vii ) (R viii ) (R ix ) N + X "
  • R vi to R ix for four identical or different, in particular two long and two short-chain, alkyl radicals and X " for an anion , in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
  • Further suitable cationic surfactants are the quaternary surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • the 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 contain enzymes preferably in total amounts of from 1 ⁇ 10 -6 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.
  • 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 Medium proteases included.
  • 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.
  • These 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, sparing in water and / or mixed with stabilizers or further auxiliaries.
  • the enzymes can be encapsulated for both the solid and liquid dosage forms.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • 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 in particular between 0, 8 and 10 wt .-% of the enzyme protein.
  • detergents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of enzyme preparations.
  • the glass corrosion inhibitors used are preferably zinc salts, in particular zinc acetate. Glass corrosion inhibitors are preferably present in compositions according to the invention in an amount of from 0.05 to 5% by weight, in particular in an amount of from 0.1 to 2% by weight.
  • the detergent immediately after production has a viscosity above 2000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 ° C), in particular between 2000 and 10,000 mPas.
  • the viscosity may be higher, for example greater than 10,000 mPas, for example in the range 10000-50000 mPas, preferably around 35000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 5 rpm, 20 ° C).
  • the cleaning agent may be in a water-insoluble, water-soluble or water-dispersible packaging.
  • the invention therefore also relates to kits which tel included with such packaging.
  • the cleaning agent can be made up so that disposable portions are each packed separately.
  • the cleaning agent according to the invention is preferably contained in a water-soluble packaging.
  • the water-soluble packaging allows a portioning of the cleaning agent.
  • the amount of detergent in the sachet is preferably 5 to 50 g, more preferably 10 to 30 g, especially 15 to 25 g.
  • 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 casing contain polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer exhibit good stability with sufficiently high water solubility, in particular cold water solubility.
  • 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 is in the range from 10,000 to 1,000,000 gimol " , preferably from 20,000 to 500,000 gimol " 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, methacrylic esters or mixtures thereof.
  • the film material contains further additives.
  • the film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof.
  • Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents 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 dimensions of the disposable portions in the form of water-soluble bags should be designed so that the bags can not be swallowed by children.
  • the standard gull test is used based on the European Standard 71-1 standard (modified version of the ISO 8124.1 standard).
  • the standard gullet is a test cylinder, which has the size of a Kinderschlundes.
  • the Standard Maw is usually used to test whether toys or small parts can be swallowed on toys of infants under the age of 3 years.
  • the dimensions of the standard throat (in mm) are as follows:
  • parts with a width of 31, 7 mm and a length of at least 31, 7 mm must have a height (thickness) of 25.4 mm in order to pass the standard gullet test. With a larger width, the height (thickness) can also be slightly smaller.
  • disposable portions are preferably provided in the form of water-soluble bags which have a width of at least 32 mm, in particular from 32 to 40 mm and more preferably from 33 to 38 mm and a height of at least 25 to 30 mm and in particular from 25 to 27 mm.
  • the length of the disposable portions can be flexibly designed; By definition (and for safety reasons) the length should be at least equal to the width.
  • the maximum length is determined by the size of the dosing chambers in automatic dishwashers and should therefore not exceed 50 mm.
  • Disposable portions in the form of water-soluble pouches which contain cleaning agents according to the invention are distinguished by dimensional stability.
  • the dimensional stability of the disposable portion can be defined by the weight constancy during storage of the detergent contained in the water-soluble bag.
  • the highest possible weight constancy during storage of the detergent contained in the water-soluble bag is given when the pure agent (without the bag packaging) as high a constant weight in the test described below has 50 mg of the detergent (without bag packaging) in an open Aluminum crucible under isothermal conditions (40 ° C) for several hours under purge gas (air, 3 l / h) kept.
  • the weight of the filled crucible is checked and the residue of the dishwashing detergent or the weight loss of dishwashing detergent is determined.
  • weight loss is highest in the first two hours of the given test.
  • dimensional stability of the disposable portions in the form of water-soluble pouches is understood to mean that the detergent in the specified test has a weight loss of not more than 15% by weight after 2 hours, preferably after 4 hours.
  • the weight loss after one hour is not above 10% by weight. It is even more advantageous if the weight loss after 2 hours is not above 10% by weight.
  • the cleaning agents according to the invention or the kits which contain the cleaning agents according to the invention in a water-soluble packaging can be used as dishwashing detergents, in particular automatic dishwasher detergents.
  • the corresponding use is also the subject of the invention.
  • the invention likewise relates to a dishwashing method, in particular a machine dishwashing method, in which a cleaning agent or a kit which contains a cleaning agent according to the invention in a water-soluble packaging is used according to the invention.
  • the invention also relates to processes for the preparation of a cleaning agent, in particular a machine dishwashing agent, wherein presented in a first step, water, aqueous solutions and organic solvents and then added in a second step, the solid components.
  • solid sodium-containing constituents in particular the phosphate- and sodium-containing builder component (s)
  • solid potassium-containing constituents in particular the phosphate and potassium containing builder component (s). Suitable methods are known to those skilled in the art.
  • the method comprises the following steps:
  • step (1) either the solvent can be initially charged and the aqueous solution of the at least one sulfo polymer added, or conversely, the solution of the sulfo polymer presented and the organic solvent is added.
  • the at least one sulfopolymer or its aqueous solution is preferably as defined above.
  • the at least one phosphate-containing builder component in particular tripolyphosphate, is preferably added in the form of a powder or granules.
  • the at least one phosphate-containing builder component is a tripolyphosphate, especially a tripolyphosphate salt, as defined above.
  • the addition of the sodium salt be due to its poorer solubility prior to the addition of the potassium salt.
  • the addition of builders differing from the at least one phosphate-containing builder component, in particular citrate and / or phosphonate, can be carried out before step (2) or before step (3).
  • the method according to the invention comprises the addition of citrate before step (2) or step (3).
  • the builders may also be added after stirring in step (3).
  • phosphonate is added after stirring in step (3). All builders other than the at least one phosphate-containing builder component can be used as solids or in the form of their aqueous solutions in the preparation of the formulations according to the invention.
  • the sodium containing ingredients such as sodium citrate, are added prior to step (2).
  • one or more further constituents of the cleaning agent can then be added.
  • these may, for example, without limitation, be selected from nonionic surfactants, for example hydroxy mixed ethers, and pH adjusters.
  • the addition can be carried out, for example, in the order: nonionic surfactant (s), pH adjuster. Since an exothermic neutralization reaction takes place when the pH-adjusting agent is added, the reaction mixture is preferably cooled. In general, it is preferred that during the addition of ingredients, the mixture is stirred continuously.
  • the said additional ingredients are preferably added after the neutralization reaction, ie the pH adjustment and optionally a stirring step carried out during the pH adjustment or thereafter.
  • one or more of the substances selected from the group consisting of cationic surfactants, amphoteric surfactants, zinc acetate, dyes, fragrances, bittering agents, enzymes, and preservatives are added.
  • the necessary stirring steps for example after the addition of the tripolyphosphate to dissolve the same, and at the pH adjustment and the necessary neutralization, preferably in a mixer with Wandauerem stirring, in particular an anchor or helical stirrer performed.
  • the agitator has a stirrer geometry d / D of at least 0.9, preferably greater than 0.9 to 0.99, where d is the diameter of the agitating tool and D is the diameter of the mixer.
  • the detergents prepared by the process according to the invention are distinguished on the one hand by their composition and on the other hand by the fact that they are stable on storage and even after a prolonged period no phase separation occurs.
  • the cleaning agents M1 1, M12, M21, M22, M31 and M32 (according to the invention) as well as V1, V2 and V3 (comparative examples not according to the invention) were produced.
  • the compositions are shown in Tables 1-3 below, the quantities are in wt .-% active ingredient. In the following, the rinse performance of the formulations was tested.
  • Acrylic acid polymer 0.2 0.2 0.2

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Abstract

La présente invention concerne des produits de nettoyage liquides, contenant des phosphates, pauvres en eau à exempts d'eau, en particulier un produit de lavage de vaisselle en machine, qui contient au moins un composant d'adjuvant contenant des phosphates, de préférence un polyphosphate, des ions de potassium et de sodium et au moins un alcool polyvalent, choisi parmi le glycérol et des mélanges de glycérol et de 1,2-propylèneglycol et qui présente une teneur en eau inférieure à 25 % en poids. Selon l'invention, le rapport massique de glycérol à 1,2-propylèneglycol est de 1:1 ou plus, de préférence de 2:1 ou plus et le rapport massique des ions de potassium aux ions de sodium dans le produit de nettoyage est soit de 2:1 ou plus, soit de 1,5:1 ou moins. Des procédés pour leur préparation et leur utilisation sont également décrits.
EP13732544.5A 2012-12-05 2013-07-01 Produits de nettoyage liquides, pauvres en eau à exempts d'eau Withdrawn EP2929002A1 (fr)

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DE201210222268 DE102012222268A1 (de) 2012-12-05 2012-12-05 Wasserarme bis wasserfreie flüssige Reinigungsmittel
PCT/EP2013/063774 WO2014086505A1 (fr) 2012-12-05 2013-07-01 Produits de nettoyage liquides, pauvres en eau à exempts d'eau

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DE19925275A1 (de) * 1999-06-02 2000-12-07 Henkel Kgaa Nichtwäßrige flüssige Geschirreinigungsmittel
US7271141B2 (en) 2000-08-25 2007-09-18 Reckitt Benckiser N.V. & Reckitt Benckiser (Uk) Limited Water soluble packages containing liquid compositions
US6492312B1 (en) * 2001-03-16 2002-12-10 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Water soluble sachet with a dishwashing enhancing particle
WO2013104607A1 (fr) * 2012-01-11 2013-07-18 Henkel Ag & Co. Kgaa Emballage parfumé soluble dans l'eau
DE102012202176A1 (de) * 2012-02-14 2013-08-14 Henkel Ag & Co. Kgaa Sulfopolymer-haltiges flüssiges Reinigungsmittel mit geringem Wassergehalt

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