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
  • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in 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

Definitions

• the invention relates to rinse aid for machine dishwashing.
• the rinse aid is usually dosed automatically after the main rinse program.
• Another possibility is that so-called 2-in-1 or 3-in-1 systems are used.
• the necessary components for the rinse cycle which are integrated in the cleaner, z. B. in the form of a rinse aid of the detergent tablet, with the detergent formulation already at the beginning of the cleaning cycle in the machine and the necessary components for the rinse cycle are entrained in the rinse cycle.
• EP-A 0 851 021 discloses rinse aid formulations containing low foaming nonionic surfactants, hydrotopes, polycarboxylates and phosphate esters.
• polycarboxylates homopolymers or copolymers of acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid are mentioned.
• DE-A 195 32 542 discloses rinse aids containing nonionic surfactants, organic carboxylic acids and certain cationic polymers.
• DE-U 200 19 913 discloses rinse aids which contain nonionic surfactants, solvents, hydrotopes, acidifiers and copolymers of unsaturated carboxylic acids and sulfonic acid group-containing monomers.
• WO-A-02/20708 discloses dishwashing detergent compositions containing a hydrophobically modified polycarboxylic acid.
• the object of the invention is to provide rinse-aid formulations which give stain-free and coating-free dishes in machine dishwashing.
• copolymers a as defined above, in dishwashing rinse aids for reducing stain and deposit formation.
• hydrophobically modified polycarboxylates used according to the invention significantly improve the rinsing result. This is lower film and Deposit formation as well as an improved execution behavior determined.
• These are polycarboxylates which additionally contain hydrophobic monomers.
• the common polyacrylates such as polyacrylate homopolymer or maleic-acrylic acid copolymers, also very effectively disperse water hardness, their interaction with the typical soil produced by machine dishwashing is low.
• the copolymers used according to the invention assist in the dispersion of dirt during machine dishwashing, so that film and deposit formation are reduced.
• the polymers mentioned support the dispersion of water-insoluble salts, which are contained either in the rinse water or in the food residues. These are, for example, calcium or magnesium carbonates or phosphates.
• the rinse aid formulations according to the invention can be used both for household applications and for industrial applications.
• the composition of the cleaner is irrelevant.
• Both phosphate-based systems and phosphate-free cleaners can be used in combination with the rinse aid formulations.
• the rinse aid formulations themselves may also be part of a dishwashing detergent formulation.
• Suitable monomers a1) are 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.
• Suitable monomers a2) are 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.
• Suitable monomers a3) are 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docoses, 1-tetracoses and 1-hexacoses.
• Further preferred copolymers a) contain as monomers a3) monomers 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 on average 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 -alpha-olefin, a mixture of C 20 -C 24 -alpha-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).
• the rinse aid formulations according to the invention contain weakly foaming nonionic surfactants.
• the surfactants of formula (II) 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 ,
• nonionic surfactants which can be used beyond this are alkyl glycosides, amine oxides, fatty acid alkanolamides and polyhydroxy fatty acid amides, as described, for example, in US Pat DE-U 200 19 913 are described.
• the rinse aid formulations according to the invention may contain nonaqueous solvents.
• Suitable, non-aqueous solvents are mono- or polyhydric alcohols, alkanolamines or glycol ethers, preferably ethanol, n-propanol, i-propanol, 1-butanol, 2-butanol, ethylene glycol, propanediol, butanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexylene glycol , Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl ether or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol
• the rinse aid formulations according to the invention may contain solubilizers (hydrotopes).
• Suitable solubilizers are 1 to 5-fold with C 1 -C 5 alkyl-substituted benzenesulfonates such as toluene, cumene or xylenesulfonate, dihexylsulfosuccinate and short-chain alkyl sulfates.
• Suitable solubilizers are in US 3,563,901 and US 4,443,270 described.
• the rinse aid formulations according to the invention may contain acidifying agents.
• Suitable acidifying agents are inorganic or organic acids, preferably solid mono-, oligo- or polycarboxylic acids or sulfonic acids, for example citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid, polyacrylic acid and amidosulfonic acid and mixtures thereof, for example a mixture of succinic acid, glutaric and adipic acid, which is available under the trade name Sokalan ® DCS from BASF AG.
• Sokalan ® DCS from BASF AG.
• the rinse aid formulations according to the invention may comprise further additives such as anionic, cationic, zwitterionic or amphoteric surfactants, dyes, fragrances and corrosion inhibitors.
• Suitable anionic surfactants are, for example, sodium or potassium alkyl sulfates, in particular those obtained by sulfation of C 8 -C 18 -alcohols, such as those obtained from glycerides of tallow or coconut oil. Further examples are sodium and potassium alkylbenzenesulfonates having 9 to 15 C atoms in the alkyl chain, the linear alkylbenzenesulfonates having 11 to 13 C atoms in the alkyl group being particularly preferred.
• alkyl glyceryl ether sulfonates in particular ethers of higher alcohols, as can be obtained from tallow or coconut oil, sulfonates and sulfates of coconut oil fatty acid monoglycerides, alkylphenol ether sulfates having 1 to 10 ethylene oxide units and 8 to 12 carbon atoms in the Alkyl group, alkyl ether sulfates having 1 to 25 ethylene oxide units and 10 to 20 C atoms in the alkyl group, and ⁇ -sulfonated fatty acid esters having 6 to 20 C atoms in the fatty acid alkyl group and 1 to 10 C atoms in the ester group, and 2 Acyloxyalkanesulfonic acids containing 9 to 23 C atoms in the alkyl group and 8 to 20 C atoms in the acyl group.
• Particularly preferred anionic surfactants are the alkali metal salts of C 11 -C 13 -alkylbenzenesulfonates, C 12 -C 18 -alkyl sulfates and C 12 -C 18 -alkyl ether sulfates containing 1 to 10 mol of ethylene oxide.
• anionic surfactants are also the sulfosuccinates, which are monoesters and / or diesters of sulfosuccinic acid with fatty alcohols or ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C 8 -C 18 fatty alcohol radicals.
• anionic surfactants are soaps, for example the salts of lauric acid, myristic acid, palmitic acid, steararic acid, hydrogenated erucic acid and behenic acid and soap mixtures derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acid.
• the anionic surfactants including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di-triethanolamine, preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts ,
• the copolymers to be tested were mixed into a rinse aid formulation.
• the test was carried out under the specified conditions at 3 ° dH and with addition of IKW ballast dirt, according to S ⁇ FW- Journal, 124th year, 14/98, p. 1029 , performed in main and rinse cycle.
• the (co) polymer was used in the following rinse aid formulation: 20% by weight Low-foaming nonionic surfactant based on fatty alcohol alkoxylates 10% by weight Hydrotop (cumene sulphonate) 5% by weight isopropanol 4% by weight copolymer 61% by weight water
• Dishwasher Miele G 686 SC rinses: 1 rinse 55 ° C normal (without pre-rinse) ware: Knife (WMF table knife Berlin, monobloc); Glasses (Willy cup, 0.3 l); black KS plates, black dessert plates; EMSA Superline - Box (cover PE blue, PP box transparent) Dishwashing liquid: 21 g ballast soil 50 g in the main rinse cycle; 2 g in the rinse cycle Rinse temperature: 65 ° C Rinse-aid: 1 g Water hardness: 3 ° dH (German hardness, corresponding to 53 mg CaCO 3 / kg water)
• the door was opened and the dishes were left to dry for 60 minutes with the machine door open.
• the washware was then evaluated by visual matching in a black painted light box with halogen spot and pinhole using a score scale of 0 (very poor, very strong filming, very spotting, more than 50% of the surface covered with spots) to 4 (very good, no filming, no spots).

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

Priority Applications (1)

Applications Claiming Priority (2)

Publications (2)

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• 2004
  • 2004-09-14 DE DE102004044402A patent/DE102004044402A1/de not_active Withdrawn
• 2005
  • 2005-09-12 ES ES05784277T patent/ES2358121T3/es active Active
  • 2005-09-12 AT AT05784277T patent/ATE495236T1/de active
  • 2005-09-12 JP JP2007530668A patent/JP2008512532A/ja active Pending
  • 2005-09-12 PL PL05784277T patent/PL1791938T3/pl unknown
  • 2005-09-12 CN CNA2005800308878A patent/CN101018850A/zh active Pending
  • 2005-09-12 EP EP05784277A patent/EP1791938B1/de not_active Not-in-force
  • 2005-09-12 US US11/573,450 patent/US20080242577A1/en not_active Abandoned
  • 2005-09-12 DE DE502005010849T patent/DE502005010849D1/de active Active
  • 2005-09-12 CA CA002578291A patent/CA2578291A1/en not_active Abandoned
  • 2005-09-12 WO PCT/EP2005/009789 patent/WO2006029794A1/de active Application Filing

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