DE4210363A1 - Low alkali dishwasher compsn. prodn. free from chlorine, silicate and phosphate - Google Patents

Abstract

The prodn. comprises preparing the builder by premixing Na salts of (meth)acrylic acid (co)polymers with Na2CO3 and NaHCO3, granulating with agglomeration, with addn. of liq., opt. reducing the granulate to a uniform grain size in a 2nd granulation stage, drying with agitation in a stream of warm air, sieving out fine and coarse components, and mixing with the bleaching agent, and opt. a bleach activator, bleach stabiliser, perfume, enzymes, nonionic tensides, builders and/or dyes.

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 laundry detergents and cleaning agents, 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 wt .-% water, preferably from
  • 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 th compounds.

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 heap to 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 41 37 470.3 relates to 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 contain, when used as builders sodium salts of homo 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. before Partly when drying is therefore 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. These include bleaches, optionally bleach activators, bleach bilisers, 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 adjustment of the pH values via the buffer system Alkaline carbonate / bicarbonate at about 9.0-10.0 is important for the prevention of Lime deposits on the machine interiors or on the items to be washed in Areas with particularly high water hardness or not working properly used softener systems of dishwashers.

The poly (meth) acrylates may be in powder form, but preferably in granules ter form can be used. Useful polyacrylates include Al cosperse® from Alco: Alcosperse® 102, 104, 106, 404, 406); acrylic sole® from Norsohaas: Acrysole® A 1N, LMW 45 N, LMW 10 N, LMW 20 N, SP 02 N, Norasole® WL1, WL2, WL3, WL4, Degapas® from Degussa; Good-Rite® K-XP 18 from Goodrich. Also copolymers of polyacrylic acid and maleic acid (poly (meth) acrylates) can be used, for example Sokalane® from BASF: Sokalan® CP 5, CP 7; Acrysole® the Company Norsohaas: Acrysol® QR 1014, Alcosperse® from Alco: Alcosper SE® 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 bicarbonate should preferably in coarse compacted form with a Grain size in the main fraction between 0.4 to 1.0 mm are used.

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 tetrahydrate 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 (Pentaacetylglucose), DADHT (1,5-Diacetyl-2,2-dioxo-hexahydro-1,3,5- triazine) and ISA (isatoic anhydride). Moreover, the addition ge Ringer quantities of known bleach stabilizers such as Phosphonates, borates or metaborates and Metasilikaten expedient his.

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 Mo lekül having 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 finished 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 having a degree of polymerization of about 1-4 can be used. In order to ensure a uniform distribution of alkyl polyglucosides, must be diluted to its viscosity reduction to about 35% active substance. In addition, a bleached quality should be used, otherwise a brown granulate is formed.

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; Maxa cal® CX 450 000, Maxapem® from Ibis, Savinase® 4.0 T, 6.0 T, 8.0 T, the company Novo or Experase® T the company Ibis and amylases such as Ter mamyl® 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 Lipolase® 30 T from NOVO.

Examples

In the following examples meant:
AS: active substance
Plurafac® LF 403: Alkyl (C ₁₂ -C ₁₈ ) -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 approx. 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 in a discontinuous working ploughshare mixer premixed and with the addition of 2.8 kg H₂O granulated. The wet granules also baked after being stored temporarily hardly together and was dried with movement in a stream of hot air. After screening off the coarse and fine grain fractions, the granules were replaced by Mi the following proportions are processed into the finished product:

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 5.5%

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 detergent additive (as in example 1) | 29,1% Sodium bicarbonate, compressed 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 Sokalan® 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 highly alkaline formulation containing 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. Cleaner II contained the weaker alkaline carbonate and disilicate instead of metasilicate.
Formulation III was a weakly alkaline formulation according to the present invention with a pH of 9.5 (1 wt .-% aqueous solution). It contained over the prior art large quantities of Na-hydrogen carbonate.
Formulation IV was an even weaker alkaline formulation according to the prior invention with a pH of 9.2 (1gew .-% aqueous solution Lö).

Table I lists the formulations of the four cleaners that are listed in clearly distinguish between the alkalinity.

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

Table III gives a comparison of the precipitation formation of the four reini with different pH values in hard water again.

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.

Determination of precipitation

Dishes (glasses, porcelain dishes, stainless steel cutlery) is in the Ge Dishwasher rinsed 10 times. Into the machine is used every rinse 50 g Mischanschmutzung (starch, protein) given. Rinsing takes place in a 65 ° C Program under hard water conditions (16 ° d). Each rinse will be 20 g Cleaner dosed from the storage vessel in the main wash cycle.  

evaluation

After 10 rinses the dishes are judged in the "black box". The grading scale ranges from 0-10. 0 means that there are no deposits on the Dishes were found. The pads up to grade 5 are only in "black Box "visible., Coverings from grade 6 are also outside, that is also for the Consumers visible.

The interior of the machine is judged according to the same grading scheme like the dishes, so that two values are obtained.

Table I

Table II

Comparison of cleaning performance

Table III

Comparison of the formation of limescale

Claims (11)

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, premixed with sodium carbonate and sodium bicarbonate in any mixer, agglomerated granulated with the addition of liquids, the resulting granules optionally in a second granulati onsstufe sets to a uniform particle size distribution, it under loading movement in a 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, fragrance, 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. The method according to claim 1 to 9, characterized in that the Ratio of sodium carbonate to sodium bicarbonate so chooses that Detergent in 1 wt .-% aqueous solution has a pH of about 9 to about 10. 11. 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 wt% lipase
0-1% by weight perfume
0-1% by weight of dye
3-15% by weight of water,
wherein all ingredients used give a total of 100 wt .-% and in 1gew .-% aqueous solution has a pH of about 9 to about 10.