HUT73203A - Dishwasher agents with biodegradable builders - Google Patents

Abstract

The invention concerns low-alkaline agents for use in dishwashing machines, the agents containing builders which are readily biodegradable. These readily biodegradable builders are copolymers synthesized from the monomers of a monoethylenically unsaturated C3-C8 carboxylic acid, a 2-alkylallylsulphonic acid or 2-arylallylsulphonic acid and a carbohydrate, preferably saccharose.

Description

BACKGROUND OF THE INVENTION The present invention relates to a weakly alkaline dishwashing detergent having a biodegradable film forming component for machine cleaning.

The latest generation of weakly alkaline dishwashing detergents for machine cleaning contain, in addition to oxygen-based bleaches, surfactants and enzymes, a combination of water-soluble film-forming materials, which include complexing agents such as citrate, alkaline carriers such as soda, bicarbonate or disilicate, for a reason. Other possible film-forming components are organic phosphonic acids, aminocarboxylic acids, or crystalline layer silicones. Previously used phosphates, such as pentanedio tripolyphosphate, are now largely abandoned for ecological reasons.

Polycarboxylates, such as maleate / acrylate copolymers, used in today's dishwashing detergents prevent the formation of lime coatings with high residual water hardness during the cleaning and purging process, and thus also improve the purification effect of the high salt loading of the purging fleet.

The disadvantage of such polycarboxylates is that they are difficult to biodegrade. Therefore, there is a need for machine dishwashing detergents that contain biodegradable film-forming ingredients, but at the same time display the usual power spectrum of modern dishwashing detergents. Certain readily biodegradable film-forming components, such as oxidized starch or polyaspartic acid, are good dispersants for precipitated calcium carbonate, but poor complexing agents for water hardness.

Surprisingly, it has been found that certain biodegradable copolymers, made up of at least three building blocks, are well suited as film-forming components in machine dishwashing detergents.

FIELD OF THE INVENTION The present invention relates to a weakly alkaline machine dishwashing agent having a 1% w / w aqueous solution having a pH of 8.5 to 11.5, preferably 9 to 10.5, and comprising water-soluble film forming components and oxygen bleaching agents. containing a copolymer of a monoethylenically unsaturated component as a water-soluble film forming component

It is composed of monomers of a C3-C8 carboxylic acid, a 2-alkyl allylsulfonic acid or an aryl allylsulfonic acid and a carbohydrate.

Also included in the rinse aids of the present invention are those in which the copolymers are partially or wholly substituted for the salts of the copolymers, i.e. copolymers in which the carboxylic swept cause has been partially or completely converted to carboxylate groups.

In the simplest case, the copolymers used according to the invention contain two carboxylic acids and / or carboxylic acids and a carbohydrate as a monomer. The first acidic monomer or a salt thereof can be derived from a monoethylenically unsaturated C 3 -C 8 monocarboxylic acid, preferably C 3 -C 4 monocarboxylic acid, in particular / meth / acrylic acid. The second acidic monomer or a salt thereof is an allylsulfonic acid derivative substituted in the 2-position by an alkyl group, preferably a C 1 -C 4 carbon atom, or by an aromatic group, preferably benzene or benzene derivatives ···· · ··· « _{Μ β} • ·« · · ·

- * · · · ··· ··· • · · ··· ♦ · «· ** * · ··« 4 can be deduced. Therefore, the incorporation of further monomer units in the copolymer is not excluded. Preferred copolymers are 40 to 60% by weight, in particular 45 to 55% by weight, of meth / acrylic acid or / meth / acrylate, in particular of acrylic acid or acrylate, 10 to 30% preferably of 15 to 25% by weight of methylsulfonic acid and / or also containing methacrylic acid-polyethylene glycol ester formed by the addition of 1 to 10 ethylene oxide units which can be partially substituted by the methylsulfonic acid and the methylsulfonate, and then the weight ratio of methacrylic acid to polyethylene glycol and sulfate in the range from 1: 10 to 10: 1, and copolymers also contain from 15 to 40% by weight of carbohydrate, preferably from 20 to 40% by weight. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, with mono-, di- or oligosaccharides being preferred. The incorporation of carbohydrate creates so-called binding breakage points in polymers which are responsible for the degradation of the polymer. As the carbohydrate, sucrose is particularly preferred. The copolymers used in the present invention can be prepared according to all known and conventional methods. In addition, in particular, the monomeric acids react with the carbohydrate and then optionally neutralize the acids to the corresponding alkali salts, such as sodium or potassium salts, or ammonium salts, or alkanolamines, such as monoethanolamine salts or triethanolamine salts.

Similar to known / co / polymeric polycarboxylic acids or polycarboxylates, such as homo- or copolymer acrylic acids or acrylates, copolymers are preferred.

- which are wholly or at least partially, in particular more than 50%, neutralized with respect to the carboxylic acid present. In particular, a fully neutralized copolymer which is thus preferably composed of salts of monomeric acids, in particular sodium or potassium salts of monomeric acids, and a carbohydrate is preferred. The relative molecular weights of the copolymers are generally between 1000 and 200,000, preferably between 2000 and 50,000 and especially between 3,000 and 10,000. They are preferably used as spray-dried powders. Particularly preferred copolymers are prepared by the process described in P 42 21 381.9. German Patent Application Laid-Open Patent Application No. 4,600,900.

The preferred dish rinse aids of the present invention comprise a copolymer in an amount of from 0.5 to 30% by weight, preferably from 2 to 20% by weight, an oxygen based bleaching agent from 0.5 to 20% by weight, preferably from 5 to 15% by weight. containing up to 5% by weight, preferably 2% by weight, of nonionic surfactants, in addition to being free from anionic, cationic or amphoteric surfactants.

In a preferred embodiment, the agents contain up to 60% by weight, preferably 5 to 50% by weight, of alkali carbonate and / or bicarbonates, in particular sodium salts, as alkaline carriers.

Further water-soluble film-forming components of the present invention, such as salts of the polymerization products of unsaturated carboxylic acids, such as polyacrylates, polymethacrylates, poly (6-limaleinates) or alcohols containing maleic anh 30% by weight, preferably 2-20% by weight. Suitable polyacrylates include, for example, Alcoperse '102, 104, 106, 404, 406 from Alco, Acrysole ^^ A NI, LMW 45 N, LMW / r /

N from Norsohaas, Degapas, a product of Degussa; suitable copolymers of polyacrylic acid and maleic acid are, for example, Sokalan ^^ CP 5, CP 7 from BASF, Acrysol ^^ QR 1014 / r / a from Norsohaas and Alcosperse '175 from Alco. In principle, dish rinse aids may also contain phosphates or zeolites, but are preferably free of zeolites and phosphate-containing film forming components.

For surfactants useful in the agents of the present invention, their foam retention is crucial. Due to the mechanics of the machine, low-foam compounds are preferred. These are primarily nonionic surfactants. The dishwashing detergents of the present invention are therefore preferably free from anionic, cationic or amphoteric surfactants. The amount of nonionic surfactants is not more than 5% by weight, preferably not more than 2% by weight. The nonionic surfactants are preferably 1-20 mol of ethylene oxide (EO) and / or 1-20 mol of propylene oxide / PO / 1 mol of a C10-20 aliphatic compound. addition products of alcohols, carboxylic acids, fatty amines, carboxylic amides and compounds of the alkanesulfonamides group. In addition to water-soluble non-ionic surfactants, polyglycol ethers, both non-soluble and not completely water-soluble, having 2-7 ethylene glycol ethers in the molecule are also important, preferably water. · · ······ «« · «<·.

- Used in combination with 7 soluble nonionic surfactants. In addition, alkyl polyglycosides of the formula R-O- / G, wherein R is a primary, straight or branched aliphatic C8-C22, preferably C12-C18 aliphatic residue, G is a C5 or C6 The degree of oligomerization x is between 1 and 10.

The rinse aids of the present invention also contain complexing agents containing from 0.5 to 60% by weight, preferably from 20 to 50% by weight, of the di- and multifunctional organic carboxylic acids or their salts, for example nitrilotriacetic acid, especially citric acid or its salts. quantities.

Common alkaline disinfectants used in weakly alkaline machine dishwashing detergents include alkali carbonates, bicarbonates, and alkali silicates, which have a SiO ₂ / M ₂ 0 molar ratio / M = alkaline atom / 1.5: 1 to 2.5: 1. The alkali carbonates and bicarbonates incorporated in the agents of the present invention are sodium carbonate and bicarbonate, which are present in the amounts given above. The use of highly alkaline metasilicates as alkaline carriers is advantageously dispensed with. Metasilicates are preferably used instead of alkali silicate reason, especially the sodium silicate MOT s _o SiC / Na 0 1.5 are used in a molar ratio of from 1 up to 30 wt%, preferably 5-20% by weight: 1 to 2.5 in relation to the total weight of the dish rinse aid.

Among the oxygen-based compounds for the blanch őszerekként sodium perborate tetrahydrate / NaB0 ₂ .h ₂ 0 ₂ · 3H ₂ 0 /, sodium perbo- 8 Rat monohydrate / náboje ₂ · Η ₂ 0 and the peroxy carbonate / Na ₂ C0yl, 5 H ₂ 0 ₂ / of particular importance. Other useful bleaching agents include, for example, peracid salts of organic acids such as perbenzoate or diperdodecanedioic acid. Preferably 0.5 to 20% by weight, in particular 5 to 15% by weight, of oxygen-based bleaching agent, in particular alkali metal perborate and / or percarbonate, are used. In addition, small amounts of bleach stabilizing agents, such as borates or metaborates and metasilicates, and magnesium salts, such as magnesium sulfate, may be useful.

Suitable bleach activators are in particular N-acyl and O-acyl compounds, preferably tetraacylated diamines such as Ν, Ν, Ν ', N * tetraacetyl ethylenediamine (TAED). The agents of the present invention contain from 0.1% to 10% by weight of such conventional whitening active agents, preferably from 1 to 5% by weight. The agents of the invention are preferably free from activating chlorine cleaving agents such as trichloroisocyanuric acid.

Preferably, the agents may contain enzymes such as proteases, amylases, lipases or celluloses, such as BLAp / R / 140 from Henkel, Optimase ^^ - M-440, for better dissolution of protein or starchy food residues. Optimase ^^ - M-330, Opticlean ^^ - M-375, Opticlean ^^ - M-250 from Solvay Enzymes, Maxacal ^^ CX 450,000, Maxapen from Ibis, Savinase '4 , 0 T, 6.0 T, 8.0 T from Novo or Expera / r / '/ r / se' T from Ibis; amylases such as Termamyl 60 T, / r /

T, which is a Novo product, Amylase-LT from Solvay Ensymes, or Maxamy ^ P 5000, CXT 5000 or CXI 2900 from Ibis; lipases such as Lipase '30 T, a product of Novo;

- 9 / ρ / a celluloses, such as Celluzym ⁷ '0.7 T from Νσνο Nordisk. The enzymes are present in the agents of the invention in an amount of from 0.1 to 5% by weight, preferably from 1 to 3% by weight, based on the total amount of dish rinse aid.

Optionally, silver protective agents, such as those described in P 43 15 397.6, may be used to prevent silver cutlery from engaging. In particular, water-soluble Mn / II / salts can be used in amounts of up to 2% by weight, preferably 0.1% to 0.5% by weight.

The dish rinse aids of the present invention are preferably in the form of powder, granular or tablet formulations which can be prepared in a manner known per se, for example by mixing, granulating, roller compacting and / or spray drying. In addition, it is also possible to use the polymers of the invention as admixtures in admixture with other granular constituents of dish rinse aids.

In the preparation of the cleansers of the present invention in tablet form, it is preferable to mix all the ingredients in a blender and compress the blend into tablets using a conventional tablet press, such as an excenter press or a rotary press. In this way, breakage-free and yet satisfactory dissolving tablets with a bending strength above 150 N are normally obtained. The weight of the tablets thus obtained ranges from 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of 35 mm to 40 mm.

The preparation of machine dishwashing detergents in the form of non-dusting, storage-stable, free-flowing powders and / or granules, preferably having a compactness in the range of 800 to 900 g / l, for example by first forming the coating components with at least a portion of the liquid blend components. mixing while increasing the compactness of the premix and then, if desired after intermediate drying, combining the remaining portions of the rinse aid with the resulting premix.

Since the alkali carbonate content strongly influences the formation of the product, the intermediate drying is preferably carried out in such a way that the decomposition of the sodium bicarbonate to the sodium carbonate is as low as possible / or as constant as possible. The proportion of sodium carbonate formed during drying must be taken into account in the formulation of the granulate. Low drying temperatures not only prevent the decomposition of sodium bicarbonate but also increase the solubility of the granular detergent in use. Thus, during drying, it is advantageous to keep the temperature of the introduced air as low as possible, on the one hand, in order to avoid decomposition of the bicarbonate, and on the other hand, to as high as necessary to obtain a product having good storage properties. The temperature of the introduced air during drying is preferably about 80 ° C. Thus, the granulate itself should not be heated to temperatures above 60 ° C.

In the first step of the mixing process, the layering agent is usually applied in combination with at least one other component of the dish rinse agent together with the liquid components. A first step is contemplated here, in which the film-forming components are mixed with perborate and used in combination with the liquid nonionic surfactants and / or the perfume solution and thoroughly mixed therewith. Subsequently, the remaining components are added to the mixture and the whole mixture is thoroughly processed and homogenized in the mixer. The use of additional amounts of liquid, in particular the addition of additional water, is not usually required here. The resulting material mixture is then formed as a bulk non-dusting powder having a density of about 800 to 900 g / liter.

The pre-granules are then mixed with the remaining components of the dish rinse aid to give the finished product. In all cases described herein, the mixing time is in the range of a few minutes, for example 1 to 5 minutes, both during the introduction of the liquid components during the upstream mixing step and during final mixing with the other components.

In a particular embodiment, it may be desirable to provide further stabilization and equilibration by dusting the surface of the granulate formed to produce fine granulate particles. Small amounts of water glass powder or powdered alkaline carbonate are particularly suitable.

The machine dishwashing detergents of the present invention have a superior performance over conventional modem dishwashing detergents, particularly with respect to antifouling and clean rinsing.

The following examples further illustrate the rinse aids of the present invention, but the scope of the invention is not limited to those described in the examples.

Examples

Granular pot rinse aids having the following compositions are prepared, wherein A is the agent of the invention and B is the comparator agent C is also the agent of the invention.

Agent A contains 10% by weight of a copolymer as disclosed in P 42 21 381.9. According to the old German patent application no. 506, it is prepared from 50% by weight of acrylic acid, 33% by weight of sucrose and 17% by weight of 2-methylsulfonic acid and the product is completely neutralized.

Comparative Example B contains 10% by weight of acrylate maleate copoly, marketed under the trade name Sikolan '' CP5 and a product of BASF.

♦♦ ·· ···· ·

- 13 ABCs

% by weight % by weight % by weight Na-citrate 30.0 30.0 40.0 Sokolan CP5 - 10.0 - the above copolymer 10.0 - 5.0 Na ₂ C0 ₅ 13.0 13.0 6.0 NaHCO 3 35.5 35.5 30.1 Na perborate 5.0 5.0 - N a-p e rka r b on - - 12.0 TAED 2.0 2.0 3.0 amylase 1.5 1.5 1.0 protease 1.5 1.5 1.0 Plurafac LF403 BASF Company 0.9 0.9 0.9

/ 0 _Ί ο-fatty alcohol χ EO x 4P0 /

perfume oils 0.6 0.6 0.6 Na ₂ S0 ₄ - - 0.4

cleaning Performance

The cleaning performance of Agents A and B was tested in a Miele G 531 pot rinse machine (universal program at 65 ° C), whereby 30 g of the product were dissolved in 7.0 liters of 16 hardnesses each time! degree water in the cleaning process / impurities as described in Th. Altenschöpf er, SÖFW, 98 Ι ~ 1312.Ι 763 - 765: tea, milk, vgdal meat, pudding, crayon, starch • · ·

Were 14 and oatmeal.

In particular, the agent A of the present invention exhibited superior cleaning performance in removing starch, minced meat, crayon and oatmeal contaminants, particularly tea contamination, in contrast to non-inventive agent B.

scale prevention

The deposition of Agents A and B was tested in a Miele G 590 type rinse machine (Universal program at 65 ° C), each time dissolving 20 g in 7.0 liters of 16 German hardness! Add 50 g of pumpable impurity in Grade water in the presence of a mixture of breast / tap, roasting sauce, mustard, potato starch, yolk, milk, margarine / 3.0 ml of pure rinse aid in 10 rinses. The cleaning effect was rated on a 1 to 8 scale with 1 being a very bad cleansing effect and 8 being a very good cleansing effect. The results of the cleansing action of the agent A of the present invention and the comparator agent B on glasses, knife blades and porcelain plates are shown in Table 1.

Table 1

B cups 61 knives blades 5.53 p orc edging 56 * · · ·

The results show that the agent A according to the invention outperforms the cleaning performance of the comparator agent B in glasses and knife blades.

The agent C of the present invention exhibits a cleaning and anti-deposition performance comparable to that of the agent A of the present invention; In the presence of MnSO 4, first of all, it exhibits superior properties with regard to inhibition of silver stock incorporation.

- 16 Patent claims

Claims (10)

Claims A weakly alkaline agent for machine dishwashing, having a pH of 8.5 to 11.5, preferably 9 to 10.5, in an aqueous solution of 1% by weight and containing water-soluble film-forming components and oxygen-based bleaching agents, characterized in that: as a water-soluble film forming component, it comprises a copolymer consisting of monomers of a monoethylenically unsaturated C 3 -C 8 carboxylic acid, a 2-alkyl allylsulfonic acid or an aryl allylsulfonic acid and a carbohydrate. Agent according to claim 1, characterized in that the copolymer is 40 to 60% by weight, preferably 45 to 55% by weight, of meth / acrylic acid, preferably acrylic acid, 10 to 30% by weight, preferably 15 to 25% by weight of metallylsulfonic acid and 15 to 40% by weight, preferably 20 to 40% by weight of carbohydrates, in particular sucrose, with the methacrylic acid polyethylene glycol ester partially substituted by the addition of 1-10 ethylene oxide units to methacrylic acid and then the weight ratio between methacrylic acid polyethylene glycol ester and metal sulfonic acid is in the range of 1: 10 to 10: 1. 3. An agent according to claim 1 or 2, characterized in that it is present in an amount of 0.5 to 30% by weight, preferably 2 to 20% by weight, of a copolymer, 0.5 to 20% by weight. Up to 17% by weight of oxygen-based bleach, mainly alkaline perborate and / or percarbonate, and free from anionic, cat-ionic or amphoteric surfactants and up to 5% by weight, preferably up to 2% by weight, of nonionic surfactants at any one time. relative. An agent according to any one of claims 1 to 3, characterized in that it contains up to 60% by weight, preferably 5-50% by weight, of alkali carbonate and / or bicarbonate. 5. An agent according to any one of claims 1 to 4, characterized in that it contains complexing agents in an amount of up to 60% by weight of the moiety selected from the group consisting of di- or multifunctional organic carboxylic acids and their salts, in particular citric acid and its salts. in an amount of from 20 to 50% by weight, based on the total weight of the agent. An agent according to any one of claims 1 to 5, characterized in that it does not exceed It contains from 30% by weight, preferably from 5 to 20% by weight, of an alkali silicate having a molar ratio of SiO 2/1 to 2 O / M of an alkali atom of 1.5: 1 to 2.5: 1. An agent according to any one of claims 1 to 6, characterized in that it is free from activating chlorine cleaving agents. An agent according to any one of claims 1-7, characterized in that it contains from 0.1 to 5% by weight of enzymes, preferably from 0.5 to 2% by weight, based on the total weight of the agent. A tablet-based agent according to any one of claims 1 to 8, characterized in that it is prepared by mixing all its ingredients in a blender and compressing the blend into tablets using a tablet press at a pressure of from 2 to 10 bar. A powder or granule agent according to any one of claims 1 to 8, characterized in that it has a density of between 750 g / l and 1000 g / l. Use of an agent according to any one of claims 1 to 10 for cleaning a vessel.