EP0591282B1 - Procede de fabrication de produits de lavage en comprimes pour le lavage de la vaisselle en machine - Google Patents

Procede de fabrication de produits de lavage en comprimes pour le lavage de la vaisselle en machine Download PDF

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Publication number
EP0591282B1
EP0591282B1 EP92912460A EP92912460A EP0591282B1 EP 0591282 B1 EP0591282 B1 EP 0591282B1 EP 92912460 A EP92912460 A EP 92912460A EP 92912460 A EP92912460 A EP 92912460A EP 0591282 B1 EP0591282 B1 EP 0591282B1
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EP
European Patent Office
Prior art keywords
weight
acrylic acid
meth
tablets
builders
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
EP92912460A
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German (de)
English (en)
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EP0591282A1 (fr
Inventor
Hans Kruse
Jochen Jacobs
Hans-Josef Beaujean
Jürgen Härer
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
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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
    • 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
    • C11D3/37—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.
  • Tablets of this type have such a broad dissolving profile that they are dissolved by at least 10% by weight of tap water in the pre-rinsing phase of an HGSM, thereby developing a pH of at least 10.0 in the rinsing liquor and at least 60 with good hot water solubility % 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.
  • German patent application DE-A-40 10 524 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 German patent application DE-A -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 recipe components and pressed in a manner known per se.
  • the present invention was based on a market trend, the task of producing a stable, bifunctional, phosphate and metasilicate-free, low-alkaline detergent tablet with a broad dissolution profile for automatic dishwashing, which is at least 10% by weight to approximately 10% by weight of tap water in the pre-rinsing phase of an HGSM 50% by weight is dissolved, a pH value of at most about 10.5 is developed in the washing liquor and at least 50% by weight to about 90% by weight is still available for the cleaning cycle with good hot water solubility.
  • the storage-stable tablets produced in accordance with the invention have a high breaking strength (greater than 140 N with a diameter of about 30 to 40 mm and a density of about 1.4 to 1.7 g / cm 3), which also remain stable during storage and within a short time Time can still increase significantly.
  • the solid alkali salts of at least one homopolymeric or copolymeric (meth) acrylic acid can be used as commercially available powders or granules or as a so-called cleaning additive.
  • 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-B-25 551, 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 be used with advantage, 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 be made, for example, from 10 to 50 wt % By weight of acrylic acid-maleic acid copolymers exist.
  • 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 polycarboxylates are used as powder, but preferably as granules.
  • the usable polyacrylates include, for example, Sokalane R CP 10, PA 10 and PM 10 from BASF, 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, Degapas R from Degussa: Degapas R 4104 N, Good-Rite R from Goodrich: Good-Rite R K-XP 18, K 739 and K 7200 N.
  • copolymers Polyacrylic acid and maleic acid
  • Sokalane R from BASF: Sokalan R CP 5, CP 7, Acrysole R from Norsohaas: Acrysol R QR 1014 and SP O2N
  • Alcosperse R from Alco: Alcosperse R 175.
  • 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.
  • 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 and alkali disilicates can also serve as builders. You tie together with the polycarboxylate-containing cleaning additive component through complex formation or dispersion, hardness-forming agents such as calcium and magnesium ions from the water or from the food residues, 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. As alkali carbonate sodium carbonate of any quality is preferably used, such as. B. calcined soda, compressed soda and also sodium bicarbonate. 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).
  • 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 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 include primarily sodium perborate mono- and tetrahydrate as well as sodium percarbonate and sodium caroate. Since active oxygen only develops its full effect on its own at elevated temperatures, so-called bleach activators are expediently used to activate it at about 60 ° C., the temperatures of the cleaning process in the HGSM.
  • bleach activators preferably 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
  • 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.
  • tabletting aids such as mold release agents, for example paraffin oil
  • mold release agents for example paraffin oil
  • paraffin oil 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.
  • Na-hydrogen carbonate is preferably used to set the desired pH.
  • the average grain size of the granular cleaning additives is usually 0.2 to 1.2 mm, the proportion of the grains below 0.1 mm advantageously 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 weight is about 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.
  • 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 counter-current dry gases in the entrance zone of the spray tower, ie 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 to less is reduced as 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 other tablet components as described, if necessary after cooling with flowing air, and then in total on conventional tablet presses with a compression 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 about 1.2 and 2 g / cm3, preferably between about 1.4 to 1.8 g / cm3.
  • the compression during the pressing process caused changes in the density, which from about 0.4 to 1.2 g / cm3, preferably about 0.6 to 1.0 g / cm3 to about 1.2 to 2.0 g / cm3, preferably about 1.4 to 1.6 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 reasons of stability, cylindrical compacts with a diameter / height ratio of approximately 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 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.
  • Nonionic surfactants are nonionic surfactants:
  • a 50 kg batch was prepared in a 130 l Lödige ploughshare mixer.
  • 6.8 parts by weight of sodium carbonate anhydrous, 32.0 parts by weight of sodium bicarbonate and 4.0 parts by weight of water were first mixed with the chopper running and then immediately further with 20.0 parts by weight of a granular alkaline cleaning additive , consisting of 40.8% by weight sodium carbonate anhydrous, 5.0% by weight sodium sulfate, 50.0% by weight of the sodium salt of the copolymer of maleic acid and acrylic acid with a molecular weight of 70,000 (Sokalan CP 5 from BASF) and 4.2% by weight of water, 20.0 parts by weight of sodium citrate dihydrate, 2.0 parts by weight of Plurafac R LF 403 and 0.2 part by weight of fragrance.
  • a granular alkaline cleaning additive consisting of 40.8% by weight sodium carbonate anhydrous, 5.0% by weight sodium sulfate, 50.0% by weight of the sodium salt of the copolymer of male

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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)

Claims (3)

  1. Procédé d'obtention de comprimés d'agents de lavage faiblement alcalins, dépourvus de phosphate et de métasilicate, bifonctionnels et stables, qui développent dans le jus de rinçage une valeur de pH au maximum d'environ 10,5, pour le lavage de la vaisselle à la machine avec une teneur en sels solides de métal alcalin d'au moins un acide (meth)acrylique homopolymère ou copolymère, des substances de squelette, des agents tensioactifs peu moussants, des agents de blanchiment, et le cas échéant des enzymes, des activateurs de blanchiment, des parfums et des colorants, caractérisé en ce qu'on met en oeuvre du carbonate de sodium qui sert comme une partie des substances de squelette sous forme anhydre, qu'on mélange en premier lieu dans une étape de mélange de préférence tout seul ou avec les autres substances de squelette et avec le sel de métal alcalin solide d'au moins un acide (meth)acrylique polymère ou copolymère conjointement avec la quantité nécessaire d'eau pour l'hydratation partielle du carbonate de sodium anhydre d'environ 5 à 40 % en poids, rapporté au carbonate de sodium anhydre mis en oeuvre comme substance de squelette, et ensuite qu'on ajoute les constituants résiduels du mélange et qu'on comprime le mélange ainsi obtenu sur une presse à comprimés usuelle.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on met en oeuvre les sels de métal alcalin, solides d'au moins un acide (meth)acrylique homopolymère ou copolymère sous forme de poudre ou de granulés.
  3. Procédé selon la revendication 1, caractérisé en ce que l'on met en oeuvre les sels de métal alcalin, solides d'au moins un acide (meth)acrylique homopolymère ou copolymère sous forme d'additifs de lavage alcalin en granulés, conformément à la demande de brevet allemand DE-A-3 937 469.
EP92912460A 1991-06-27 1992-06-19 Procede de fabrication de produits de lavage en comprimes pour le lavage de la vaisselle en machine Expired - Lifetime EP0591282B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4121307A DE4121307A1 (de) 1991-06-27 1991-06-27 Verfahren zur herstellung stabiler, bifunktioneller, phosphat- und metasilikatfreier niederalkalischer reinigungsmitteltabletten fuer das maschinelle geschirrspuelen
DE4121307 1991-06-27
PCT/EP1992/001387 WO1993000419A1 (fr) 1991-06-27 1992-06-19 Procede de fabrication de produits de lavage en comprimes pour le lavage de la vaisselle en machine

Publications (2)

Publication Number Publication Date
EP0591282A1 EP0591282A1 (fr) 1994-04-13
EP0591282B1 true EP0591282B1 (fr) 1995-09-13

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ID=6434910

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EP92912460A Expired - Lifetime EP0591282B1 (fr) 1991-06-27 1992-06-19 Procede de fabrication de produits de lavage en comprimes pour le lavage de la vaisselle en machine

Country Status (6)

Country Link
EP (1) EP0591282B1 (fr)
AT (1) ATE127835T1 (fr)
DE (2) DE4121307A1 (fr)
DK (1) DK0591282T3 (fr)
ES (1) ES2076768T3 (fr)
WO (1) WO1993000419A1 (fr)

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ATE211164T1 (de) * 1999-03-29 2002-01-15 Dalli Werke Waesche & Koerperp Sprengmittelgranulat enthaltende geschirrspülmaschinenreinigungstabletten
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US7893012B2 (en) * 2007-05-04 2011-02-22 Ecolab Inc. Solidification matrix
MX2010003825A (es) 2007-10-18 2010-04-27 Ecolab Inc Composiciones de limpieza solidas, auto-solidificables, comprimidas, y metodos para hacerlas.
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FR3047741B1 (fr) * 2016-02-11 2019-06-07 S.A. Gerlon Procede de fabrication de tablettes uni-dose
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GB2234980A (en) * 1989-07-25 1991-02-20 Unilever Plc Detergent composition for machine dishwashers
DE3937469A1 (de) * 1989-11-10 1991-05-16 Henkel Kgaa Granulares, alkalisches, phosphatfreies reinigungsadditiv
DE4010524A1 (de) * 1990-04-02 1991-10-10 Henkel Kgaa Stabile, bifunktionelle, phosphatfreie reinigungsmitteltabletten fuer das maschinelle geschirrspuelen

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ES2076768T3 (es) 1995-11-01
DE4121307A1 (de) 1993-01-07
ATE127835T1 (de) 1995-09-15
EP0591282A1 (fr) 1994-04-13
WO1993000419A1 (fr) 1993-01-07
DK0591282T3 (da) 1996-01-08
DE59203697D1 (de) 1995-10-19

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