EP0032236A1 - Détergent pour le lavage de la vaisselle - Google Patents

Détergent pour le lavage de la vaisselle Download PDF

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Publication number
EP0032236A1
EP0032236A1 EP80108195A EP80108195A EP0032236A1 EP 0032236 A1 EP0032236 A1 EP 0032236A1 EP 80108195 A EP80108195 A EP 80108195A EP 80108195 A EP80108195 A EP 80108195A EP 0032236 A1 EP0032236 A1 EP 0032236A1
Authority
EP
European Patent Office
Prior art keywords
weight
alkali metal
percent
sieve
mesh size
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP80108195A
Other languages
German (de)
English (en)
Other versions
EP0032236B1 (fr
Inventor
Jochen Dr. Kaufmann
Theodor Dr. Altenschöpfer
Klaus Dr. Schumann
Friedel Rings
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19803000981 external-priority patent/DE3000981C2/de
Priority claimed from DE19803007998 external-priority patent/DE3007998A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT80108195T priority Critical patent/ATE6269T1/de
Publication of EP0032236A1 publication Critical patent/EP0032236A1/fr
Application granted granted Critical
Publication of EP0032236B1 publication Critical patent/EP0032236B1/fr
Expired legal-status Critical Current

Links

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
    • C11D3/395—Bleaching agents
    • C11D3/3955—Organic bleaching agents
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/06—Hydroxides

Definitions

  • the application concerns alkaline, active chlorine-containing granulated, machine-applicable dishwashing detergents.
  • alkaline cleaning agents are usually used, which essentially consist of builders, alkali metal silicates, alkali metal carbonates and / or alkali metal hydroxides, compounds containing active chlorine and optionally nonionic surfactants.
  • active chlorine content of the cleaning agents the better the stain cleaning, for example in the case of tea residues, and the higher the alkali metal hydroxide content, the better the cleaning effect, in particular for dishes with burnt-on food residues.
  • the cleaning agents are generally prepared by dry mixing the individual powdery or particulate constituents, for example in rotating drums, to form the desired mixed product, any liquid constituents such as, for example, nonionic surfactants and / or water glass as such, as a mixture or in aqueous solution by spraying on the moving powder or particulate constituents or groups of constituents, whereby granulation takes place.
  • the active chlorine compounds who which is usually added at the end. In any case, an end product of free-flowing powdery to granular nature is sought, which does not cake during normal storage and is stable in terms of its constituents. This applies in particular to the compound containing active chlorine.
  • Polychlorinated cyanuric acids and their salts have proven particularly useful as active chlorine-containing compounds in powdered or granulated dishwashing detergents. Because of the highest content of active chlorine, trichloroisocyanuric acid is always of great interest. However, their low solubility in water and their poor shelf life are disadvantageous.
  • the present invention therefore relates to alkaline, active chlorine-containing granulated, machine-applicable dishwashing detergents containing builder substances, alkali metal silicates, alkali metal carbonates, alkali metal hydroxides and optionally nonionic surfactants, which are characterized in that they contain 1 to 30, preferably 3 to 15 and in particular 5 to 15 percent by weight on finely divided trichloroisocyanuric acid in granulate or prill form with the smallest possible surface and a degree of purity determined by laser-raman spectroscopy ⁇ 99% and 10 to 40, preferably 15 to 30 percent by weight of granulated alkali metal hydroxide with the smallest possible surface.
  • the finely divided trichloroisocyanuric acid used according to the invention essentially had the following grain spectrum: which was determined using a sieve set according to DIN 4188.
  • Granules were thus used, the particles of which more than 90, preferably more than 95% by weight and in particular more than 98% by weight passed through a sieve with a mesh size of 1.6 mm and more than 90% by weight. preferably more than 95% by weight and in particular more than 99% by weight have been retained by a sieve with an internal mesh size of 0.2 mm.
  • trichloroisocyanuric acids the particles of which are more than 98% by weight retained by a sieve with a mesh size of 0.4 mm, the total grain size distribution being such that at the same time preferably more than 55% by weight % of the particles are retained by a sieve with a mesh size of 0.8 mm.
  • alkali metal hydroxides The nature of the alkali metal hydroxides is of minor importance. Particularly good, reliable and unambiguous results are achieved, however, if they are used as granulated alkali metal hydroxides with a surface that is as small as possible, ie as spherical as possible. Potassium and preferably sodium hydroxide are used, namely as coarse grains or preferably as so-called prills.
  • the coarse grain essentially has the following grain size distribution: that is, more than 70, preferably more than 80% by weight of all particles pass through a sieve with a clear mesh size of 1.6 mm and less than 10% by weight of all particles pass through a sieve with a clear mesh size of 0, 2 mm (sieve set according to DIN 4188).
  • the prills preferably used according to the invention essentially have the following grain size distribution: that is, the particles are so large that they practically no longer pass a sieve with a 0.2 mm mesh size (sieve set DIN 4169).
  • the entire grain size distribution> 0.2 mm is mainly determined by the other powder or granular components of the respective recipes. In order to avoid segregation phenomena within the products, it is advantageous to avoid larger differences in the grain sizes of the individual components.
  • alkali metal polyphosphates with a molar ratio of Na 2 0 or K 2 0 to P 2 0 5, such as 1: 1 to 2: 1, can preferably be used as builders. These include sodium tripolyphosphate, which is preferred for cost reasons, sodium hexametaphosphate and sodium pyrophosphate and the corresponding potassium polyphosphates. In the case of the polyphosphates, the particle size is of no particular importance. It is therefore possible to use the commercially available products, with their hydrate water content being of minor importance.
  • the polyphosphates can also be produced, in part, by synthetically produced water-insoluble, bound water-containing aluminosilicates of the general formula which also bind the calcium hardness of the water in the cat a cation of valence n, preferably sodium, exchangeable for calcium, x a number from 0.7 to 1.5, preferably 0.9 to 1.3 and y a number from 0.8 to 6, preferably of 1, 3 to 4, which have a calcium binding capacity of 50 to 200, preferably 100 to 200 mg CaO / g of anhydrous inorganic active substance, are replaced.
  • Such connections are known, for example, under the name SASIL® from Henkel KGaA, Düsseldorf. They can make up up to 60, preferably 25 to 50% of the framework substances.
  • the alkali metal silicates used primarily act as corrosion inhibitors for the metal parts of the dishwashers.
  • the soluble alkali metal silicates used are preferably sodium or potassium metasilicates in which the ratio of alkali oxide: silicon dioxide is approximately 1: 0.5 to 3.5.
  • the anhydrous silicates are preferably used.
  • Disilicates with a ratio of alkali oxide: silicon dioxide such as 1: 2 are also suitable for use in the cleaning agents according to the invention.
  • alkali metal carbonates sodium and potassium carbonate in the form of water of hydration are primarily considered.
  • the carbonates mainly serve as fillers. If appropriate, they can also be partially or completely replaced by corresponding sulfates.
  • Nonionic surfactants which may be used are those which do not decompose in the presence of compounds containing active chlorine and alkali metal hydroxides. Low-foaming surfactants are also expediently used.
  • Suitable addition products are the adduct of 10 to 30 percent by weight of ethylene oxide with a polypropylene glycol of molecular weight 1750, the adduct of 20 moles of ethylene oxide or 9 moles of ethylene oxide and 10 moles of propylene oxide with nonylphenol, the adduct of 5 to 12 moles of ethylene oxide with a fatty alcohol mixture Chain lengths C 12 -C 18 containing about 30% oleyl alcohol and the like.
  • This exemplary list is not a limitation.
  • chlorine and alkali-resistant colors and fragrances can be added to the dish detergents.
  • the dishwashing detergents according to the invention were once produced by simply mixing the powdery or granular constituents in a conventional mixing drum.
  • granules can also be produced.
  • a so-called basic granulate was first produced in a conventional manner, which contained the framework substances, alkali metal carbonates, silicates and surfactants, the mostly liquid nonionic surfactants and possibly liquid or water-based silicates individually or as a mixture with the liquid surfactants in a controlled manner on the dry ones moving and therefore well mixed solid granulate components were sprayed on.
  • a Lödige and Eirich mixer were used as granulators.
  • This basic granulate was then mixed with appropriate amounts of granulated trichloroisocyanuric acid and alkali metal hydroxides in the form of prills or coarse grains. The respective grain sizes were obtained by sieving.
  • the basic granulate, the chlorine carrier and the alkali metal hydroxides were used in largely identical grain sizes.
  • the dishes detergent granules obtained were loose and free-flowing and neither caked during storage nor did they show signs of segregation after a shaking process simulating transport conditions.
  • trichloroisocyanuric acids I, II, III and IV used in the examples according to the invention and the comparative compositions given below and - 'NaOH coarse grain or NaOH prills had the following degree of purity and / or grain size distribution, determined in accordance with DIN 4188:
  • a corresponding agent with the trichloroisocyanuric acid IV according to the invention was prepared with the same amounts and behaved in exactly the same way as an agent of the composition given above.
  • Granulate from: basic granulate and the admixture of
  • Granulate from: basic granulate and the admixture of
  • the active chlorine content fell from the initial value of 4.55% to a final value of 0.43% and was therefore completely unusable.
  • a product of the composition according to Example 2 was investigated under the same experimental conditions as stated above, again the feared self-decomposition did not occur.
  • trichloroisocyanuric acid I with an active chlorine content.
  • same amount of granulated sodium dichloroisocyanurate dihydrate a violent self-decomposition process occurred after 7.5 hours.
  • the final reaction temperature was 220 ° C.
  • the plastic jacket of the polyethylene container had melted and the product came out.
  • the active chlorine content dropped from 7.3% in the fresh mixture to a final value of 0.5%. Even the use of sodium hydroxide prills, which are practically free of dust, did not prevent the self-decomposition of this product.
  • the experimental apparatus consisted of a cup-shaped, glass pressure vessel with a volume of 1 liter, which was surrounded by a heating jacket. This pressure vessel was filled with 1 kg each of one of the mixtures 1 to 4 specified below and sealed at the top with an insulating layer made of asbestos cardboard and rock wool. Through the patch, with a gas discharge nozzle and two. Temperature sensors provided with sensor inputs and connected to the pressure vessel by means of a clamping ring, temperature sensors were led to the edge of the pressure vessel and into the center of the mixture.
  • the pressure vessel was largely insulated so that heat exchange with the surroundings would be avoided.
  • the pressure in the vessel was kept constant by evacuating gases.
  • the pressure vessel was heated to a constant "base temperature” depending on the composition by means of an adjustable jacket and floor heating.
  • the so-called “initial time” of self-decomposition was the time in minutes after which the heating was switched off automatically. This happened at the time when the temperature of the reaction mixture exceeded that of the base temperature.
  • the temperature curve as a function of time was determined using iron / constantan Resistance thermocouples measured in the center and near the jacket of the pressure vessels. The highest temperature reached in the center of the reaction mixture as a function of time was determined. The results are shown in Table 2.
  • the cleaning agents listed in Examples 5 to 8 were each stored for 24 weeks at room temperatures between 17 and 24 ° C and at 35 ° C and 70% relative humidity in a climatic cabinet in watertight containers.
  • Examples 5 to 8 were further varied in such a way that the trichloroisocyanuric acid (TCIC) "I” used according to the invention was exchanged for two other trichloroisocyanuric acids “II” and “III", each with a low degree of purity (samples 1 to 4 A / B).
  • the trichloroisocyanuric acid was replaced by correspondingly higher amounts of potassium dichloroisocyanurate (KDCIC) and sodium dichloroisocyanurate (NaDCIC) anhydrous and as dihydrate, which provided the same amounts of active chlorine.
  • KDCIC potassium dichloroisocyanurate
  • NaDCIC sodium dichloroisocyanurate

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP80108195A 1980-01-12 1980-12-24 Détergent pour le lavage de la vaisselle Expired EP0032236B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80108195T ATE6269T1 (de) 1980-01-12 1980-12-24 Geschirreinigungsmittel.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3000981 1980-01-12
DE19803000981 DE3000981C2 (de) 1980-01-12 1980-01-12 Geschirreinigungsmittel
DE19803007998 DE3007998A1 (de) 1980-03-01 1980-03-01 Geschirreinigungsmittel
DE3007998 1980-03-01

Publications (2)

Publication Number Publication Date
EP0032236A1 true EP0032236A1 (fr) 1981-07-22
EP0032236B1 EP0032236B1 (fr) 1984-02-15

Family

ID=25783130

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80108195A Expired EP0032236B1 (fr) 1980-01-12 1980-12-24 Détergent pour le lavage de la vaisselle

Country Status (3)

Country Link
US (1) US4324677A (fr)
EP (1) EP0032236B1 (fr)
DE (1) DE3066661D1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3832885A1 (de) * 1988-09-28 1990-04-05 Ifah Inst Fuer Angewandte Hygi Verfahren zum maschinellen reinigen, desinfizieren und klarspuelen von geschirr und dafuer geeignetes mittel
EP0826768A1 (fr) * 1996-08-07 1998-03-04 Henkel Kommanditgesellschaft auf Aktien Constituants granulaires contenant du benzotriazole pour compositions pour lave-vaisselle automatique, et procédé pour leur préparation

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1206391A (fr) * 1982-04-15 1986-06-24 American Home Products Corporation Gels fluables pour lave-vaisselle
US4464281A (en) * 1983-07-28 1984-08-07 Lever Brothers Company Stabilized bleach-sensitive dyes in automatic dishwasher detergent compositions
CZ20003728A3 (cs) * 1998-04-09 2001-11-14 Unilever N. V. Blok do toalet

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1167473B (de) * 1960-12-07 1964-04-09 Azote Office Nat Ind Stabile, chlorhaltige Reinigungsmittel, enthaltend Trichlorcyanursaeure
US3166513A (en) * 1963-04-04 1965-01-19 Economics Lab Stable detergent composition
DE2219804A1 (de) * 1972-04-22 1973-10-31 Knapsack Ag Tenside fuer geschirrspuelmittel
DE2340910A1 (de) * 1972-08-17 1974-02-28 Procter & Gamble N-chlorimide enthaltende wasch- und reinigungsmittel
DE2358249A1 (de) * 1972-11-24 1974-05-30 Fmc Corp Spuelmittel, verfahren zu ihrer herstellung und ihre verwendung in geschirrspuelmaschinen

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE24412E (en) * 1948-06-25 1957-12-31 Bleaching
US3390092A (en) * 1965-03-30 1968-06-25 Fmc Corp Dishwashing detergent preparations containing sodium or potassium dichloroisocyanurate
US3352785A (en) * 1965-06-18 1967-11-14 Fmc Corp Stable dishwashing compositions containing sodium dichloroisocyanurate
US3491028A (en) * 1969-06-03 1970-01-20 Grace W R & Co Chlorine stable machine dishwashing composition
US4242216A (en) * 1979-09-27 1980-12-30 Chemed Corporation Stabilized dichlorodimethyl hydantoin

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1167473B (de) * 1960-12-07 1964-04-09 Azote Office Nat Ind Stabile, chlorhaltige Reinigungsmittel, enthaltend Trichlorcyanursaeure
US3166513A (en) * 1963-04-04 1965-01-19 Economics Lab Stable detergent composition
DE2219804A1 (de) * 1972-04-22 1973-10-31 Knapsack Ag Tenside fuer geschirrspuelmittel
DE2340910A1 (de) * 1972-08-17 1974-02-28 Procter & Gamble N-chlorimide enthaltende wasch- und reinigungsmittel
DE2358249A1 (de) * 1972-11-24 1974-05-30 Fmc Corp Spuelmittel, verfahren zu ihrer herstellung und ihre verwendung in geschirrspuelmaschinen

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3832885A1 (de) * 1988-09-28 1990-04-05 Ifah Inst Fuer Angewandte Hygi Verfahren zum maschinellen reinigen, desinfizieren und klarspuelen von geschirr und dafuer geeignetes mittel
EP0826768A1 (fr) * 1996-08-07 1998-03-04 Henkel Kommanditgesellschaft auf Aktien Constituants granulaires contenant du benzotriazole pour compositions pour lave-vaisselle automatique, et procédé pour leur préparation

Also Published As

Publication number Publication date
DE3066661D1 (en) 1984-03-22
US4324677A (en) 1982-04-13
EP0032236B1 (fr) 1984-02-15

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