EP0523095B1 - Comprimes detergents stables, bifonctionnels et sans phosphate pour lave-vaisselle - Google Patents

Comprimes detergents stables, bifonctionnels et sans phosphate pour lave-vaisselle Download PDF

Info

Publication number
EP0523095B1
EP0523095B1 EP91906795A EP91906795A EP0523095B1 EP 0523095 B1 EP0523095 B1 EP 0523095B1 EP 91906795 A EP91906795 A EP 91906795A EP 91906795 A EP91906795 A EP 91906795A EP 0523095 B1 EP0523095 B1 EP 0523095B1
Authority
EP
European Patent Office
Prior art keywords
weight
tablets
contain
anhydrous
sodium
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.)
Expired - Lifetime
Application number
EP91906795A
Other languages
German (de)
English (en)
Other versions
EP0523095A1 (fr
Inventor
Hans Kruse
Jochen Jacobs
Jürgen Härer
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
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0523095A1 publication Critical patent/EP0523095A1/fr
Application granted granted Critical
Publication of EP0523095B1 publication Critical patent/EP0523095B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D3/02—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
    • 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
    • C11D3/08—Silicates
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

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.
  • pre-clearing zone cleaning from GGSM has 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 in others Positioned in the machine, so that they could act both in the pre-rinse cycle and in the actual cleaning cycle, i.e. bifunctionally.
  • 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 as far as possible, even completely, during the pre-rinse cycle, so that no cleaning agents are left in the actual cleaning cycle Available. In addition, the stability of these tablets is unsatisfactory.
  • the present invention was therefore based on the object of developing a stable, bifunctional, phosphate-free detergent tablet with a broad dissolving profile for machine dishwashing, which in the pre-rinse cycle of an HGSM from the incoming cold tap water to at least 10% by weight to about 40% by weight is dissolved, thereby developing a pH value of at least 10.0 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.
  • Pentahydrate is understood here and below to mean a compound of the formula Na2H2SiO4.4H2O, and “nonahydrate” is a compound of the formula Na2H2SiO4.8H2O.
  • the tablets of the invention have a particularly high breaking strength at a sodium metasilicate nonahydrate content (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 can be stored within increased significantly in a short time. They can be easily manufactured on eccentric, hydraulic or rotary presses and solve well when used as intended.
  • the components of the spray-dried granular cleaning additive are added individually to the mixture of the components to be tabletted, for example in accordance with DE 2 435 479 A1, the quality of the tablets obtained therefrom is unusable for the trade since they u. a. have an insufficient breaking strength.
  • the tablets also bake on the mixtures on the upper ram of the presses.
  • 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 such as are characterized for example in EP 25 551 B1, 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.
  • Your 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 detergents 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 compositions. On the other hand, sodium sulfate is ineffective fiber when using the agents, which is why its proportion should be as low as possible.
  • fractions of 5 to 6 wt.% (C) are sufficient to contain agents with a content of approx. 50 wt.% (A), approx. 40 wt.% (B) and approx Stabilize 4% by weight (d) and ensure good pouring properties.
  • the agents may also contain minor constituents such as dyes and color pigments and may be colored uniformly or speckled.
  • the proportion of such minor components is well below 1% by weight.
  • the average grain size of the agent 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 being 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 not more than 20% by weight, in particular not more than 10% by weight % is.
  • the bulk density is 350 to 550 g / l.
  • the granules 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.
  • 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 can, if necessary after cooling with flowing air, be mixed directly with the other tablet components and compressed with them.
  • Sodium metasilicate in anhydrous and in the form of penta- and / or in particular nonahydrate, can be used as the silicate.
  • the total alkali metal silicate content of the tablets, calculated as Na2SiO3, is 30 to 80, preferably 55 to 65% by weight.
  • the tablets are particularly easy to compress if 5 to 30, preferably 5 to 25 and in particular 10 to 25% by weight, calculated as anhydrous alkali metasilicate, in the form of sodium metasilicate pentahydrate and / or 5 to 30, preferably 8 to 25 and in particular 12 to 25% by weight, calculated as anhydrous alkali metasilicate, in the form of sodium metasilicate nonahydrate, the weight ratio of sodium metasilicate pentahydrate to sodium metasilicate nonahydrate being used can be around 1: 1 to 1: 1.5.
  • the total amount of hydrates is the same as the amount when using the individual hydrates.
  • the dissolution profile can be varied within wide limits by varying the ratio of sodium metasilicate, anhydrous, to nonahydrate.
  • the weight ratio of anhydrous sodium metasilicate to nonahydrate is between 1: 0.1 to 1: 1.0 and in particular between 1: 0.15 to 1: 0.8.
  • Extremely low-foaming compounds are preferably used as nonionic surfactants. 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 chlorine carriers and active oxygen carriers are common components of cleaning agents for HGSM as bleaching agents.
  • Trichloroisocyanuric acid is preferred as the active chlorine carrier, but also other known solid compounds, such as.
  • B. sodium dichloroisocyanurate, its dihydrate and potassium chloroisocyanurate can be used in the marketable form without impairing the tablettability. Your quantities are 0.5 to 5.0, preferably 1.0 to 2.5% by weight, based on the active chlorine content and the total tableting mixture.
  • active oxygen carriers can also be used particularly advantageously. These primarily include sodium perborate mono- and tetrahydrate as well as sodium percarbonate. Their share in the total weight of the tablets is 3 to 20, preferably 5 to 18%.
  • 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.
  • anhydrous sodium carbonate can also be added in order to set a desired pH value; the amount can be 2 to 20% by weight and preferably 4 to 16% by weight.
  • the cleaning additives were then mixed in an amount of 10 to 40, preferably 15 to 35,% by weight in a Lödige mixer with the remaining constituents of the formulations, and the resulting tablet mixture was then subjected to a tablet pressure of 200 to 1 on conventional tablet presses 500. 105, preferably 300 to 600 ⁇ 105 Pa pressed.
  • the mixture of the cleaning additives, the anhydrous sodium metasilicate, the corresponding hydrates, the nonionic surfactants and the bleaching agents could be pressed in a known manner without die lubrication using commercially available eccentric presses, hydraulic presses or rotary presses.
  • the pressing conditions must be optimized with a view to setting the desired dissolution profile while at the same time having 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). Tablets with a bending strength greater than 120 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 dissolving speed of the surface exposed to the H2O attack. For stability reasons, cylindrical compacts with a diameter / height ratio of 0.6 to 3.0: 1 were produced.
  • 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.
  • Prefers are tablets of 30 to 40 g in weight and a diameter of 35 to 40 mm, one of which must be used. 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.
  • the tablet is loaded by a wedge.
  • the breaking strength corresponds to the weight of the wedge-shaped load that causes the tablet to break.

Claims (10)

  1. Comprimés détergents dépourvus de phosphate stables, bifonctionnels, pour le lavage à la machine de la vaisselle, contenant du silicate, des agents tensioactifs non ioniques faiblement moussant, des agents complexants organiques, des agents blanchissants, et de l'eau, caractérisés en ce qu'ils renferment les agents complexants organiques sous la forme de 10 à 40 % en poids, rapportés au mélange global des constituants des comprimés, d'un additif de lavage alcalin, granulaire, séché par pulvérisation, formé de :
    (a) 35 à 60 % en poids en sels de sodium d'au moins un acide (meth-)acrylique, homopolymère ou copolymère
    (b) 25 à 50 % en poids de carbonate de sodium (calculé en anhydre)
    (c) 4 à 20 % en poids de sulfate de sodium (calculé en anhydre)
    (d) 1 à 7 % en poids, d'eau
    et de 30 à 80 % en poids de silicate, calculé en tant que SiO₃Na₂, sous forme de métasilicate de sodium anhydre et de son pentahydrate et/ou nonahydrate dans un rapport pondéral de 1 : 0, 1 à 1 : 1, 0, .
  2. Comprimés selon la revendication 1, caractérisés en ce qu'ils renferment un additif de lavage alcalin, granulaire, séché par pulvérisation qui est formé de :
    (a) 40 à 55 % en poids, en particulier 45 à 52 % en poids
    (b) 30 à 45 % en poids, en particulier 30 à 40 % en poids
    (c) 5 à 15 % en poids, en particulier 5 à 10 % en poids
    (d) 2 à 6 % en poids, en particulier 3 à 5 % en poids
  3. Comprimés selon les revendications 1 et 2, caractérisés en ce qu'ils renferment de 15 à 35 % en poids d'additif de lavage alcalin, granuleux, séché par pulvérisation.
  4. Comprimés selon les revendications 1 à 3, caractérisés en ce qu'ils renferment comme silicate de 30 à 80 % en poids de métasilicate alcalin, y compris de 5 à 30 % en poids de métasilicate de sodium pentahydraté, calculés comme métasilicate alcalin anhydre.
  5. Comprimés selon les revendications 1 à 4, caractérisés en ce qu'ils renferment, rapportés au métasilicate alcalin total, de 5 à 30 % en poids de métasilicate de sodium nonahydraté, calculés omme métasilicate de sodium anhydre.
  6. Comprimés selon les revendications 1 à 5, caractérisés en ce que le rapport pondéral du métasilicate de sodium anhydre à son pentahydrate et/ou à son nonahydrate se situe entre 1 : 0,15 et 1 : 0,8.
  7. Comprimés selon les revendications 1 à 6, caractérisés en ce qu'ils renferment de 0,2 à 5 % en poids d'agents tensioactifs non ioniques peu moussants.
  8. Comprimés selon les revendications 1 à 7, caractérisés en ce qu'ils renferment comme agent de blanchiment de 0,5 à 5,0 % en poids d'agent qui dégage du chlore actif.
  9. Comprimés selon les revendications 1 à 8, caractérisés en ce qu'ils renferment comme agent de blanchiment de 3 à 20 % en poids de vecteur d'oxygène actif.
  10. Comprimés selon les revendications 1 à 9, caractérisés en ce qu'ils renferment en supplément de 0,2 à 2 % en poids d'agent antimousse.
EP91906795A 1990-04-02 1991-03-25 Comprimes detergents stables, bifonctionnels et sans phosphate pour lave-vaisselle Expired - Lifetime EP0523095B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4010524 1990-04-02
DE4010524A DE4010524A1 (de) 1990-04-02 1990-04-02 Stabile, bifunktionelle, phosphatfreie reinigungsmitteltabletten fuer das maschinelle geschirrspuelen
PCT/EP1991/000568 WO1991015568A1 (fr) 1990-04-02 1991-03-25 Comprimes detergents stables, bifonctionnels et sans phosphate pour lave-vaisselle

Publications (2)

Publication Number Publication Date
EP0523095A1 EP0523095A1 (fr) 1993-01-20
EP0523095B1 true EP0523095B1 (fr) 1995-02-15

Family

ID=6403554

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91906795A Expired - Lifetime EP0523095B1 (fr) 1990-04-02 1991-03-25 Comprimes detergents stables, bifonctionnels et sans phosphate pour lave-vaisselle

Country Status (5)

Country Link
EP (1) EP0523095B1 (fr)
AT (1) ATE118540T1 (fr)
DE (2) DE4010524A1 (fr)
ES (1) ES2068575T3 (fr)
WO (1) WO1991015568A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110612188A (zh) * 2017-05-12 2019-12-24 宝洁公司 用于制备颗粒的方法

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4112075A1 (de) * 1991-04-12 1992-10-15 Henkel Kgaa Verfahren zur herstellung stabiler, bifunktioneller, phospat- und metasilikatfreier niederalkalischer reinigungsmitteltabletten fuer das maschinelle geschirrspuelen
DE4121307A1 (de) * 1991-06-27 1993-01-07 Henkel Kgaa Verfahren zur herstellung stabiler, bifunktioneller, phosphat- und metasilikatfreier niederalkalischer reinigungsmitteltabletten fuer das maschinelle geschirrspuelen
DE4213036A1 (de) * 1992-04-21 1993-10-28 Henkel Kgaa Granulares, alkalisches, phosphatfreies Reinigungsadditiv
DE4228786A1 (de) * 1992-08-29 1994-03-03 Henkel Kgaa Geschirrspülmittel mit ausgewähltem Builder-System
DE4315048A1 (de) * 1993-04-01 1994-10-06 Henkel Kgaa Verfahren zur Herstellung stabiler, bifunktioneller, phosphat-, metasilikat- und polymerfreier niederalkalischer Reinigungsmitteltabletten für das maschinelle Geschirrspülen
AU694422B2 (en) * 1993-04-01 1998-07-23 Johnsondiversey, Inc. Solid detergent briquettes
DE69602086T2 (de) * 1995-02-17 1999-08-05 Unilever Nv Festes waschmittelstück
US6194367B1 (en) 1995-03-01 2001-02-27 Charvid Limited Liability Co. Non-caustic cleaning composition comprising peroxygen compound and specific silicate and method of making the same in free-flowing, particulate form
US6034048A (en) * 1995-03-01 2000-03-07 Charvid Limited Liability Co. Non-caustic cleaning composition using an alkali salt
US5663132A (en) * 1995-03-01 1997-09-02 Charvid Limited Liability Company Non-caustic composition comprising peroxygen compound and metasilicate and cleaning methods for using same
US5837663A (en) * 1996-12-23 1998-11-17 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets containing a peracid
US5900395A (en) * 1996-12-23 1999-05-04 Lever Brothers Company Machine dishwashing tablets containing an oxygen bleach system
BR9704788A (pt) * 1997-09-23 1999-09-08 Unilever Nv Processo para aumentar a dissolução de tabletes detergentes para máquinas de lavar louça,combinaçaõ de composição detergente com sistema de embalagem ,e,embalagem
EP1642960B1 (fr) * 2004-10-01 2007-10-31 Unilever N.V. Comprimés detergents
DE102013100195A1 (de) * 2013-01-10 2014-07-24 Budich International Gmbh Reinigertablette mit integriertem Vorreiniger

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3390092A (en) * 1965-03-30 1968-06-25 Fmc Corp Dishwashing detergent preparations containing sodium or potassium dichloroisocyanurate
DE2435479A1 (de) * 1974-07-24 1976-02-12 Henkel & Cie Gmbh Geschirrspuelmittel
DE3447291A1 (de) * 1984-12-24 1986-06-26 Henkel KGaA, 4000 Düsseldorf Phosphatfreies mittel fuer das maschinelle geschirrspuelen
CA1297376C (fr) * 1985-11-01 1992-03-17 David Philip Jones Detergents, matieres qui le composent et procedes de fabrication connexes
DE3541145A1 (de) * 1985-11-21 1987-05-27 Henkel Kgaa Einheitlich zusammengesetzte reinigungsmitteltabletten fuer das maschinelle geschirrspuelen
DE3634813A1 (de) * 1986-10-13 1988-04-14 Henkel Kgaa Reinigungsmitteltabletten fuer das maschinelle geschirrspuelen
GB2234980A (en) * 1989-07-25 1991-02-20 Unilever Plc Detergent composition for machine dishwashers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110612188A (zh) * 2017-05-12 2019-12-24 宝洁公司 用于制备颗粒的方法

Also Published As

Publication number Publication date
DE4010524A1 (de) 1991-10-10
ATE118540T1 (de) 1995-03-15
DE59104634D1 (de) 1995-03-23
WO1991015568A1 (fr) 1991-10-17
EP0523095A1 (fr) 1993-01-20
ES2068575T3 (es) 1995-04-16

Similar Documents

Publication Publication Date Title
DE4112075C2 (fr)
EP0591282B1 (fr) Procede de fabrication de produits de lavage en comprimes pour le lavage de la vaisselle en machine
EP0692020B1 (fr) Comprimes stables bifonctionnels de produits de lavage a faible alcalinite, sans phosphates, sans metasilicates et sans polymeres, pour lave-vaisselle, et leur procede de production
EP0264701B1 (fr) Comprimés de nettoyage pour le lavage de la vaisselle en machine
EP0224129B1 (fr) Pains détergents composés d'une manière uniforme pour le lavage de la vaisselle en machine
EP0224128B1 (fr) Pains détergents à plusieurs couches pour le lavage de la vaisselle en machine
EP1004656B1 (fr) Granulé densifié, procédé pour sa fabrication et son utilisation comme désintégrant dans des corps formés par compactage
EP0523095B1 (fr) Comprimes detergents stables, bifonctionnels et sans phosphate pour lave-vaisselle
EP0126963B1 (fr) Procédé pour la production de comprimés d'agent de nettoyage
EP0224135A2 (fr) Détergents sous forme compacte
DE69731189T3 (de) Tabletten und Verfahren zu deren Herstellung
DE19710254A1 (de) Wasch- oder reinigungsaktive Formkörper für den Gebrauch im Haushalt
EP0900266B1 (fr) Methode de preparation de nettoyants compacts pour lave-vaisselles industriels
EP0871698B1 (fr) Procede de production de detergents sous forme de comprimes resistant a la rupture
EP0877791B1 (fr) Procede de production de corps moules constitues d'un produit de lavage ou de nettoyage
EP0658190B1 (fr) Procede de production de comprimes de detergents
WO1993010210A1 (fr) Procede de fabrication de produits pour machine lave-vaisselle faiblement alcalins, exempts de chlore actif et de phosphate, sous forme de granules lourds
DE10123621A1 (de) Verfahren zur Herstellung einer Wasserenthärtertablette
DE19959589A1 (de) Mehrphasige Reinigungsmitteltabletten
DE19850983A1 (de) Wasch- und Reinigungsmittelformkörper mit Entschäumergranulat
DE19632283A1 (de) Verwendung von Lipasen in niederalkalischen Mitteln zum Vorspülen im Rahmen des maschinellen Geschirrspülens

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19920923

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17Q First examination report despatched

Effective date: 19931105

RBV Designated contracting states (corrected)

Designated state(s): AT BE CH DE ES FR GB IT LI NL

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB IT LI NL

REF Corresponds to:

Ref document number: 118540

Country of ref document: AT

Date of ref document: 19950315

Kind code of ref document: T

ET Fr: translation filed
REF Corresponds to:

Ref document number: 59104634

Country of ref document: DE

Date of ref document: 19950323

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2068575

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19950518

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20010228

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20010313

Year of fee payment: 11

Ref country code: AT

Payment date: 20010313

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20010319

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20010321

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20010327

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20010330

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20010515

Year of fee payment: 11

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020325

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020325

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020326

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020331

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020331

BERE Be: lapsed

Owner name: *HENKEL K.G.A.A.

Effective date: 20020331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021001

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021001

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20020325

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021129

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20021001

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030410

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050325