DE2715351B2 - Liquid, machine-use dishwashing detergent concentrates - Google Patents

Description

Hüssigc. machine-use dishwasher concentrates based on liquid substances. low foaming nonionic compounds and hydrotropes are already from the British patent 1047875 known. The concentrates described there contain mostly phosphorus fluids alkaline structural substances and as hydrotrope in each case a phosphorus-containing compound, As is well known, however, efforts are made to reduce the phosphorus content of To reduce cleaning agents or to forego the use of phosphorus-containing compounds altogether.

It is used in practice for machine cleaning of dishes, especially glasses, already commercially available phosphorus-free liquid cleaners, which are, however, strongly alkaline and therefore only can be used for a limited area of application.

The present invention therefore relates to liquid, machine-use dishwashing detergent concentrates based on structural substances, low-foaming non-ionic surfactants and hydrocopes, which are characterized in that they contain 10-25, preferably 12-2C wt .-% as structural substances Phosphorus-free organic complexing agents, as low-foaming nonionic surfactants 0.5-2.5, preferably 0.8-1.9% by weight with 3-60, preferably with 5-40 and especially with 10-30MoI Ethylene oxide and / or propylene oxide per mole of converted aliphatic alcohols, alkylamines, fatty acid amides, Fatty acid alkanolamides or alkylphenols, as well as ethylene oxide / propylene oxide block polymers, the terminal hydroxyl groups of which can optionally be blocked by acetalization, or mixtures of these surfactants, as hydrotropes 5-20, preferably 10-15 wt .-% sodium or potassium cumene sulfonate and additionally contain 5-20, preferably 6-10% by weight of alkyloamines. Possibly these concentrates can also contain up to 2, preferably 0.1-0.5% by weight of corrosion inhibitors can be added.

These liquid detergents are particularly suitable for use in dishwashers lead to excellent cleaning effects and shiny, practically free of deposits, especially with glasses Glasses. A good cleaning result is achieved even if the concentrate happens to be as it often happens in practical application in ignorance of the respective water hardness, in Underdosing, d. H. with sub-stoichiometric amounts of organic complexing agents in the cleaning liquor is used or if the items to be cleaned are soiled more than normal. Particularly the moderate alkalinity of the concentrates is advantageous.

The constituents of the binding of hardness Hydroxypolycarboxylic acids belong to the water-serving phosphorus-free organic complexing agents such as citric acid, tartaric acid and carboxymethyltartronic acid and the aminopolycarboxylic acids

. such as ethylenediaminetetracetic acid and nitrilotriacetic acid and their alkali salts, especially the sodium and potassium salts. The sodium salt is preferred which uses nitrilotriacetic acid.

As low-foaming non-tonic surfactants

i come alkylene oxide adducts, preferably ethylene oxide adducts or mixed adducts of Äthylenoxkl and Pmpylciioxid to higher primary or secondary, monomeric or dinate, saturated oiler unsaturated aliphatic alcohols, for example fatty alcohols

such as dodccyl alcohol, l'alniityl alcohol, stearyl alcohol, Olcyl alcohol and mixtures thereof, to secondary alcohols with 8-18. preferably 12-18 carbon atoms or to synthetic, elwn produced by oxo synthesis

Alcohols of chain lengths Cj ₂ -C ₂ ,, on alkylamines of chain lengths C ₍ , -C _lg> on fatty acid and fatty acid alkanolamides of chain lengths C _n -C _w on alkylphenols with 8-18 carbon atoms in the alkyl radical, in particular on nonylphenol, as well as preferably the water-soluble addition products, containing 20-250 ethylene glycol ether groups and 10-100 propylene glycol ether groups, of ethylene oxide with polypropylene glycol with a molecular weight of 900-4000, acylenediamine-polypropylene glycol and alkylpolypropylene glycols with 1-10 carbon atoms, in which the polypropylene glycol chain acts as the residual hydrophylene glycol chain. The alkylene oxide adducts with higher molecular weight fatty alcohols or alkylphenols have proven to be of particular technical interest. They are produced in a known manner by adding the alkylene oxides in question in the presence of acidic or alkaline catalysts, optionally under pressure and at elevated temperatures, with up to three times the amount by weight of the starting compounds of alkylenox £ which is deposited.

Examples of suitable addition products are the adduct of 15 mol of ethylene oxide with dodecyl alcohol, the adduct of 20 mol of ethylene oxide with a fatty alcohol mixture of chain length C _n -C ₁₁ , the adduct of 35 mol of ethylene oxide with stearyl alcohol, the adduct of 15 mol of ethylene oxide with oleyl alcohol , the adduct of 5 moles of ethylene oxide and 13 moles of propylene oxide with one mole of a coconut fatty alcohol mixture, the adduct of 7 moles of propylene oxide and 20 moles of ethylene oxide with dodecyl alcohol, the adduct of 37 moles of ethylene oxide and the adduct of 40 moles of ethylene oxide and 20 moles of Pro> Oil oxide to an alcohol mixture produced from dimerized fatty acids of chain lengths C ₁₆ -C ₁₈ by reduction, the adduct of 30 mol of ethylene oxide and 24 mol of propylene oxide to a fatty alcohol mixture of chain lengths of C ₁₂ -C ₁₈ , a fatty amine reacted with 15 mol of ethylene oxide -Mixture of chain lengths C ₁₂ -C. ,, the adduct of 10 moles of ethylene oxide with a coconut fatty acid amide mixture of chain lengths C ₁₂ -C ₁₈ , the addu kt of 30 moles of ethylene oxide in nonylphenol, the adduct of 21 moles of ethylene oxide and 5 moles of propylene oxide in nonylphenol and the addition products of ethylene oxide with a polypropylene glycol ether of molar weights 950-4000, the proportion of polypropylene glycol ether being 90-60% by weight and the proportion of Polyäthylcnglykoläthers 10-40 wt .-% makes up.

Also acetates and / or ketals of those mentioned above Connections come into consideration. They are made by reacting 1 mole of an aldehyde or Kctons each containing 2 moles of such a compound. Come for the acetal formation primarily formaldehyde and acetaldehyde. However, other aldehydes, such as Propionaldchyd, benzaldehyde, acrolein, glycolaldehyde, glyoxal and others can be used. For the Formation of the ketals Suitable ketones are z. B. acetone, acetophenone and methyl ethyl ketone. ι

Examples of suitable acetals or ketals are the formaldehyde acetals of the following adducts: Nonylphenol -f 20 Viol ethylene oxide, Hcllaikoholgcmisch Cj ₂ -C ₁₈ + 20 mol ethylene oxide, dodecyl alcohol 4-12 mol ethylene oxide, dodecyl alcohol + '5 mol Pro-. pylene oxide I 25 moles of ethylene oxide, Myristinsiitiremonoäthanolamid f 10 moles of ethylene oxide. Linolenic acid I - 20 moles of ethylene oxide. Alkali-1,2- (li <> lucmisih the chain length C ₁₂ -C ₁₈ + 20 mol ethylene oxide, furthermore the acetaldehyde acetal of an adduct of dodecylphenol + 30 mol of ethylene oxide, the ketal of acetone and an adduct of nonylphenol + 25 mol of ethyl

»Lenoxide; preferably the formaldehyde and / or acetaldehyde acetals of the alkylene oxide systems

products of higher molecular weight fatty alcohols and alkylphenols are used

The alkali salts of the Curnol-

«> Sulfonic acid, especially the sodium and potassium salts. Surprisingly, these are far superior to other known hydrotropes.

The low molecular weight amines are particularly suitable as alkylolamines Connections such as mono-, di- and

i ^r > triethanoiamine into consideration.

In particular, known compounds such as benzotriazole and phosphoric acid esters can be used as corrosion inhibitors.
In addition to the examples mentioned, the requested

- '»said concentrates are common constituents of such Funds included. Other possible additives are buffering substances, dyes, perfumes, Preservatives, microbicides, or the like. Liquid products are expediently

- '"> dissolve the individual components in water and then Mix the solutions obtained. It can be useful, in particular, to the organic Bring components into solution, solubilizers such as ethanol, propanol or isopropanol with-

Hi to use.

The application form of the concentrates is included about 2-10, preferably about 6-10 g / l. The pH levels the cleaning liquors are between pH 7 and 12, preferably pH 8 and 11.

r. The cleaning concentrates are at temperatures Storage stable between 0 and 40 ° C. They have a visually appealing appearance and one that is fragrance-free Condition has a neutral odor, which is even described as pleasant in the application liquor

κ. can be. In addition, they develop practically no foam, especially in the application temperature range of around 40-70 ° C, and are skin-friendly.
It has been shown to be particularly surprising that

r <the combined use of sodium salts Nitrilotriacetic acid and cumene sulfonic acid to a synergistically increased cleaning effect Dishes leads.

Example I.

Components of the liquid dish detergent concentrate in% by weight

Sodium salt of nitrilotriacetic acid 20.0
Addition product of 5 moles 1.2

Ethylene oxide and 13 mol propylene oxide
to a C. ₂ -C _u fatty alcohol mixture
terminally acetalized addition 0.7
product of 20 moles of ethylene oxide
1 mole of nonylphenol

Cumene sulfonic acid sodium salt 10.0

Triethanoiamine 8.0

Water 60.1

The sodium salt of nitrilotriacetic acid (NaNTA) was completely dissolved in water at room temperature, the solution with the sodium salt of cumene sulfonic acid (SCSA) stirred, that by closing

was brought into solution by triethanolamine. A further addition of the low-foaming nonionic Surfactant mixture from the adduct of 5 moles of ethylene oxide and 13 moles of propylene oxide to a C ^ -C ^ fatty alcohol mixture and a terminally acetalized adduct of 20 mol of ethylene jride and 1 mol of nonylphenol gave a stable concentrate with a density of about 1.2. Its pH was 10.7.

Example 2

In an analogous manner, a product was produced which, instead of the acetal mentioned there, had the same weight Amount of the product Puronic L 42 (80% by weight polyoxypropylene MG 1200 + 20% by weight Polyoxyethylene) contains The product can be stored between 0 and 40 ° C.

Example 3

Products according to Example 1 and Example 2 were used in a dosage of 3 g / l cleaning liquor in dishwashers metered in. Was rinsed with water of 12 ° d. The items to be washed glasses used for the test and porcelain cups - with similar coffee, tea and cocoa soiling turned 24 Kept for hours at a temperature of "50 ° C, to make the cleaning conditions more difficult and to increase the informative value of the test accordingly. This crockery was then tested ten times with 20 soiled crockery items each time. After cleaning in a one-tank dishwasher, the cleaning was successful for 3 people Visually graded according to the following scheme: 1 = completely clean, residue-free and shiny, 5 = soiling practically not removed from the dishes. Under these test conditions, the following were found Average values of the assessments:

Example 1: Grade 2

Example 2: Grade 1-2.

In both cases, practically no glass corrosion was observed. The cleaned and dried Dishes showed a striking shine.

An increase in the application concentration to 6 g / l gave a product according to example 1 the rating 1 to 2 and a product according to example 2 the rating \.

Example 4

To demonstrate the synergetic cleaning effect the combination of the sodium salts of nitrilotriacetic acid and cumene sulfonic acid three different concentrates were prepared in analogy to Example 1, which a) instead of 20 only 10 wt .-% NaNTA and no SCSA, but 80.1 wt .-% water, b) no NaNTA and instead of 10 only 5 wt .-% SCSA and 85.1% by weight of water and c) instead of 20 only 10% by weight NaNTA, instead of 10 only 5% by weight SCSA and 75.1% by weight of water with constant triethanolamine and nonionic Surfactant content included.

Glasses and cups were used for these experiments with soiling from coffee, milk, milk-coffee, Put milk tea, grease pencil on glass and grease pencil on porcelain and dry for 24 hours at 70 ° C. The cleaning and testing procedures were as outlined in Example 3 but were only 2 g / l dishwashing detergent concentrate added to the machine. The ones shown in the table below Grading results show the synergistic effect.

Grading

in soiling 0.2 g / l 0.1 e '\ 0.2 g / l NaNTA NaNTA NaQiA and 0.1 g / l SCSA coffee 2 2 2 ,. milk 3.5 2.8 2 - 'MiJch coffee 2.5 3.0 2.5 Tea and milk 3.5 3.5 2.5 Grease pencil on glass 3.0 4.0 2.0 Grease pencil on porcelain 4.0 4.5 3.0

Comparative example

The advantageous properties of the dishwasher concentrate according to the invention according to Example 2 compared to a commercially available alkaline liquid cleaner, consisting of 27% by weight potassium hydride, 17 wt .-% NaNTA and 56 wt .-% water were tested and led to the following results:

Under the normal conditions according to Example 3, the same grades were obtained, although that according to the invention Dishwashing detergent concentrate has a significantly lower alkalinity than the commercially available one. If both concentrates are otherwise otherwise the same Conditions with a water hardness of 19 ° d are used, the rating remains with the invention Concentrate obtained while it was with the commercial concentrate due to chalky residue clearly drops to 4-5. Only an increase in the concentrate dosage to 5 g / l cleaning solution gave the commercially available concentrate a grade of 2. However, the cleaning effect of the e.The concentrate according to the invention was graded almost unanimously with 1.

Claims (7)

Patent claims: 1. Liquid, machine applicable dishwashing concentrates based on builders, low-foaming nonionic surfactants and hydrotropes, characterized in that they contain 10-25% by weight of phosphorus-free organic complexing agents and 0.5-2.5% by weight as low-foaming nonionic surfactants 3-60 moles of ethylene oxide and / or propylene oxide per mole of aliphatic alcohols, alkylamines, fatty acid amides, fatty acid alkanolarines or alkylphenols and ethylene oxide / propylene oxide block polymers, the terminal hydroxyl groups of which can optionally be blocked by acetalization, or mixtures of these surfactants, as hydrotropes 5- Contain 20% by weight of sodium or potassium cumene sulfonate and an additional 5-20 % by weight of AJkyloIamine. 2. Liquid dishwashing detergent concentrates according to claim 1, characterized in that they Contain 0.8-1.9% by weight of low-foaming nonionic surfactants. 3. Liquid dishwashing concentrates according to claim 1 and 2, characterized in that they as phosphate-free organic complexing agents hydroxypolycarboxylic acids, citric acid, tartaric acid or carboxymethyltartronic acid and / or aminopolycarboxylic acids such as ethylenediaminetetraacetic acid or nitrilotriacetic acid or contain the alkali salts, especially the sodium and potassium salts of these acids. 4. Liquid dishwashing detergent concentrates according to claim 1 to 3, characterized in that they contain the sodium salt of nitrilotriacetic acid as a phosphate-free organic complexing agent. 5. Liquid dishwashing detergent concentrates according to claim 1 to 4, characterized in that they act as a low-foaming nonionic surfactant, the addition product of 5 moles of ethylene oxide and 13 moles of propylene oxide with a C ₁₂ -C ₁₄ -FeUaI alcohol mixture, the addition product of 20 wt. % Ethylene oxide to 80% by weight of polyoxypropylene with a molecular weight of 1200 or a terminally acetalized adduct of 20 moles of ethylene oxide to one mole of nonylphenol or mixtures thereof. 6. Liquid dishwashing detergent concentrates according to claim 1 to 5, characterized in that they contain triethanolamine as alkylolamine. 7. Liquid dishwashing detergent concentrates according to claim 1 to 6, characterized in that sic up to 2% by weight of a corrosion inhibitor contain.