HUT73202A - 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 of [meth]acrylic acid or [meth]acrylate, maleic acid or maleate and vinyl alcohol and/or vinyl acetate.

Description

FIELD OF THE INVENTION The present invention relates to weakly alkaline cleaning agents for dishes which contain biodegradable film-forming components. The biodegradable film forming components are copolymers formed from / meth / acrylic acid / / / meth / acrylate, maleic acid or maleate and vinyl alcohol and / or vinyl acetate.

• ·

61 206 / HF

S.B.G. & Κ.

International Patent Office

H-1062 Budapest, Andrássy út 113. Phone: 34-24-950, Fax: 34-24-313

Posted by p ·

Bin Flush Dispenser Biodegradable Coating Machine

HENHEL KOMMANDITGESELLSCHAFT AUF ACTENE, DÜSSELDORF,

GERMANY

Inventors: BUCHMEIER Willi, ΜΕΓΤΜΑΝΝ, ANDREE Hans, LEICHL INGEN, KRINGS Peter, KREFELD, BURG BIRGIT, ALPEN, Jürgen HARER, DÜSSELDORF, JESCHKE Peter, NEUSS, GERMANY

Date of filing: 20.06.1994

Priority: ^ 993- ° ⁶ * ^{28, 21 4} 30.4 /

GERMANY

International Application Number: PCT / EP 94/020 00

International Publication Number: WO 95 / 002J

BACKGROUND OF THE INVENTION The present invention relates to a slightly 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 bleaching agents, surfactants, and enzymes, a combination of water-soluble film-forming agents which include complexing agents such as citrate, alkaline carriers such as soda, bicarbonate or disil for a reason. Other possible film-forming components are organic phosphonic acids, aminocarboxylic acids or crystalline film silicates. Previously used phosphates, such as pentanedio tripolyphosphate, are now largely abandoned for ecological reasons.

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

A 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 components, but at the same time display the usual power spectrum of modem dishwashing detergents. Although many biodegradable film-forming components, such as oxidized starch or polyaspartic acid, are good dispersants for precipitated calcium carbonate, they are bad complexers for water hardness.

U.S. Patent No. 3,887,480 discloses a dish and textile cleaning agent comprising a polymer comprising 35 to 70 mol% maleic acid, 20 to 45 mol% vinyl acetate and 2 to 40 mol% acrylic acid. EP 0 193 50 00 B1 describes zeolite-containing textile detergents containing a polycarboxylate polymer consisting of C3-C10 monocarboxylic acid, C4-C6 dicarboxylic acid and a nonionic bulking agent such as vinyl alcohol. U.S. Patent No. 3,755,264 discloses copolymers consisting of, for example, 85 to 99 mol% maleic anhydride and 1 to 15% mixture consisting of acrylic acid and vinyl acetate. EP 0 076 992 A1 discloses, among other things, the use of polymers composed of 50 to 94% by weight of acrylic acid, 0.5 to 5% by weight of vinyl acetate and up to 49% by weight of maleic acid, which are present as crust inhibitors. and cleaning products.

Surprisingly, it has been found that copolymers of the weight ratios (meth / acrylic acid / meth / acrylate, maleic acid / maleate and vinyl alcohol and / or vinyl acetate) described in certain of the above-mentioned literature are suitable as excellent film-forming components. protection products.

FIELD OF THE INVENTION The present invention relates to a weakly alkaline dishwashing agent having a pH of 8.5 to 11 »5», preferably 9 to 10.5, in 1% aqueous solution and containing water-soluble film-forming components and oxygen-based bleaching agents. characterized in that the water-soluble layer forming component is a copolymer, wherein the copolymer is 60-95% by weight, preferably 70-90% by weight of meth / acrylic acid or / meth / acrylate, in particular of acrylic acid or acrylate, 4-40% by weight of maleic acid and / or maleate and 5 to 40% by weight, preferably 10 to 25% by weight of vinyl alcohol and / or vinylacetate, in addition the ratio by weight / meth / acrylic acid / / meth / acrylate to maleic acid / maleate 5: 1 to 4: 1, preferably 2: 1 to 2.5: 1, the amounts and weight ratios are for acids, and copolymers of acid salts and vinyl alcohol are preferred.

The copolymers used in the present invention may be prepared according to any of the known and conventional methods. In addition, in particular, meth (acrylic acid), preferably acrylic acid and maleic acid, is reacted with vinyl alcohol and / or vinyl acetate, optionally in the form of neutralization, preferably to an alkali salt such as sodium or potassium or ammonium or alkanolamine salts such as mono and optionally partially or completely cleaving the vinyl acetate to vinyl alcohol.

Similar to known / copolymeric polycarboxylic acids or polycarboxylates, such as homo- or copolymer acrylic acids or acrylates, copolymers that are neutralized in whole or at least in part, in particular more than 50% relative to the carboxyl groups present, are preferred. Particularly preferred is a completely neutralized copolymer which is thus a salt of / meth / acrylic acid, preferably acrylic acid, and maleic acid, particularly sodium or potassium salts, and vinyl alcohol.

- 5 available. Copolymers generally have a relative molecular weight of 1000 and

200,000, preferably 2,000 to 50,000 and especially 3,000 to 10,000. They are preferably used as spray-dried powders. Particularly preferred copolymers are prepared according to one of the processes described in P 43 00 772.4. German Patent Application Laid-Open.

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. in the form of alkaline perborate and / or percarbonate, and contain up to 5% by weight, preferably 2% by weight, of nonionic surfactants, while 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 the alkaline carriers.

The water softeners of the present invention are further water-soluble film-forming components, such as synthetic polymers, which include the salts of the polymerization coatings of unsaturated carboxylic acids and include, for example, polyacrylates, polymethacrylates, polymaleinates, by weight, preferably from 2 to 20% by weight. Suitable polyacrylates are, for example, Alcosperse / R / 102, 104, 106, 404, 4θ6 from Alco, Acrysole ^^ NI, LMW 45 N, LW 10 N from Nor / r / neveras, Degapas '' which Degussa product; suitable copolymers of polyacrylic acid and maleic acid, e.g.

in principle, they may also contain phosphates or zeolites, but are preferably free of zeolites and phosphorus-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 in particular 1-20 mol of ethylene oxide (EO) and / or 1-20 mol of propylene oxide / PO / 1 mol of C10-20 aliphatic compounds such as alcohols, addition products of a carboxylic acid, a fatty amine, a carboxylic acid amide and a alkane-parent onamide. In addition to water-soluble non-ionic surfactants, polyglycol ethers, both non-soluble and not completely water-soluble, having from 2 to 7 ethylene glycol ether residues in the molecule are also important, preferably in combination with water-soluble nonionic surfactants. In addition, as nonionic surfactants, R-O- / G / general image.X.

Alkyl polyglycosides according to the invention may also be used wherein R is a primary, straight or branched aliphatic residue having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, G from 5 to 6 carbon atoms and an oligomerization tooth value of x from 1 to 10.

The rinse aids of the present invention further comprise 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, such as nitrilotriacetic acid, in particular citric acid or its salts. quantities.

Common alkalisers used in the weakly alkaline machine dishwashing detergent include alkali carbonates, bicarbonates and alkaline silicates with a SiOO / M ^O molar ratio / M = alkaline atom / 1.5: 1 to 2.5: 1. change. The alkali carbonates and bicarbonates included in the compositions of the present invention are sodium carbonate and bicarbonate, which are present in the amounts given above. The highly alkaline metasilicates as alkali carriers are preferably dispensed with. Preferred alkali metal silicates, in particular sodium silicates, are used in place of the metasilicates in a molar ratio of SiO ₂ / Na ₂ O of 1.5: 1 to 2.5: 1, up to 50% by weight, preferably 5-20% by weight. in relation to the total weight of the dish rinse aid.

Oxygen-based bleaching agents include sodium perborate tetrahydrate (NaBO ₂ .H ₂ O ₂ · JH ₂ O), sodium perborate monohydrate (NaBO ₂ .H ₂ O ₂ ), and peroxycarbonate (Na ₂ O). C0 → 1.5 H ₂ 0 ₂ / are 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 agents, 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 ', Ν'-tetraacetyl ethylenediamine (TAED). The agents of the present invention contain from 0.1 to 10% by weight, preferably 1 to 5% by weight, of such conventional bleach activators. The agents of the invention are preferably free from activating chlorinating agents such as trichloroisocyanuric acid.

Preferably, the protein or chemist opens the enzyme, such as proteases, amylases, lipases or cellulases, to better dissolve art apple residues; for example, proteases such as BLAp / R / 140 from Henkel, Otimase®-M-440, Optimase / ^R -M-33O, Opticlean-M-375, Opticlean-M-250a Product from Solvay Enzymes, Maxacal ^^ CX 450,000, Maxapem ^^ from Ibis, Savinase / ^ / 4.0T, 6.0T, 8.0T from Novo or Expe / r / / r / rase '' T from Ibis; amylases such as Termamyl '' 6θ T, / r /

T, which is a Novo product, Amylase® from Solvay Ensymes or Maxamy® 5000 P, CXT 5000 or CXT 2900 from Ibis; lipases such as Lipolase '30 T, a product of Novo; / r / cellulases such as Celluzym '0.7 T from Novo Nordisk. The enzymes in the agents of the invention are present in an amount of from 0.1 to 5% by weight, preferably from 1 to 3% by weight, based on the amount of total rinse aid.

Optionally, silver protective agents, such as those described in P 43 15 397.6, may be used to prevent silver cutlery. In particular, water soluble Μη / II / salts can be used

and then, if desired after intermediate drying, further portions of the rinse aid are combined with the resulting premixes.

Since the alkali carbonate content strongly influences the alkalinity of the product, the intermediate drying is preferably carried out in such a way that the decomposition of the sodium hydrogen carbonate to the sodium carbonate is as little / as possible / as constant as possible. The proportion of sodium carbonate produced during drying must be taken into account in the formulation of the granulate recipe. 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 layer forming agent is usually used in admixture with at least one other component of the rinse aid in combination 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. Application of additional quantities of liquid, in particular additional water

9 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 that the polymers of the present invention are used as additives in admixture with other granular ingredients of dish rinse aids.

In the preparation of the cleansers of the present invention in tablet form, it is preferable to mix all 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 still 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 / liter, is accomplished by blending at least a portion of the liquid blend components adding the compactness of the premix, so it is not usually necessary 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 resulting granulate to produce fine granulate particles. Small amounts of water glass powder or powdered alkaline carbonate are particularly suitable for this purpose.

The machine dishwashing detergents of the present invention provide products which, in addition to their better biodegradability, outperform conventional modern dishwashing detergents, particularly with respect to inhibition of deposition and purification.

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

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- 12 Examples

Granular dish rinse agents having the following compositions are prepared (Agent A and Comparative B and Agent C according to the invention).

Agent A contains 10% by weight of a copolymer as disclosed in P 00 772.4. 80% by weight of acrylic acid and maleic acid used in a ratio of 7: 3 by weight and 20% by weight of vinyl acetate, and the product is completely neutralized.

Comparative Example B contains 10% by weight of acrylate maleate copolymer marketed under the tradename Sokalan CP CP and manufactured by BASF.

The crowd % B % by weight Weight C ¹ Na-citrate 30.0 30.0 40.0 Sokalan CP5 - 10.0 - the above copolymer 10.0 - 5.0 Na ₂ C0 ₃ 13.0 13.0 6.0 NaHCCv 35.5 35.5 30.1 Na perborate 5.0 5.0 - Na-p e rka rb 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

/ Ci2 / iQ-FatQQ ° lxE0x4 PO /

THE % by weight B% by weight C % by weight perfume oils 0.6 0.6 0.6 MnSO ^ - - 0.4

Cleanse live performance

The cleaning performance of Agents A and B was tested in a Miele G 531 pot rinse machine / universal program at 65 ° C / 30g in 7.0 liters of 16 g of water each time in the cleaning process / contaminants as Th. Altenschöpfer, SÖFW, 98/1972 / 763-765 described in literature: were tea, milk, minced meat, pudding, crayon, starch and oatmeal.

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

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! in water of 50 ° C with 50 g pumpable impurity / in the presence of a mixture of tap, roasting sauce, mustard, potato starch, egg 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 effect achieved with the agent A of the present invention and the agent B for comparison on glasses, knife blades and porcelain plates are shown in Table 1.

Table 1 cups 51 knife blades 53 porcelain plates 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.

Agent C of the present invention exhibits cleaning and deposition inhibitory performance comparable to agent A of the present invention; In the presence of MnSO4 ·, first of all, it exhibits superior properties with respect to inhibition of silver stock incorporation.

Claims

Claims (10)

A slightly alkaline agent for machine dishwashing, having a pH of 8.5 to 11.5, preferably 9 to 10.5, by weight in an aqueous solution and containing water-soluble film-forming components and oxygen-based bleaching agents, characterized in that they are water-soluble. comprising as copolymer 60-95% by weight, preferably 70-90% by weight of meth / acrylic acid or / meth / acrylate, in particular of acrylic acid or acrylate, 4-40% by weight of maleic acid or maleate by weight, preferably from 10 to 25% by weight, of vinyl alcohol and / or vinyl acetate, the weight ratio of / meth / acrylic acid / / methacrylate to maleic acid / maleate being 1.5: 1 and 4: 1, preferably in the range of 2: 1 to 2.5: 1, the amounts and weight ratios are for acids and copolymers of acid salts and vinyl alcohol are preferred. An agent according to claim 1, characterized in that the copolymer is present in an amount of 0.5 to 50% by weight, preferably 2 to 20% by weight, preferably 0.5 to 20% by weight, preferably 5% by weight. containing from about 15% to about 15% by weight of oxygen-based bleach, mainly alkaline perborate and / or percarbonate, and free from anionic, cationic or amphoteric surfactants and up to 5% by weight, preferably up to 2% by weight of nonionic surfactant, O- - 16 referenced. 3. An agent according to claim 1 or 2, characterized in that it contains up to 60% by weight, preferably 5-50% by weight, of alkali carbonate and / or hyalicarbonate. 4. An agent according to any one of claims 1 to 3, characterized in that it contains complexing agents in an amount of up to 60% by weight, in the range of 0.5% by weight of the divalent or multifunctional organic carboxylic acids or salts thereof, 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 4, characterized in that it does not exceed Preferably, 30% by weight contains 5-20% by weight of alkali silicate having a SiO 2 molar ratio (M = alkali atom) of 1.5: 1 to 2.5: 1. An agent according to any one of claims 1 to 5, characterized in that it is free from activating chlorine cleaving agents. An agent according to any one of claims 1 to 6, characterized in that it contains from 0.1 to 5% by weight, preferably from 0.5 to 2% by weight, of enzymes based on the total weight of the agent. The tablet according to any one of claims 1 to 7, 17 compositions characterized in that they are prepared by mixing all of its ingredients in a blender and compressing the blend into tablets using a press press at a pressure of 7 psi. A powder or granule agent according to any one of claims 1 to 7, 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 9 for cleaning a vessel. / Aíw / NEW