DE4205071A1 - Low alkalinity dishwashing machine compsn. - free from active chlorine silicate and phosphate, contains sodium salt of (meth)acrylic] acid (co)polymer, sodium (bi):carbonate as builders - Google Patents

Abstract

Prepn. of low alkalinity cleaning compsn. free from active chlorine, silicate and phosphate for dishwashing machines, contg. builders, bleaching agents, water, opt. nonionic surfactants as well as usual additives, comprises premixing builders comprising Na salts of (meth)acrylic acid homo-or copolymers with Na2CO3 and NaHCO3 in a mixer, addn. of a liq. to cause agglomerating granulations, opt. subjecting the obtd. granules to a second granulation step to give a uniform particle distribution, drying the granules in a warm air stream, sieving the fine and coarse particles and subsequently mixing with a bleaching activator and opt. a bleach stabiliser, perfume, enzymes, nonionic surfactants, further builders and/or dyes. ADVANTAGE - The process gives a storage stable, freeflowing, dustfree granulate with high bulk density (750-1100 g/l)

Description

The invention relates to a novel process for the preparation of lower alkali shear, active chlorine, silicate and phosphate-free mechanically applicable Dishwashing detergent in the form of a storage-stable free-flowing dust-free Granules with high bulk densities - especially in the range of about 750 up to 1100 g / l.

In the course of the ecological waiver of phosphates or polyphosphates In detergents and cleaners, these are becoming increasingly new Scaffolding substances developed and optimized. Also coming soon with a Labeling requirement of cleaning agents that are subject to EC regulations comply with the guidelines. Thereafter, the proportion of "irritating" Substances such as alkali carbonate plus alkali perborate plus surfactant 20 wt .-% of do not exceed the total mean. Finally, funds are desired which are neither "irritant" nor "corrosive" to declare. Therefore, should they contain "irritating" alkalis only in quantities that contain no require drawing. Nevertheless, one expects such dishwashing detergents an undiminished good cleaning performance.

For the inventive method is as phosphate-substituted cal ciumbindende framework substance powdery poly (meth) acrylate with a Active substance content of about 92-95 wt .-% and / or a granular alka Cleaning additive based on sodium salts of homopolymers or copolymeric (meth) acrylic acids used, the subject of the German published patent application 39 37 469. This consists of:

• a) from 35 to 60% by weight of sodium salts of at least one homopolymer or copolymeric (meth) acrylic acid,
• b) 25 to 50% by weight of sodium carbonate (calculated anhydrous),
• c) 4 to 20 wt .-% sodium sulfate (anhydrous calculated) and  
• d) 1 to 7% by weight of water,
  preferably off
• a) 40 to 55% by weight, in particular 45 to 52% by weight,
• b) from 30 to 45% by weight, in particular from 30 to 40% by weight,
• c) 5 to 15 wt .-%, in particular 5 to 10 wt.% And
• d) 2 to 6 wt .-%, in particular 3 to 5 wt .-% of the above-mentioned connections.

Lower alkaline are already active on the basis of such cleaning additives Chlorine- and phosphate-free machine dishwashing detergents containing calcium binding framework substances, soda, water glass, solid per compounds, acti vatoren and surfactants and optionally other conventional ingredients such agent, in the form of a shelf-stable, free-flowing, dust-free Granules with bulk densities required for practical use above 650 g / l have been developed, containing at least a proportion of liquid components and, if desired, a proportion of finely divided Solid components of the machine dishwashing detergent in a first Sub-stage premixed and subsequently with the remaining components of Machine dishwashing detergents have been combined. You have Schüttdich ranging from 750 to 1000 g / l and are the subject of the earlier, unpublished German patent applications P 41 10 510.9 and P 41 37 470.3.

In the dishwasher produced according to P 41 10 510.9 can a Interim storage have the consequence that the wet granules in the pile too sammenbackt. This heap does not completely decay when loosening up the original granule structure, resulting in a larger average grain diameter and leads to a lower bulk density. The present Invention also provides an advantageous development in this regard of the older method.

The contrast developed process for the production of dishes Flushing according to the German patent application P 41137470.3 concerns just if low-alkaline, active chlorine and phosphate-free detergents for Machine dishwashing containing granular, alkaline Cleaning additives according to the German patent application DE 39 37 469,  other builders such as silicates, bleach, water and give low-foaming nonionic surfactants, enzymes, bleach activators, Perfumes and / or dyes, wherein powdery poly (meth) acry lat and / or the said granular, alkaline cleaning additives with compressed sodium carbonate and other builders premixed, with Water and optionally with other liquid components in per se granulated in a known manner agglomerating, then the granules with the bleach, and optionally a bleach activator, perfume, Enzyme and / or dye mixed, the resulting, still slightly sticky Granules dusted with powdered sodium carbonate, and finally with the proportion of nonionic surfactants sprayed, causing excess Sodium carbonate is bound and a product dedusting takes place. The Addition of the sodium carbonate in turn prevents a rapid Ver Bake the granules in the pile. As a result, the granule structure on obtained the way into the gutter of the drying zone. By pollination with sodium carbonate powder is also an increase in the weight of the liter reached to 850 to 1000 g. Another increase in the weight of the liter is reached when the granulation first with the addition of liquid What serglas and then water or water carried out alone, if the in the granulation step submitted sodium carbonate partially hydrated or when the batch size is increased. The produced by this method Dishwashing detergents contain silicates. The object of the invention was u. a. the Production of silicate-free formulations.

It has now been found that mild to mild alkaline, active chlorine, Silicate- and phosphate-free cleaning agents for machine Ge dishwashing, the builders, bleach, water, if necessary nonionic surfactants and other substances customary for such agents contains, when sodium salts of homoge- or copolymeric (meth) acrylic acids with sodium carbonate and sodium bicarbonate bonat in any mixer, for example in a Pflugscharmi shear, and then with the addition of liquids such as water, a nonionic surfactant or liquid poly (meth) acrylate agglomerie Granulated, the resulting granules optionally in a second Granulation level sets to a uniform grain distribution, it under  Movement in a stream of hot air dries, fine and coarse fractions are removed and then with the bleaching agent and optionally a bleach activator, a bleach stabilizer, fragrance, enzymes, nonionic Surfactants, other builders and / or dyes mixed.

Since the alkali carbonate content is included in the EU Dangerous Preparations Directive, must the drying be carried out so that the bicarbonate decay of Na triumbicarbonate to sodium carbonate as low as possible (or at least possible constant). An additional by the drying resulting Na In fact, the proportion of triumcarbonate would have to be reduced in the formulation of the granules Re be taken into account. Low drying temperatures are effective not only counteracts sodium bicarbonate decay, but also increase the Solubility of the granulated detergent in use. benefit is therefore liable during drying a supply air temperature, on the one hand to Avoidance of bicarbonate decay should be as low as possible and on the other hand must be as high as necessary to a product with good La To obtain properties. Preference is given during drying a Zulufttem temperature of approx. 80 ° C. The granules themselves should not be at temperatures be heated above about 60 ° C. In contrast to the manufacturing process is the decomposition of the sodium bicarbonate in the later use in the Reini gungsverfahren in the dishwasher quite desirable, because here By the alkalinity of the fleet and thus their cleaning performance increased. The in situ formation of sodium carbonate (eye irritant and irritant to the skin) from sodium bicarbonate (non-irritating) defuses dangers for the consumer, z. B. inappropriate use by children.

As a further builder substance is in particular sodium citrate into consideration. It can be added already in the granulation, but also after drying and subsequent Siebklassierungsstufe the granules also added be mixed as the other ingredients of dishwashing detergents. here include bleaching agents, optionally bleach activators, bleach dispersants, enzymes, dyes and fragrances.

For frame recipes as well as all possible ingredients of the invention The granular detergents prepared in accordance with the invention come approximately as follows  Areas related to the active ingredient content in weight percent in consideration:

The poly (meth) acrylates can be used as a powder, but preferably in granulier ter form. Useful polyacrylates include Al cosperse® from Alco: Alcosperse® 102, 104, 106, 404, 406); Acrylic sole® from Norsohaas: Acrysole® A1N, LMW45N, LMW10N, LMW20N, SP02N, Norasole® WL1, WL2, WL3, WL4, Degapas® from Degussa; Good-Rite® K-XP 18 from Goodrich. Copolymers of polyacrylic acid and maleic acid (poly (meth) acrylates) can also be used, for example Sokalane® from BASF: Sokalan® CP 5 , CP 7 ; Acrysole® from Norsohaas: Acrysol® QR 1014, Alcosperse® from Alco: Alcosper® 175; granular alkaline cleaning additive according to DE 39 37 469.

The sodium citrate is anhydrous trisodium citrate or trisodium citrate trihydrate dihydrate. Trisodium citrate dihydrate can be used as a powder be set. It then has an average grain size of about 0.2 mm. However, higher bulk densities are achieved with crystalline citrate.  

As the alkali carbonate, anhydrous sodium carbonate is suitably arbitrary Quality used, such. As calcined soda or dense soda. Under compacted soda is granular calcined sodium carbonate ver which is commercially available (eg V-soda from Matthes & Weber). The alkali bicarbonate is preferably sodium bicarbonate. The sodium bicar Preferably, carbonate should be in coarse compacted form with a grain size be used in the main fraction between 0.4 to 1.0 mm.

For some time, the preferred bleaching agents are active oxygen carriers common ingredients of household dishwashing detergents machines (HGSM). These include primarily sodium perborate mono- and -te trahydrate and sodium percarbonate. Because of the increase in bulk weight For example, compacted sodium perborate monohydrate is preferred. Because active oxygen develops its full effect only at elevated temperatures, be activated at about 60 ° C, the temperatures of the Reini tion process in the HGSM, so-called bleach activators used. When Bleach activators are preferably TAED (tetraacetylenediamine), PAG (Penta acetylglucose), DADHT (1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine) and ISA (isatoic anhydride). Moreover, the addition of small amounts can also known bleach stabilizers such as phosphonates, Borates or metaborates and Metasilikaten be useful.

As non-ionic surfactants that serve the better separation of fatty food residues and as granulating aids, usually extremely low-foam compounds are used. These include preferably C ₁₂ -C ₁₈ - alkylpolyethylene glycol polypropylene glycol ethers having in each case up to 8 mol of ethylene oxide and propylene oxide units in the molecule. But you can also use other than non-foam known nonionic surfactants, such as. B. C ₁₂ -C ₁₈ -Alkylpolyethylenglykol polybutylenglykolether each with up to 8 moles of ethylene oxide and butylene oxide in the molecule, as well as the foaming, but ecologically attractive C ₈ -C ₁₀ -Alkylpolyglucoside and / or C ₁₂ -C ₁₄ -Alkylpolyethylenglykole with 3-8 ethylene oxide units in Mole molecule with a degree of polymerization of about 1-4, this then together with about 0.2 to 4, preferably 0.2 to 2 wt .-%, based on the final detergent, of defoaming agents such. As silicone oils, mixtures of silicone oil and hydrophobized silica, paraffin oil / Guerbet alcohols and hydrophobized silica. C ₈ -C ₁₀ -Alkylpolyglucoside with a poly merisierungsgrad of about 1-4 can be used. In order to ensure a uniform distribution of Alkylpolyglucoside must be diluted to their Viskosi tätsemiedrigung to about 35% active ingredient. In addition, te bleached quality should be used, otherwise a brown Granu lat arises.

For better replacement protein or starch-containing food residue as other usual ingredients of such agents z. B. still enzymes such as Pro teases, amylases and lipases, for example proteases such as BLAP® 140 from Henkel; Opitmase® M-440, Optimase® M-330, Opticlean® -M-375, Opticlean® -M-250 from Solvay Enzymes; Maxacal ® CX 450 000, Maxapem® from Ibis, Savinase® 4.0 T 6.0 T 8.0 T the company Novo or Experase® T from Ibis and amylases such as Termamyl ® 60 T, 90 T from Novo; Amylase-LT® from Solvay Enzymes or Maxamyl® P 5000, CXT 5000 or CXT 2900 from Ibis, lipases such as Li polase® 30 T from NOVO.  

Examples

In the following examples meant:
AS: active substance,
Plurafac® LF 403: alkyl (C₁₂-C₁₈) -polyethylene glycol (<8 EO) -polypropylene glycol - (<8 PO) ether (BASF)
APG 225: C ₈ -C ₁₀ fatty alcohol polyglucoside having a degree of polymerization of 1-4, bleached.
Sokalan® CP 5: poly (meth) acrylate (BASF)
Norasol WL 4: polyacrylate / soda granules (Norsohaas)

example 1

12.6 kg granular cleaning additive according to DE 39 37 469 with about 50% AS, 21.7 kg of compacted sodium bicarbonate with a bulk density of 900-1000 g / l and 2.9 kg of compressed soda were premixed in a batch plowshare mixer and under Granulated adding 2.8 kg of H ₂ O. The wet granules hardly caked even after an intermediate storage and was dried with movement in a stream of hot air. After screening off the coarse and fine grain fractions, the granules were processed into the finished product by mixing the proportions indicated below:

Granules | 60.0% trisodium 30.0% tetraacetylethylenediamine 2.0% Plurafac® LF 403 0.9% amylase 0.5% protease 0.5% Perfume 0.6% Perborate monohydrate, compactate 5.5%

In the treatment, a trisodium citrate dihydric grade with a Bulk density of about 810 g / l used. The bulk density of the finished product was 920 g / l.

Example 2

In the granulation, the following batch (40 kg) was used:

Granular detergent additive (as in example 1) | 32.9% Sodium bicarbonate, compressed 50.0% Soda, condensed 7.6% APG 225 (35%) 6.5% water 3.0%

After premixing the solids, the aqueous APG solution was first and then the water is added. Otherwise, the production of the granules in this and Examples 3 to 5 identical to that of Example 1. The treatment was as follows:

Granules | 56.4% trisodium citrate 35.0% tetraacetylethylenediamine 2.0% protease 0.5% amylase 0.5% Perfume 0.6% perborate 5.0%

The bulk density of the finished product was 894 g / l.

Example 3

The granular detergent additive was partially permeated in the granulation Norasol® WL 4 from Norsohaas replaces:

Norasol® WL 4 | 16.4% Granular detergent additive (as in Example 1) 23.1% Sodium bicarbonate, compressed 53.5% water 7.0%

The treatment was identical to that of Example 1. The bulk density of the finished product was 890 g / l.  

Example 4

Sodium citrate, which may optionally be fine-grained or coarsely crystalline, was not mixed in the processing, but already in the Granu used:

Granular detergent additive (as in example 1) | 20.3% Sodium bicarbonate, compressed 31.0% trisodium 35.7% Soda, condensed 3.2% APG 225 (35%) 5.9% water 3.9%

The bulk density after the treatment was 920 g / l:

Granules | 91.4% perborate 5.0% amylase 0.5% protease 0.5% tetraacetylethylenediamine 2.0% Perfume 0.6%

Example 5

The nonionic surfactant Plurafac® was ver as granulating applies:

Granular Cleaning Additive (as in Example 1) | 29.1% sodium bicarbonate 52.4% Soda, condensed 9.8% Plurafac® LF 403 1.5% water 7.2%

In the processing, perborate was stabilized by percarbonate can be replaced,

Granules | 60.5% trisodium 30.0% percarbonate 6.0% tetraacetylethylenediamine 2.0% amylase 0.5% protease 0.5% Perfume 0.5%

The bulk density of the finished product was 900 g / l.

Example 6

In the granulation instead of the granular cleaning additive was a Soka lan® CP5 granules from BASF are used:

Sokalan® CP5 Granules | 17.5% Sodium bicarbonate, compressed 60.0% Soda, condensed 18.1% water 4.4%

After the addition of water, the wet granules became more fine-grained with 0.5-2% Soda mixed and then processed according to Example 1.

The treatment was carried out as in Example 1. The bulk density of Finished product was 940 g / l.

For comparison with the prior art, the following experiments were carried out leads:

Formulation I was a commercial high alkaline formulation with meta silicate and phosphate. The pH of a 1% solution was 12.5.

Formulation II was a low-alkaline formulation according to DE 41 37 470. A 1% solution of this cleaner had a pH of 10.5. cleanser II contained instead of metasilicate the weaker alkaline carbonate so like disilicate.  

Formulation III was a weakly alkaline formulation according to the present the invention with a pH of 9.5 (1% solution). It contained ge Compared to the state of the art, large amounts of sodium bicarbonate.

Table I lists the formulations of the three cleaners, which are listed in clearly distinguish between the alkalinity.

Table II gives a comparison of the cleaning results of the three Formu again. From this list it appears that more surprising wise also the weakly alkaline cleaner a well-just Spülergeb nis supplies. The slight under-performance is due to the high ecologi value of the recipe by far.

test conditions

Dishwasher Miele G 590
55 ° C universal program
Detergent dosage 25 g.

Assessment: Grading scale from 0-10
0 no cleaning
10 optimal cleaning
3-fold assessment by 4 test persons.

Table I

recipes

Table II

Comparison of cleaning performance

Claims (10)

1. A process for the preparation of low alkaline, active chlorine, silicate and phosphate-free detergents for automatic dishwashing with a content of builders, bleaches, water, where appropriate nonionic surfactants and other conventional ingredients of such agents, characterized in that zen as Gerüstsubstan sodium salts mono- or copolymeric (meth) acrylic acids, mixed with sodium carbonate and sodium bicarbonate in any mixer before, agglomerated granulated with the addition of liquids, the resulting granules optionally in a second granulation stage adjusts to a uniform particle size distribution, it under BeWe supply in one Hot air stream dries, fine and coarse grains from sieves and then mixed with the bleaching agent and optionally a bleach activator, a bleach stabilizer, perfume, enzymes, nonionic surfactants, other builders and / or dyes. 2. The method according to claim 1, characterized in that as Natri salts of mono- or copolymeric (meth) acrylic acids pulverulent and / or liquid poly (meth) acrylate and / or granular, alkaline Cleaning additive according to DE 39 37 469 used. 3. The method according to claim 1 and 2, characterized in that the finished granules are admixed as a further builder sodium citrate. 4. The method according to claim 1 to 3, characterized in that the Sodium citrate already adds to the premix to be granulated. 5. The method according to claim 1 to 4, characterized in that one for Granulate used as liquid water. 6. The method according to claim 1 to 5, characterized in that one for Granulating used as liquid nonionic surfactants.   7. The method according to claim 1 to 6, characterized in that one for Granulate liquid sodium salt solutions of mono- or copolymers (Meth) acrylic acids used. 8. The method according to claim 1 to 7, characterized in that as Sodium carbonate compressed soda used. 9. The method according to claim 1 to 8, characterized in that Na triumbicarbonate used in compressed form. 10. Composition, produced according to one of claims 1 to 9, characterized by a content of
5-30% by weight of poly (meth) acrylate
10-50% by weight of trisodium citrate dihydrate
2.5-20% by weight of alkali carbonate
10-60% by weight alkali bicarbonate
3-15% by weight of bleach
0-4 wt .-% bleach activator
0-4 wt .-% bleach stabilizer
0-4 wt .-% nonionic surfactant
0-2 wt% protease
0-2% by weight of amylase
0-2% by weight of lipase
0-1% by weight perfume
0-1% by weight of dyes
3-15% by weight of water,
wherein all ingredients used give a total of 100 wt .-%.