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
  • C11D3/26—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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0073—Anticorrosion 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
  • 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

Definitions

• the present invention relates to the use of a phosphate-reduced builder system based on alkali metal polyphosphate and sodium iminodisuccinate for producing material-saving dishwashing detergent formulations for automatic, automatic dishwashing.
• Phosphate-reduced are those formulations whose phosphate content is insufficient to bind the resulting from the water hardness and hardness-forming ions of the dish soil maximum total hardness in the wash liquor and compensate for this gap with a non-belonging to the group of phosphates complexing agent. Levels of tripolyphosphate of about 50% have been found to be adequate (+/- 5%). So phosphate-reduced formulations in the context of the present invention are characterized by a phosphate content of 25 to 40 wt.% Alkalitriphosphat.
• dishwashing in dishwashers takes place at a higher pH and a higher temperature, preferably between 45 ° and 70 ° C.
• the alkaline medium used in this process sapes grease and oil-like soiling and thus removes it from the items to be washed.
• Colored stains, such as tea stains, are removed by oxidation by a bleach system.
• Starch and protein components are hydrolytically split by enzymes and thus more easily removed.
• Surfactants play a role only as a wetting agent in low concentrations and, in contrast to hand dishwashing detergents, have low foaming properties.
• fragrances as the fifth element.
• the various components are most recently integrated or combined in dishwashing tablets, e.g. "3 in 1" or "5 in 1".
• the first automatic dishwashing products consisted of more than 90% sodium tripolyphosphate (NTPP), about 3% of sodium metasilicate to increase alkalinity and corrosion protection, and contained sodium trichloroisocyanurate as a bleaching agent.
• NTPP sodium tripolyphosphate
• the first automatic dishwashing products consisted of more than 90% sodium tripolyphosphate (NTPP), about 3% of sodium metasilicate to increase alkalinity and corrosion protection, and contained sodium trichloroisocyanurate as a bleaching agent.
• NTPP Due to the alkalinity of NTPP and Metasilikat a detachment of the fatty dirt by saponification of the fats could be ensured; In addition, NTPP combines good complexing ability for calcium and magnesium ions with a preservation of glass, porcelain and metal.
• biodegradable organic complexing agents with low toxicity have been developed.
• the medium strength Complexing agent called sodium iminodisuccinate (Na-IDS) and the stronger complexing agent sodium methylglycine diacetate (Na-MGDA). These chelating agents have also been used for phosphate-free dishwashing detergents.
• US 3,697,453 A describes the use of phosphate-reduced builder systems with salts of iminodisuccinic acid and up to 40% polyphosphates for the production of machine dishwashing detergents.
• Such a phosphate-free formulation is described for use as a cleaning formulation for machine dishwashing.
• This formulation contains 1 to 20 wt.% Copolymers, which are composed of the monomers maleic acid, maleic anhydride and acrylic acid, and of isobutene, styrene, etc. are.
• Copolymers based on maleic acid / acrylic acid which may also be hydrophobed, together with the complexing agents form the builder system in many cleaning formulations.
• the builder system to be used according to the invention contains from 25 to 35% by weight of component a) and from 15 to 25% by weight of component b).
• Alkali is understood according to the invention potassium and sodium.
• the inventive combination of a) and b) for use in dishwashing detergents is surprising because this combination reaches the level of classic, exclusively phosphate-containing formulations, especially since Na-IDS is classified among the complexing agents only as a moderate complex and the expert had to assume that Na-IDS will not show the desired success when used in dishwashing machines.
• the inventive combination of a) and b) shows in the stated amounts of the individual components over the prior art significantly improved corrosion behavior compared to the material to be cleaned, as the known from the prior art combinations this being the legal requirements for a modern phosphate reduced dishwashing detergent fulfill.
• the mixture to be used according to the invention may contain, in addition to the two skin constituents alkali polyphosphate and Na IDS as complexing agent, preferably NTPP and Na IDS, further constituents which support or improve the effect of the two.
• these components include polymers and copolymers (which may also be hydrophobed), such as polyacrylic acid or its salts, copolymers of acrylic acid with other comonomers or their salts, polycarboxylic acid based polyaspartic acid or its salts, carboxymethylcellulose or its salt, oxidized starch or cellulose , Metasilicates, phyllosilicates, orthosilicates, carbonates or bicarbonates.
• the complexing agents to be used according to the invention may contain, in addition to Na-IDs, one or more complexing agents of the series nitrilotriacetic acid or its salts, hydroxyethylenediaminetriacetic acid or its salts, ethylenediaminetetraacetic acid or its salts, diethylenetriaminepentaacetic acid or its salts, methylglycinediacetic acid or its salts, glutamic diacetic acid or its salts, and hydroximinodisuccinic acid or its derivatives Salts, ethylenediamine disuccinic acid or salts thereof and also aspartic acid diacetate and salts thereof.
• the formulation may be processed as a tablet, powder, gel, capsule or solution. These may be formulations for both household and commercial applications.
• Cleaning apparatuses in which the combination of components a) and b) or the cleaning formulations obtainable therefrom can be used are domestic dishwashers, dishwashers in commercial kitchens and dishwashing machines on ships, in vehicles and aircraft, but also apparatus cleaning machines in medical or chemical laboratories.
• the cleaning formulations according to the invention containing components a) to d) contain weakly or low foaming nonionic surfactants. These are in Generally in proportions of 0.1 to 20 wt .-%, preferably 0.1 to 15 wt .-%, particularly preferably 0.25 to 10 wt.% Contain.
• Low-foaming or low-foaming nonionic surfactants are preferably end-capped fatty alkyl ethoxylates and obtainable from fatty alcohols and differently arranged ethylene oxide and propylene oxide / butylene oxide blocks (J. Tropsch, H. Gümbel, G. Oetter, New low-foaming surfactants for diskwasher detergents and rinse aids , S ⁇ FW J. 2001, 127, H. 11, 2-5)
• p is an integer from 1 to 5 and m is an integer from 0 to 30.
• the surfactants of formula (I) 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 0 851 023 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 dishwashing detergent formulations according to the invention comprising component a) to d) comprise bleaching agents 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 and 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-diperoxyazelaic 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-diperoxyazelaic acid, diperoxoisophthalic acid or 2-decyldiperoxybutane-1,4-diacid.
• 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 dishwashing detergent formulation.
• Chlorine-containing bleaches as well as the combination of bleach with peroxide-containing bleaches may 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 trichlorethyleneamine.
• 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 dishwashing 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 peroxocarboxylic 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 dishwashing detergent formulation.
• the dishwashing detergent formulations according to the invention which contain components a) to d) may contain further builders. It is possible to use water-soluble and water-insoluble builders whose main task is to bind calcium and magnesium.
• Preferred monomers a1) are, for example, maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid.
• Preferred copolymers a) contain as monomers a1) monomers which are selected from the group consisting of maleic acid, maleic anhydride and acrylic acid.
• Optionally used preferred monomers a2) are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene.
• Further preferred copolymers a) comprise as monomers a2) monomers which are selected from the group consisting of isobutene, diisobutene (2-methyl-3,3-dimethyl-1-butene) and styrene.
• Optionally used preferred monomers a3) have at least 10, preferably 10-26 C-atoms.
• Particularly preferred monomers a3) are 1-decene, 1-dodecane, 1-tetradecene, 1-hexadecene, 1-octadene, 1-eicosene, 1-docoses, 1-tetracoses and 1-hexacoses.
• Further preferred copolymers a) contain as monomers a3) monomers which are selected from the group consisting of 1-dodecene, 1-octadecene, C 22 - ⁇ -olefins and polyisobutene having an average of 12 to 100 carbon atoms.
• particularly preferred copolymers a) contain both monomers a1), which are selected from maleic acid, maleic anhydride and acrylic acid, as well as monomers a2) which are selected from isobutene, diisobutene and styrene as well as monomers a3), which are selected from the group consisting of 1-dodecene, 1-octadecene, C 22 - ⁇ -olefin, a mixture of C 20 -C 24 - ⁇ -olefins and polyisobutene having an average of 12 to 100 carbon atoms.
• copolymers of 30 to 70% by weight of maleic acid and maleic anhydride as monomers a1), 20 to 40% by weight of isobutene as monomers a2) and 5 to 20% by weight of octadecene as monomers a3).
• Component (f) of the invention may contain enzymes containing the components of the invention containing components a) to d).
• the Geschminein Dritz can be added between 0.1 and 8 wt .-% of enzymes, based on the total preparation, to increase its performance or to ensure the cleaning performance of the same quality under milder conditions.
• the most commonly used enzymes include lipases, Amylases, cellulases and proteases.
• esterases, pectinases, lactases and peroxidases can be used.
• the dishwashing detergent formulations according to the invention which contain components a) to d) may additionally contain, as component g), further additives such as anionic or zwitterionic surfactants, bleach catalysts, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents and water.
• further additives such as anionic or zwitterionic surfactants, bleach catalysts, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents and water.
• EP-A 446 982 and EP-A 453 003 be known sulphonic imines and / or bleach-enhancing transition metal salts or transition metal complexes as so-called bleach catalysts in the dishwashing detergent formulations of the invention.
• transition metal compounds include those of DE-A 19 529 905 known manganese, iron, cobalt, ruthenium or molybdenum complexes and their DE-A 19 620 267 known N-analogues consisting of DE-A 19 536 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in DE-A 19 605 688 described manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which DE-A 19 620 411 known cobalt, iron, copper and ruthenium amine complexes which are known in DE-A 4 416 438 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 443 651 .
• EP-A 458 397 EP-A 458 398 .
• EP-A 549 272 EP-A 544 490 and EP-A 544 519 described manganese complexes.
• Combinations of bleach activators and transition metal bleach catalysts are for example DE-A 19 613 103 and WO 95/27 775 known.
• TMTACN 1,4,7-trimethyl-1,4,7-triazacyclononane
• Suitable bleach catalysts are preferably bleach-enhancing transition metal complexes or transition metal 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 .
• Bleaching catalysts may 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 dishwashing detergent formulation.
• alkali carriers may be present as further constituents of the dishwashing detergent formulations according to the invention containing components a) to d).
• 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 and mixtures of the abovementioned substances, preference being given to ammonium and / or Alkali carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate can be used.
• 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 which can markedly reduce the corrosion of the silver surface.
• oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g.
• salt and complex inorganic compounds such as salts of metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
• Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably from the group of cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl ) Complexes, the chlorides of cobalt or manganese and of manganese sulfate.
• zinc compounds or bismuth compounds can be used to prevent corrosion on the items to be washed.
• Paraffin oils and silicone oils can be optimally used as defoamers and for the protection of plastic and metal surfaces. Defoamers are preferably used in proportions of 0.001 wt .-% to 5 wt .-%.
• dyes such as patent blue, preservatives such as Kathon CG, perfumes or other fragrances may be added to the invention containing the components a) and b) and c) and d) dishwashing detergent formulations.
• the dishwashing detergent formulations according to the invention for machine dishwashing on the basis of a builder system with the components a) and b) and also the components c) and d) can be used both in powder form and as tabs.
• Pentasodium triphosphate 45.5% share Phosphonates (Hyodroxyethylenediamine) 5% sodium polycarboxylates 6% soda 20% sodium disilicate 5% sodium 10% Bleach activator TAED (tetraacetylethylenediamine) 2% Protease and amylase 4% Low-foaming surfactants 2% silver protection 0.2% fragrances 0.2%
• sodium tripolyphosphate is partially replaced by sodiumiminodisuccinate, sodium methylglycine diacetate, trisodium citrate, and sodium sulfate.
• the percentages for certain types of dirt are based on a gravimetric determination.

Landscapes

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

Applications Claiming Priority (3)

Publications (2)

Family

ID=39269305

Family Applications (1)

Country Status (12)

Families Citing this family (8)

Family Cites Families (52)

• 2007
  • 2007-01-19 DE DE102007003885A patent/DE102007003885A1/de not_active Ceased
• 2008
  • 2008-01-18 TW TW097101860A patent/TW200846463A/zh unknown
  • 2008-01-18 CA CA002675811A patent/CA2675811A1/en not_active Abandoned
  • 2008-01-18 JP JP2009545936A patent/JP2010516832A/ja active Pending
  • 2008-01-18 WO PCT/EP2008/050541 patent/WO2008087200A1/de active Application Filing
  • 2008-01-18 CN CN200880002413A patent/CN101631848A/zh active Pending
  • 2008-01-18 EP EP08707986A patent/EP2113024B1/de not_active Not-in-force
  • 2008-01-18 AR ARP080100247A patent/AR064974A1/es not_active Application Discontinuation
  • 2008-01-18 CL CL200800155A patent/CL2008000155A1/es unknown
  • 2008-01-18 MX MX2009007599A patent/MX2009007599A/es unknown
  • 2008-01-18 US US12/523,673 patent/US20100144576A1/en not_active Abandoned
• 2009
  • 2009-07-16 IL IL199890A patent/IL199890A0/en unknown

Also Published As

Similar Documents

Legal Events