DE1767384A1 - Low-foaming detergents and cleaning agents for washing dishes - Google Patents

Description

Henkel & CIe GmbH Düsseldorf, May 2, 1968

Patent department, Henkelstrasse 67

Dr. Bz / Et 1767384

Patent application
D 3617 ■

Low-foaming detergents and cleaning agents for washing dishes

(Addition to patent application H 65 60I IVa'2 ^ e (German Patent)

Subject of the main patent ... ... (patent application H 65 601 IVa / 2Je) are highly effective and extremely low-foam rinsing and detergent combinations for dishwashers that because of their biological harmlessness do not pose any wastewater problems. The means of the main patent are indicated by a salary of

A) 70 to 98 percent by weight of water-soluble polyvinyl alcohols the molecular weights 1000 to 4ooo and

B) 2 to J) Q percent by weight of surface-active compounds with a content of polyoxypropylene residues and / or polyoxybutylene residues with 2 to 9o oxypropylene or oxybutylene units and preferably a further content of oxyethylene residues or polyoxyethylene residues, the proportion of oxypropylene or oxybutylene units in the The total number of oxyalkylene units is at least J> o mole percent.

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Further processing of the subject matter of the main patent has now shown that low-foam and biologically safe dishwashing detergents and cleaning agents are also obtained if the surface-active compounds of group B of the main patent are replaced by foam-inhibiting compounds from the group of higher aliphatic alcohols, carboxylic acids, carboxamides and amines replaced. The present invention accordingly relates to low-foam dishwashing detergents and cleaning agents for dishwashing, which are characterized by a content of

A) 70 to 98 percent by weight of water-soluble polyvinyl alcohols the molecular weights 1000 to 4,000, and

B) 2 to 3o percent by weight of foam-inhibiting compounds from the group of higher aliphatic alcohols, carboxylic acids, carboxamides and amines, the at least one aliphatic or aliphatic-cycloaliphatic radical containing 8 to 22 carbon atoms.

As in the case of the main patent, the claimed combinations also have the advantage of being extremely low-foaming under extreme conditions of use in household dishwashers or commercial dishwashers. As a result of the high polyvinyl alcohol content, they have an excellent wetting effect on hard surfaces such as porcelain, plastics or metals, which is why they are particularly good

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as a low-foaming rinse aid for dishes and cutlery everyone Type, if necessary after an alkaline pre-cleaning process, as well as for cleaning alkali-sensitive glassware, such as drinking glasses and the like. You get a flawless one The rinse water drains and the dishes are clear and stain-free.

There is a particular advantage of the agents according to the invention in that the requirement for harmlessness to fish and other Viasser organisms is largely fulfilled. Although the Polyvinyl alcohol used as component A is only slightly biodegradable, it can physiologically are considered completely harmless, as it does not have any toxic properties towards the organisms living in water. Type B foam inhibitors are generally relatively readily biodegradable. Disturbing loads of the wastewater are not to be expected even if the biodegradability due to chain branches or the like is lower, since the proportion of component B in Mixture is always relatively low in practice.

In the claimed combination, the polyvinyl alcohols correspond the molecular weights of 1,000-4,000 of component A of the main patent. The vinyl alcohols are known and commercially available products. They ierden obtained, for example, by hydrolysis of Pclyvinyl-

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acetates with corresponding degrees of polymerization. According to the invention, those polyvinyl alcohols are preferred which have a degree of hydrolysis of 85 to 9 % and molecular weights of about 1,000 to 3,000.

The foam-inhibiting compounds claimed as replacements for group B of the main patent are primarily saturated

W or unsaturated fatty alcohols with 10 to 18 carbon atoms. In practice, mixtures of fatty alcohols such as those obtained from natural fats and oils are mainly used. Examples of suitable fatty alcohols are dodecyl alcohol, hexadecyl alcohol, tallow alcohol mixtures with chain lengths of C ₁ g to C ₁ Q, coconut _{fatty alcohol mixtures with chain lengths of C 12} to C ₁ Q and the like. Instead of natural fatty alcohols, synthetic routes, ζ. B. alcohols of appropriate chain lengths produced by the Ziegler process can be used.

^ Furthermore, branched-chain alcohols come with up to

22 carbon atoms, as they are, for. B. by oxo synthesis or by Guerbet reaction can be obtained.

Further suitable compounds of group B are fatty acids of chain lengths Co to C _22. Here too, preference is given to those fatty acids or fatty acid mixtures which have been obtained from natural fats and oils, such as. B. fatty acid mixtures obtained from coconut fats with chain lengths of C ₁₀ to C ₁₂ or

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^C 12 ~ ^C 18 * Oleic acid, behenic acid and first run fatty acids, which contain larger proportions of fatty acids of chain lengths Cg - C. The fatty acids containing more than 18 carbon atoms can also be used in the form of their alkali salts.

Finally, fatty acid amides or fatty amines of chain lengths C ₁ to C ₂₂ are also suitable as foam inhibitors, such as, for. B. tallow fatty acid-N ^ N-diethylamide, dodecylamine, the tallow fatty acids of chain lengths C - g - Co produced from 'M tallow amine mixture and the like.

The proportions of the individual components in the mixture are about 7o to 98 percent by weight of component A and 2 to 3o percent by weight of component B, in practice have in particular mixtures of 85 to 95 percent by weight of component A and 5 to 15 percent by weight of component B. proven to be useful.

If the mixtures are used to clean dishes, in particular drinking glasses, concentrations of about 0.05 to 0.5 g / l _4, preferably 0.1 to 0.4 g / l, are required in the cleaning liquor. When used as a rinse aid after an alkaline cleaning cycle, about 0.01 to 0.25, preferably 0.02 to 0.1 g / l are used. The concentrations depend to a certain extent on the hardness of the water and the type of dishes. In particular, hard and salty water or plastic dishes require slightly higher amounts of rinse aid. 109847/1722

The application is advantageously carried out in the form of aqueous concentrates containing from about 1o to Jo by weight of the components A and B. The concentrates are useful with the aid of automatic dosing devices, as are common for such purposes metered into the cleaning or KlarspUlflotte.

The foaming behavior ' . various nonionic surfactants and detergent mixtures according to the invention were comparatively tested. The ones shown in the table Test results demonstrate the extraordinarily favorable foaming behavior of the claimed mixtures. The one used The foam apparatus is constructed similarly to a modern dishwasher that works according to the nozzle system. Using a circulation pump circulates about 170 liters of water per minute and sprayed into the measuring chamber by a rotating spray arm provided with nozzles. Viewing heights from ο to 280 mm can be reproduced ^ can be measured in a reduced manner, while larger amounts of foam can no longer be determined exactly and are therefore included in the table "> 28o" must be specified. The liquor temperature was at the tests 50 ° C, the hardness of the water used 16 dH and the duration of the foaming test 5 minutes. The foam height was read off immediately after standstill or after 5 seconds after the machine has come to a standstill. The foam apparatus is described in "Fette, Seifen, Anstrichmittel" 66 (1964), page 529 ·

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The letters A and B in the table below designate the components according to the description text.

TABEL

Example composition of the concentration mix. g'l

A polyvinyl alcohol

(Viscosity of the 4 # solution at 2o ° C 3 cP, degree of hydrolysis 88 %) o,

Foam height, in mm for Still-Jo see. the machine came to a standstill

> 28o> 28o

A polyvinyl alcohol (corresponding to 1a)

B dodecyl alcohol

o, oo9

A polyvinyl alcohol (corresponding to 1a)

B hexadecyl alcohol

A polyvinyl alcohol (corresponding to 1a)

B dodecylamine

o, 12 o, oo9

o, o, o2

2o

A polyvinyl alcohol (corresponding to 1a)

B sodium behenate

o, 12 o, oo9

To

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Example composition of the concentration mix g'l

Foam height in rnm at still- ^ o see " the machine came to a standstill

A polyvinyl alcohol (corresponding to 1a)

B Tallow fatty acid-N, N-diethylamide

o, 12.009

1o

Example 6

A liquid rinse aid suitable for commercial dishwashers has the following composition:

2o, o % polyvinyl alcohol (viscosity of the 4% solution

at 2o ° J cP, degree of hydrolysis 88 %)

o, 7% of dodecyl alcohol 79.3% water

The product foams at application temperatures between 5o and 9o ° practically not. After the main alkaline cleaning of the dishes, it is added to the rinse aid water in concentrations from 0.4 to 0.6 g'l added. A spot-free, shiny dishes.

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~ 9 - '■■

Example 7

An extremely low-foam detergent for household dishwashers has the following composition:

1o, o % polyvinyl alcohol (viscosity of the 4 # solution

at 2o ° 15 cP, degree of hydrolysis '86 %)

ο, 6 % sodium behenate
89, ^ % water

At application _{concentrations of o A} 5 - 1 * 5 S ¹ ^ l you get a perfect cleaning and clear drying effect.

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Claims (1)

- 1ο PATENT CLAIMS 1. Low-eye dishwashing detergents and cleaning agents for washing dishes according to patent (patent application H 65 601 IVa / 2j5e) i characterized by a content of A) 7-0 to 98 percent by weight of water-soluble polyvinyl alcohols the molecular weights 1000 to 4,000, and B) 2 to 10 percent by weight of foam-inhibiting compounds from the group of higher aliphatic alcohols, carboxylic acids, carboxamides and amines which contain at least one aliphatic or aliphatic-cycloaliphatic radical having 8 to 22 carbon atoms. 2. Low-foam dishwashing detergent and cleaning agent according to claim 1, characterized in that component A is polyvinyl alcohol of molecular weights I000 to 3000 used by Hydrolysis of polyvinyl acetates have been obtained, and which have a degree of hydrolysis of 85-90 #. 5. Means according to claims 1 and 2, characterized in that that as component B natural or synthetic fatty alcohols with 10-18 carbon atoms or branched synthetic ones Alcohols with 10 to 22 carbon atoms can be used. - 11 109847/1722 k. Agent according to claims 1 and 2 / characterized in that fatty acids with 8-22 carbon atoms or alkali salts of fatty acids with more than 18 ~ carbon atoms are used as component B. 5. Means according to claims 1 and 2, characterized in that that used as component B tallow fatty acid-N, N-diethylamide will. 6. Means according to Claims 1 to 5> characterized by a content of 85-95 percent by weight of component A. and 5 ~ 15 weight percent of component B. 7. Agent according to Claims 1 to 6 in the form of aqueous concentrates with a content of 1o to 50 percent by weight of the Components A and B. HENKEL & CIE. GmbH. M. in general (Dr. Haas) 109847/1722 Blank page