DE1467618A1 - Low-foaming detergents and cleaning agents - Google Patents

Description

cz CIe. GmbH., -Düsseldorf, HenkelstreSe 07

Düsseldorf, November 3rd, 1965 Dr. Bz / Mü

New patent applications

. "Low-foaming detergents and cleaning agents" (addendum to patent ... .... (patent application H 51 558 IVa / 2Je))

Subject of the main patent (patent application H 5I

IVa / 23> e) are low-foam dishwashing and cleaning agents for machine use Cleaning of dishes and other objects of all kinds made of glass., Porcelain, ceramics, metal, plastics, etc .. The Means are characterized by a content of

A) Polyoxyalkylene radicals and higher molecular weight, if appropriate Compounds containing substituted hydrocarbon radicals, at least 50 mol percent of which are polyoxyalkylene radicals Oxyäthylenresten exist while an equal or less molar fraction can also consist of higher Oxyälkylenresten

B) Acetals and / or ketals of compounds of the. "Group A)

C) Polyoxyalkylene radicals and compounds containing higher molecular weight, optionally substituted hydrocarbon radicals, the polyoxyalkylene radicals of which consist of more than 50 mol percent of oxypropylene radicals and / or higher oxyalkylene radicals, while a smaller molar proportion also consists of oxyethylene radicals

- 2 - 909803/0996

aerroehan can, and / or acetals or ketals of these compounds.

The present invention also relates to low-foam dishwashing detergents and cleaning agents, in particular for use in dishwashers; the invention is based on the object of further developing and supplementing the subject matter of the main patent by including other known, easily accessible compounds. The solution path consists in that in the detergent composition of the main patent component A is wholly or partially replaced by a ethylene oxide adduct containing 35-85 mole percent oxyethylene radicals to a propylene oxide polymer with a molecular weight of 1,000-4,000, preferably 1700-3250 and / or component C wholly or partially by a propylene oxide polymer with a total molar weight of 1000-5000, preferably 1700-41oo, to which up to J> o mol percent of ethylene oxide can be added. The term "Mo]. Percent" relates to the total number of alkylene oxide radicals in the molecule. In this way, extremely low-foaming and highly effective dishwashing detergents and cleaning agents are also obtained.

The ethylene oxide adducts to propylene oxide polymers to be used instead of component A of the main patent are known compounds. They are obtained, for example, by polymerizing propylene oxide in the presence of alkaline catalysts, such as Sodium hydroxide, sodium methylate and the like to a polypropylene glycol and subsequent addition of 35-85 mole percent ethylene oxide, based on the total number of alkylene oxide radicals in the Molecule. The preparation of the propylene oxide polymer can also be carried out by adding propylene oxide to at least two reactive polymers Low molecular weight hydroxyl and / or hydrogen atoms containing Aliphatic or aromatic compounds containing amino groups ^ with 2-6 carbon atoms, such as glycols, glycerine, sugar alcohols,

- 3 -i 909803/0996 -j.

Henkel & Cie. GmbH., Düsseldorf, Henkelstrasse 67

- = _: - U6761.8

D 3O59- '' ■■ ^:: '-'

• ^. '' JT. ' ■■. .: ■

Ethylenediamine, phenylenediamine, alkanolamines, and the like.

Examples of compounds of the type mentioned are the adducts of 17, 60 or 159 moles of ethylene oxide with a polypropylene glycol with a molecular weight of 1,750, the adduct of 51 moles of ethylene oxide with a polypropylene glycol with a molecular weight of 2250, the adduct of 250 moles of ethylene oxide with one of 48 oxypropylene residues , existing polypropylene oxide, the adduct of 295 moles of ethylene oxide with a polypropylene S ^ d consisting of 56 oxypropylene residues, the adduct of J> o moles of propylene oxide and 26.5 moles of ethylene oxide or 48 moles of propylene oxide and 42 moles of ethylene oxide with ethylene diamine, the adduct of 48 moles of propylene oxide and 42 moles of ethylene oxide in ethylene glycol.

The propylene oxide polymers to be used instead of component C of the main patent are obtained in a manner similar in principle to the compounds A by polymerization of propylene oxide or * r

-: -: ■:; - ;; · v; i9v r \ u

by addition of propylene oxide to at least 2 reactive hydrogen atoms containing low molecular weight compounds with 2 6 carbon atoms. Preferably, up to 50 mol percent of ethylene oxide, based on the total number of alkylene oxide radicals in the molecule, are added to the propylene oxide polymer formed. Eel.spiele for compounds of the type mentioned are the adduct of 4.5 moles of ethylene oxide with a polypropylene glycol of molecular weight 1750, the adduct of 7 or 16 moles of ethylene oxide with a folypropylene glycol of molecular weight 2750, there? Adduct. of 8.5 mol? 'of ethylene oxide to a poly-

■■ ■■ - '■■' ■ -. ti ... ■

- ■■■ '- ■ - * ■■' ■■ ..:. - :: V5OV. ■■ ORIGINAL BATHROOM

Henkel & CIe. GmbH., Düsseldorf, Henkelstrasse 67 1467618

propylene glycol, the adduct of 35 moles of propylene oxide with glycerine, the adduct of 48 moles of propylene oxide and 7 moles of ethylene oxide with ethylenediumine.

The ones used as component B in the detergent composition Connections correspond to connections B of the main patent.

The low-foam dishwashing detergents and cleaning agents according to the invention exist accordingly from one of the following combinations:

A) an ethylene oxide adduct containing 35-85 mole percent oxyethylene radicals to a propylene oxide polymer with a molecular weight of 1000-4000, preferably 1700-325o,

B) an acetal or ketal of a polyoxyalkylene group and higher molecular weight, Compound containing optionally substituted hydrocarbon radicals, whose polyoxyalkylene radicals are at least 50 mole percent consist of oxyethylene residues, while an equal or a lower molar proportion also consist of higher oxyalkylene radicals, in particular oxypropylene or oxybutylene radicals can, ^

C) Polyoxyalkylene radicals and higher molecular weight, if appropriate Compounds containing substituted hydrocarbon radicals, the polyoxyalkylene radicals of which are more than 5o mol percent of oxypropylene radicals and / or higher oxyalkylene radicals, while a smaller molar proportion also consists of oxyethylene radicals may exist, and / or acetals or ketals of these compounds

fertilize,. ·

.- 5 , 90980 3/0996

A) Polyoxyalkylenes te and higher molecular weight, if appropriate Compounds containing substituted hydrocarbon radicals, at least 5o mol percent of their polyoxyalkylene radicals consist of oxyethylene residues, while an equal or less molar proportion also from higher oxyalkylene radicals, in particular May consist of oxypropylene or oxybutylene residues,

B) acetals and / or ketals of compounds of group A)

C) a Propylenoxydpolymeren of Qesamtmolgewichtes 1ooo - 5000, preferably 1700 to 4100, can be attached to the mole percent up to Jo Ä'thylenoxyd

A) an ethylene oxide adduct containing 35-85 mole percent Öxyäthylenreste to a propylene oxide polymer with a molecular weight of 1000-4000, preferably 1700-525o,

B) an acetal or ketal of a polyoxyalkylene radical and higher molecular weight, Compound containing optionally substituted hydrocarbon radicals, whose polyoxyalkylene radicals are at least 50 mole percent consist of oxyethylene residues, while an equal or a lower molar proportion also consist of higher oxyalkylene radicals, in particular oxypropylene or oxybutylene radicals can,

C) a propylene oxide polymer with a total molar weight of 1000-5000, preferably. 1700 - 4ioo, may be attached to the up to Jo mole percent ethylene oxide.

The proportions of the individual components in the mixture are generally 5 to 79 * 5 Ge weight percent 9 ^ 9 (^ «p ^ gejjplegA, 0.5 to 75

- ⁶ - 909803/0996

BATH ORIGINAL

Henkel & Cie. GmbH., Düsneidorf, Henkelstrasse 67 1467618

D 5059

Weight percent of component B and 2o to 9 ^, 5 percent by weight of component C. In practice, mixtures of 20 to 5 percent by weight of component A and 5 to 20 percent by weight are particularly suitable of component B and 3> o to 75 percent by weight of Component C proved useful. The quantities of such mixtures used in the cleaning liquor are approximately in the concentration range from 0.02 to 1.0 g / l, preferably 0.05 to 0.5 g / l, calculated on the sum of components A, B and C.

The composition can be within the specified proportions the mixtures can be varied without losing the particular advantage of the extraordinary low foaming. In particular it is desirable that a relatively high proportion of component A, which by itself tends to produce more foam, should be present in the mixture is present, since this has a positive effect on the drainage and dry-dry effect as well as the cleaning and wetting effect.

Concentrated liquid products, as they are preferably used in dishwashers equipped with automatic dosing devices, can be removed by dissolving the mixtures in water,. optionally with the use of water-miscible organic solvents. Such concentrates preferably contain about 20-70 % of components A, B and C. By varying the constituents, such liquid concentrates can be adjusted so that they. have good temperature resistance and do not tend to precipitate or delaminate. In a corresponding way, the dehydration

⁷ "909803/0996 ^{BAD 0R} ^

Henicel & Cie. GmbH., Düsseldorf, Henkelstrasse 67 1467618

• Change the temperature of the mixtures in aqueous solution and the adapt to the respective requirements, for example the wash temperature, Extremely low foaming is achieved in particular when when the dehydration temperature of the mixtures is below the rinse temperature.

909803/0996

Henkel & Cie. GmbH., Düsseldorf, Henkelstrasse 67 »

- 8th - Examples

The foaming behavior different detergent mixtures tested comparatively. The test results shown in the table demonstrate the extraordinarily favorable foaming behavior of the claimed mixtures compared to corresponding 2-component mixtures.

The foam device used is constructed similarly to a modern dishwasher that works according to the nozzle system. Be there by means of a circulation pump approx. 17o 1 water per minute circulated and injected into the measuring chamber by a rotating spray arm provided with nozzles. Foam heights of ο to 280 mm can be can be measured reproducibly, while larger amounts of foam can no longer be determined exactly and are therefore included in the table "^ 280" must be specified. The liquor temperature was at the Try 5 °° C, the hardness of the water used 16 ° dH and » the duration of the foaming test 5 minutes. The reading of the foam height took place immediately after the masohine came to a standstill. The foam apparatus is described in "Fats, Soaps, Paints" 66: 529 (1964).

The abbreviations used in the table have the following meanings: ·

50 a mole of ethylene oxide

■ * «

PrO «moles of propylene oxide

- 9 - 909803/0996

PIon.:ol & Cie. GmbH., Dü. <Vseldori ^% , Henkelntraße 67 1467.618

D ^ 59

■ ■ *

The letters A, B and C denote the connection types ent speaking the description text.

TABEL

No. Composition of the mixture Conc.

g / l height in

mm

1a A. Adduct of 4o mol Ά'Ο to a polypropylene

glycol of molecular weight 174o 0.24

C. _{Coconut fatty alcohol - C 19} - C ₁ O - 5 äO -

13 PrO ^{l £ i OK} 0.12

1b A. Adduct of 4o mol Xo to a palypropylene

glycol of molecular weight 17 ^ o 0.24

B. Nonylphenol - 2o SO - formaldehyde acetal 0.025

C. Coconut fatty alcohol - C ₁₉ - C ₁ O - 5 AO -

13 PrO ^{l4i IO} 0.12

2a A. Adduct of 4o mol Άθ to a polypropylene

glycol of molecular weight 17 ^ o. o, 12

C. Coconut fatty alcohol - C _1O - C " _o - 5 XO -

13 PrO ^{ld 1Ö} o, 24

2 b A. Adduct of 40 moles of A'O to a polypropylene

glycol of molecular weight 174o o, 12

B. Pettalcohol - C _1P - C ₁₂ , - 20 Ä'O - Pormaldehydacetal o, o5

C. _{Coconut fatty alcohol - C 10} - C ₁ O - 5 Ä'O -

13 PrO ^{Λά Ί0} ο, 24

3a A. Ethylenediamine - 48 PrO - 146 Xo o, 12

C. Petroleum alcohol - C ₁₂ - C ₁₈ - 5 XO - 13 PrO 0.06 " ² °

3b A. ethylenediamine - 48 PrO - 146 ÄO o, 12

B. Nonylphenol - 20 AO - Formaldehyde acetal 0.007

C. Pet alcohol - C ₁₂ - C ₁ Q - 5 A'O - 13 PrO 0.06

- 10 -909803/0996 b * d

Henkel & Cie. G; nbH., Düsseldorf, Henkelstrasse 67 146761.8

D Jo59

- 1o -

No. Composition of the mixture Conc. \ Foam

g / l 'height in mm

4a A. Nonylphenol - 2o A'O '0.12 155'

C. Glycerin - 35 ^Pr0 °> ² ^

b A. Nonylphenol - 2o A'O 0.12

B. Nonylphenol - 2o; 'O - formaldehyde acetal 0.025 1o.

C. Glycerin - 35 PrO 0.24

4c A. Nonylphenol - 2o KO 0.12

B. Fatty _{Alcohol - C 19} - C ₁ O - 20 EO - Formaldehyde ^{Acetal XlL} 0.025

C. Glycerin - 35'PrO · 0.24

a A. Nonylphenol - 20; tO S " 0.12

C. Adduct of 6 moles of KO to a polypropylene / glycol of molecular weight 22oo 0.24

5b A. Nonylphenol - 2o 30 0.12

B. Nonylphenol - 2o A'O - formaldehyde acetal 0.025

C. adduct of 6 moles of A'O to a polypropylene glycol in the molecular weight ^ 22oo 0.24

a A. Fatty alcohol - C ₁₀ - C ₁ O - 2o A'O 0.12

C. Adduct of 4.5 moles 50 to a polypropylene '

Lenglycol with a molecular weight of 174o '0.24

6b A. Fatty alcohol - C ₁₂ - C ₁ Q - 2o KO '0.12

B. Fatty alcohol - C ₁₀ - C ₁ Q - 2o AO - formaldehyde acetal 0.03

C. Adduct. of 4.5 mol A'O to a polypropylene - * Lenglycol with a molecular weight of 174o 0.24

a A. Adduct of 129 moles of A'O to a polypropylene glycol with a molecular weight of 17 ² IO 0.12. ·

C. Adduct of 4.5 moles of A "0 to a polypropylene glycol with a molecular weight of 17 ² 10 0.06

9098 03/0996

Henkel & Cie. GmbH., Düsseldorf, Henkelstrasse 67 1 4 6 7 6 1; 8

D> 59.

'■ - 11 -

No. Composition of the mixture Conc.

- g / l "height in mm

7b A. Adduct of 129 mol AO with a polypropylene glycol the molecular weight 174o 0.12

B. Nonylphenol - 2o AO - Formaldehyde acetal 0.016

C. adduct of 4.5 moles / to pylenglykol to a polypro- ¹ ^ the molecular weight 174o 0.06

8 a A. Adduct of '4o mol A'O to a polypropylene

Lenglycol with a molecular weight of 174o 0.20 _OE . _C.

C. Glycerin - 55 PrO O, 16

8b A. Adduct of 40 mol to a polypropylene

Lenglycol with a molecular weight of 174o '0.2o

B. Nonylpnenol - 2o Ά0 - formaldehyde acetal 0.025

C, glycerin - 55 PrO 0.16

8c A. Adduct of 40 moles EO to a polypropylene

Lenglycol with a molecular weight of 174o 0.2o

B. Pettalkohol - C _fi - C ₁₀ -) 0 ÄO - Pormalde- '„hydacetal ^{ö Λά} . 0.05 ^

C. Glycerin - 55 PrO O, 16 ^f

9. An extremely low-foaming liquid detergent for household dishwashers has the following composition:

18.5% of the adduct of 159 mol of ethylene oxide with a polypropylene glycol the molecular weight 174o

9.0 % of the adduct of 4.5 moles of ethylene oxide with a polypropylene glycol of molecular weight 174o

2.5 % of the formaldehyde acetal of an adduct of 20 moles of ethylene oxide with nonylphenol

10.0 % ethanol
60.0 % water

- 12 -

909803/0996

Henkel & Cie. .GmbH., Düsseldorf, Henkelstrasse 67 146/8 18 · '

- 12 -

With a bet of 0, J> - 0.5 g / l ensures good water drainage from the dishes without the formation of drops, even with hard water. No disruptive foaming occurs.

10. In a dishwasher with a pre-wash and rinse zone the items to be washed, consisting of porcelain and glass dishes as well as metal cutlery using an alkaline, free alkali, soda, Containing phosphates and optionally chlorine-containing bleaching agents Fleet, pre-cleaned. After passing through the pre-cleaning zone, the items to be washed move into the final-rinse zone, where they are washed with an aqueous one Solution of the following combination is rinsed clear:

12 parts by weight of nonylphenol - 2o Ä'O 2.5 "parts by weight of nonylphenol - 2o 30 - acetal 24 parts by weight of glycerin - 35 per 10 parts by weight of isopropanol
51.5 parts by weight of water

The mixture is liquid and has a cloud point of 4o. It is dosed into the final rinse liquor in quantities of 0.2-0.4 g / l by means of an automatic dosing device, with the Fleet temperature is about 8o °. This achieves a quick drying of dishes after washing. The finished dishes are glossy and free of residues and stains. Even in high-performance machines with large water circulation, this does not occur either when starting up the cold machine or in permanent storage a disruptive foam in the hot machine that affects the cleaning process. 909803/0996 BADORiGiNAL

Claims (1)

Godparents t a η. f η γ ü c h e 1. Faulty dishwashing detergents and cleaning agents according to patent (Patent application H 51 558 IVa / 25e), characterized in that da3: i; ai '; la the cleaning agent composition of the main patent, the grain 'poi'ioüte A wholly or partly by a methylene oxide adduct containing 55 to 5 mol% of oxyethylene radicals to a propylene oxide poly- .. lerc :; of the molecular weight 1ooo - -iooo, preferably 17oo - j; 25o and / or the component C wholly or partly by a propylene oxide polymer, the total molar weight 1ooo - ^: j> ooo, preferably "ijoo - 41oo, up to 5 ° Holprozent iithylenoxyu unstored r: a can, replaced. 2. Means according to claim 1, characterized by a content of etc.) a 55 - 85 mole percent Oxyäthylenreste 'containing' thylenoxydaddukt to a Propylenoxydpolymeres the molecular weight Iooo 4ooo, preferably 1 oo - 5250> 3) an acetal or ketal of a polyoxyalkylene radical as well as higher molecular weight, Compound containing optionally substituted hydrocarbon radicals, at least their Polycxyulkylenreste 50 mole percent consist of oxyethylene residues, while an equal or a lower molar proportion can also consist of higher oxyalkylene residues, in particular oxypropylene or oxybutylene residues, C) Poiyoxyalkylenreste and higher molecular weight, optionally substituted Compounds containing hydrocarbon radicals, the polyoxyalkylene radicals of which are more than 50 mol percent of oxypropylene radicals and / or higher oxyalkylene radicals exist, while a smaller molar proportion also consists of oxyethylene residues BATH ORIGINAL '909803/0996 _1A 67618 can and 'or acetals or ketals of these compounds. j. i'iiutel ge; ii .-: "o Claim 1, characterized by a content of A) polyoxyalkylenes to and higher molecular weight, optionally substituted hydrocarbon radicals containing compounds whose polyoxyalkylene radicals consist of at least 50 mol percent of oxyethylene radicals, while the same or lower molar proportion of higher oxyalkylene residues, in particular oxy-propylene or O, youtylene residues, may exist, S) .-. Cotal en and / or ketulene of compounds of the group !.), G) eifior.i Propylenoxydpoly / nerea of Gesamtmolgewichtes 1ooo 5ooo .- - • orzug ^ v / eiofc .700 - ^J [1oo can be .ungelagert to the mole percent up to Jo '''thylenoxyd. '4. Agent according to claim 1, characterized by a content of A) a ^ 5-85 Moiprozent Oxyüthylenreste containing "thylenoxydaddukt to a Propylenoxydpolymeres the molecular weight I000 ^■; rooo, preferably I700 - 325Oj B) an acetal or ketal of a polyoxyalkylene radicals as well as a compound containing higher molecular weight, optionally substituted hydrocarbon radicals, the polyoxyalkylene radicals of which consist of at least 50 mol percent of oxyalkylene radicals, mainly an equal or lower molar proportion also of higher oxyalkylenes rust, in particular oxypropylene or oxybutylene arcs exist C) oi.:en; Propylenoxjdpolyr.ieren the total molar weight 1000-5000, - 15 - 909 803/0896 ^{BATHROOM 0RiGINAL} Henkel & Cie. GmbH., Düsseldorf, Henkelstra2e 67 ■■. D 3o59. . ■ ' --15- preferably 1700-4ioo, of up to 30 mole percent of ethylene oxide may be attached. 5. I-Mttel according to Claims 1, 2 and 4, characterized in that component A is an adduct of 40 to 300 moles: ethylene oxide to a polypropylene glycol with a molecular weight of 1700 - j> 25o. o. Gown according to claims 1, 2 and 4, characterized in that "that : Iio component A an adduct of 3 ° to 56 moles of propylene oxide and 4o to 3oo mol /'.thylenoxid to a v; at least 2 reactive Low molecular weight hydroxyl and / or amino group-containing aliphatic or aromatic compound containing hydrogen atoms with 2-6 carbon atoms. 7. Composition according to claims 1, j> and k, characterized in that component C is an investment product of 2 - 10 mol "'ethylene oxide to a polypropylene glycol dec molar weight 1700-4ioo. 3. Agent according to claims 1, 5 and 4, characterized in that component C is an adduct of ^ o to 56 moles of propylene oxide and 2 - 10 moles of ethylene oxide with a low molecular weight hydroxyl and / or amino group containing at least 2 reactive hydrogen atoms containing aliphatic or aromatic compound having 2-6 carbon atoms. 9. Agent according to claims 1, ~ j and 4, characterized in that component C is an adduct of 30 to 56 mol of propylene _ _{16 m} 909803/0996 BAD ORiüiNAL Henkel & Cie. GmbH., Düsseldorf, Henkelstrasse 67 1467618 D 5059 4 * - 16 - oxide to one containing at least 2 reactive hydrogen atoms Aliphatic or aromatic compound containing low molecular weight hydroxyl and / or amino groups and having 2-6 carbon atoms is. * 10. Agent according to claims 1-9t characterized by a content of 5 to 79 * 5 percent by weight of component A, 0.5 to 75 percent by weight of component B and 2o to 9 ^> 5 percent by weight of component C. 11. Low-foam dishwashing and cleaning agent according to claims 1 - 1o in the form of a liquid concentrate, characterized by a content of 2o - 70 % of components A, B and C in aqueous or aqueous-alcoholic solution. Heijke 1 & Cie. GmbH. * i.V. BAD ORiGiNAL 909803/0996