DE2228252A1 - laundry detergent - Google Patents

Description

fetoftttt

t) r. In ₀ . Walter Abte 8, JUNE 1972

Dr. Dieter F. Morf Dr. Hans -A. Brown·

Valter Sven Erwin Hentschel, Director Anders Matteonegatan 20, 415 06 Göteborg mid Gerhard Oskar Hentschel, chemists Oktobergatan 3 »415 15 Gothenburg, Sweden

Wagchiaittel.

Inventor: Gerhard Oskar Hentschel, chemist

The present invention relates to a washing, rinsing, and Detergents in powder, granular, pasty or liquid form Form, with the Phoiphate, which was previously used in such detergents in whole or in part from an eutrophication point of view seen far more suitable W & Bcheheniik & lien auegotausche *

According to the German patent specification ...... «(the German PateritSR- Eldung P 20 26 739.4) are not due to butrofinance reasons Desired phosphates by aliphatic carboxylic acid and / or their salts, b.B. Llilclisäure »Esfilgsäur®j, tartaric acid vesS

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2? 28252

or duroh aromatic! carboxylic acids, for example benzoic acid.;. _t ΓΙ, '- iialsäure and tri-, penta and ITexabenzolkarbonsaur © \ ^ xüßjvz, "salts become replaced," The present invention taa'.iht relying on the use of the salting particular eng fruit acids, as these have proven to be very useful as a substitute for phosphates. This is because they are degradable with less toxicity and do not add any phosphorus or nitrogen to the recipients.

And for reasons of washing technology, the effect of these carboxylic acids still remains in addition, to increase it, it has proven advantageous to form monoesters, or at least some of the detergents incoming carboxylic acids in alcohols lower * .7ertes let it take effect. The AUcalisalze dex acid esters have partly lipophilic properties (alleyl groups) and partly hydrophilic properties (Carbonyl group, -COOIIa). However, since dirt particles are often embedded in grease, these monoesters are particularly suitable for a mixed Pett-7 / water system in which the The alkyl group gives the molecule its lipophilic property, while the non-esterified COOH groups give the molecule its typical oxygen character, that is, its property of complex formation of heavy metal ions give thanks to the reinforced lipophilic The dispersibility and emulsifiability properties also become character increased in such connections. The real reason in this regard to turn to monoesters restrict is that the higher esters are poorly soluble and therefore do not lead to the same effects in detergents. Further The biodegradation of the compound concerned must be taken into account and the biological oxygen consumption, BS, value is with the monoesters less than with the so-called higher esters.

Esters are generally made by esterifying the anhydrous acid with the alcohols in question using a suitable one Catalyst or other suitable methods.

In the following formulas, X means Ua, K or IJH ^ mid R alcohol radical with 3 carbon atoms.

Examples of monoesters:
XO ₂ G-CII = GH-CO ₂ -R

1) Sodium ethyl dicarboxylic acid monoethyl ester

ITa-O -C-CH = CH-CO 0 -CH ₀ H, -2 2 d. O

2) Potassium ethylenedicarboxylic acid monoEieth.yl ester KO ₂ C-CH = CH-CO ₂ -CH ₃

3) Potassium ethylenedicarboxylic acid Rionobu.tyl ester

KO ₀ C-CH = CH-CO ₀ -CH _n
2 2 4 9

-CO ₂ -Ii

4-) Sodium oxyäthandi carboxylic acid 1,4-nonoethyl ester! Ta-O ₂ C-CH ₂ -CII (OH) -CO ₂ -CH ₃

5) Liatrium-oxyätliandicarbonsäare-nonoisoarQylester ITa-O ₂ C-CH ₂ -CII (011) -CC ₂ -C -H ₁₁

6) AiaQoniuin ether andicarbonic acid moiiopropyl ester

7) Potassium ethane dicarboxylic acid nonoethyl ester KO ₂ C-CH ₂ -CH ₂ -CO ₂ -C ₂ H ₅

XO ₂ G-CH (OH) -CHCOH) -CO ₂ -Ii

8) ITodium dioxysuccinic acid monoinetliyl ester ITa-O ₂ C-CH (OH) -CII (OII) -CO ₂ -CII-

9) KaliuEi-dioxysuccinic acid-Kiono-sec-batyl ester K-0 _o C-CH (OH) -CH (OH) -CO ₂ -CH (CH) C ₂ II ₅

XO ₂ C-CH ₂ = C (CO ₂ H) -CH ₂ -CO ₂ -R

10) sodium 1,2,3-propane tricarbo3cylic acid aorLOethyl ester ITa-O ₂ C-CH ₂ = C (CO £ 1) -CII ₂ -CO _O -C _g H

XO ₂ C-CE _o t CII (CO pH) -CH p-CO _Q -II

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11) Ammonium tricarballylaic acid monohexyl ether

-CO ₂ -C ₆ H ₁ _

IO "CC (OH J-CH ₂ -

12) Sodium-2-hydroxypropane-tricarboxylic acid-mono-boaagrleBter Na-O ₂ C-CH ₂ -C (OH J-CO ₂ H-CH ₂ -CO ₂ -C ₅ H ₁₁

15) Potassium 2-hydroxypropan-tricaxbonaic acid monopropyl ester ρ KO ₂ C-CH ₂ -C (OH) -CO ₂ H-CH ₂ -CO ₂ -C ₃ H ₇

The invention is of course not limited to the above monoesters, but other toxicologically harmless carbonic acid monoesters can also be used. A prerequisite, however, is that they can be approved from the water maintenance point of view. ^In terms of water technology, they must also guarantee satisfactory results. In order to improve the results of the esters mentioned, it has proven advantageous to add polyvalent higher alcohols in an amount of up to $ 25, preferably $ 0.5-8, calculated on the amount of the esters mentioned.

Dfe in itteln according to the invention any anionic, double ionic or non-ionic surfactants contained in their molecule has at least one hydrophobic group with 8-3Ο carbon atoms and a water-solubilizing group of anionic or nonionic character. As an anionic,. detergent substance and Soaps, sulfonates, and sulfates are important. Phosphate surfactants can also come into use. Sulfonates can be derived from alkylarylsulfonates, Alkyl sulfonates, alkene sulfonates, oxyalkene sulfonates and oxyalkane - ~: sulfonates exist. Sulfonated esters can also be used come. Sulphates can, for example, from alkyl sulphates, fatty alcohol ether sulphates, sulfated amides of fatty acids, sulfated monoglycerides sulfated products of etoxylated and / or propoxylated petroleum alcohols, alkylphenols, fatty acid amides etc. exist. Sulphonates of fatty acid esters of Otarthanaulphonic acid and dioxypropanesulfonic acid, fatty alcohol esters less aliphatic and aromatic 3ulfmono- and dicarboxylic acids, as well as condensate are ionic products of fatty acids with amino alkanesulfonic acids

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applicable. Synthetic capillary active carboxylates and condensation products of fatty acids with aminocarboxylic acids or with silicon hydrolyzate, Phosphate esters of fatty alcohols and fatty acids can also be used.

As nicl & onic surfactants, for example, alkylphenols, fatty alcohol, Alkylamine, fatty acid, fatty acid alkyloamide fatty amide polyglycol ethers, Phosphate esters of etoxylated fatty alcohols, block polymers of ethylene oxide and propylene oxide, etc. can be used.

Auth amphoteric surfactants can be used, such as Imidazokine derivative of fatty acids, carboxy betaines, compounds with phosphoric acid groups in the acidic residue or with sulfo or sulfuric acid groups.

Likewise, foam stabilizers or foam retardants, as well as corrosion retardants, polluted substances, optical ice makers, perfume, bactericides, enzymes, dyes and water enter. Also different types of acidic or chlorine-containing bleaching agents and associated activators and stabilizers can come in.

In summary, it should be mentioned that all im ^ ueamment: „ig Surfactants and auxiliaries occurring with 7! TaBCh and cleaning agents can be combined with the principle of the present invention, and that the "list given above" is by no means a Limitation matters.

The following examples illustrate the invention:

Example 1. White detergent, sprayed

10 parts of sodium dodecylbenzenesulfonate

5. "Fatty alcohol polyglycol ethers

7 "xylene sulfonate

2 ^M ITatriom soap, 80 percent 2. "Phosphate Ester Etoxylated Fatty Alcohol 15" sodium perborate

15 ^M sodium ethanedicarboxylic acid monopropyl ester 15 ^N potassium 2-hydroxypropane tricarboxylic acid lionoamyl ester

5 ^N sodium citrate

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4th π 20th N 20th If 15th N 20th J » 5 η 4th ft 6th η

Share Ea-Silicate

^K EDTA or NTA

ⁿ Na-SaIa from Benzoltetrakarbonaäuz · ** "CMCp opt. Weisemacher, Mg-SiliLit

Example 2. Yorw aschfflltte JL _f palmer _p granular

Parts of alkyl sulfate, sodium salt

"Lauric acid monoethanolamide sulfosuccinic acid

half-ester

Na salt

Fstsäurepolygiolester

Soda, grainy

Sodium bicarbonate

Na-dieilicate

Sodium monoisoamyl ~ 2-hydroxypropane tricar-

bone acid ester

Sodium ethane dicarboxylic acid monoethyl ester

Pentaerythritol

CMC, opt, y / eissnacher, enzymes, water

Example 3. Fine detergent, grainy parts, 50 percent alkylbenzenesulfonate, fatty alcohol polyglycol ether

"Sulfosuccinic acid half-esters of fatty acid

polyglycol ethers, sodium salts

"Coconut fatty acid monoethanolamide or fatty acid amide polyglycol ether Na silicate Manna sugar Sodium citrate

Sodium monobutylmellitic acid ester Mellitic Soda, Granular S eskvikarbonat Natri urn ulf at, kai ζ. CMC, opt. Catfish makers, perfume, water

Example 4 H auptwaachmlttel, granular

"2 parts of fatty alcohol polyglycoether with 30 mol.ED (ethylene oxide) ^R tallow fatty alcohol

"

2.5 "

"

»

3.5 "

» " ^H

"

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Example 5. Example 6.

Parts of cumene sulfonate "sodium ethylenedicarboxylic ^{acid monoethyl ester n} potassium ethylenedicarboxylic acid monomethyl ether, sodium acetate, soda, calcined sodium bicarbonate, sodium percarbonate, sodium disilicate

CMC, perfume, opt. 7 / ice maker, magnesium silicate, Enzymes and '.Yasser

Main detergent, powder

Parts of DodecyTbenzenesulfonat calculated as 100 percent "Alkylpheruene polyglycol ether, cloud point

5 5

20 10 15

1Q. 8th

fl

dd

70 ° -74 °

1 2 6

20 10

Fatty acid diethanolamide

Na toluenesulfonate

Sodium soap

Sodium perborate

Potassium 1,2,3-propane tricarboxalic acid monobaty

lester

Sodium dioxysuccinic acid monomethyl ester

Sodium tripolyphosphate

D-sorbitol

Na-V / water glass crystall.

CIiC, perfume, opt. Whiteners, enzymes and water

Machine detergent parts Polypropylene-Ethyl-Oxide-addition product

20 5 4

10 11

25 25 15

15 U

! Tat r i iunalky Ip ο Iy glyko lathe r pho sphat

Acetic ITatron

Sodium sulfate

ITatriun-monoethyltricarballylic acid- monohexyl-

eater

Sodium Monomethyl-2- Tlydfoxypropan ^ ü.rlkar-

boric acid ester

Perfume, paint, bactericides,? / Ater

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Example 7. Washing and cleaning paste

Parts fatty acid imidazoline derivative, 50 percent

Succinic acid-2-ethylhexyl monoeter

And e cylenic acid monoethanolamide

Fatty acid condensation result with methyl taurine

Glycil derivative

"atrium-ilonoethyl-ethanedicarboxylic acid ester

ITatriun- Oxyäthandi carboxylic acid 1,4- monobutyl-

ester adipic acid CMC '.Tasser

Example 8. Liquid detergent and cleaning agent Parts of a mixture of Λ uranium and alkene sulfonates

Di alley lphen ο Ip ο lyglyko lathe r

Undecylenic Acid Monoethanolamide Sulpho Amber

acid half ester, ITa-SaIz

Fatty acid amine oxide

Pine oil ethyl diglycol

ITII. -l'onopropy-Oxyä thandicarbonsäureester

Sorbitol «vaseer, perfume,

arbe, Aaimonial: u.a ·

To get the real effect of the 7 / ash agent similar to Example 12 in Relation to the previously known phosphate and ITTA-containing detergents the final results of the washing tests carried out are given below:

.Table I

', Detergent dosage Prewash g / kg Main wash g / kg ' I. 6th 26th II 6th 24 III 6th 25th IV 7th 27

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Tabel?

Washing program and requirements Table 3 Colored laundry, white laundry 5 kg 2.5 kg Automatic laboratory - '. 7aschinasoliine Removed dirt in # 2, 14th 1:14 Capacity 1: 6th ■ 1: 6 Fill factor 1: 4 ° dH 5.4 ° dH Bath ratio 5, Min. 75 min. Water hardness 66 Min. 17 min. Total wash time 19th Min. 11 min. Before you go 13th ⁰ G (5 Min.) 40 ⁰ G (5 min.) Preheating time 45 Min. 34 min. Maximum-7 / as cht emp er at ur 24 Min. 23 min. Main wash 12th ⁰ G (10 Min.) 85 ⁰ G (10 min.) Warning time 60 Min. 18 min. Maximum washing temperature 18th Min. 4 min. Flushing 4th Min. each with flow through 1st rinse 4th Min. 5 min. 2nd, 3rd and 4th rinse 5 - Spin dry

Do not worry I pigment dirt ζ wash dirt EMPA standard dirt 85.3

Eiweiaa dirt

blood

cocoa

Blood, milk, ink 90.3

Lead bear-rS chmut g
Bleach test
Cotton, raw
Hot wine

Multi Colored-wash

II III IV

Weieswäache

II III IV

85.3 15.5 90.8 88.8 92.1 88.2 93.5 93.7 ' 94.8 92.9 90.3 14.2 98.2 89.9 95.7 95.7 98.4 98.9 96.6 97.2 90.3 26.8 39.1 48.5 77.6 49.4 45.0 79.0 82.4 72.7 90.3 9.2 85.1 47.7 84.6 69.0 81.8 80.1 85.2 73.9 85.3 28.0 23.2 26.0 28.2 27.8 32.5 41.6 39.1 39.8 90.3 59.4 21.4 18.5 24.2 23.1 39.8 41.2 39.3 39.8 90.3 40.5 60.4 62.9 72.1 66.0 92 _r 9 92.3 92.2 92.4

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ίο .7228252

I detergent according to example 4

II detergent soap base with 10 '/? Tropolyphosphate ai; i $ 20 Ha-

Perborate

III Synthetic detergent with 30 ^ tripoliphatic: .ra & 25% ITa-

Perborate

IV Synthetic Detergent with £ 10 UTA, $ 10 Tripolyphosphate and

17a-porborate

Table 4

* Veraschungsreet after prewash 10 wash cycles average value average value Multi Colored-wash Attempt 1 45 ^O / I main wash 6O ⁰ C 0.13 / 0.09 / 0.15, ' Attempt 2 0.06 / 0.09 # I. 0.06 / 0.12 / 0.05 / 0.07 / II 0.05 / 0.05 / 0.05 / 0.06 / III 0.05 / 0.05 / 40 ° C / main wash 85 ⁰ C IV prewash 0.05 / Attempt 2 Whites Attempt 1 0.09 / 0, Off / 0.08 / I. 0.10 / $ 0.065 II 0.07 / 0.05 / III 0.07 / IV

The above results show that by exchanging the Phosphates and NTA according to the present invention, a detergent is obtained which has an equally good washing effect without thereby increasing the incrustation, which can be seen from Table 4. Paa detergent of the present invention thus leads to very acidic drawn washing results without the recipient with phosphorus and nitrogen-containing nutrient salts.

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Claims (8)

Fat claims MJ detergents, dishwashing detergents and cleaning agents in powder, granular, paö ~ in liquid or liquid form with water softener and ash effect enhancer, characterized in that the Water softeners and 7 / ash effect enhancers are monoesters that by esterification of bivalent or polyvalent organic, aliphatic! carboxylic acids with 0-9 carbon atoms in the chain and / or aromatic 2- or mhrbasi see carboxylic acids and alcohols with 1 or more hydroxyl functions and with 1-8 carbon atoms are made in the chain, in addition to which the detergent contains the monoesters in an amount of 5-3O ^. 2. Detergent according to claim 1, characterized in that that the carboxylic acids are oxycarboxylic acids. 3. Detergent according to claim 1 or 5 »characterized in that that the free carboxyl groups of the monoesters are wholly or partially neutralized with alkali. 4. Detergent according to one of claims 1,5 and 6, characterized characterized in that the monoesters individually or together be added mixed. 5. Y / ash means according to any one of claims 1-4 * thereby marked that the monoesters individually or with the Salts of the carboxylic acids can be added mixed. 6. Detergent according to one of claims 1-4 »thereby marked that the monoesters are added individually or mixed with the free carboxylic acids. 7. Detergent according to one of the preceding claims, characterized marked that it contains polyhydric alcohols in an amount up to about $ 25, but preferably in one Amounts from $ 0.5-8.0, based on the weight of the carboxylic acids, are added. 8. detergent according to claim 7, characterized in that that the polyhydric alcohols from sorbitol, mannazucker, pentaerythritol, trimethylpropanol, trimethyethanol, hexanetriol, butanetriol (1,2,4) exist, 2QS852 / 0992