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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3917—Nitrogen-containing compounds
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/667—Neutral esters, e.g. sorbitan esters
• • 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
• • 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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/10—Carbonates ; Bicarbonates
• • 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2086—Hydroxy carboxylic acids-salts thereof
• • 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
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38609—Protease or amylase in solid compositions only

Definitions

• Machine dishwashing generally consists of a pre-rinse cycle, a cleaning cycle, one or more intermediate rinse cycles, a rinse cycle and a drying cycle. This applies to machine washing both in the home and in business.
• HGSM HGSM
• GGSM In the case of a commercial dishwasher, hereinafter referred to as GGSM, the so-called pre-clearing zone corresponds in principle to the pre-rinse cycle of an HGSM.
• the cleaning agent metered into the cleaning zone is used by overflow in the pre-clearing zone to support the cleaning of the adhering food residues.
• GGSM in which the pre-clearing zone is only operated with fresh water, but a pre-clearing zone with detergent additive is more effective than pre-clearing with fresh water alone.
• pre-clearing zone cleaning from GGSM has also already been transferred to HGSM and dosing of cleaning agents has already been made possible for the pre-rinse cycle by dosing cleaning agents in tablet form and one or more suitable tablets, for example in a free part of the cutlery basket. but also positioned elsewhere in the machine, as a result of which they could act both in the pre-rinse cycle and in the actual cleaning cycle, that is to say bifunctionally.
• Such tablet-shaped cleaning agents is described, for example, in DE-OS 3541 145.
• These are uniform Compound cleaning agent tablets with a broad dissolving profile for machine dishwashing, which contain the usual alkaline components, in particular from the group of alkali metal silicates and pentaalkali metal triphosphates, active chlorine compounds and tabletting aids, and in which the alkali metal silicates are made from a mixture of "sodium metasilicate nonahydrate" (Na2 ) and anhydrous sodium metasilicate and the pentaalkali metal triphosphate consists of anhydrous pentasodium triphosphate, the weight ratio of anhydrous sodium metasilicate: sodium metasilicate nonahydrate being between 1: 0.3 and 1: 1.5 and the weight ratio of pentasodium triphosphate to sodium metasikate, each being water-free , 2: 1 to 1: 2, preferably 1: 1 to 1: 1.7.
• Tablets of this type have such a broad dissolution profile that they are already dissolved in the tap water to at least 10% by weight in the pre-rinsing step of an HGSM, thereby developing a pH value of at least 10.0 in the rinsing liquor and with good hot water solubility at least 60% by weight, preferably at least 70% by weight, are still available for the cleaning process.
• the dissolution profile is understood to mean the weight ratio of the proportions of the tablet to the entire tablet which are dissolved from the usual HGSM under the conditions of the pre-rinse cycle.
• phosphate-free detergent tablets for machine dishwashing have also been on the market for some time and contain essentially silicates, nonionic surfactants, organic complexing agents and percarbonate. If these tablets are placed inside the machine (e.g. in the basket), they will dissolve as far as possible, even completely, during the pre-rinse cycle, so that the actual cleaning cycle table no more detergent is available. In addition, the stability of these tablets is unsatisfactory.
• DE-OS 4010524 describes stable, bifunctional, phosphate-free detergent tablets for machine dishwashing containing silicate, low-foam nonionic surfactants, organic complexing agents, bleaches and water, the organic complexing agents according to DE-OS 39 37 469 in the form of a granular, alkaline cleaning additive consisting of sodium salts of at least one homopolymeric or copolymeric (meth) acrylic acid, sodium carbonate, sodium sulfate and water.
• the granular alkaline cleaning additives were mechanically mixed with the other mostly powdery formulation components and pressed in a manner known per se.
• the sodium carbonate serving as part of the builders was used in anhydrous form and initially in a mixing cycle, preferably alone or with the other builders such as sodium citrate and optionally sodium hydrogen carbonate and the solid alkali salts of at least one homopolymer or copolymer ( Meth-) acrylic acid together with the amount of water required for the partial hydration of the anhydrous sodium carbonate of about 5-40, preferably about 7-20% by weight, based on the anhydrous sodium carbonate used as the framework substance, added - The remaining substances were then added to the mixture and the mixture thus obtained was compressed on a conventional tablet press.
• the other builders such as sodium citrate and optionally sodium hydrogen carbonate and the solid alkali salts of at least one homopolymer or copolymer ( Meth-) acrylic acid
• the storage-stable tablets produced in this way have a high breaking strength (greater than 140 N with a diameter of approximately 30 to 40 mm and a density of approximately 1.4 to 1.7 g / cm 3), which also remains stable during storage and thereby changes within a short time Time can still increase significantly.
• the present invention now relates to stable, bifunctional, phosphate-, etasilicate- and now also polymer-free, low-alkaline cleaning tablets for automatic dishwashing, which are characterized in that they contain sodium citrate, further builders, enzymes and optionally bleach activators, nonionic surfactants, color - and contain fragrances. They correspond to the following basic formulation:
• Trisodium citrate dihydrate 5 - 50% 20 - 30%
• Tetraacetylethylenediamine 0.5 - 4% 2 - 4% non-ionic surfactant 0 - 4% 0.5 - 2%
• a process has been found in which such stable, bifunctional, phosphate-, metasilicate- and now also polymer-free, lower-alkaline detergent tablets for automatic dishwashing with a content of sodium citrate, other scaffold substances, low-foam surfactants, bleaches and optionally Enzymes, bleach activators, fragrances and dyes come when you first moisten sodium citrate dihydrate and / or sodium citrate with a small amount of water of about 3 - 10, preferably about 4 - 6 wt .-%, based on the total composition, then dusted with anhydrous sodium carbonate and then sodium hydrogen carbonate and the bleach activator are added, enzymes, non-ionic surfactants, fragrances / dyes and optionally paraffin oil are added, finally the active oxygen-releasing compound is mixed in with a low energy input and the total mixture obtained in this way on a conventional tablet press at a relative atmospheric humidity 15 to 60, preferably about 20 to 30% with a compression pressure of about 2 to 11, preferably about 4 to 6, MPa to tablets.
• paraffin oil can also take place together with the addition of the sodium citrate, preferably in the form of a mixture which, in an advanced, separate mixed cut, preferably comprises 1 to 3% by weight, in particular approximately 2% by weight.
• Paraffin oil based on the total detergent mixture and sodium citrate. Also advantageous is a hydrophobization of the sodium bicarbonate carried out in a preferred mixing step with paraffin oil.
• a desired further delay in the dissolution in the pre-rinse cycle of an HGSM can take place if the water added at the beginning is already mixed with the nonionic surfactant, to which the fragrance can also be added, or with a glyceride mixture and sprayed onto the sodium citrate and then adding the residual substances.
• a further preferred embodiment of the process according to the invention consists in first applying all liquid components of the composition to the sodium citrate, then dusting the anhydrous sodium carbonate and then in succession, each with a low energy input, sodium bicarbonate, the bleach activator and finally the active oxygen releasing compound are added and the total mixture thus obtained is pressed as indicated above.
• Low energy input means gentle mixing without using the high-speed cutter heads with only short dwell times in the mixer.
• the storage-stable tablets produced according to the invention have a high breaking strength (greater than 140 N with a diameter of about 30 to 40 m and a density of about 1.4 to 1.7 g / atß), which can increase significantly within a short time during storage , and which also remain stable.
• alkali metal nitrilotriacetates, alkali phosphonates and alkali disilicates can also be used as builders. They bind hardening agents such as calcium and magnesium ions from the water or from the food residues through complex formation or dispersion and thus prevent the formation of limescale deposits in the dishwasher and on the dishes. They can be used as anhydrous and / or as hydrate salts. Water-free trisodium citrate or trisodium citrate dihydrate are suitable as sodium citrate. Sodium carbonate of any quality is preferably used as the alkali carbonate, such as. B. soda ash or compressed soda. Any origin can be used as sodium hydrogen carbonate.
• Preferred alkali metal phosphonate is the tetrasodium salt of l-hydroxyethane-1,1-di-phosphonic acid (Turpinal ( R ) 4 NZ from Henkel).
• Dried water glass with the module SiO 2 : Na2 ⁇ 1: 2-2.5, (for example Portil ( R ) A or AW from Henkel, Britesil ( R ) H 24 or C) is suitable as sodium disilicate 24 from Akzo).
• Extremely low-foaming nonionic compounds are preferably used as low-foaming surfactants, which serve to better remove fatty food residues and as pressing aids. These preferably include C12-C18 alkyl polyethylene glycol polypropylene glycol ethers, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule. Their share in the total weight of the finished tablets is generally about 0.2 to 5, preferably about 0.5 to 3,% by weight. But you can also use other non-foaming surfactants known as low foams, such as. B.
• Ci2-Ci8-Alkylpolyethy- lenglykol-polybutylene glycol ether each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule and then optionally about 0.2 to 2, preferably about 0.2 to 1 wt .-%, based on the total Tablet, on defoaming agents such.
• B. Add silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffin oil / Guerbet alcohols and hydrophobicized silica.
• Active oxygen carriers are now preferably bleaches which are customary constituents of cleaning agents for HGSM. These include primarily sodium perborate mono- and tetrahydrate as well as sodium percarbonate and sodium uearoat. Since active oxygen only develops its full effect on its own at elevated temperatures, so-called bleach activators are also expediently used to activate it at about 60 ° C., the temperatures of the cleaning process in the HGSM.
• TAED tetraacetylenediamine
• PAG penentaacetylglucose
• DADHT 1,5-di-acetyl-2,4-dioxo-hexahydro-l, 3,5-triazine
• ISA isatoic anhydride
• Enzymes such as proteases and amylases can also be used to better remove protein or starch-containing food residues, for example proteins such as BLAP ( R ) from Henkel, Opitmase ( R ) -M-440, Optimase ( R ) - -M -330, Opticlean ( R ) -M-375, Opticlean ( R ) -M-250 from Solvay Enzy ⁇ mes, Maxacal ( R ) CX 450,000, Maxapem ( R ) from Ibis, Savinase ( R ) T from Novo or Esperase ( R ) T from Ibis and amylases such as Termamyl ( R ) 60 T, 90 T from Novo, Amylase-LT ( R ) from Solvay Enzymes or Maxamyl ( R ) P 5000 from Ibis.
• proteins such as BLAP ( R ) from Henkel, Opitmase ( R ) -M-440, Optimase (
• Customary oxidation-stable dyes and fragrances can also be added to the tablet mixtures.
• the tablets can also be pressed in colored layers with otherwise the same composition.
• tableting aids such as mold release agents, for example paraffin oil, or mixtures of mono-, di- and triglycerides of C12-C18, preferably Ci ⁇ -Ci ⁇ fatty acids, for example commercially available glyceride mixtures sold as baking agents, e.g. Boeson VP (Boehringer, Ingelheim) is not necessary for compressing the tablets according to the invention and can usually be omitted if the tablet mixtures contain nonionic surfactants which essentially take on this task.
• the addition of paraffin oil and / or glyceride mixtures can nevertheless be expedient, as indicated, because it leads to a delay in dissolution of the tablets, so that a higher proportion of the tablet is available in the cleaning cycle.
• the desired pH is preferably set via the sodium hydrogen carbonate portion.
• the mixture produced as described would be pressed on conventional tablet presses with a pressure of about 2 to 11 MPa, preferably about 4 to 6 MPa.
• the pressing could be carried out in known manner without die lubrication using commercially available eccentric presses, hydraulic presses or rotary presses. No caking of the tablet mixture was observed on the pressing tools. Tools coated with hard plastic as well as uncoated delivered tablets with smooth surfaces, so that in most cases it was also possible to dispense with coating the punches with soft plastic.
• the pressing conditions were optimized with regard to the setting of the desired dissolution profile with sufficient tablet hardness.
• the flexural strength can serve as a measure of the tablet hardness (method: compare Ritschel. Die Tablette, Ed. Cantor, 1966, p. 313). According to this, tablets with a bending strength greater than 100 N, preferably greater than 150 N, are sufficiently stable under simulated transport conditions.
• the bending or breaking strength of the tablets can be controlled by the degree of compression, ie the compression pressure, regardless of their
• the specific weight of the compacts was between about 1.2 and 2 g / cm 3, preferably between about 1.4 and 1.8 g / cm 3.
• the compression during the pressing process caused changes in the density, which ranged from about 0.4 to 1.2 g / cm 3, preferably about 0.6 to 1.0 g / i 3 to about 1.2 to 2.0 g /, preferably about 1 .4 to 1.6 g / cm3 rose.
• the shape of the tablet can also influence the breaking strength and the dissolving speed via the outer surface exposed to the H2O attack. For reasons of stability, cylindrical compacts with a diameter / height ratio of approximately 0.6 to 4.0: 1 were produced.
• the breaking strength corresponds to the weight of the wedge-shaped load, which leads to the tablet breaking.
• the amounts of the substance mixture to be compressed for the individual tablets can be varied as desired within technically reasonable limits. Depending on their size, 1 to 2 or even more tablets per machine filling are preferably used in order to provide the entire cleaning process with the necessary active substance content of cleaning agent. Tablets of about 20 to 40 g in weight and a diameter of about 35 to 40 mm are preferred, of which one must be used in each case. If sodium carbonate was not hydrated or used as a full hydrate, the quality of the tablets obtained from the mixture was unusable for the trade since, among other things, they had insufficient breaking strength. The tablets also caked on the mixtures on the upper ram of the presses.
• a batch of 50 kg was prepared in a 130 l Lödige ploughshare mixer by first spraying 4 parts by weight of water onto 7.5 parts by weight of sodium carbonate and 48 parts by weight of sodium hydrogen carbonate and then with 30 parts by weight of sodium citrate dihydrate, 2 parts by weight of TAED granules and 1 part by weight of BLAP ( R ). 170 and 1 part by weight of Termamyl ( R ) 60 parts were mixed while spraying 0.9 parts by weight of Dehydol LS4 and 0.6 parts by weight of fragrance. 5 parts by weight of perborate onohydrate were then gently mixed into the mixture thus obtained. As can be seen from the table containing the pressing conditions and tablet properties, the mixture gave tablets with only limited resistance to breakage that dissolve too quickly in the pre-rinse cycle.
• Example A With the same composition as described in Example A, the sodium citrate dihydrate was first sprayed with water in 130 l Lödige mixer according to the invention, followed by dusting with soda. Then TAED granules, sodium hydrogen carbonate, Blap 170, Termamyl 60 T and a mixture of perborate monohydrate, fragrance and dehydol LS4 were added. The much more favorable properties of the tablets obtained in this way can be seen from the tables below, as in the examples below.
• the mixture was prepared as in Example 1, but after the addition of the dehydol LS4, the perborate monohydrate was finally mixed in separately.
• Example 4 The mixture was prepared as described in Example 1, but 1% paraffin oil was additionally sprayed onto the mixture at the end.
• Example 4
• TAED tetraacetylethylenediamine
• Boeson VP commercially available glyceride mixture Examples table

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• Inorganic Chemistry (AREA)
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• 1993
  • 1993-04-01 DE DE4315048A patent/DE4315048A1/de not_active Withdrawn
• 1994
  • 1994-03-23 DK DK94912526T patent/DK0692020T3/da active
  • 1994-03-23 EP EP94912526A patent/EP0692020B1/fr not_active Expired - Lifetime
  • 1994-03-23 ES ES94912526T patent/ES2110742T3/es not_active Expired - Lifetime
  • 1994-03-23 CZ CZ19952531A patent/CZ286894B6/cs unknown
  • 1994-03-23 DE DE59404581T patent/DE59404581D1/de not_active Expired - Lifetime
  • 1994-03-23 WO PCT/EP1994/000932 patent/WO1994023011A1/fr active IP Right Grant
  • 1994-03-23 AT AT94912526T patent/ATE160169T1/de active
  • 1994-03-23 HU HU9502850A patent/HUT72020A/hu unknown
  • 1994-03-23 US US08/530,114 patent/US5691293A/en not_active Expired - Fee Related
  • 1994-03-23 PL PL94310951A patent/PL177250B1/pl unknown

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