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WO1995019422A1 - Produit d'entretien en forme de batonnet pour machines - Google Patents

Produit d'entretien en forme de batonnet pour machines Download PDF

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Publication number
WO1995019422A1
WO1995019422A1 PCT/EP1995/000066 EP9500066W WO9519422A1 WO 1995019422 A1 WO1995019422 A1 WO 1995019422A1 EP 9500066 W EP9500066 W EP 9500066W WO 9519422 A1 WO9519422 A1 WO 9519422A1
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WO
WIPO (PCT)
Prior art keywords
water
fatty acid
care
machine
cleaning
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.)
Ceased
Application number
PCT/EP1995/000066
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German (de)
English (en)
Inventor
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 WO1995019422A1 publication Critical patent/WO1995019422A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C11D17/0052—Cast detergent compositions

Definitions

  • the commercially available powdery alkaline or acidic dishwashing, cleaning or rinsing agents are not or only insufficiently suitable for cleaning the so-called "problem areas" of the dishwashers which are at risk of contamination, since they are metered into and dissolved in the cleaning or rinsing cycle of the dishwashers can, but either not touch the soiled areas or touch them for a short time. For this reason, for a long time it was only necessary to manually clean such zones.
  • the detergents used for cleaning dishes are unsuitable for such cleaning because they attack the skin too strongly.
  • Commercial cleaning agents for hard surfaces are also available for these not suitable for special applications, since they generally contain highly foaming surfactants, the residues of which in dishwashers can lead to various types of faults.
  • EP 033 111 describes the use of a liquid, aqueous or aqueous-alcoholic, acidic agent containing water-soluble organic mono- or polybasic carboxylic acids, optionally substituted by hydroxyl groups, with 2 to 6 carbon atoms in the molecule, water-soluble polyhydric alcohols, low-foaming
  • Non-ionic surfactants and other additives from the group of fragrances, dyes, solubilizers and / or corrosion inhibitors for cleaning and maintaining the inner surfaces of household dishwashers are known, the agent being used manually in concentrated form on an absorbent substrate or in amounts of 5 to 40 g / 1 water volume of the machine in the cleaning aisle of the unloaded machine and let the cleaning run as usual. It was therefore an object of the invention to find an ecologically more economical, yet user-friendly form of offer.
  • the unpublished DE 42 33 698 describes that the components of this liquid machine cleaner can be formulated in a wax base instead of in water. As a result, lower amounts of use are possible and therefore a more economical consumption of ingredients compared to the liquid machine maintenance. In addition, the number of ingredients could be reduced to the active substances, since the use of solubilizers in addition to the wax is no longer necessary.
  • the machine care pen can, depending on the degree of soiling of the machine and the capacity of the dishwasher, also be divided into pieces of any length and thereby portioned, so that the use of chemicals can be further reduced as a result.
  • the invention now relates to pens for the care of unloaded dishwashers, which are characterized in that they have a solidified mixture of wax, nonionic surfactants, water-soluble polyhydric alcohols, water-soluble organic mono- or polybasic carboxylic acids, optionally substituted by hydroxyl groups, with 2 up to 6 carbon atoms in the molecule and, if appropriate, colorants and / or fragrances, small amounts of solubilizers for these and corrosion inhibitors and the nonionic surfactants completely or to a substantial extent of at least 50% by weight from nitrogenous compounds there exist.
  • Wax-like compounds or wax mixtures that form the matrix of the machine care stick must melt completely in the range between 40 ° C. to 60 ° C. and preferably in the range between 45 ° C. to 55 ° C. so that the cleaning and care components are released in the dishwasher ⁇ can be set.
  • Low-melting polyethylene waxes as well as macrocrystalline n-paraffin are therefore preferred as wax-like compounds.
  • Higher melting waxes such as the microcrystalline waxes of petrochemical origin or natural waxes such as carnauba wax, candellila wax, beeswax, montan waxes can only be used in combination with low-melting polyethylene waxes or low-melting macrocrystalline n-paraffins or petroleum jelly.
  • Polyethylene glycols with an average molecular weight (MW) of about 1,000 to 12,000, preferably 3,000 to 6,000 and a melting (softening, dripping) point of about 40 to 60, preferably about 45, are preferably used as waxes. 55 ° C used. Their amount in the pen is about 45 to 95, preferably about 50 to 90% by weight. Although this appears to be a great deal in comparison with the water content of the known liquid care products, comparatively little packaging effort is required for the pen.
  • the liquid cleaning and care products are offered in disposable polyethylene bottles. This use of packaging material is not necessary for the machine care pen.
  • the wax matrix and the polyvalent water-soluble alcohols dissolved in the care stick serve as care components with which the rubber parts of the dishwasher are coated can be so that they remain supple and their life is extended.
  • Nonionic surfactants which are preferably used are those which are readily biodegradable and / or which are based on renewable raw materials.
  • fatty acid amides are also referred to below as "fatty acid amides”.
  • the fatty acid amides to be used according to the invention are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides, as represented by the following formula:
  • IIIIR 1 CO-N-CH 2 -CH-CH-CH-CH-CH2 ⁇ H.
  • Suitable raw materials for the preparation of the agents used according to the invention are fatty acid N-alkylpolyhydroxyalkylamides of the formula R ⁇ -C0- (R2) (Z), in which R * C0 for an acyl radical having 6 to 12 carbon atoms, R 2 for a methyl group and (Z) stands for reduced glucose residue.
  • R * C0 for an acyl radical having 6 to 12 carbon atoms R 2 for a methyl group
  • (Z) stands for reduced glucose residue.
  • fatty acid N-methylglucamides are particularly preferred, which are obtained by reductive amination of glucose with methylamine and subsequent acylation with a C6-Ci2 fatty acid or a corresponding derivative.
  • the fatty acid comes one in particular Cg-Cio fraction in question, which is obtained, for example, as a preliminary step in the distillation of technical coconut fatty acid.
  • fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • Overviews can be found u. a. in Tens.Surf.Det. 25., 8 (1988) and in S ⁇ FW-Journal, 119. (1993) pages 794-808.
  • process for their production reference is also made to US Pat. Nos. 1,985,424, 2,206,962 and 2,703,798 , the German Auslegeschrift DE-AS 12 61 861 and the international patent application WO 92/06984 referenced.
  • fatty acid amides mentioned is also the subject of a large number of publications. Their use as a thickener is known, for example, from European patent application EP-AI 0 285 768 (Hüls). French patent application FR-A 1 580 491 (Henkel) describes aqueous detergent mixtures based on sulfates and / or sulfonates, nonionic surfactants and, if appropriate, soaps, which contain fatty acid N-alkylgluca ide as foam regulators.
  • nonionic surfactants can also be added to the care stick composition.
  • This includes in particular te of about 2 to 15, preferably about 2 to 10, mol of ethylene oxide (EO) of fatty alcohols with about 8 to 22, preferably about 12 to 18, carbon atoms in the alkyl radical and modified fatty alcohol ethoxylates, the end group of which has a short-chain alkyl radical (for example butyl ) is closed.
  • EO ethylene oxide
  • Suitable alkyl polyglycol ethers are, for example, the dehydol () types from Henkel, such as dehydol ( R ) LS 2, dehydol ( R ) LS 4, dehydol ( R ) LS 5 and dehydrol ( R ) LT 2, dehydol ( R ) LT 3 and Dehydol ( R ) LT 4.
  • dehydol () types from Henkel such as dehydol ( R ) LS 2, dehydol ( R ) LS 4, dehydol ( R ) LS 5 and dehydrol ( R ) LT 2, dehydol ( R ) LT 3 and Dehydol ( R ) LT 4.
  • the dehydol products of the LS series are EO adducts with fatty alcohols with a chain length in the range of approximately C12-C14 and the LT series are those in the chain length range of approximately C ⁇ -Ci ⁇ - Modified alkyl polyglycol ethers are, for example, alkyl ethoxylates which are end group-capped with a butyl group, such as, for example, Dehypon ( R ) LS 104, Dehypon ( R ) LT 104 and Dehypon ( R ) LT 054 from Henkel.
  • Suitable alkyl polyglycol ethers based on oxo alcohol are lutensol ( R ) A 03, lutensol ( R ) A 04 from BASF, and also alkyl ethylene oxide / propylene oxide adducts, in particular adducts of about 1 to 10 mol of ethylene oxide and about 1 to 8 mol of propylene oxide with higher molecular weight fatty alcohols with about 8 to 20, preferably about 12 to 18 carbon atoms in the molecule or mixtures thereof, and also on synthetic alcohols, for example produced by oxosynthesis, of the possible chain length C13-C15.
  • nonionic surfactants can also be alkyl polyglycosides with alkyl chains in the range of approximately C ⁇ -C12 and a degree of polymerization of approximately 1 ⁇ x 3, but preferably alkyl polyglycosides with alkyl chains in the range of approximately Cg-C10 and a degree of polymerization of approximately 1 ⁇ x ⁇ 3 are used.
  • Their amount is 0 to about 3, preferably about 0.01 to 2.5% by weight, based on the fatty acid amide.
  • alkyl polyglycolsides such as, for example, APG ( R ) 225 (Henkel), also known as Plantaren ( R ) 225, Lutensol ( R ) GD 70 (BASF) are preferably used.
  • APG R ) 225 (Henkel)
  • Plantaren R
  • Lutensol R
  • GD 70 BASF
  • the difficult or only partially biodegradable EO-PO block polymers or alkylphenol polyglycol ethers can be used, such as ethylene oxide adducts with higher molecular weight propylene glycols with a molecular weight of 900 to 4000, e.g.
  • Suitable alkylphenyl polyglycol ethers are, for example, Lutensol ( R ) AP 6, Lutensol ( R ) AP 7 from BASF.
  • the total amount of nonionic surfactants is about 0.5 to 15, preferably about 1 to 10,% by weight, the ratio of fatty acid amides to other nonionic surfactants being about 2: 0 to 1: 1.
  • Ethylene glycol, propylene glycol and preferably glycerin are used as water-soluble polyhydric alcohols. Their amounts are about 0.01 to 10, preferably about 0.05 to 7 percent by weight.
  • carboxylic acids with 2 to 6 carbon atoms in the molecule preference can be given to those polyvalent acids which, based on the first dissociation stage, have a K s value of> 10 ⁇ 6.
  • polyvalent acids which, for example, adipic acid, succinic acid, tartaric acid, malic acid, glutaric acid, oxalic acid, malonic acid, succinic acid and preferably citric acid.
  • Their amount is about 5 to 50, preferably about 10 to 40% by weight.
  • the agents may also contain small amounts of about 0.1 to 2.5% by weight of solubilizers for the fragrances, for example dipropylene glycol, and corrosion inhibitors, for example one under the name Rodine 58 ( R ) Gerhard Collardin GmbH, Cologne, known condensation product made from aldehydes and amines, as well as long- and short-chain fatty acids, produced in an acid medium.
  • solubilizers for the fragrances for example dipropylene glycol
  • corrosion inhibitors for example one under the name Rodine 58 ( R ) Gerhard Collardin GmbH, Cologne, known condensation product made from aldehydes and amines, as well as long- and short-chain fatty acids, produced in an acid medium.
  • the care products according to the invention dissolve and remove both the greasy food residues as well as lime and cleaning agent residues in the dishwashers.
  • the tarnish also disappears when rubbed off.
  • the stick is prevented from drying out prematurely. This not only keeps rubber and plastic seals or connections soft and elastic in the machine area, but also stubborn dirt is softened and easy to wipe off due to the delay in re-drying.
  • the organic carboxylic acid is stirred into the liquefied wax which has been heated to its melting point, then the nonionic surfactant (s), the water-soluble polyhydric alcohols and, if appropriate, the colorants and / or fragrances , Solution mediator for this and a corrosion inhibitor stirred.
  • the still hot mass is then poured into sleeves lined with a protective film, for example with a capacity of about 100 g, and allowed to solidify. The complete wrapping with the protective film takes place automatically. The pins thus encased can then be removed from the sleeves.
  • the wax matrix is melted and the organic carboxylic acid and the other formulation components such as nonionic surfactant (s), water-soluble polyhydric alcohols, optionally colorants and / or fragrances, a solubilizer therefor, and Corrosion inhibitors, mechanically dispersed therein.
  • the liquid care stick mass is then poured into a release agent, e.g. Poured water, painted metal or plastic mold. After cooling, the machine care stick is released from the mold and placed in a protective film, e.g. packed in a polyethylene, polypropylene or in a hot water soluble polyvinyl alcohol film.
  • a warm water-soluble polyvinyl alcohol film has the advantage that the packaged machine care stick can be placed directly in the machine, so that the consumer does not have to have any contact with the product.
  • part of the protective film can first be removed from the pen while it is held in hand with the rest and thus rubbing in the rubber parts of the dishwasher. Then you remove the Protective film completely, lets the remaining pin slide into the cutlery box and the usual cleaning program runs with the otherwise unloaded machine. A further increase in gloss in the interior of the machine can be achieved if the care process taking place in the cleaning cycle is followed by a rinse cycle equipped with a rinse aid.
  • Polyethylene glycol MG 1500 58.95 Glycerin 1.0
  • Polyethylene glycol MG 1500 59.45
  • E0 ethylene oxide
  • I lime dissolving
  • II cleaning ability
  • III cleaning performance
  • IV drying
  • V foam behavior
  • the dishwasher fully loaded with dishes was operated in a 65 ° C normal program with hard water (16 ° C).
  • 120 g of 50% sodium hydroxide solution were added to the cleaning cycle.
  • five washing cycles were carried out.
  • the limescale deposits produced in the manner described above could be removed easily with the machine care formulations 1 and 2 according to the invention.
  • 100 g of machine care pen were placed in the cleaning aisle of a standard Miele G 590 dishwasher; the maximum rinse temperature was 55 ° C ⁇ 3 ° C.
  • the rinsing liquor in the cleaning cycle had a water volume of 5 ⁇ 0.5 1.
  • the original, clean, white plastic surface served as the white standard. During the measurement, this clean surface was set to 100 percent and the soiled area to 0 percent. The stated values of the cleaned plastic surfaces are to be regarded as percent cleaning capacity (% RV). They are averages from a 4-fold determination. A% RV of 21 was obtained with tap water.
  • the result of the machine application of the agent according to the invention for cleaning the interior of the dishwashers was, inter alia, also determined in the form of cleaning performance.
  • an agent according to Example 1 was added to the cleaning cycle of a standard Miele G 590 dishwasher; the maximum rinse temperature was 55 ° C ⁇ 3 ° C.
  • Example 1 50 g of defrosted frozen spinach 100 g drinking milk; 1.5% fat content 100 g drinking oat flakes 200 g mashed potatoes 400 g gravy, brown applied with a brush in the form of a strip and left to dry for 20 hours at room temperature. Then a pen according to Example 1 was placed in the cleaning cycle of the dishwasher and started as usual; the result was then assessed by three test subjects. The original new stainless steel inner surface was rated 10 (absolutely clean) and the stainless steel surfaces obtained after the soiling had dried on with 0. The cleaning grade 5.5 was achieved with pure water treatment.
  • the drying effect is the application-technical criterion with which the effectiveness of the machine operator is assessed. After the rinse cycle has ended, it is checked whether the interior of the dishwasher is dry. For this purpose, the door of the dishwasher is fully opened 15 minutes after the end of the washing program. After 5 minutes, the drying is determined by counting the remaining drops in the machine ceiling and on the upper crockery basket and the cutlery basket. The evaluation is graded and comprises seven grades: 0 points - the interior of the machine is still completely wet, 6 points - stand for an optimally dry interior of the dishwasher.
  • Table 4 shows the drying values of recipes 1 and 2. Drying is particularly good if fatty acid amide / fatty alcohol ethoxylate mixtures are used and if additional rinse aid is added in the rinse cycle.
  • Machine Bauknecht GSF 1162
  • Machine care dosage 100 g
  • Rinse aid dosage 3 ml
  • Rinse aid composition Somat Citrus rinse aid (Henkel KGaA)
  • the foam development of the machine operator was determined with the aid of a circulating pressure measuring device.
  • the machine operator was metered in during the cleaning process.

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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)

Abstract

Des bâtonnets pour l'entretien de lave-vaisselle vides sont constitués d'un mélange solidifié de cire, d'agents tensioactifs azotés et le cas échéant d'autres agents tensioactifs non ioniques, d'alcools polyvalents solubles dans l'eau, d'acides carboxyliques organiques à une ou plusieurs bases solubles dans l'eau, le cas échéant substitués par des groupes hydroxyle et contenant 2 à 6 atomes de carbone dans la molécule, et le cas échéant de colorants et/ou d'arômes, de quantités réduites de solubiliseurs de ceux-ci et d'inhibiteurs de la corrosion. Les agents tensioactifs azotés non ioniques sont des polyhydroxyalcoylamides-N(R) d'acides gras, notamment des glucamides-N(R) d'acides gras ayant la formule générale R1-CH2-CO-N(R)-CH2(CHOH)4-CH2OH, dans laquelle R désigne H, -CH3, -C2H5, -C3H7, -C4H9 et R1 désigne CnH2n+1, n étant compris entre 8 environ et 16. L'invention concerne également le procédé de production de ces bâtonnets et leur utilisation.
PCT/EP1995/000066 1994-01-17 1995-01-09 Produit d'entretien en forme de batonnet pour machines Ceased WO1995019422A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4401104.0 1994-01-17
DE19944401104 DE4401104A1 (de) 1994-01-17 1994-01-17 Maschinenpflegestift

Publications (1)

Publication Number Publication Date
WO1995019422A1 true WO1995019422A1 (fr) 1995-07-20

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/000066 Ceased WO1995019422A1 (fr) 1994-01-17 1995-01-09 Produit d'entretien en forme de batonnet pour machines

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DE (1) DE4401104A1 (fr)
WO (1) WO1995019422A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006063231A1 (fr) * 2004-12-08 2006-06-15 The Procter & Gamble Company Procede pour nettoyer un lave-linge ou un lave-vaisselle
US9267097B2 (en) 2007-02-15 2016-02-23 Ecolab Usa Inc. Fast dissolving solid detergent
WO2021122886A1 (fr) * 2019-12-20 2021-06-24 Henkel Ag & Co. Kgaa Procédés de nettoyage et de soin pour lave-vaisselle automatique

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19961660A1 (de) * 1999-12-21 2001-07-12 Henkel Kgaa Pflegemittel für Wasch- und Geschirrspülmaschinen
DE102007029837A1 (de) * 2007-06-28 2009-01-02 Siemens Ag Zusatz für ein Reinigungs- und/oder Pflegemittel zur Verwendung in Haushaltsgeräten sowie derartiges Reinigungs- und/oder Pflegemittel

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994007991A1 (fr) * 1992-10-07 1994-04-14 Henkel Kommanditgesellschaft Auf Aktien Batonnet pour l'entretien de machines

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994007991A1 (fr) * 1992-10-07 1994-04-14 Henkel Kommanditgesellschaft Auf Aktien Batonnet pour l'entretien de machines

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006063231A1 (fr) * 2004-12-08 2006-06-15 The Procter & Gamble Company Procede pour nettoyer un lave-linge ou un lave-vaisselle
US9267097B2 (en) 2007-02-15 2016-02-23 Ecolab Usa Inc. Fast dissolving solid detergent
US10005986B2 (en) 2007-02-15 2018-06-26 Ecolab Usa Inc. Fast dissolving solid detergent
US10577565B2 (en) 2007-02-15 2020-03-03 Ecolab Usa Inc. Fast dissolving solid detergent
US11261406B2 (en) 2007-02-15 2022-03-01 Ecolab Usa Inc. Fast dissolving solid detergent
WO2021122886A1 (fr) * 2019-12-20 2021-06-24 Henkel Ag & Co. Kgaa Procédés de nettoyage et de soin pour lave-vaisselle automatique

Also Published As

Publication number Publication date
DE4401104A1 (de) 1995-07-20

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