WO2014139654A2 - Compositions détergentes de lavage de vaisselle automatique exemptes de tensioactifs non ioniques et comprenant des acides carboxyliques d'éther ou leurs sels - Google Patents

Compositions détergentes de lavage de vaisselle automatique exemptes de tensioactifs non ioniques et comprenant des acides carboxyliques d'éther ou leurs sels Download PDF

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Publication number
WO2014139654A2
WO2014139654A2 PCT/EP2014/000595 EP2014000595W WO2014139654A2 WO 2014139654 A2 WO2014139654 A2 WO 2014139654A2 EP 2014000595 W EP2014000595 W EP 2014000595W WO 2014139654 A2 WO2014139654 A2 WO 2014139654A2
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WO
WIPO (PCT)
Prior art keywords
automatic dishwashing
dishwashing detergent
detergent composition
composition according
compounds
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PCT/EP2014/000595
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English (en)
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WO2014139654A3 (fr
Inventor
George Italo Pitombeira Nunes
Carste Cohrs
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Clariant International Ltd
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Publication date
Priority claimed from US13/804,868 external-priority patent/US20140261561A1/en
Application filed by Clariant International Ltd filed Critical Clariant International Ltd
Priority to US14/774,630 priority Critical patent/US20160017260A1/en
Priority to EP14709194.6A priority patent/EP2970822A2/fr
Publication of WO2014139654A2 publication Critical patent/WO2014139654A2/fr
Publication of WO2014139654A3 publication Critical patent/WO2014139654A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds

Definitions

  • compositions which are free of nonionic surfactants and comprise specific ethercarboxyiic acids or ethercarboxyiic acid salts.
  • n is a number from 1 to 20
  • M is a counter ion
  • the automatic dishwashing detergent compositions contain no chloride ions or wherein the total amount of chloride ions in the automatic dishwashing detergent compositions is below 0.5 % by weight, referring to the total composition, and which are characterized in that the automatic dishwashing detergent compositions are free of nonionic surfactants.
  • the present invention therefore provides automatic dishwashing detergent compositions comprising
  • R is a linear or branched saturated alkyl group comprising from 8 to 30 carbon atoms or a linear or branched unsaturated alkenyl group with one or more double bonds and comprising from 8 to 30 carbon atoms,
  • n is a number from 1 to 20
  • M is a counter ion
  • the automatic dishwashing detergent compositions contain no chloride ions or wherein the total amount of chloride ions in the automatic dishwashing detergent compositions is below 0.5 % by weight, referring to the total composition, and which are characterized in that the automatic dishwashing detergent compositions are free of nonionic surfactants.
  • R is a linear or branched saturated alkyl group comprising from 8 to
  • n is a number from 1 to 20
  • M is a counter ion
  • automatic dishwashing detergent compositions are free of nonionic surfactants.
  • a low chloride ion content is not necessarily mandatory.
  • the inventive automatic dishwashing detergent compositions show a favorable anti-spotting behavior and possess a favorable cleaning performance.
  • the surfactants of the formula (I) do not impart to major foaming and insofar the inventive compositions are furthermore low foaming.
  • the surfactants of the formula (I) are biodegradable and are based - due to their alcohol component RO - on renewable primary products and insofar the inventive automatic dishwashing detergent compositions are also environment-friendly.
  • inventive automatic dishwashing detergent compositions furthermore have the advantage that the one or more surfactants of the formula (I) contained therein reveal their advantageous properties and in particular provide a favorable anti- spotting behavior also in phosphate-free compositions. Compared with common low foaming non-ionic surfactants the one or more surfactants of the formula (I) often lead to an improved anti-spotting behavior.
  • surfactants belong to the group of nonionic surfactants and which surfactants do not belong thereto.
  • alkyl alcohols or alkoxylated alkyl alcohols (such as ethoxylated alkyl alcohols) belong to the group of nonionic surfactants but surfactants bearing a carboxylic group -COOH do not belong to the group of nonionic surfactants (but to the group of anionic surfactants).
  • the carboxylic group -COOH of the respective surfactant bearing it dissociates in water at 20 °C resulting in a surfactant bearing an anionic -COO " group and protons H + .
  • the degree of dissociation is e.g. dependent on the pH value of the environment of the surfactant bearing the carboxylic group.
  • US 4,272,394 discloses automatic dishwashing detergents containing blends of low foaming nonionic surfactants, where the second surfactant has a relatively low cloud point.
  • WO 94/22800 describes low cloud point epoxy capped poly(oxyalkylated) alcohols and automatic dishwasher compositions containing them.
  • EP 1 757 676 describes the use of charged surfactants
  • ethercarboxylates namely alkylethoxycarboxylates, alkylethoxysulfates with specific chainlengths and EO (ethyleneoxy -CH 2 CH 2 O-) levels, sulfobetaines, alkylpolyethoxysulfates, alkylpolyethoxycarboxylates and alkyl sulfates and sulfonates.
  • a low foaming nonionic specifically a low cloud point surfactant with a cloud point below 30 °C in water, is present in the composition to prevent the foaming issues.
  • the counter ion M preferably is selected from the group consisting of H + , Na + , K + , Mg 2+ /2, Ca 2+ /2, NH 4 + ,
  • the counter ion M is selected from the group consisting of H + , Na + and K + .
  • alkyl and alkenyl groups R of the compounds of the formula (I) are e.g. the alkyl and alkenyl groups of the following alcohols R-OH: 1-octanol (capryl alcohol), 2-ethyl hexanol, 1-nonanol (pelargonic alcohol), 1-decanol (capric alcohol), 1-undecanol, 1-dodecanol (lauryl alcohol), 1-tridecanol, isotridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), cis-9-hexadecen-1-ol (palmitoleyl alcohol), 1-heptadecanol, 1 -octadecanol (stearyl alcohol), cetearyl alcohol, 16-methylheptadecan-1-ol (isostearyl alcohol),
  • R-OH 1-octanol (capryl alcohol
  • 9E-octadecen-1-ol (elaidyl alcohol), cis-9-octadecen-1-ol (oleyl alcohol), mixture comprising oleyl alcohol and cetyl alcohol, 9Z, 12Z-octadecadien-1-ol (linoleyl alcohol), 9E, 12E-octadecadien-1-ol (elaidolinoleyl alcohol), 9Z, 12Z,
  • the groups R of the compounds of the formula (I) can be derived from naturally occurring alcohols R-OH which usually comprise mixtures of different residues R.
  • the groups R of the compounds of the formula (I) can also be derived from synthetically prepared alcohols R-OH such as oxo alcohols, e.g. oxo alcohol C12-15.
  • R preferably is a linear or branched saturated alkyl group comprising from 12 to 18 carbon atoms or a linear or branched unsaturated alkenyl group with one or more double bonds and comprising from 12 to 18 carbon atoms.
  • R is a linear or branched saturated alkyl group comprising from 16 to 18 carbon atoms or a linear or branched unsaturated alkenyl group with one or more double bonds and comprising from 16 to 18 carbon atoms.
  • the one or more compounds of the formula (I) 50 wt.-% or more of the groups R are linear or branched unsaturated alkenyl groups with one or more double bonds.
  • R is a linear group.
  • R is a mixture comprising an oleyl group and a cetyl group.
  • Oleyl is a group derived from oleyl alcohol which is an octadecenol or cis-9-octadecen-1-ol
  • cetyl is a group derived from cetyl alcohol a saturated fatty alcohol comprising 16 carbon atoms.
  • n preferably is a number from 1 to 3. Particularly preferably, in the one or more compounds of the formula (I) n is 2.
  • Most preferred compounds of formula (I) are mixtures of alkyloxydiethoxy- /alkenyloxydiethoxy carboxylic acid.
  • a preferred group of these compounds belongs to the group of Ci6-alkyl-C-
  • Preferred compounds of this group are derived from Ci 6 -Ci8 fatty acid alcohols with 2 ethylene oxide units being covalently bound to acetic acid, wherein the alkyloxy component is derived from cetyl alcohol as main component and the alkenyloxy component is derived from oleyl alcohol as main component.
  • a product comprising these compounds is available as Emulsogen® COL 020 from Clariant.
  • the compounds of formula (I) used in the automatic dishwashing detergent compositions of this invention contain no halides or low amounts of halides, especially of chlorides.
  • Preferred are automatic dishwashing compositions have a chloride content between 0 and 0.1 % by weight, preferably between 0 and 0.05 % by weight, and most preferably between 0.001 and 0.05 % by weight, referring to the total composition.
  • the chloride content is determined via ion exchange chromatography using the following test procedure.
  • a sample of the automatic dishwashing detergent composition is introduced into a sample loop of known volume.
  • a buffered aqueous solution as the mobile phase carries the sample from the loop onto a column that contains a stationary phase material.
  • This is typically a resin or gel matrix consisting of polystyrene beads with covalently bonded ammonium functional groups.
  • the target analytes (chloride anions) are retained on the stationary phase but can be eluted by increasing the concentration of a similarly charged species that will displace the analyte (chloride) ions from the stationary phase.
  • chloride exchange chromatography the negatively charged analyte chloride is displaced by the addition of negatively charged bromide ions.
  • the concentration of the chloride ions of interest is then be detected by UV/Visible light absorbance.
  • the inventive automatic dishwashing detergent compositions comprise the one or more compounds of the formula (I) preferably in amounts from 0.1 to 15 wt.-%, more preferably in amounts from 0.2 to 10 wt.-% and particularly preferably in amounts from 0.2 to 5 wt.-%, in each case based on the total weight of the inventive automatic dishwashing detergent composition.
  • the variable "n" in the one or more compounds of the formula (I) represents molar averages, i.e. the inventive automatic dishwashing detergent compositions may comprise several compounds of the formula (I) that differ in the ethoxylation degree.
  • inventive automatic dishwashing detergent compositions may comprise more than one compound of the formula (I).
  • inventive automatic dishwashing detergent compositions may e.g. comprise more than one compound of the formula (I) that differ in the group "R” and/or that differ in the ethoxylation degree and/or that differ in the counter ion "M".
  • inventive automatic dishwashing detergent compositions comprise the one or more builder substances b) preferably in amounts from 5 to 90 wt.-% and more preferably in amounts from 5 to 80 wt.-%, in each case based on the total weight of the inventive automatic dishwashing detergent composition.
  • the builder substances b) as well as other ingredients usable in the inventive automatic dishwashing detergent compositions are e.g. described in
  • the builders b) are carbonates, hydrogencarbonates, organic builders, silicates, phosphates, phosphonates, methylglycinediacetic acid (MGDA), and alkali-metal hydroxides. It is particularly preferred to use carbonate(s) and/or hydrogencarbonate(s), by preference alkali carbonate(s), particularly preferably sodium carbonate. These substances are preferably used in quantities from 2 to 50 wt.-%, by preference from 10 to 30 wt.-%, and in particular from 10 to 25 wt.-%, based on the total weight of the inventive automatic dishwashing detergent composition.
  • Organic builders b) include polycarboxylates/polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, and dextrins.
  • Usable organic builders b) include polycarboxylic acids, which can be used in the form of the free acid and/or its sodium salts, "polycarboxylic acids" being
  • citric acid examples are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, and
  • NTA nitrilotriacetic acid
  • Free acids typically also have an acidifying component in addition to their builder effect, and thus also serve to establish a lower and milder pH for the inventive automatic dishwashing detergent compositions.
  • citric acid succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof.
  • inventive automatic dishwashing detergent compositions contain citrate as one of their builders b).
  • inventive automatic dishwashing detergent compositions containing from 2 to 40 wt.-%, preferably from 5 to
  • Polymeric carboxylates are also suitable as organic builders b). These are, for example, the alkali-metal salts of polyacrylic acid or of polymethacrylic acid, for example, those having a relative molecular weight from 500 to 70,000 g/mol.
  • Suitable polymeric carboxylates are, in particular, polyacrylates, preferably having a molecular weight from 2000 to 20,000 g/mol. Because of their superior solubility, short-chain polyacrylates having molar weights from 2000 to 10,000 g/mol, and particularly preferably from 3000 to 5000 g/mol, may in turn be preferred.
  • copolymeric carboxylates in particular, those of acrylic acid with methacrylic acid, and acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid containing from 50 to 90 wt.-% acrylic acid and from 10 to 50 wt.-% maleic acid have proven particularly suitable.
  • Their relative molecular weight, based on free acids, is preferably from 2000 to 70,000 g/mol, more preferably from 20,000 to 50,000 g/mol, and in particular from 30,000 to 40,000 g/mol.
  • inventive automatic dishwashing detergent compositions comprise one or more (co)polymeric carboxylates, the amount of these (co)polymeric
  • inventive automatic dishwashing detergent compositions preferably is from 0.5 to 20 wt.-% and in particular from 3 to 10 wt.-%, based on the total weight of the inventive automatic dishwashing detergent composition.
  • inventive automatic dishwashing detergent compositions may preferably contain, as a builder b), crystalline sheet-form sodium silicates of the general formula
  • amorphous sodium silicates having a Na 2 O:Si0 2 modulus 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 by preference are dissolution-delayed and exhibit secondary washing properties.
  • the inventive automatic dishwashing detergent compositions comprise one or more silicates
  • the amount of these silicates in the inventive compositions preferably is from 5 to 30 wt.-% and more preferably from 10 to 25 wt.-%, based on the total weight of the inventive automatic dishwashing detergent composition.
  • Phosphates have proven to be effective builders in terms of cleaning performance.
  • alkali-metal phosphates have the greatest significance in the washing- and cleaning-agent industry, particularly pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
  • Alkali-metal phosphates is the summary designation for the alkali-metal
  • Phosphates have a combination of advantages: they act as alkali carriers, prevent lime deposits on machine parts and contribute to cleaning performance.
  • Phosphates that are technically especially important are pentasodium triphosphate Na 5 P 3 Oio (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate K5P3O10 (potassium tripolyphosphate). Further preferred phosphates are the sodium potassium tripolyphosphates.
  • compositions preferred compositions contain phosphate(s), preferably alkali-metal phosphate(s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) in quantities from 2 to 50 wt.-%, preferably from 2 to 30 wt.-%, more preferably from 3 to 25 wt.-%, and particularly preferably from 3 to 15 wt.-%, based in each case on the total weight of the inventive automatic dishwashing detergent composition.
  • phosphate(s) preferably alkali-metal phosphate(s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) in quantities from 2 to 50 wt.-%, preferably from 2 to 30 wt.-%, more preferably from 3 to 25 wt.-%, and particularly preferably from 3 to 15 wt.-%, based in each case on the total weight of the inventive automatic dishwash
  • inventive automatic dishwashing detergent compositions can contain phosphonate(s).
  • the weight proportion of phosphonate, based on the total weight of the inventive automatic dishwashing detergent composition, preferably is from 0.5 to 20 wt.-%, and more preferably from 1.0 to 10 wt.-%.
  • Complexing phosphonates include a number of different compounds such as 1 -hydroxyethane-1 , 1 -diphosphonic acid (HEDP) or diethylenetriaminepenta- (methylenephosphonic acid) (DTPMP). Hydroxyalkane- and aminoalkane- phosphonates are particularly preferred. Among the hydroxyalkanephosphonates, 1 -hydroxyethane-1 , 1 -diphosphonate (HEDP) is of particular importance, preferably as a cobuilder. It is preferably used as a sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in alkaline fashion (pH 9). Suitable
  • aminoalkanephosphonates include ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and their higher homologs. They are preferably used in the form of the neutrally reacting sodium salts (e.g. as a hexasodium salt of EDTMP or as a hepta- and octasodium salt of DTPMP). Of the class of the phosphonates, HEDP is preferred.
  • MGDA nnethylglycinediacetic acid
  • the amount of this compound in the inventive compositions preferably is from 0.5 to 25 wt.-% and more preferably from 5 to 20 wt.-%, based on the total weight of the inventive automatic dishwashing detergent composition.
  • Inventive automatic detergent dishwashing compositions can contain as further builders b) alkali-metal hydroxides. These alkali carriers are used preferably only in small quantities, preferably in quantities of 10 wt.-% or less, more preferably 6 wt.-% or less, by preference 5 wt.-% or less, particularly preferably from 0.1 to 5 wt.-%, and in particular from 0.5 to 5 wt.-%, based on the total weight of the inventive automatic detergent dishwashing composition.
  • inventive automatic dishwashing detergent compositions comprise one or more builder substances b) selected from the group consisting of carbonates, citrates and phosphates.
  • inventive automatic dishwashing detergent compositions comprise one or more builder substances b) selected from the group consisting of carbonates and citrates.
  • the inventive automatic detergent dishwashing compositions can contain the aforementioned builders b) both individually and as mixtures of two, three, four or more builders.
  • the inventive automatic dishwashing detergent compositions comprise a bleaching system. They comprise the bleaching system preferably in amounts from 0.1 to 40 wt.-%, more preferably in amounts from 0.5 to 30 wt.-% and particularly preferably in amounts from 3 to 25 wt.-%, in each case based on the total weight of the inventive automatic dishwashing detergent composition.
  • the bleaching system of the inventive automatic dishwashing detergent preferably in amounts from 0.1 to 40 wt.-%, more preferably in amounts from 0.5 to 30 wt.-% and particularly preferably in amounts from 3 to 25 wt.-%, in each case based on the total weight of the inventive automatic dishwashing detergent composition.
  • compositions comprises at least one bleaching agent c) and optionally at least one bleach catalyst d) and/or optionally at least one bleach activator e).
  • Bleaching agents c) may be compounds reacting with bleach activators e) and forming peroxyacids, which at low temperatures (e.g. at ⁇ 70 ° C) bleach much more effectively than the bleaching agents alone.
  • the inventive automatic dishwashing detergent compositions can contain an oxygen bleaching agent.
  • an oxygen bleaching agent Among the compounds that serve as bleaching agents and yield H2O2 in water, sodium percarbonate, sodium perborate tetrahydrate, and sodium perborate monohydrate are particularly significant.
  • Other usable bleaching agents c) include peroxypyrophosphates, citrate perhydrates, and peracid salts or peracids that yield H 2 O 2 , such as perbenzoates,
  • Organic bleaching agents c) can also be used.
  • Typical organic bleaching agents c) are diacyl peroxides such as dibenzoylperoxide.
  • Further typical organic bleaching agents c) are peroxy acids such as alkylperoxy acids and arylperoxy acids.
  • Preferred bleaching agents c) are inorganic peracids and/or their salts.
  • More preferred bleaching agents c) are inorganic perhydrate salts, most preferred perborate, percarbonate, perphosphate, persulfate and persilicate salts.
  • Inorganic perhydrate salts are normally alkali metal salts.
  • the inorganic perhydrate salt may be included as the crystalline solid without additional protection.
  • the salt can be coated.
  • Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates for use herein.
  • the percarbonate is most preferably incorporated into the products in a coated form which provides in-product stability.
  • a suitable coating material providing in product stability comprises mixed salt of a water-soluble alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB-A-1 ,466,799.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1 : 200 to 1 : 4, more preferably from 1 : 99 to 19, and most preferably from 1 : 49 to 1 : 19.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na 2 SO 4 ⁇ n ⁇ Na 2 C0 3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
  • Another suitable coating material providing in product stability comprises sodium silicate of Si0 2 : Na 2 O ratio from 1.8: 1 to 3.0: 1 , preferably 1.8:1 to 2.4:1 , and/or sodium metasilicate, preferably applied at a level of from 2% to 10%, (normally from 3% to 5%) of Si0 2 by weight of the inorganic perhydrate salt.
  • Magnesium silicate can also be included in the coating. Coatings that contain silicate and borate salts or boric acids or other inorganics are also suitable.
  • Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility herein.
  • Particularly preferred inorganic bleaching agents c) are sodium perborate
  • Preferred inventive automatic dishwashing detergent compositions contain, based on the total weight of the composition, from 1.0 to 20 wt.-%, preferably from 4.0 to 8 wt.-%, and more preferably from 8 to 15 wt.-% of a bleaching agent c), preferably sodium percarbonate.
  • compositions according to the invention can comprise one or more substances selected from the following group: polyacylated alkylene- diamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1 ,5-diacetyl-2,4-dioxohexahydro-1 ,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyloxy- or n-lauroyloxybenzenesulfonate (NOBS or LOBS), acylated phenolcarboxylic acids, in particular nonanoyloxy- or decanoyloxybenzoic acid (NOBA or DOBA), carboxylic
  • TAED t
  • acylated sugar derivatives in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and acetylated, optionally N-alkylated glucamine and gluconolactone, and/or
  • N-acylated lactams for example N-benzoylcaprolactam. Hydrophilically
  • substituted acylacetals and acyllactams are likewise preferably used.
  • nitrile derivatives such as n-methylmorpholinium acetonitrile methylsulfate (MMA) or cyanomorpholine (MOR) can be used as bleach activators.
  • MMA n-methylmorpholinium acetonitrile methylsulfate
  • MOR cyanomorpholine
  • Combinations of conventional bleach activators can also be used.
  • bleach activators e) are tetraacetylethylenediamine, decanoyloxybenzoic acid, n-nonanoyloxybenzenesulfonate or
  • Bleach activators e), in particular TAED are preferably used in quantities of up to 10 wt.-%, in particular from 0.1 to 8 wt.-%, particularly from 2 to 8 wt.-%, and particularly preferably from 2 to 6 wt.-%, based in each case on the total weight of the bleach activator e) containing inventive automatic dishwashing detergent composition.
  • Bleaching agents c) may be also other compounds acting without bleach. Suitable such bleaching agents c) are peracids or salts thereof. Particularly preferred peracids or peracid salts are peroxycarboxylic acids and salts thereof of the formula R-CO-O-O " X + wherein R is an alkyi group, aralkyl group, cycloalkyl group, aryl group or heterocyclic group, preferably a linear or branched, substituted or unsubstituted alkyi group, particularly preferred an alkyi group having 6-9 carbon atoms, and X + is a suitable counterion, preferably a H + , potassium or sodium ion. Especially preferred are peroxyhexanoylacid, peroxyheptanoylacid, peroxyoctanoylacid, peroxynonanoylacid, peroxydecanoylacid and their salts.
  • peracids or peracid salts are peroxy sulfonic acids and their salts according to the formula
  • R-S(O) 2 -O-O " X + wherein R is an alkyi group, aralkyl group, cycloalkyl group, aryl group or heterocyclic group, preferably a linear or branched, substituted or unsubstituted alkyi group, particularly preferred an alkyi group having 6-9 carbon atoms, and X + is a suitable counterion, preferably a H + , a potassium or sodium ion.
  • peracids or peracid salts are peroxophthalic acids and salts thereof, phthalimino peracids and salts thereof, diperoxy carboxylic acids and salts thereof, or peroxysulphuric acids and salts thereof.
  • the bleaching agents c) that act without bleach activator e especially the peracids or salts thereof are preferred, which are selected from the group consisting of monoperoxyphthalic acid and their salts, N, N-phthaloylamino- peroxycaproic acid (PAP) and their salts, diperazelaic acid and its salts, diperdodecanedioic acid and their salts, monoperoxy sulfuric acid and their salts, wherein the salts are preferably selected from the sodium and/or potassium salts.
  • monoperoxy sulfuric acid and their salts in particular the potassium peroxymonosulphate (sold under the trade name Caroat ® ) is preferred.
  • the bleaching agent c) is N, N-phthaloylaminoperoxycaproic acid.
  • the inventive automatic dishwashing detergent compositions contain so-called bleach catalysts d). These components d) can be used in addition to or instead of conventional bleach activators.
  • the inventive automatic dishwashing detergent compositions may contain and preferably do contain so-called bleach catalysts.
  • components d) can be used in addition to or instead of conventional bleach activators e).
  • Suitable bleach catalysts d) are preferably bleach-boosting transition metal salts or complexes of manganese, iron, cobalt, ruthenium, molybdenum, titanium or vanadium.
  • These substances are preferably bleach-enhancing transition-metal salts or transition-metal complexes such as, for example, Mn, Fe, Co, Ru, or Mo salts or complexes, preferably carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V, and Cu complexes having nitrogen-containing tripod ligands, as well as Co, Fe, Cu, and Ru amine complexes, are also usable as bleach catalysts d).
  • Preferred bleaching catalysts d) are one or more manganese complex compounds of general formula (1)
  • a coordinating or bridging species which is selected from the group H 2 O, O 2 2" -, O 2" -, O 2 " , OH “ , HO 2" -, SH-, S 2" , SO, CI “ , N 3 " , SCN “ , N 3 “ , RCOO “ , NH 2 " and NR 3 , wherein R is a radical selected from hydrogen, alkyl, preferably Ci-C -alkyl, and aryl, preferably phenyl, independently of one another are organic ligands, comprising each at least two nitrogen atoms coordinating at manganese,
  • manganese complexes in oxidation states II, III, IV or V, preferably containing one or more macrocyclic ligand(s) having the donor functions N, NR, PR, O, and/or S.
  • Ligands having nitrogen donor functions are preferred.
  • Preferred organic ligands L are at least nine-membered rings wherein at least two, preferably three or four ring nitrogen atoms are present and coordinate with the manganese.
  • macromolecular ligands are: 1 ,4,7-triazacyclononane (TACN), 1 ,4,7-trimethyl-1 ,4,7-triazacyclononane (1 ,4,7-Me3-TACN),
  • Manganese complexes of general formula (1) include 1 ,4,7-trimethyl-1 ,4,7- triazacyclononane (1 ,4,7-Me3-TACN) and 1 ,2-bis-(4,7-dimethyl-1 ,4,7- triazacyclonon-1 -yl)-ethane (Me4-DTNE). Most preferred is 1 , 4, 7-trimethyl-1 ,4,7- triazacyclononane (1 ,4,7-Me3-TACN). .
  • Suitable manganese complexes of general formula (1) include
  • inventive automatic dishwashing detergent compositions contain a bleach catalyst d) chosen from bleach-enhancing transition-metal salts and transition-metal complexes, preferably from manganese complexes with 1 ,4,7-trimethyl-1 ,4,7-triazacyclononane
  • Preferred bleach catalysts d) for use herein include the manganese triazacyclo- nonane and related complexes (US-A-4,246,612, US-A-5,227,084); Co, Cu, Mn and Fe bispyridyl-amine and related complexes (US-A-5,114,611); and pentamine acetate cobalt(lll) and related complexes (US-A-4, 810,410).
  • a bleach catalyst d) is typically present in a level of from 0.01 to 10%, preferably from 0.5 to 2% by weight, based on the total weight of the composition.
  • the bleaching system comprises one or more bleaching agents c) and optionally one or more bleach catalysts d) and/or optionally one or more bleach activators e).
  • Particularly preferably the bleaching system comprises one or more bleaching agents c) and one or more bleach activators d).
  • the bleaching system comprises one or more bleaching agents c) and one or more bleach activators d) and one or more bleach catalysts e).
  • inventive compositions may comprise other ingredients commonly used in automatic dishwashing detergent compositions.
  • inventive automatic dishwashing detergent compositions comprise one or more compounds selected from the group consisting of enzymes, glass corrosion inhibitors, water, organic solvents, thickening agents, further surfactants (but no nonionic surfactants), suds suppressors, color speckles, silvercare, anti-tarnish and/or anti-corrosion agents, dyes, fillers, germicides, hydrotropes, anti-oxidants, enzyme stabilizing agents, perfumes, solubilizing agents, carriers, processing aids, pigments, and pH control agents.
  • inventive automatic dishwashing detergent compositions can also contain enzymes. These include proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, or oxidoreductases, as well as preferably mixtures thereof. These enzymes are, in principle, of natural origin. Improved variants based on the natural molecules are available for use in automatic dishwashing detergent compositions and are correspondingly preferred for use.
  • inventive automatic dishwashing detergent compositions contain enzymes preferably in amounts from 1x10 "6 to 5 wt.-%, based on active protein and furthermore based on the total weight of the inventive automatic dishwashing detergent compositions. Protein concentration can be determined by known processes such as the BCA process or biuret process.
  • a protein and/or enzyme can be protected, especially during storage, from damage such as inactivation, denaturing, or decomposition (e.g. resulting from physical influences, oxidation, or proteolytic cleavage). Inhibition of proteolysis is particularly preferred in microbial recovery of proteins and/or enzymes, particularly when the inventive automatic dishwashing detergent compositions also contain proteases.
  • inventive automatic dishwashing detergent compositions can contain stabilizers for this purpose; the provision of such agents in inventive automatic dishwashing detergent compositions represents a preferred embodiment of the present invention.
  • inventive automatic dishwashing detergent compositions containing, based on the total weight of the composition, from 0.1 to 12 wt.-%, by preference from 0.2 to 10 wt.-%, and in particular from 0.5 to 8 wt.-% of enzyme preparation, are particularly preferred.
  • Glass corrosion inhibitors are further preferred ingredients of inventive automatic dishwashing detergent compositions. Glass corrosion inhibitors prevent the occurrence of clouding, smearing, and scratches, as well as iridescence, on the glass surface of automatically cleaned glassware. Preferred glass corrosion inhibitors include magnesium and zinc salts and magnesium and zinc complexes.
  • Inventive automatic dishwashing detergent compositions can be prepared in solid or liquid form, as well as a combination of solid and liquid presentation forms.
  • inventive automatic dishwashing detergent compositions Because elevated alkalinity of the inventive automatic dishwashing detergent compositions contributes to the cleaning performance of these compositions, but also to the corrosive and irritating effect of these compositions, preferred inventive automatic dishwashing detergent compositions have a pH at 20 °C from 8 to 14, preferably from 9 to 11.5, and more preferably from 9.5 to 11.5, measured as a solution of 10 wt.-% of the liquid or solid inventive automatic dishwashing detergent composition in water. Cleaning performance of inventive automatic dishwashing detergent compositions can be improved by addition of organic solvents.
  • a preferred embodiment of the present invention is therefore automatic dishwashing detergent compositions that contain at least one organic solvent.
  • Preferred liquid inventive automatic dishwashing detergent compositions contain, based on the total weight of the composition, organic solvent in quantities from 0.2 to 15 wt.-%, by preference from 0.5 to 12 wt.-%, and particularly preferably from 1 .0 to 10 wt.-%.
  • organic solvents derive, for example, from monoalcohols, diols, triols or polyols, the ethers, esters, and/or amides.
  • Organic solvents that are water-soluble are particularly preferred in this context, "water-soluble" solvents for purposes of the present application being solvents that are completely miscible with water (i.e. with no miscibility gap) at room temperature.
  • Organic solvents from organic amines and/or alkanolamines are effective in cleaning performance, and particularly with regard to cleaning performance on bleachable stains, in particular on tea stains.
  • thickening agents can be added thereto. Thickening agents commonly used in automatic dishwashing detergent compositions can also be used in the inventive compositions. It is advantageous if the respective liquid inventive automatic dishwashing detergent compositions contain the thickening agent in quantities preferably from 0.1 to 8 wt.-%, more preferably from 0.2 to 6 wt.-%, and particularly preferably from 0.4 to 4 wt.-%, based on the total weight of the inventive automatic dishwashing detergent compositions.
  • the surfactants may be chosen from either zwitterionic surfactants, anionic surfactants or mixtures thereof.
  • the zwitterionic surfactant preferably is chosen from the group consisting of C 8 to C-I 8 (preferably C 12 to Ci 8 ) amine oxides and sulfo and hydroxy betaines, such as N-alkyl-N,N-dimethylammino-1 -propane sulfonate where the alkyl group can be C 9 to C-I 8, preferably Cio to C 14 .
  • the anionic surfactant preferably is chosen from alkylethoxysulfates, with the degree of ethoxylation greater than 3 (preferably 4 to 10; more preferably 6 to 8), and chain length in the range of C 8 to Ci 6 , preferably C-n to C-
  • branched alkylcarboxylates have been found to be useful for the purpose of the present invention when the branch occurs in the middle and the average total chain length is 10 to 18, preferably 12 to 16 with the side branch 2 to 4 carbons in length.
  • An example is 2-butyloctanoic acid.
  • the anionic surfactant is typically of a type having good solubility in the presence of calcium. Such anionic surfactants are further illustrated by sulfobetaines, alkyl(polyethoxy) sulfates (AES), and short chained C 6 -Ci 0 alkyl sulfates and sulfonates. Straight chain fatty acids have been shown to be ineffective due to their sensitivity to calcium.
  • inventive automatic dishwashing detergent compositions do not comprise other surfactants in addition to the one or more compounds of the formula (I).
  • the suds suppressors, color speckles, silvercare, anti-tarnish and/or anti-corrosion agents, dyes, fillers, germicides, hydrotropes, anti-oxidants, enzyme stabilizing agents, perfumes, solubilizing agents, carriers, processing aids, pigments, and pH control agents can be chosen from the respective substances commonly used in automatic dishwashing detergent compositions.
  • inventive automatic dishwashing detergent compositions do not comprise phosphates, i.e. they are phosphate-free.
  • the inventive automatic dishwashing detergent compositions are liquid at 20 °C.
  • Liquid presentation forms preferably based on water and/or organic solvents, can exist in thickened form as gels.
  • the inventive liquid compositions comprise up to 60 wt.-% of water, more preferably from 10 to 60 wt.-% of water and even more preferably from 25 to 60 wt.-% of water, in each case based on the total weight of the inventive liquid automatic dishwashing detergent composition.
  • This liquid composition can be provided in the form of a liquid, paste, cream or gel and can be optionally encapsulated, packaged in a single- or multi-compartment pouch, or absorbed onto a porous carrier material.
  • the inventive automatic dishwashing detergent compositions are solid at 20 °C. Powders, granulates, extrudates, or compactates, particularly tablets, are especially suitable as solid presentation forms.
  • the inventive solid compositions comprise less than 20 wt.-% of water, more preferably from 0.1 to 20 wt.-% of water and even more preferably from 0.5 to 5 wt.-% of water, in each case based on the total weight of the inventive solid automatic dishwashing detergent composition.
  • the inventive automatic automatic dishwashing detergent compositions are solid at 20 °C. Powders, granulates, extrudates, or compactates, particularly tablets, are especially suitable as solid presentation forms.
  • the inventive solid compositions comprise less than 20 wt.-% of water, more preferably from 0.1 to 20 wt.-% of water and even more preferably from 0.5 to 5 wt.-% of water, in each case based on the total weight of the inventive solid automatic dishwashing detergent composition.
  • dishwashing detergent compositions are water-free.
  • inventive automatic dishwashing detergent compositions are provided in an all-in-one dosing system, preferably in a mono- or multi-compartment pouch made from a water-soluble film, for example a film comprising polyvinyl alcohol, or a tablet containing all
  • the automatic dishwashing detergent compositions may be provided as multiphase detergent compositions delivering separate portions thereof into the same cycle or into different cycles of an automatic dishwashing machine.
  • the multiphase detergent composition could take the form of a multi-layer liquid (e.g. coacervate) or of a gel contained in a bottle, or of a multiphase tablet incorporating a liquid composition in the form of a gel contained within a preformed cavity or recess within the main tablet body.
  • the hardness of water is determined by the concentration of multivalent cations in the water. Usually, the cations have the charge +2. Common cations found in hard water include Ca 2+ and Mg 2+ . With hard water, soap solutions foom a white precipitate instead of producing lather. This effect arises because the 2+ ions destroy the surfactant properties of the soap by forming a solid precipitate. Hardness can be quantified by instrumental analysis. The total water hardness in terms of this specification is the sum of the molar concentrations of Ca 2+ and Mg 2+ , in mol/L units.
  • Water hardness is often not expressed as a molar concentration, but rather in various units, such as German degrees (°dH).
  • the various alternative units represent an equivalent mass of calcium oxide (CaO) or calcium carbonate (CaCO 3 ) that, when dissolved in a unit volume of pure water, would result in the same total molar concentration of Mg 2+ and Ca 2+ .
  • 1 °dH is formally defined as 10 mg CaO per 1 Liter water.
  • the inventive automatic dishwashing detergent compositions reduce the hardness of the water used in the dishwashing process to a hardness between 1 and 13 °dH, preferably to a hardness between 4 and 12 °dH, and most preferred to a hardness between 6 and 10 °dH.
  • inventive automatic dishwashing detergent compositions are advantageously suited for washing tableware in automatic dishwashing machines, whereby soiled tableware is treated in an automatic dishwashing machine with an aqueous alkaline composition comprising an inventive automatic dishwashing detergent composition. Therefore, the present invention also provides a method of washing tableware in an automatic dishwashing machine, comprising treating soiled tableware in an automatic dishwashing machine with an aqueous alkaline composition comprising an inventive automatic dishwashing detergent composition.
  • the pH value of the aqueous alkaline composition preferably is 8 or higher and more preferably 9 or higher.
  • Dishwashing detergent performance test spotting: dishwasher: Miele G 1222 SC GSL items to test spotting: new items are all pre-treated with demineralized water in Normal eco program of a Bosch logixx dishwasher using 5 times the cleaner combination to be tested, then once 20 g of citric acid, finally once pure water in the upper rack: 8 Hibal Schott "Paris" on the left and on the right in the lower rack: 3 black porcelain plates
  • A is melted in a 1 liter-beaker with the microwave at 600 W for 5 minutes.
  • the components of B are added one after another to I by mixing well with hand-held blender.
  • the components of C are added one after another into a 10 liter-pail and blended well with the blender.
  • II When II is lukewarm, it is added to III by mixing thoroughly.
  • the soil is weighed by 50 g into square 100 ml-jars. In between it is mixed up with the blender.
  • Example 1 the amount in wt.-% is not related to the active ingredient but to the product as is Example 1
  • Alkyloxydiethoxy-/Alkenyloxydiethoxy acetic acid 1) (alkyloxy component derived from cetyl alcohol as main component and alkenyloxy component derived from oleyl alcohol as main component) 100 % by wt
  • Alkyloxydiethoxy-/Alkenyloxydiethoxy acetic acid 1) (alkyloxy component derived from cetyl alcohol as main component and alkenyloxy component derived from oleyl alcohol as main component) 40 % by wt. nonionic surfactant with cloud point 18 °C (1 % by wt. in water), (1 ,2
  • Example 1 shows a very good overall cleaning performance.

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Abstract

La présente invention concerne des compositions détergentes de lavage de vaisselle automatique comprenant : a) un ou plusieurs composés de la formule (I) RO-(CH2CH2O-)nCH2-COOM (I), où R est un groupement alkyle saturé linéaire ou ramifié comprenant de 8 à 30 atomes de carbone ou un groupement alkyle non-saturé linéaire ou ramifié avec une ou plusieurs doubles liaisons et comprenant de 8 à 30 atomes de carbone, n est un nombre de 1 à 20 et M est un contre-ion; b) une ou plusieurs substances à rôle d'adjuvants; et c) un ou plusieurs agents de blanchiment, les compositions détergentes de lavage de vaisselle automatique ne contenant ni ions chlorure ou la quantité totale d'ions chlorure dans les compositions détergentes de lavage de vaisselle automatique étant inférieure à 0,5 % en poids, par rapport à la composition totale, et caractérisés en ce que les compositions détergentes de lavage de vaisselle automatique sont exemptes de tensioactifs non ioniques. Les compositions détergentes de lavage de vaisselle automatique de l'invention présentent en particulier un comportement anti-taches avantageux.
PCT/EP2014/000595 2013-03-14 2014-03-08 Compositions détergentes de lavage de vaisselle automatique exemptes de tensioactifs non ioniques et comprenant des acides carboxyliques d'éther ou leurs sels WO2014139654A2 (fr)

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US14/774,630 US20160017260A1 (en) 2013-03-14 2014-03-08 Automatic Dishwashing Detergent Compositions Comprising Ethercarboxylic Acids Or Their Salts, Which Are Free Of Nonionic Surfactants
EP14709194.6A EP2970822A2 (fr) 2013-03-14 2014-03-08 Compositions détergentes de lavage de vaisselle automatique exemptes de tensioactifs non ioniques et comprenant des acides carboxyliques d'éther ou leurs sels

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US13/804,868 2013-03-14
US13/804,868 US20140261561A1 (en) 2013-03-14 2013-03-14 Automatic Dishwashing Detergent Compositions Comprising Ethercarboxylic Acids Or Their Salts, Which Are Free Of Nonionic Surfactants
US201313912929A 2013-06-07 2013-06-07
US13/912,929 2013-06-07

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2627565A (en) * 2022-12-22 2024-08-28 Innospec Performance Chemicals Italia Srl Detergent compositions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3941710A (en) * 1972-04-24 1976-03-02 Lever Brothers Company Phosphate - free dishwashing compositions containing an alkyl polyether carboxylate surfactant
US4242215A (en) * 1972-06-13 1980-12-30 Chem-Y, Fabriek Van Chemische Produkten B.V. Substantially environmental-pollution-free laundry detergent composition
DE19926627A1 (de) * 1999-06-11 2000-12-14 Henkel Kgaa Bleich- und Desinfektionsmittel
EP1757676A1 (fr) * 1996-09-11 2007-02-28 The Procter and Gamble Company Composition peu moussante pour le lavage de la vaisselle en machine
WO2013083277A1 (fr) * 2011-12-09 2013-06-13 Clariant International Ltd Compositions détergentes de lavage de vaisselle automatique exemptes de tensioactifs non ioniques et comprenant des acides carboxyliques d'éther ou leurs sels

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3941710A (en) * 1972-04-24 1976-03-02 Lever Brothers Company Phosphate - free dishwashing compositions containing an alkyl polyether carboxylate surfactant
US4242215A (en) * 1972-06-13 1980-12-30 Chem-Y, Fabriek Van Chemische Produkten B.V. Substantially environmental-pollution-free laundry detergent composition
EP1757676A1 (fr) * 1996-09-11 2007-02-28 The Procter and Gamble Company Composition peu moussante pour le lavage de la vaisselle en machine
DE19926627A1 (de) * 1999-06-11 2000-12-14 Henkel Kgaa Bleich- und Desinfektionsmittel
WO2013083277A1 (fr) * 2011-12-09 2013-06-13 Clariant International Ltd Compositions détergentes de lavage de vaisselle automatique exemptes de tensioactifs non ioniques et comprenant des acides carboxyliques d'éther ou leurs sels

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2627565A (en) * 2022-12-22 2024-08-28 Innospec Performance Chemicals Italia Srl Detergent compositions

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