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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0047—Detergents in the form of bars or tablets
  • C11D17/0065—Solid detergents containing builders
  • C11D17/0073—Tablets
  • C11D17/0091—Dishwashing tablets

Definitions

• the present invention relates to the use of copolymers containing alkylene oxide units which
• R 1 I 2 H 2 C C - COO - RH-RO- -R 4 in which the variables have the following meaning:
• R 1 is hydrogen or methyl;
• R 2 is a chemical bond or unbranched or branched CC 6 alkylene;
• R 3 are the same or different unbranched or branched C 2 -C 4 alkylene radicals;
• R 4 unbranched or branched n 3 to 50,
• the invention relates to rinse aid for automatic dishwashers which contain these copolymers as a deposit-inhibiting additive and detergent tablets for automatic dishwashers which contain the copolymers formulated in the rinse aid core as a deposit-inhibiting additive.
• the dishes In the case of automatic dishwashing, the dishes should be cleaned in a residue-free state with an immaculately shiny surface.
• the wash ware should not should only be completely cleaned of food residues and should not show any whitish stains caused by the presence of lime or other inorganic and organic salts when water droplets dry out.
• rinse aid has been used for a long time.
• the rinse aid is automatically dispensed from the dosing tank into the interior of the dishwasher in the final rinse cycle after passing through the cleaning program, which usually consists of a pre-rinse cycle and a main rinse cycle that is interrupted by intermediate rinse cycles, and ensures that the water flows out of the washware flatly and as completely as possible during the rinse cycle and drying cycle and the washware surfaces are residue-free and flawlessly shiny at the end of the wash program.
• rinse aid surfactants are already integrated in the detergent formulation, so that the additional dosing of a rinse aid can be avoided.
• Modern machine "3in1" cleaners combine the three functions of cleaning, rinsing and water softening in a single detergent formulation, so that the refill of salt with water hardness of 1 to 3 is also superfluous for the consumer.
• Sodium tripolyphosphate is usually added to these cleaners to bind the hardness-forming calcium and magnesium ions. This in turn results in calcium and magnesium phosphate deposits on the wash ware.
• the object of the invention was to provide polymeric additives which, when used in the rinse aid of an automatic dishwasher, are notable for their deposit-inhibiting action.
• R 1 is hydrogen or methyl;
• R 2 is a chemical bond or unbranched or branched CC 6 alkylene;
• R 3 are the same or different unbranched or branched C 2 -C 4 alkylene radicals;
• R 4 unbranched or branched C 1 -C 6 alkyl; n 3 to 50,
• copolymerized randomly or in blocks found as deposit-inhibiting additives in the rinse cycle of the automatic dishwasher.
• rinse aids for automatic dishwashers have been found which contain these copolymers as a deposit-inhibiting additive.
• Detergent tablets for automatic dishwashers have also been found which contain these copolymers as a deposit-inhibiting additive formulated in the rinse aid core.
• copolymers to be used according to the invention are described in the unpublished DE-A-102 25 594 as an additive to detergents and cleaning agents.
• copolymers containing alkylene oxide units to be used according to the invention contain, as copolymerized components (a) and (b), acrylic acid or methacrylic acid 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 (a) in the copolymers to be used according to the invention is 50 to 93 mol%, preferably 65 to 85 mol% and particularly preferably 65 to 75 mol%.
• copolymers to be used according to the invention contain 5 to 30 mol% of methacrylic acid (b), preferably 10 to 25 mol% and especially 15 to 25 mol%.
• the copolymers contain, as component (c), nonionic monomers of the formula I.
• R 1 H 2 C C - COO - R- -RO- - n R * in which the variables have the following meaning:
• R 1 is hydrogen or preferably methyl;
• R 2 unbranched or branched CrCe alkylene or preferably a chemical bond;
• R 3 are the same or different unbranched or branched C 2 -C 4 alkylene radicals, especially C 2 -C 3 alkylene radicals, especially ethylene;
• R 4 unbranched or branched Ci-Ce alkyl, preferably C 1 -C 2 alkyl; n 3 to 50, preferably 5 to 40, particularly preferably 10 to 30.
• the polyalkylene glycols contain 3 to 50, especially 5 to 40 and especially 10 to 30 alkylene oxide units.
• the proportion of nonionic monomers (c) in the copolymers to be used according to the invention is 2 to 20 mol%, preferably 5 to 15 mol% and especially 5 to 10 mol%.
• the copolymers to be used according to the invention generally have an average molecular weight M w of 3,000 to 50,000, preferably 10,000 to 30,000 and particularly preferably 15,000 to 25,000.
• the K value of the copolymers is usually 15 to 40, in particular 20 to 35, especially 27 to 30 (measured in 1% strength by weight aqueous solution at 25 ° C., according to H. Fikentscher, cellulose chemistry, Vol. 13, pp. 58-64 and 71-74 (1932)).
• the copolymers to be used according to the invention can be produced by radical polymerization of the monomers. All known radical polymerization processes can be used. In addition to bulk polymerization, the methods of solution polymerization and emulsion polymerization should be mentioned in particular, with solution polymerization being preferred.
• the polymerization is preferably carried out in water as a solvent. However, it can also be carried out in alcoholic solvents, in particular CrC 4 alcohols, such as methanol, ethanol and isopropanol, or mixtures of these solvents with water.
• thermally activatable polymerization initiators include initiators with a decomposition temperature in the range from 20 to 180 ° C., in particular from 50 to 90 ° C., are preferred.
• suitable thermal initiators are inorganic peroxo compounds, such as peroxodisulfates (ammonium and preferably sodium peroxodisulfate), peroxosulfates, percarbonates and hydrogen peroxide; organic peroxo compounds, such as diacetyl peroxide, di-tert.-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didcanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toloyl) peroxide, succinyl peroxide, tert.-butyl peryl acetate, tert.-butyl acetate .-Butyl perisobutyrate, tert.-butyl per
• initiators can be used in combination with reducing compounds as starter / controller systems.
• reducing compounds include phosphorus-containing compounds, such as phosphorous acid, hypophosphites and phosphinates, sulfur-containing compounds, such as sodium bisulfite, sodium sulfite and sodium formaldehyde sulfoxilate, and hydrazine.
• photoinitiators examples include benzophenone, acetophenone, benzoin ether, benzyl dialkyl ketones and their derivatives.
• Thermal initiators are preferably used, inorganic peroxo compounds, in particular sodium peroxodisulfate (sodium persulfate), being preferred.
• the peroxo compounds are used particularly advantageously in combination with sulfur-containing reducing agents, in particular sodium bisulfite, as the redox initiator system.
• sulfur-containing reducing agents in particular sodium bisulfite
• copolymers are obtained which contain -SO 3 " Na * and / or -SO 4 ' Na + as end groups and are distinguished by a particular coating-inhibiting effect.
• starter / regulator systems containing phosphorus can also be used, for example hypophosphites / phosphinates.
• the quantities of photoinitiator and starter / regulator system must be matched to the substances used. If, for example, the preferred system peroxodisulfate / hydrogen sulfite is used, 2 to 6% by weight, preferably 3 to 5% by weight, of peroxodisulfate and usually 5 to 30% by weight, preferably 5 to 10% by weight are used .-%, hydrogen sulfite, each based on the monomers (a), (b) and (c), used.
• polymerization regulators can also be used.
• the compounds known to the person skilled in the art e.g. Sulfur compounds such as mercaptoethanol, 2-ethylhexylthioglycolate, thioglycolic acid and dodecyl mercaptan.
• the amount used is generally 0.1 to 15% by weight, preferably 0.1 to 5% by weight and particularly preferably 0.1 to 2.5% by weight, based on the monomers (a), (b) and (c).
• the polymerization temperature is generally 30 to 200 ° C, preferably 50 to 150 ° C and particularly preferably 80 to 120 ° C.
• the polymerization can be carried out under atmospheric pressure, but is preferably carried out in a closed system under the self-developing pressure.
• the monomers (a), (b) and (c) can be used as such in the preparation of the copolymers to be used according to the invention, but reaction mixtures which are obtained in the preparation of the monomers (c) can also be used.
• reaction mixtures which are obtained in the preparation of the monomers (c) can also be used.
• methoxypolyethylene glycol methacrylate the monomer mixture obtained in the esterification of polyethylene glycol monomethyl ether with an excess of methacrylic acid can be used.
• the esterification can advantageously also be carried out in situ in the polymerization mixture by combining (1) acrylic acid, (2) a mixture of methacrylic acid and polyethylene glycol monomethyl ether and (3) radical initiators in parallel.
• a catalyst required for the esterification such as methanesulfonic acid or p-toluenesulfonic acid, can additionally be used.
• copolymers to be used according to the invention can also be obtained by a polymer-like reaction, e.g. by reacting an acrylic acid / methacrylic acid copolymer with polyalkylene glycol monoalkyl ether.
• a polymer-like reaction e.g. by reacting an acrylic acid / methacrylic acid copolymer with polyalkylene glycol monoalkyl ether.
• the radical copolymerization of the monomers is preferred.
• the aqueous solutions obtained in the preparation of the copolymers containing carboxylic acid groups to be used according to the invention can be neutralized by adding base, in particular sodium hydroxide solution or partially neutralized, ie adjusted to a pH in the range 4-8, preferably 4.5-7.5.
• copolymers used according to the invention are notable for their outstanding deposit-inhibiting action when used in the rinse aid of automatic dishwashers.
• coverings are caused by the components of the detergent formulation carried over into the rinse cycle by the "carry-over effect", such as coverings of calcium and magnesium phosphate, calcium and magnesium silicate and calcium and magnesium phosphonate, and coverings resulting from the Dirt constituents of the washing liquor originate, such as fat, protein and starch deposits.
• the copolymers to be used according to the invention sustainably improve the cleaning result due to their deposit-inhibiting effect.
• they promote the drainage of the water from the wash ware, even in low concentrations, so that the proportion of rinse aid surfactants in the dishwashing detergent can be reduced. Accordingly, particularly clear glasses and high-gloss metal cutlery are obtained, especially when the dishwasher is operated without water regeneration salt for water softening.
• copolymers used according to the invention can be used directly in the form of the aqueous solutions obtained in the preparation and also in dried, e.g. form obtained by spray drying, fluidized spray drying, roller drying or freeze drying.
• Suitable coating material for this purpose is, for example, polyvinyl alcohol produced by incomplete hydrolysis of polyvinyl acetate (degree of hydrolysis generally from 88 to 98%, preferably 89 to 95%, particularly preferably 91 to 92%).
• Suitable matrix materials are, for example, gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, cellulose and their derivatives, starch and their derivatives and mixtures of these materials.
• the copolymer according to the invention was used together with a commercially available 3in1 dishwashing formulation in tablet form (Saturday), the copolymer only being added in the rinse cycle in order to simulate a delayed release of further copolymer.
• the test was carried out under the following washing conditions with the addition of IKW ballast dirt (S ⁇ FW-Journal, 124th year, 14/98, p. 1029) in the main washing cycle and made in addition to the copolymer in the rinse aid. In addition, neither regenerated salt nor rinse aid formulation was used.
• Rinsing conditions Dishwasher: Miele G 686 SC Rinses: 1 rinse 55 ° C normal (without pre-rinsing) Wash items: Knives (WMF table knife Berlin, monoblock); Glasses (Willy Becher, 0.3 I); black plastic plates, black dessert plates; EMSA Superline Box (lid PE blue, PP can transparent) Dishwashing liquid: Somat 3 in 1 ballast dirt: 50 g in the main wash cycle; 2 g in the rinse aid copolymer: 210 mg in the rinse aid rinse temperature: 65 ° C
• the copolymer was added directly to the rinse aid formulation. The test was carried out under the conditions specified below with the addition of IKW ballast soiling in the main and rinse cycle.
• sodium tripolyphosphate 50% by weight sodium tripolyphosphate (Na 3 P 3 O 10 6 H 2 O)
• the copolymer was used in the following rinse aid formulation:
• Rinses 1 rinse 55 ° C normal (without pre-rinsing)
• Knives Knives (WMF table knife Berlin, monoblock); Glasses (Willy Becher, 0.3 I); black plastic plates, black dessert plates; EMSA Superline box (lid PE blue, PP box transparent)
• Ballast dirt 50 g in the main wash cycle; 2 g rinse aid
• Rinse aid temperature 65 ° C
• Rinse aid dosage i g

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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)
• Peptides Or Proteins (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Applications Claiming Priority (2)

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• 2003
  • 2003-10-28 DE DE10350420A patent/DE10350420A1/de not_active Withdrawn
• 2004
  • 2004-10-23 US US10/577,261 patent/US7530360B2/en not_active Expired - Fee Related
  • 2004-10-23 EP EP04790785A patent/EP1682645B1/fr not_active Expired - Lifetime
  • 2004-10-23 CA CA002543543A patent/CA2543543A1/fr not_active Abandoned
  • 2004-10-23 JP JP2006537146A patent/JP2007510021A/ja active Pending
  • 2004-10-23 DE DE502004008984T patent/DE502004008984D1/de not_active Expired - Lifetime
  • 2004-10-23 ES ES04790785T patent/ES2318349T3/es not_active Expired - Lifetime
  • 2004-10-23 AT AT04790785T patent/ATE422533T1/de active
  • 2004-10-23 WO PCT/EP2004/011994 patent/WO2005042684A1/fr active Application Filing

Non-Patent Citations (1)

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