WO1994007991A1

WO1994007991A1 - Machine care stick

Info

Publication number: WO1994007991A1
Application number: PCT/EP1993/002636
Authority: WO
Inventors: Jürgen Härer; Theodor Altenschöpfer; Peter Jeschke
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1992-10-07
Filing date: 1993-09-28
Publication date: 1994-04-14
Also published as: DE4233696A1

Abstract

Sticks for the care of unloaded dishwashers consisting of a solidified mixture of wax, non-ionic tensides, water-soluble multivalent alcohols, water-soluble organic, mono or polybasic carboxylic acids, possibly substituted by hydroxyl groups, with 2 to 6 carbon atoms in the molecule and possibly colorants and/or perfumes, small quantities of dissolving agents and corrosion inhibitors.

Description

"machine care pen"

In the area of the door seals, hose connections and low-flow zones of dishwashers, that is to say where the surfaces of the interior of the dishwasher are not exposed to the direct and intensive operating pressure of the cleaning liquor, dirt accumulates over the course of time, which is essentially sufficient there are finely divided, fatty food residues.

Occasional, unavoidable, technical faults in the ion exchange system of dishwashers, which serve to soften the water used, or through continuous underdosing of the detergents by the users, gradually, deposits form on the inner surfaces of the machines a mixture of lime from hard water and detergent residues. In some cases so-called "tarnish colors" are formed, as the rainbow-colored discolorations of stainless steel parts in dishwashers are called.

These dirt deposits offer an undesirable breeding ground for putrefaction processes which are noticeable through an unpleasant odor, especially when the dishwashers are opened after a long period of non-use. In addition, however, the hose and sealing materials, especially on the doors, are also damaged by long-term exposure to these dirt deposits.

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 be, but the do not touch dirty areas at all or touch them too briefly. 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 unsuitable for this special application, since they generally contain highly foaming surfactants, the residues of which in dishwashers can lead to various types of malfunctions.

Machine cleaners for household dishwashing machines are already offered as such on the market, in liquid form. The bottle required for this and the associated bottle closure mean, from an ecological point of view, a high packaging effort. The object of the invention was therefore to find an ecologically more favorable, yet application-friendly form of offer. For example, EP 033111 describes the use of a liquid, aqueous or aqueous-alcoholic, acidic agent containing water-soluble organic single- or honor-based carboxylic acids with 2 to 6 carbon atoms in the molecule, optionally substituted by hydroxyl groups, water-soluble polyhydric alcohols, low-foaming nonionic 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 quantities of 5 up to 40 g / 1 water volume of the machine in the cleaning cycle of the unloaded machine and let the cleaning cycle run as usual.

It has now been found that the components of this liquid machine care product can be formulated in a wax base instead of in water. As a result, lower amounts are used 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 is no longer necessary in addition to the wax. In contrast to the liquid products used in bottles, the machine care pen can be used depending on the degree of soiling of the machine and the capacity of the dishwasher also divide into pieces of any length and thereby portion them, so that the use of chemicals can be further reduced as a result.

The invention relates to pens for the care of unloaded dishwashers, which are characterized in that they consist of 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 there are up to 6 carbon atoms in the molecule and, if appropriate, colorants and fragrances.

Wax-like compounds or wax mixtures which 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 and macrocrystalline n-paraffins 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, candella 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 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 45-55 ° C. are preferably used as waxes. 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 No maintenance pen required. In addition, the wax matrix and the polyhydric alcohols dissolved in the care stick served as care components with which rubber parts of the dishwasher can be coated so that they remain supple and their service life is extended.

Nonionic surfactants preferably include those that are readily biodegradable and / or based on renewable raw materials.

Alkyl ethoxylates / alkyl polyol ether

These include, in particular, addition products of about 2 to 15, preferably about 2 to 10, moles of ethylene oxide (E0) to fatty alcohols with about 8 to 22, preferably about 12 to 18, carbon atoms in the alkyl radical, as well as modified fatty alcohol ethoxylates, the end group of which has a short-chain alkyl radical (e.g. Butyl) is closed. Suitable alkyl polyglycol ethers are, for example, Henkel's Dehydol ( ^R ) types such as Dehydol ( ^R ) LS 2, Dehydol ( ^R ) LS 4, Dehydol ( ^R ) LS 5 and Dehydol ( ^R ) LT 2, Dehydol ( ^R ) LT 3 and Dehydol ( ^R ) LT 4. The dehydol products of the LS empires 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 C12-C18 . Modified alkyl polyglycol ethers are, for example, alkyl ethoxylates 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.

Alkyl ethylene oxide propylene oxide adducts:

These include, in particular, adducts of about 1 to 10 moles of ethylene oxide and about 1 to 8 moles 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 their mixtures, and with synthetic ones, for example those prepared by oxosynthesis Alcohols of any chain length C13-C15.

From a purely technical point of view, of course, instead of the readily biodegradable fatty alcohol polyglycol ethers or alkylpolyglycosides, the difficult or only partially biodegradable EO-PO block polymers or alkylphenol polyglycol ethers can be used. EO-PO block polymers are ethylene oxide adducts in higher molecular weight propylene glycols with a molecular weight of 900 to 4000. Suitable block polymers are, for example, the Pluronic ( ^R ) types from BASF such as Plusonic ( ^R ) PE 3100, Plusonic PE 4300. Suitable alkylphenyl polyglycol ethers are lutensol ( ^R ) AP 6, Lutensol () AP 7 from BASF.

The biodegradable and rapidly degradable adducts of ethylene oxide with higher molecular weight fatty alcohols are preferably used, in particular the adduct of 2 to 15 mol and preferably 2 to 10 mol of ethylene oxide with a mixture of Ci2-Ci8-fatty alcohols and / or alkyl polyglycosides of the general formula C _n H2n ₊ l-0- (C6Hκ) θ5) χH, in which n = 8 - 16 and 1 <x <3. Their amounts are about 0.5 to 15%, preferably about 1 to 10% by weight.

Ethylene glycol, propylene glycol and preferably glycerin are used as water-soluble polyhydric alcohols.

As water-soluble organic mono- or polybasic, optionally substituted by hydroxy groups, 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. These are, for example, adipic acid, succinic acid, tartaric acid, malic acid, glutaric acid, oxalic acid, malonic acid, succinic acid and preferably citric acid. Mixtures of such acids can also be used. Their amount is about 5 to 50, preferably about 10 to 40,% by weight.

In addition to dyes and fragrances, 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 known as Rodine 58 ( ^R ) Company 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 grease-containing food residues as well as lime and cleaning agent residues. stands in the dishwashers. The tarnish also disappears when rubbed off. The content of polyhydric alcohols prevents the pen from drying out prematurely. This not only keeps rubber and plastic seals or connections in the machine area soft and elastic, but also stubborn dirt is softened and easily wiped off due to the delay in re-drying.

To produce the care product according to the invention, the citric acid heated to 153 ° C. is stirred into the wax heated to 60 ° C., then the nonionic surfactant and optionally the colorants and / or fragrances, corrosion inhibitor, water-soluble polyhydric alcohols and a dye solubilizer stirred in. The still hot mass is then poured into sleeves lined with polyethylene (PE) film with a capacity of 100 g and allowed to solidify. The complete covering with the PE film takes place automatically.

In a further preferred production process, the wax matrix is melted, and the citric acid and the other formulation components such as nonionic surfactants, water-soluble polyhydric alcohols, fragrances, corrosion inhibitors, dyes are mechanically dispersed or dissolved in the melted wax matrix. Then the liquid care stick mass is 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 packaged in a polyethylene, polypropylene or in a 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.

It is advisable to wrap the finished care pens before packaging in film by immersing them in n-paraffin with a melting point of about 30 ° C to 60 ° C, preferably about 45 ° C to 50 ° C. This not only makes contact with the stylus more pleasant, but also reduces the amount of foam that might otherwise occur. During use, part of the PE film can first be removed from the pen while it is being held with the rest in the hand and thus rubbing in the rubber parts of the dishwasher. Then you remove the PE film completely, let the remaining pin slide into the cutlery box and run the usual cleaning program with the otherwise empty machine. A further increase in the gloss of the interior of the machine can be achieved if the maintenance process in the cleaning cycle is followed by a rinse cycle equipped with a rinse aid.

B e i s p i e l e

The following non-coated and paraffin-coated care pens were produced in the manner described:

Table 1 without paraffin coating

Example 1 2 3

with paraffin coating (2-3 g n-paraffin with F: 46 ° C - 48 ° C per stick)

Example 4 5 6 7

APG 225 3.0 1.0 1.0 1.0

Ci2-Cχ8 fatty alcohol + 3E0 - 2.0 -

Ci2-Ci8 fatty alcohol + 4E0 - - 2.0 2.0

Citric acid anhydrous 35.0 35.0 35.0 35.0

Perfume 0.25 0.25 0.25 0.25

Polyethylene glycol MG = 1500 60.45 61.35 61.35 56.35

Glycerin - 5.0

Water from raw materials 1.3 0.4 0.4 0.4 The practice-relevant application and effectiveness of the pens according to the invention for cleaning the interior of dishwashers was determined on the basis of the lime dissolving (I) and the cleaning power (II) as well as cleaning performance (III) and drying (IV). Another important criterion is the foam behavior (V) of the machine care worker in the dishwasher.

I. Descaling property

For this purpose, the dishwasher fully loaded with dishes was operated in a 65 ° C normal program with hard water (16 ° C). In addition, 120 g of 50% sodium hydroxide solution were added to the cleaning cycle. For the production of stubborn, accumulated limescale deposits on dishes, cutlery and in the interior of the dishwasher, five washing cycles were carried out.

Removal of limescale

The lime deposits produced in the manner described above could be removed without problems using the machine care formulations 1-7 according to the invention. For this purpose, 100 g of machine care pen were placed in the cleaning cycle 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.

Table 3

The following test application was used to determine the cleaning power of the manually applied agents of rubber and plastic parts of a dishwasher. On a plastic Test plates measuring 26 x 28 cm were applied with the aid of a surface coater, uniformly 2 g of an artificial soiling consisting of a mixture of carbon black, machine oil, triglycerides of saturated fatty acids and low-boiling aliphatic hydrocarbons. A plastic sponge was soaked in each case with 12 ml of the cleaning agent solution to be tested according to Examples 1 to 3 and moved mechanically on the test surface. After 6 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning mixture, that is to say the whiteness of the plastic surface cleaned in this way, was measured with a photoelectric color measuring device LF 90 (Dr. B. Lange). 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. Averaged% RV of 21 was obtained with tap water.

example

% RV 42 38 38

III. Reiniαunqsleistunq

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. For this purpose, with a water content of the machine of 10.0 ± 0.5 1, each 250 ml of one of the agents according to Examples 1 to 3 was added to the cleaning cycle of a standard Miele G 590 dishwasher; the maximum rinse temperature was 55 ° C ± 3 ° C. On stainless steel surfaces of the interior of the dishwasher of 3 Miele G 590 machines, 30 g of soiling each consisted of

100 g margarine 50 g raw egg (white and yellow) 50 g defrosted frozen spinach 100 g drinking milk; 1.5% fat content 100 g drinking oat flakes 200 g potato puree 400 g gravy, brown applied with a brush in a strip form and left to dry for 20 hours at room temperature. Then an agent according to Examples 1 to 3 was added to the cleaning cycle of the dishwashers and this was started as usual; the result was then assessed by three test subjects. The original, new stainless steel interior 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.

example

Cleaning performance 7.0 8.0 8.0

IV. Drying effect

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 formulations 1-6. Drying is particularly good if APG / fatty alcohol ethoxylate mixtures are used and if additional rinse aid is added in the rinse cycle. Machine: Bauknecht GSF 1162

Program: 65 ° C normal program

Water: soft 3 ° dH

Machine care dosage: 100 g

Rinse aid dosage: 3 ml

Rinse aid composition: Somat Citrus rinse aid (Henkel KGaA)

Rating:

0 points = no drying

6 points = completely dry dishwasher inside

Table 4

Application machine care pen

Example without rinse aid with rinse aid

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.

Machine: Miele G 590

Program: 65 ° C normal program

Water: hard 16 ° dH

Dosage: 100 g pen

Here mean:

0 points = no foam development 1 point = weak foaming

2 points = medium foam development (still acceptable)

3 points = strong foaming

Table 3

Claims

1. pens for the care of unloaded dishwashers, characterized in that they consist of a solidified mixture of wax, non-ionic 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 optionally dyes and / or fragrances, small amounts of solubilizers for these and corrosion inhibitors.

2. Pencils according to claim 1, characterized in that as waxes about 45 to 95, preferably about 50 to 90 wt .-% of a polyethylene glycol with a MW of 1,000 to 12,000, preferably from 3,000 to 6,000 and a softening point of about 40 ° C to 60 ° C, preferably from about 45 ° C to 55 ° C can be used.

3. pens according to claim 1 and 2, characterized in that as nonionic surfactants addition products of about 2 to 15 mol, preferably from about 2 to 10 mol of ethylene oxide to fatty alcohols having about 8 to 22, preferably about 12 to 18 carbon atoms in the alkyl radical and / or alkyl polyglycosides of the general formula C _n H2n ₊ l-0- (C6Hιoθ5) χH, in which n = 8 - 16; 1 <x <3 mean, in amounts of approximately 0.5 to 15, preferably approximately 1 to 10% by weight and in the weight ratio to one another of approximately 1: 2, preferably approximately 1: 1.

4. pens according to claim 1 to 3, characterized in that glycerol is used as the water-soluble polyhydric alcohol.

5. pens according to claim 1 to 4, characterized in that about 5 to 50, preferably about 10 to 40 wt .-% anhydrous citric acid are used as the carboxylic acid.

6. A process for the production of pens according to claim 1, characterized in that the organic carboxylic acids are heated to their melting point and stirred into the liquefied wax, after which the non-ionic surfactant and, if appropriate, the colorants and / or fragrances, a solubilizer therefor and a corrosion inhibitor and a water-soluble polyhydric alcohol are added with stirring, the still hot mass is poured into sleeves lined with polyethylene film, allowed to solidify and with simultaneous automatic closing of the polyethylene film Takes pods.

7. Use of the pens according to claim 1, characterized in that after partial removal of the polyethylene film with the pen strokes over rubber sealing parts of the machine, then the film is completely removed, the remaining pen is slid approximately into the cutlery box and then runs the usual cleaning program with the otherwise empty machine.

8. Use according to claim 7, characterized in that the cleaning process taking place in the cleaning cycle is followed by a rinse cycle equipped with a rinse aid.