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
  • 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

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 a commercial dishwasher, hereinafter referred to as GGSM, the so-called pre-clearing zone corresponds in principle to the pre-wash cycle of an HGSM.
• the detergent added to 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.
• Such tablets have such a broad dissolution profile that at least 10% by weight of the tap water to be run in is already dissolved in the pre-rinse cycle of an HGSM, thereby developing a pH value of at least 10.0 in the rinsing liquor and, with good hot water solubility, too at least 60% by weight, preferably at least 70% by weight, are available for the cleaning cycle.
• the dissolving profile is understood to mean the weight ratio of portions of the tablet, dissolved under the conditions of the pre-rinse cycle, of conventional HGSM to the entire tablet.
• the known tablets still contain phosphates, which are known to be undesirable.
• phosphate-free detergent tablets for machine dishwashing on the market (eg Hui rinsing tabs from Roth GmbH, Bad Ems), which essentially contain silicates, nonionic surfactants, organic complexing agents and percarbonate. If these tablets are placed inside the machine (e.g. in the cutlery basket), however, they dissolve largely or completely even during the pre-rinse cycle, so that practically no detergent is available in the actual cleaning cycle. In addition, the stability of these tablets is unsatisfactory.
• DE 40 10 524 A1 describes stable, bifunctional, phosphate-free detergent tablets for machine dishwashing containing silicate, low-foam nonionic surfactants, organic complexing agents, bleaching agents and water, the organic complexing agents according to DE 39 37 469 A1 in the form of a granular one , 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 recipe components and pressed in a manner known per se.
• the present invention was based on the object of producing a stable, bifunctional, phosphate- and metasilicate-free, low-alkaline detergent tablet with a broad dissolving profile for machine dishwashing, which at least 10 wt. up to about 40% by weight, thereby developing a pH value of at most about 10.5 in the rinsing liquor and at least 60% by weight to about 90% by weight being available for the cleaning cycle with good hot water solubility .
• the tablets produced according to the invention have a high breaking strength (greater than 140 N with a diameter of 35 to 40 mm and a density of about 1.6 to 1.8 g / cm 3), which remains stable during storage and even remains within a short time can significantly increase. When used as intended, the tablets dissolve with a broad dissolution profile.
• Component (a) consists of homopolymeric or copolymeric carboxylic acids in the form of the sodium salts.
• Suitable homopolymers are polymethacrylic acid and preferably polyacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid). If only homopolymeric polyacrylic acids (in salt form) are used, their molecular weight is preferably 1,000 to 80,000 (based on acid) in the interest of good flowability and storage stability.
• Suitable copolymers are those of acrylic acid with methacrylic acid and preferably copolymers of acrylic acid or methacrylic acid with maleic acid.
• Copolymers of acrylic acid with maleic acid as are characterized, for example, in EP 25 551 81, have proven to be particularly suitable. These are copolymers which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid. Copolymers in which 60 to 85% by weight of acrylic acid and 40 to 15% by weight of maleic acid are present are particularly preferred.
• Their molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000.
• Mixtures of different homopolymers and copolymers can also advantageously be used, in particular mixtures of homopolymeric acrylic acid and the copolymers of 50 to 90% by weight of acrylic acid and 50 to 10% of maleic acid described above.
• Such mixtures which are characterized by favorable grain properties and high storage stability, can consist, for example, of 10 to 50% by weight of homopolymeric acrylic acid and 90 to 50% by weight of acrylic acid-maleic acid copolymers.
• Highly polymeric polyacrylic acids can also be used in these mixtures which, when used alone, have a slightly greater tendency to stick or melt than the low molecular weight polyacrylates.
• the sodium carbonate (b) and the sodium sulfate (c) are used in anhydrous form. With proportions of sodium carbonate of approx. 40% by weight and more, it is advisable to reduce the water content (d) of the additives to less than 6% by weight or to choose a somewhat higher proportion of sodium sulfate, for example in the range 8 to 15% by weight. Sodium sulfate contents of more than 10% by weight, preferably 15 to 20% by weight, fundamentally improve the grain properties and the shelf life of the additives. On the other hand, sodium sulfate is ineffective fiber when using the additives, which is why its proportion should be as low as possible.
• fractions of 5 to 6% by weight (c) are sufficient to add additives with a content of approx. 50% by weight (a), approx. 40% by weight (b) and approx Stabilize 4% by weight (d) and ensure good pouring properties.
• the cleaning additives can contain minor components such as dyes and color pigments and can be colored uniformly or speckled.
• the proportion of such minor components is well below 1% by weight.
• Sodium citrates, nitrilotriacetate, phosphonates, alkali carbonates and alkali disilicates can serve as builders. Together with the polycarboxylate-containing cleaning additive, 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, it also being possible for hydrate salts to form in agglomerating granulation from about 5 to 10, preferably about 6 to 8 parts by weight of water and anhydrous salts.
• the polycarboxylates are used as powder, but preferably as granules.
• the usable polyacrylates include Alcosperse R from Alco: Alcosperse R 102, 104, 106, 404, 406), Acrysole R from Norsohaas: Acrysole R A 1N, LMW 45 N, LMW 10 N, LMW 20 N, SP 02N, Degapas R from Degussa: Degapas R 4104 N, Good-Rite R from Goodrich: Good-Rite R K-XP 18.
• Copolymers (polyacrylic acid and maleic acid) can also be used, for example Sokalane R from BASF: Sokalan R CP 5, CP 7, Acrysole R from Norsohaas: Acrysol R QR 1014, Alcosperse R from Alco: Alcosperse R 175.
• Anhydrous trisodium citrate or trisodium citrate dihydrate are suitable as sodium citrate.
• the preferred phosphonate is the tetrasodium salt of 1-hydroxyethane-1,1-di-phosphonic acid (Turpinal R 4 NZ from Henkel).
• alkali carbonate sodium carbonate of any quality is preferably used, such as. B. calcined soda, compressed soda and also sodium bicarbonate.
• Extremely low-foaming compounds are preferably used as nonionic surfactants, which serve to better remove fatty food residues and as a pressing aid. 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 0.2 to 5, preferably 0.5 to 3% by weight. But you can also use other non-foaming surfactants known as low foams, such as. B.
• C12-C18 alkyl polyethylene glycol polybutylene glycol ether each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule and then optionally 0.2 to 2, preferably 0.2 to 1 wt .-%, based on the entire tablet, of defoaming agents such as B. 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 primarily include sodium perborate mono- and tetrahydrate as well as sodium percarbonate. Since active oxygen only develops its full effect on its own at elevated temperatures, so-called bleach activators are used to activate it at approx. 60 ° C, the temperatures of the cleaning process in the HGSM.
• Preferred bleach activators are TAED (tetraacetylenediamine), PAG (pentaacetylglucose), DADHT (1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine) and ISA (isatoic anhydride).
• Enzymes such as proteases and amylases can also be used to better remove protein or starch-containing food residues, for example proteases such as BLAP R from Henkel, Opitmase R -M-440, Optimase R -M-330, Opticlean R -M-375 , Opticlean R -M-250 from Solvay Enzymes, 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.
• proteases such as BLAP R from Henkel, Opitmase R -M-440, Optimase R -M-330, Opticlean R -M-375 , Opticlean R -M-250 from Solvay Enzymes, Maxacal R CX 450,000
• tabletting aids such as mold release agents, for example paraffin oil
• mold release agents for example paraffin oil
• 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.
• the following areas can be considered for frame formulations of the detergent tablets produced according to the invention: Components: Area preferred area granular cleaning additive 5 - 30% 6 - 25% Trisodium citrate dihydrate 5 - 40% 9 - 30% Nitrilotrine sodium acetate 0 - 25% 0 - 20% Sodium phosphonate 0 - 10% 0 - 5% Sodium carbonate, anhydrous 5 - 60% 10 - 50% Sodium disilicate 0 - 60% 2 - 30% Sodium bicarbonate 0 - 60% 0 - 30% Sodium perborate monohydrate 3 - 15% 5 - 10% Tetraacetylethylenediamine 0.5 - 4% 1 - 2% nonionic surfactant 0 - 4% 1 - 2% Protease 0.1 - 1% 0.2 - 0.5% Amylase 0.1 - 1% 0.2 - 0.5% Fragrance 0 - 1% 0.1 - 0.5% water 3 - 15% 5 - 10%
• the average grain size of the granular cleaning additives is usually 0.2 to 1.2 mm, the proportion of the grains being below 0.1 mm not more than 2% by weight and above 2 mm not more than 20% by weight.
• at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.2 to 1.6 mm, the proportion of the grains between 0.1 and 0.05 mm not more than 3% by weight .-%, in particular not more than 1% by weight and the proportion of the grains between 1.6 and 2.4 mm is not more than 20% by weight, in particular not more than 10% by weight.
• the bulk density is 350 to 550 g / l.
• the granular cleaning additives are produced by spray drying an aqueous slurry.
• the slurry concentration is between 50 and 68% by weight (non-aqueous fraction), preferably between 55 and 60% by weight, the viscosity of the paste being decisive, which should not exceed 10,000 mPa ⁇ s and advantageously 2,500 to 6,000 mPa ⁇ S is.
• the temperature of the slurry is usually between 50 and 100 ° C.
• the pressure at the spray nozzles is generally 30 to 80 bar, preferably 40 to 70 bar.
• the temperature of the countercurrent dry gases in the entrance zone of the spray tower, i.e. H. in the so-called ring channel is advantageously between 200 and 320 ° C, in particular between 220 and 300 ° C.
• the drying is preferably conducted so that the water binding is reduced to less than 1 mole of H2O per mole of sodium carbonate.
• Conventional spray drying systems spray towers
• spray drying can be used for spray drying, it being possible for the spray nozzles to be arranged in one or more levels.
• the spray material leaving the tower was mixed with the framework substances and water and, if appropriate, nonionic surfactant, again agglomerated in a manner known per se, for example in a Lödige mixer or also mixers from the companies Imatec, Unimix, Drais or Papenmeier, with the Bleach, optionally a bleach activator, colors and fragrances and / or enzymes mixed and then in total on conventional tablet presses with a pressure of 200 to 1500. 105, preferably 300 to 1000. 105 Pa pressed.
• the pressing could be carried out in a 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, supplied tablets with smooth surfaces, so that in most cases there was no need to coat 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, regardless of their format, can be determined by the degree of compaction, i. H. the baling pressure can be controlled.
• the specific weight of the compacts was between 1.2 and 2 g / cm3, preferably between 1.4 and 1.8 g / cm3.
• the compression during the pressing process caused changes in the density, which from 0.6 to 1.2 g / cm3, preferably 0.8 to 1.0 g / cm3 to 1.2 to 2.0 g / cm3, preferably 1.6 to 1.8 g / cm3 rose.
• the shape of the tablet can also influence the breaking strength and the rate of dissolution via the outer surface exposed to the H2O attack. For stability reasons, cylindrical compacts with a diameter / height ratio of 0.6 to 4.0: 1 were produced.
• the tablet was loaded with a wedge to measure the breaking strength.
• the breaking strength corresponds to the weight of the wedge-shaped load that causes the tablet to break.
• 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 20 to 40 g in weight and a diameter of 35 to 40 mm are preferred, one of which must be used in each case. Larger tablets are generally more sensitive to breakage and, moreover, are compressed at a slower rate. With smaller tablets, the handling advantage compared to granular or powder detergents would be reduced.
• Nonionic surfactants are nonionic surfactants:
• example 2 A 2 B Cleaning additive (granular)% 22.0 19.87 Tri-Na citrate x 2H2O% 5.0 20.00 Sodium disilicate% 20.0 - Sodium carbonate, anhydrous% 29.0 44.93 Sodium bicarbonate% 9.4 - Sodium perborate x 1H2O% 7.0 7.00 % Tetraacetylethylenediamine 2.0 2.00 Termamyl R (amylase)% 0.5 0.50 BLAP R (protease)% 0.5 0.50 Plurafac LF 403% 4.0 2.00 Perfume % 0.6 0.20
• example 2 A 2 B Bulk weight the mixture g / l 870 620 Tablet weight g 25th 25th Tablet diameter mm 38 38 Tablet density g / cm3 1.57 1.39 * Press force KN 13.5 25th Breaking strength after manufacture N 140 90 after 1 week N 140 82 Detachment after pre-rinse g about 10 10th * A higher compression was not possible because the tablet was then "capped", which means that part of the tablet mass got stuck on the ram of the compact.
• tablets were pressed from the following recipes: raw materials 3rd 4th Granular cleaning additive 19.87 19.87 Turpinal 4 NZ 2.00 2.00 Sodium carbonate, anhydrous 45.93 45.93 Sodium citrate, anhydrous 20.00 20.00 Sodium perborate monohydrate 7.00 7.00 TAED 2.00 2.00 Termamyl 60 T (protease) 0.50 0.50 BLAP 140 (amylase) 0.50 0.50 Plurafac LF 403 2.00 2.00 Fragrance 0.20 0.20 water 2.88 6.88 Bulk density (g / l) 610 605 Tablet weight (g) 23.8 23.8 Tablet height (mm) 14.3 14.1 Tablet diameter (mm) 38 38 Tablet density (g / ml) 1.46 1.4g Hardness immediately (N) 220 285 Hardness after 1 day (N) 310 341 Hardness after 4 days (N) 270 390

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)

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• 1991
  • 1991-04-12 DE DE4112075A patent/DE4112075A1/de active Granted
• 1992
  • 1992-04-03 AT AT92907884T patent/ATE123804T1/de not_active IP Right Cessation
  • 1992-04-03 WO PCT/EP1992/000744 patent/WO1992018604A1/de not_active Ceased
  • 1992-04-03 ES ES92907884T patent/ES2073295T3/es not_active Expired - Lifetime
  • 1992-04-03 EP EP92907884A patent/EP0579659B1/de not_active Expired - Lifetime
  • 1992-04-03 DK DK92907884.8T patent/DK0579659T3/da active
  • 1992-04-03 DE DE59202554T patent/DE59202554D1/de not_active Expired - Fee Related
  • 1992-04-03 JP JP50712892A patent/JP3147901B2/ja not_active Expired - Fee Related
  • 1992-04-03 US US08/137,106 patent/US5358655A/en not_active Expired - Fee Related

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