DE2330481A1 - DISH AND RINSE AGENT FOR DISHES AND THE LIKE - Google Patents

Description

The invention relates to storage-stable, acidic or neutral aqueous washing and rinsing agents for dishes and the like.

For the manual washing of dishes, nan usually uses v.'eise surface-active substances that have good emulsifying properties and are fat-dissolving. This is mainly used for this anion-active wetting agents or mixtures of anion-active agents and non-ionic compounds. Often these funds contain also small amounts of lipid replenishing substances. Such mixtures primarily ensure a closed one Film of water, so that the water runs off the dishes well and runs smoothly drying can be dispensed with.

In machine dishwashing, on the other hand, a distinction must be made between two processes. Once the actual cleaning cycle, including alkaline Means are used, and on the other hand the after-rinse or final rinse with a special rinse aid. The rinse aid ensures that the dishes are shiny and clear and no longer show any salt residues or foam streaks are. In contrast to the manual detergents, the rinse aid for dishwashers is allowed because of the strong movement of the liquor The dishwasher does not contain any high-foaming, anionic wetting agents, but instead wetting agents or combinations used on the basis of preferably non-ionic compounds. These connections are preferably made up with physiologically harmless acids or salts thereof in order to

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Klarnpulc-rgebri-i .: r: o :: iiitl \ ch to improve with hard water. Color and smell of Te köiVüC-i. weruen also incorporated.

However, all these known detergents and rinse aid have the Disadvantage that they are unable to carry germs or bacteria through the water in the sink or the dishwasher registered v / earth to make ineffective.

Investigations have shown that especially in the base exchanger !! from dishwashers or to the water outlet valves accumulate pathogens germs, which often multiply strongly. The strain Pseudomonas is considered to be of particular concern aeruginosa viewed, as in the article by R. Ruschke on "Pseudomonas aeruginosa - a germ of civilization - evidence of its Propagation in. Cation exchangers of dishwashers "has been reported. Other types of bacteria were also observed found like coil, staph, etc.

Bactericidal substances for regenerating salt in dishwashers admitting is not effective with absolute certainty, since there is often considerable time between the individual regeneration intervals in which bacterial growth is possible or the housewife often uses normal table salt without bactericides Addition is taken.

The ones usually found in the sinks or dishwashers Temperatures of approx. 30 to 40 ° C / 60 ° C are also not sufficient for reliably killing all germs in the allotted time. Occurring temperature drops also increase the risk. Furthermore, in dishwashers with condensation drying A reinfection of sterile crockery can occur through running cold water.

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It has now been found that these disadvantages do not occur when Detergents or rinse aid are used in addition to the usual The raw materials used contain bactericidal substances.

Suitable bactericidal substances are quaternary Am ::. Oiiliuüsu.l '/. E, guanidine derivatives, ampholytes or combinations thereof.

Quaternary ammonium compounds, for example, the BTC ^r ("(6 from Organon, a modified alkyldiinethylbenzylbenzyliaonium chloride, or lutensite K-LC from BASF, a dimethyl C 12 / C lh fatty alkylbenzylammorium chloride, and quaternary ammonium compounds which are known under the trade names Dimanin (uayer), Germoeid (BASF), Arquad (Armor), Quat V 531 (Raschig), Barquat HB'jiO (Chemiea), methylpyridine chloride (Hubbe) and benzalkonium chloride (Hubbe).

Further bactericidal compounds according to the invention are ampholytic Substances such as LS ampholytes, for example potassium-N-alkylaminopropiohat or Tego-Betaines from Goldschmidt, and also guanidine derivatives, e.g. Vantocil IB from Imperial Chemical Industries or mixtures of guanidine derivatives and quaternary ammonium compounds such as the Dodigen 180 product from Farbwerke Maximum.

The concentration of the bactericidal substances in the agents according to the invention should be 3 to 60%, preferably 20 to 10%.

The products according to the invention are used in amounts from 0.2 to 0 *! ml / 1 added so that 10 to 200ppm, preferably 100 ppm, the bactericidal? Compound in the washing liquor are included.

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In addition to the bactericidal substances, the invention can Rittel non-ionic surfactants such as alkyl polyglycol ethers, alkylphenol polyglycol ethers, Alkyl aininopoly ^ j ycolether, Pe tt acid polyglycolester, Fatty alcohol ethoxylates, polypropylene-ethylene adducts etc. included.

You can also use the means to avoid lime scale incrustations especially in the case of hard water, acids that form complexes with the hardness constituents of the water are added, for example Citric acid, tartaric acid, nitrilotriacetic acid., Ethylenediaminetetraacetic acid or others. Acids such as mineral acids, sulfamic acid, phosphoric acid and the like.

In addition to the ingredients mentioned, the detergents can also contain other components customary in dishwashing detergents or rinsing agents, for example those with moisturizing properties such as alkanolamides as well as perfumes and dyes.

The dishwashing and rinsing agents according to the invention can be removed by simply dissolving the individual components in water or water / alcohol mixtures produce.

The agents according to the invention ensure reliable killing of all germs, both gram-positive and gram-negative, under the given rinsing conditions. In addition, the new means in that they can be stored for long periods of time without losing their bactericidal effect.

In laid-open specification 1 617 100, compounds that split off oxygen or chlorine, for example hydrogen peroxide, Rinse aid for dishwashers added. These fabrics are said to be stains of color caused by tea or coffee soiling be removed. Chlorine and oxygen releasing agents

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Compounds of the ArO described there are unsuitable for the agents according to the invention since they ^{are unstable and disintegrate in aqueous: 1} solution and especially at acidic pH and thus no aqueous, stable detergents and rinsing agents with a bactericidal effect can be obtained. This is shown in the following examples.

Example 1 (neutral toilet rinse containing chlorine)

7.5 % nonionic polypropylene ethylene block polymer 2.0% potassium dichloroisocyanurate 90.5% v / water

Initial chlorine content: 1.2 %

The product was stored for a week at ^ 0 ⁰ C and had after
this time still had a chlorine content of 0.8 %. Decrease: 33.0 %.

Example 2 (oxygen-releasing acidic rinse aid)

7.5 ί nonionic polypropylene-ethylene block polymer, 30.0 % citric acid

25.0 % Perhydrol (calculated as 100 # ig) remainder V / water

Initial value: 22.3 % hydrogen peroxide

The product was ^{stored at ^ 0 °} C. for one week. After this time, the hydrogen peroxide content was 17.4 %, decrease: 22 %.

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In contrast, the remedies yem'iis eier invention showed after 8 weeks Storage at 40 ° C no decrease in bactericidal effect.

A liquid neural rinse aid for dishwashers according to the invention can have the following composition:

30 - 80 % non-ionogenic detergent substance 0 - 30 % alcohol 3 - 60 # bactericidal compound 0 - 70 % v / ater

Example 3

40 % Pluronic L 42
10 % Pluronic L 92
15 % Vantocil IB from Imperial Chemical Industries (a

Guanidine derivative) 20 % isopropyl alcohol 15% v / water

Pluronic L 42 = polypropylene-ethylene block polymer, molecular weight

of polyoxypropylene 1200 with 20 % polyoxyethylene

Pluronic L 92 = molar weight of polyoxypropylene 2750 with 20 %

Polyoxyethylene

A liquid acidic rinse aid for dishwashers can have the following composition:

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ΙΟ. - 30 % nJLchtioriogerie detergent compound 10 - 30 % acid

3 - 60 55 bactericidal compound Rest water

example

10 % nonylphenol polyglycol ether with 7 moles of ethylene oxide 5 % nonylphenol polyglycol ether with 3 moles of ethylene oxide 15 % tartaric acid
30 % Dodigen 180 from Farbwerke Hoechst (mixture of guanidine

derivative and quaternary ammonium compound) kO% water

A liquid detergent for manual dishwashing can be used as follows be composed:

10 - 50 % non-ionogenic detergent substance

2 - 5 nights refatting

3 - 60 % bactericidal compound

Remainder water, coloring, perfume, thickener

Example 5

15,000 % nonylphenol polyglycol ether with 9 moles of ethylene oxide

2.000 % coconut fatty acid diethanolaraid 0.004% color 0.200 % perfume

20,000 % LS-Arapholyt (potassium N-alkylaminopropionate) 62,800 % water

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Show the surprisingly good effect of agents according to the invention

the following attempts: ' _:

There were rinse aid according to the invention in comparison to a known clear rinse aid in various commercial households crockery machines tested and after each cleaning cycle and at the beginning and the end of the rinse cycle, samples are taken from the washing compartment and bacteriologically examined. It was certainly:

I. The total germ content on standard I agar from Merck Composition of the agar:

Special peptone 15.6 g / l

Yeast extract 2.8 g / l

Sodium chloride 5.6 g / l

D (+) - glucose "1.0 g / l.

Agar-agar x 12.0 g / l

The agar was prepared in the usual way.

10 ml of the nutrient medium were placed in a Petri dish to which 1 ml of the solution to be examined had previously been added. The mixture was then ^{incubated at 30 °} C. for 48 hours.

II. The content of Coli germs on fuchsin-lactose agar according to Endo from Merck

Composition of the agar:

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Peptone from meat. . "10.0 κ / 1

Lactose 10.0 g / l

Sodium sulfite, anhydrous 2.5 g / l

Fuchsin basic 0, 'i g / l

Dipotassium hydrogen phosphute 3.5 g / l

Agar-agar 12.5 g / 1

10 ml of the nutrient medium were placed in a Petri dish into which 1 ml of the solution to be examined had previously been placed

Subsequently, 24 storms were incubated at 37 ⁰ O.

III. Enterobacteriaceae content on DHL agar "iJissuI" Composition of the agar:

Meat extract peptone lactose sucrose sodium citrate Sodium thiosulphate sodium deoxy cholate Iron ammonium citrate neutral red agar-agar

10 ml of your culture medium were poured into a Petri dish, into which 1 ml of the solution to be examined had previously been added, followed by incubation at 37 ° C. for 10 to 24 hours.

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3.0 g / l 20.0 g / l 10.0 g / l 10.0 g / l 1.0 g / l 2.3 g / l 1.0 g / l 1.0 g / l 0.03 g / l 15.0 s / i

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IV. Content of pseudomonas on glutamate-St ^; a-ke - phenol red agar according to Kielwein.

Composition of the agar:

Sodium (l +) - glutamate 10.0 g / l

Starch water-soluble 20.0 g / l potassium dihydrogen phosphate 2.0 g / l

Magnesium sulfate 0.5 g / l

Phenol red 0.36 g / l

Agar-agar 12.0 g / l

For selective cultivation, after autoclaving, 100,000 i and 0.5 / 5 pimafucin mixed in homogeneously.

Culture medium cooled to approx. 55 ° C 100,000 IU penicillin G sodium

The culture medium poured into the Petri dish and solidified was inoculated with test liquid, in the present Pall I ml, in such a way that isolated colonies grew.

The tests were carried out in the AEQ Favorite dishwasher LE, Bosch Exquisit E and Miele G 500.

Rinse aid with the following composition was tested:

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Example 6

15 % non-ionic detergent substance = 'fatty alcohol ethoxylate,

Chain length C 10 - C 12 with 6 to 8 moles of ethylene oxide 25 lbs citric acid

a) without bactericidal substance

b) 33 % bactericidal substance

c) 16.5 % bactericidal substance

d) 3.3 % bactericidal substance, remainder water

All experiments were carried out with the following bactericidal substances:

A. = Vantocll IB (a guanidine derivative)

B. = Dodigen 180 (mixture of guanidine derivative and quater

near ammonium compound)

C. = BTC 776 (a modified alkyldiinethylbenzyl

ammonium chloride)

carried out.

3 ml of the rinse aid to 10 l were used in each case Water. The results of the tests are shown in Table 1.

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Testing the effectiveness of the agents according to the invention

Hash. At-' Sampling time . Germ content / ml endo- on Pseuccrncnadsn Disinfect ionic agents IO Ik% 50 game in the of the samples Standard-I- DHL agar in 1 ml ^ 11 V "\ c; i ~ O T ~> r " ppm in _ * PO
CO took 0 AFP agar Rinsing liquor ICO ' CO 10 Miele Cleaning g. end 0 118 0 negative without 50 O 6a Rinse cycle Beginning innumerable 0 25th positive without CO Kiar rinse End . . 17th 12th 0 positive without 6b Rinse cycle Beginning 212 0 49 positive 10 Rinse cycle end 0 Vf 0 negative A. 100 5c Rinse cycle Beginning 345 0 innumerable ¹ p O 3 X C1V Rinse cycle end 0 304 0 negative A. 50 co 6d Rinse cycle Beginning innumerable 0 193 positive OO
00 Rinse cycle end 0 0 0 negative A. ίο · Ni Bosch Cleaning g. end 0 83 0 negative without - * 6a Rinse cycle Beginning innumerable 62 35 positive without Rinse cycle end 720 32 9 positive without cn 6b Rinse cycle Beginning 192 0 35 positive Rinse cycle end 0 20th 0 negative 3 6c Rinse cycle Beginning 296 0 112 positive - B. Rinse cycle end Q 253 0 negative 6d Rinse cycle Beginning 810 0 23 positive Rinse cycle end 0 0 0 negative B. AEG Cleaning g. end 0 96 0 negative without 6a Rinse cycle Beginning innumerable 7th 56 positive without Rinse cycle end 166 54 4th positive without 6b Rinse cycle Beginning 176 0 30th positive Rinse cycle end 0 46 0 negative C. 6c Rinse cycle Beginning 145 0 7th positive Kiar rinse end 0 67 0 negative C. 6d Rinse cycle Beginning 392 0 12th positive Rinse cycle end 0 0 negative C.

The results zei; -on, (iaß the samples after the puri ^ un ^ ogang were germ-free on all nutrient burdens, but that the disconnection was closed Beginning of the iilar flushing length uncountable and also the evidence of ßnterobacteriaceae on DHL agar and eggs from Fseudomonads in positive v / ar in each case. At the end of the KJ.arspül ^ ane :; was with that Rinse aid without bactericidal addition, the germ content zv: ai reduced but still not allowed; high. Enterobacteriaceae and pseudomonads were still detectable. With the according to the invention In contrast, rinse aids were all germ-free after the rinse cycle.

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Claims (6)

Claims Il \ Acid or neutral aqueous dishwashing detergents or rinse aid for dishes or the like, characterized in that they contain bactericidal substances in addition to the usual raw materials. 2. dishwashing or hair washing agent according to claim 1, characterized in that that they are quaternary ammonium salts as bactericidal substances, Contain guanidine derivatives, ampholytes or combinations thereof. 3. rinsing or iiachopülniittel according to claim 1 and 2, characterized in that the amount of bactericidal substances is 3 to 60 % _t, preferably 20 % to 40 % _t . k . Use of an acidic or neutral aqueous rinsing or rinsing solution according to Claims 1 to 3> characterized in that it contains 10 to 200 ppm, preferably 100 ppm, of bactericidal substances. 5. Process for the automatic washing of dishes in dishwashers, characterized in that acidic or neutral aqueous rinse aid with a content of bactericidal Fabrics used. 6. A method for manually washing dishes, characterized in that that one uses acidic oder.neutrale aqueous detergents with a content of bactericidal substances. 409882/1105 BATH ORIGINAL