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
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
• • 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
  • C11D3/40—Dyes ; Pigments
• • 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
  • C11D3/50—Perfumes

Definitions

• the invention relates to cleaning formulations for machine dishwashing.
• the items to be washed should be produced in a residue-free, cleaned condition with an impeccably glossy surface.
• the items to be washed must be cleaned of food residues and the detached contaminants must be dispersed or emulsified so that they do not re-deposit on the dishes surfaces.
• no whitish spots or deposits should occur, which arise due to the presence of lime or other inorganic and organic salts in the drying of water droplets or reflected by deposition of dirt or inorganic salts already during the rinsing process.
• the multifunctional cleaners eg 3-in-1 cleaners
• the functions of cleaning, rinsing and water softening in a single detergent formulation are combined, so that for the consumer both the refilling of salt (in water from 0 ° to 21 °) as well as rinse aid becomes superfluous.
• polymers are frequently used for inhibiting coating. These may be, for example, sulfonate-containing polymers in phosphate-containing cleaners, which show, in particular, effects on the inhibition of calcium phosphate precipitates.
• the surfactants used are chosen so that they drag themselves into the rinse cycle, where they ensure optimal wetting and a good rinse aid result.
• Other common polymers are polycarboxylates such as polyacrylic acids.
• phosphate-based Many of the formulations on the market are phosphate-based.
• the phosphate used is ideal for use because it combines many useful properties that are needed in machine dishwashing.
• phosphate is able to disperse water hardness (i.e., insoluble salts of water hardness causing ions such as calcium and magnesium ions). This task is still achieved via the ion exchanger of the machines.
• water hardness i.e., insoluble salts of water hardness causing ions such as calcium and magnesium ions
• This task is still achieved via the ion exchanger of the machines.
• a large proportion of dishwashing products today are offered in the form of so-called 3-in-1 formulations, in which the function of the ion exchanger is no longer necessary.
• the phosphate usually takes over the softening of the water in combination with phosphonates. Furthermore, the phosphate disperses the detached dirt and thus prevents re-deposition of the dirt on the dishes.
• EP-A 0 778 340 describes the use of copolymers of allyl alcohol ethoxylates and acrylic acid in phosphate-free dishwashing detergent compositions.
• WO2005 / 042684 describes the use of special copolymers of acrylic acid, methacrylic acid and acrylic acid alkoxylates as deposit-inhibiting additives in machine dishwashing.
• WO2006 / 029806 describes the use of a combination of specific hydrophobically modified polycarboxylates and specific chelants as a builder system in dishwashing detergent formulations.
• WO 02/34870 describes the combination of hydrophobically modified polycarboxylates, acrylic acid (co) polymers and phosphonates to give an antiscaling and antispotting effect. Both phosphate-containing and phosphate-free dishwashing detergents are described.
• the object of the invention is to provide improved phosphate-free cleaning formulations for machine dishwashing which give an improved dishwashing result.
• the object of the invention is, in particular, to provide such formulations which, without the use of additional rinse aid, result in a dish-free, covering-free and drip-free dish.
• the formulation may be processed as a tablet, powder, gel, capsule or solution. These may be formulations for both household and commercial applications.
• the object is further achieved by the use of a combination of hydrophobically modified polycarboxylates a1) and hydrophilic modified polycarboxylates a2) as co-builders in cleaning formulations for machine dishwashing.
• Suitable monomers a11) for the hydrophobically modified polycarboxylates a1) are, for example, maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid.
• Preferred hydrophobically modified polycarboxylates a1) contain as monomers a11) monomers which are selected from the group consisting of maleic acid, maleic anhydride and acrylic acid.
• Suitable monomers a12) are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene.
• Further preferred hydrophobically modified polycarboxylates a1) contain as monomers a12) monomers which are selected from the group consisting of isobutene, diisobutene and styrene.
• Suitable monomers a13) have at least 10, generally 10-26, carbon atoms.
• Suitable monomers a13) are, for example, 1-decene, 1-dodecane, 1-tetradecene, 1-hexadecene, 1-octadene, 1-eicosene, 1-docoses, 1-tetracoses and 1-hexacoses.
• hydrophobically modified polycarboxylates a1) contain as monomers a13) monomers which are selected from the group consisting of 1-dodecene, 1-octadecene, C 22 -alpha-olefin, a mixture of C 20 -C 24 -alpha-olefins and Polyisobutene with an average of 12 to 100 carbon atoms.
• Particularly preferred hydrophobically modified polycarboxylates contain both monomers a11), which are selected from maleic acid, maleic anhydride and acrylic acid, and also monomers a12) which are selected from isobutene, diisobutene and styrene, as well as monomers a13), which are selected from the group consisting of 1-dodecene, 1-octadecene, C 22 -alpha-olefin, a mixture of C 20 C 24 -alpha-olefins and polyisobutene having an average of 12 to 100 carbon atoms.
• the hydrophilically modified polycarboxylates II contain as copolymerized components a21) and a22) acrylic acid, optionally a further acidic monomer, and / or water-soluble salts of these acids, in particular the alkali metal salts, such as potassium and especially sodium salts, and ammonium salts.
• the proportion of acrylic acid a21) to the hydrophilically modified polycarboxylates II is 50 to 99 mol .-%, preferably 55 to 90 mol .-% and particularly preferably 60 to 85 mol .-%.
• the further acidic monomer a22) is in the hydrophilically modified polycarboxylates II to 0 to 50 mol .-%, preferably to 5 to 40 mol .-%, particularly preferably from 10 to 35 mol% and especially to 15 to 30 mol. -% contain.
• Acid monomers a22) are, for example, methacrylic acid, maleic acid, sulfonate groups or phosphonate group-containing monomers, preference being given to methacrylic acid and maleic acid.
• nonionic monomers (a23) are: allyl alcohol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate , Ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, with methoxypolyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate being preferred and methoxypolyethylene glycol methacrylate being particularly preferred.
• the polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units.
• the proportion of nonionic monomers a23) to the hydrophilically modified polycarboxylates II is 0.1 to 20 mol .-%, preferably 1 to 15 mol .-% and especially 2 to 10 mol .-%.
• the ethoxylated allyl alcohol a23) is preferably alkoxylated with 5 to 40 mol, more preferably with 10 to 30 mol of ethylene oxide.
• the weight-average molecular weight M w of the hydrophilically modified polycarboxylates a2) is generally 500 to 500,000 g / mol, preferably 1000 to 300,000 g / mol, particularly preferably 5,000 to 100,000 g / mol.
• the hydrophilically modified polycarboxylates preferably have a calcium insensitivity, which corresponds to a cloud point of a solution containing 250 mg / L of the hydrophilically modified polymer at pH 10 at a calcium concentration of> 2000 mg / L Ca 2+ , that is to say turbidity only above this calcium concentration the polymer solution by precipitation of calcium salts.
• the cleaning formulations according to the invention contain 1 to 20 wt .-%, preferably 1 to 10 wt .-% of the mixture of hydrophobically modified polycarboxylates a1) and hydrophilic modified polycarboxylates a2), wherein the proportion of hydrophobically modified polycarboxylates a1) 5 to 95 wt. %, preferably 10 to 90 wt .-% and particularly preferably 20 to 80 wt .-%, and the proportion of hydrophilically modified polycarboxylates a2) 5 to 95 wt .-%, preferably 10 to 90 wt .-% and particularly preferably 20 to 80 wt .-%, based on the sum of a1) and a2), is.
• the cleaning formulations according to the invention may contain one or more complexing agents.
• Preferred complexing agents are selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid and methylglycinediacetic acid, glutamic acid diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, Ethylenediamine disuccinic acid, aspartic acid diacetic acid and salts thereof.
• Particularly preferred complexing agents b) are methylglycinediacetic acid and its salts.
• the cleaning formulations according to the invention contain weakly or low-foaming nonionic surfactants. These are generally present in proportions of 0.1 to 20 wt .-%, preferably 0.1 to 15 wt .-%, particularly preferably 0.25 to 10 wt .-%.
• the surfactants of formula (III) may be both random copolymers and block copolymers, preferably block copolymers.
• di- and multiblock copolymers composed of ethylene oxide and propylene oxide are used, for example, under the name Pluronic ® (BASF Aktiengesellschaft) or Tetronic ® (BASF Corporation) are commercially available.
• Pluronic ® BASF Aktiengesellschaft
• Tetronic ® BASF Corporation
• reaction products of sorbitan esters with ethylene oxide and / or propylene oxide can be used.
• amine oxides or alkyl glycosides are also suitable.
• suitable nonionic surfactants are the EP-A 851 023 as well as the DE-A 198 19 187 ,
• the formulations may further contain anionic or zwitterionic surfactants, preferably in admixture with nonionic surfactants. Suitable anionic and zwitterionic surfactants are also in EP-A 851 023 such as DE-A 198 19 187 called.
• the cleaning formulations according to the invention comprise bleaches and optionally bleach activators.
• Bleaching agents are subdivided into oxygen bleaching agents and chlorine-containing bleaching agents.
• Use as oxygen bleach find alkali metal perborates and their hydrates as well as alkali metal percarbonates.
• Preferred bleaching agents here are sodium perborate in the form of the mono- or tetrahydrate, sodium percarbonate or the hydrates of sodium percarbonate.
• oxygen bleaching agents are persulfates and hydrogen peroxide.
• Typical oxygen bleaches are also organic peracids such as perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelain acid, diperoxoisophthalic acid or 2-decyldiperoxybutane-1,4-diacid.
• organic peracids such as perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelain acid, diperoxoisophthalic acid or 2-decyldiperoxybutane-1,4-diacid.
• oxygen bleaches can also be used in the detergent formulation:
• Oxygen bleaching agents are used in amounts of generally from 0.5 to 30% by weight, preferably from 1 to 20% by weight, particularly preferably from 3 to 15% by weight, based on the total detergent formulation.
• Chlorine-containing bleaches as well as the combination of chlorine-containing bleach with peroxide-containing bleaches can also be used.
• Known chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, dichloramine T, chloramine B, N, N'-dichlorobenzoylurea, p-toluenesulfondichloroamide or trichloroethylamine.
• Preferred chlorine-containing bleaching agents are sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, magnesium hypochlorite, potassium dichloroisocyanurate or sodium dichloroisocyanurate.
• Chlorine-containing bleaching agents are used in amounts of generally from 0.1 to 20% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.3 to 8% by weight, based on the total detergent formulation ,
• bleach stabilizers such as phosphonates, borates, metaborates, metasilicates or magnesium salts can be added in small amounts.
• Bleach activators are compounds which, under perhydrolysis conditions, comprise aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or substituted perbenzoic acid.
• Suitable compounds are those which contain one or more N- or O-acyl groups and / or optionally substituted benzoyl groups, for example substances from the class of the anhydrides, esters, imides, acylated imidazoles or oximes.
• TAED tetraacetylethylenediamine
• TAMD tetraacetylmethylenediamine
• TA-GU tetraacetylglycoluril
• TAHD tetraacetylhexylenediamine
• N-acylimides such as N-nonanoylsuccinimide (NOSI)
• NOSI N-nonanoylsuccinimide
• acylated phenolsulfonates such as n-nonanoyl or isononanoyloxybenzenesulfonates (n or iso-NOBS)
• PAG pentaacetylglucose
• DADHT 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine
• ISA isatoic anhydride
• bleach activators are nitrile quats, such as, for example, N-methyl-morpholinium
• Bleach activators are preferably suitable from the group consisting of polyacylated alkylenediamines, particularly preferably TAED, N-acylimides, particularly preferably NOSI, acylated phenolsulfonates, more preferably n- or iso-NOBS, MMA and TMAQ.
• Bleach activators are used in amounts of generally 0.1 to 10 wt .-%, preferably from 1 to 9 wt .-%, particularly preferably from 1.5 to 8 wt .-%, based on the total detergent formulation.
• the cleaning formulations of the invention may contain further builders. It is possible to use water-soluble and water-insoluble builders whose main task is the binding of calcium and magnesium.
• the cleaning formulations of the invention may contain enzymes.
• the cleaning agent can be added between 0 and 8 wt .-% of enzymes, based on the total preparation, to increase the performance of the detergents or to ensure under mild conditions, the cleaning performance of the same quality.
• the most commonly used enzymes include lipases, amylases, cellulases and proteases.
• esterases, pectinases, lactases and peroxidases can be used.
• the cleaning agents according to the invention may contain, as component g), further additives such as anionic or zwitterionic surfactants, bleach catalysts, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, disintegrating agents, organic solvents and water.
• further additives such as anionic or zwitterionic surfactants, bleach catalysts, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, disintegrating agents, organic solvents and water.
• EP-A 446 982 and EP-A 453 003 known sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes may be present as so-called bleach catalysts in the inventive cleaning formulations.
• transition metal compounds include those of DE-A 195 29 905 known manganese, iron, cobalt, ruthenium or molybdenum-salene complexes and their DE-A 196 20 267 known N-analogues consisting of DE-A 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in DE-A 196 05 688 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which DE-A 196 20 411 known cobalt, iron, copper and ruthenium-amine complexes which are known in DE-A 44 16 438 described manganese, copper and cobalt complexes, which in EP-A 272 030 described cobalt complexes consisting of EP-A 693 550 known manganese complexes that are made EP-A 392 592 known manganese,
• TMTACN 1,4,7-trimethyl-1,4,7-triazacyclononane
• Suitable bleach catalysts are preferably bleach-enhancing transition metal complexes or salts from the group consisting of the manganese salts and complexes and the cobalt salts and complexes. Particularly suitable are the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate or [(TMTACN) 2 Mn IV Mn IV ( ⁇ -O ) 3 ] 2+ (PF 6 - ) 2 .
• Bleach catalysts can be used in amounts of from 0.0001 to 5% by weight, preferably from 0.0025 to 1% by weight, particularly preferably from 0.01 to 0.25% by weight, based on the total detergent formulation ,
• alkali carriers may be present.
• Suitable alkali carriers are ammonium and / or alkali metal hydroxides, ammonium and / or alkali metal carbonates, ammonium and / or alkali metal hydrogencarbonates, ammonium and / or alkali metal sesquicarbonates, ammonium and / or alkali metal silicates.
• Ammonium and / or alkali metal silicates and mixtures of the aforementioned substances preference being given to using ammonium and / or alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate.
• silver protectants from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
• active chlorine-containing agents are often used in cleaner formulations, which can significantly reduce the corrosion of the silver surface.
• oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g.
• Salts and complex inorganic compounds such as salts of the metals Mn, Ti, Zr Hf, V, Co and Ce are often used.
• the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably from the group of the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl ) Complexes, the chlorides of cobalt or manganese and manganese sulfate used.
• zinc compounds or bismuth compounds can be used to prevent corrosion on the items to be washed.
• Paraffin oils and silicone oils can optionally be used as defoamers and for the protection of plastic and metal surfaces. Defoamers are generally used in proportions of 0.001 wt .-% to 5 wt .-%.
• dyes such as patent blue, preservatives such as Kathon CG, perfumes and other perfumes may be added to the cleaning formulation of the invention.
• a suitable filler is, for example, sodium sulfate.
• ballast dirt were added to the dishwasher at the beginning of the experiment. The test was carried out under the following rinsing conditions.
• the evaluation of the dishes was carried out 18 hours after cleaning by visual inspection in a black painted light box with halogen spot and pinhole.
• the coverings on knives and glasses were rated on a grading scale from 10 (very good) to 1 (very bad).
• the highest grade of 10 corresponds to a surface free of deposits, from grades ⁇ 5 coverings are already recognizable with normal room lighting, so are perceived as disturbing.

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• Chemical & Material Sciences (AREA)
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• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2008
  • 2008-10-10 US US12/682,260 patent/US8262804B2/en not_active Expired - Fee Related
  • 2008-10-10 CA CA2702425A patent/CA2702425C/en not_active Expired - Fee Related
  • 2008-10-10 ES ES08839722T patent/ES2371698T3/es active Active
  • 2008-10-10 WO PCT/EP2008/063646 patent/WO2009050123A2/de active Application Filing
  • 2008-10-10 CN CN2008801111324A patent/CN101821370B/zh not_active Expired - Fee Related
  • 2008-10-10 JP JP2010528415A patent/JP5606319B2/ja not_active Expired - Fee Related
  • 2008-10-10 KR KR1020107009707A patent/KR101529351B1/ko not_active IP Right Cessation
  • 2008-10-10 AT AT08839722T patent/ATE522595T1/de active
  • 2008-10-10 AU AU2008313803A patent/AU2008313803B2/en not_active Ceased
  • 2008-10-10 MX MX2010003792A patent/MX2010003792A/es active IP Right Grant
  • 2008-10-10 EP EP08839722A patent/EP2201090B1/de not_active Not-in-force
  • 2008-10-10 BR BRPI0818439-9A patent/BRPI0818439B1/pt not_active IP Right Cessation
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