DE2230453A1 - BASIC MATERIAL APPROACH FOR DETERGENTS AND DETERGENTS - Google Patents

Description

The invention relates to a basic material approach; for laundry and cleaning agents consisting of citric acid or its salts and surfactants.

In detergents and cleaning agents, pentasodium tripolyphosphate is mostly used as a construction salt. Besides the effect As a complexing agent, the phosphate has the task of masking hardness components in the water and of removing dirt particles in suspension hold and increase the cleaning power of the detergent substance.

On the other hand, the polymer phosphates have disadvantages. It is known that they are subject to hydrolysis in aqueous solutions. Furthermore, there will probably be certain in stagnant waters living algae due to the phosphates in their growth excessively promoted. R.ian calls this process eutrophication. When dead algae are broken down by aerobic bacteria, it sinks the oxygen content of the water decreases very strongly. This disturbance of the biological balance has negative consequences for the fish population and the self-cleaning heating of the water. Therefore "one endeavors to reduce the phosphate content of V.'aschrnittsln not to increase beyond a certain percentage or to reduce it significantly compared to the previously usual proportions.

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309883/1209

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Wire address Tienckiser Li ci. \. Gihaf «nrhein

This inevitably leads to a significant reduction in washing power and means a step backwards in development modern detergents. There are therefore efforts to replace the polymer phosphates with phosphorus-free substances and at the same time to improve the cleaning power and the biodegradability of the mixtures.

For example, certain amino-polycarboxylic acids (Nitrilotriacetic acid, ethylenedianntetraesslgic acid) the phosphate content partially or completely replace. The disadvantages of these compounds are corrosive effects, uncertainties about biological ones Degradation times and products in sewage treatment plants and possible toxic effects of certain metal complexes.

In addition, the breakdown products of the amino compounds are suspected of being the phosphorus compounds as nitrogen nutrients comparable to cause eutrophication with all undesirable consequences. Therefore, the use of a phosphorus and nitrogen-free builders consisting only of carbon, hydrogen and oxygen are essential in detergents Contribute to keeping our environment clean.

Citric acid or its alkali salt (trinatrium citrate) is one such a framework. It is a component of many natural foods and an often used food additive non-toxic and also easily and completely biodegradable.

In addition to the well-known good complex binding properties against water hardness builders show citrates as well as other phosphate

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Substitutes as a detergent component in conventional detergent formulations the disadvantage of a lower detergency compared to phosphate. This is based on the work of P. Berth, G. Jacobi and E. Schmadel, Chemiker-Zeitung 95 (1971) p. 548 - · 553 as well as P. Berth and W.K. Fischer, Tenside 8 (1971) pp. 1-9 as well as CA. V / ilham and CL. Mehltretter, Journal Am. Oil Chem. Social VOL 48 Ho. 11 (1971) pp. 682-683.

Finally, in the German Offenlegungsschrift No. 2 026 739 generally all organic aliphatic and / or aromatic carboxylic acids, the hydrophobic part no longer than 8 carbon atoms, as well as their alkali salts or anhydrides claimed as structural substances in detergents and cleaning agents and cited formulations for this purpose on the mode of action As well as the detergency of these substances and the detergent formulations notified, however, no information is given made, also no washing results are compared to the technically known state of the use of sodium triphosphate or of known substitutes.

The previously given way of replacing the phosphate fraction removed from a given formulation with substitutes such as To replace aminopolycarboxylic acids or citrates, or else In the case of complete replacement, a fundamentally changed formulation with a high proportion in terms of the composition of the surfactants known common anion-active surfactants (e.g. linear alkyl benzene sulfonate = LAS), could not always lead to satisfactory washing results. The - often off Cost reasons - with large proportions selected additional introduction of a wide variety of synthesis and filler salts such as silicates, carbonates, Sulphates and acetates also could not contribute to an improvement or brought other problems with them (see B.

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dangerous high alkalinity for household use a pH of more than 12). Phosphate-based detergents, in which the phosphate is partially replaced by sodium carbonate, sodium metasilicate and / or sodium citrate in German Offenlegungsschrift No. 1 964 023 and 1 964 024 claimed.

A basic approach to detergents and cleaning agents has now been found which does not address the disadvantages outlined here. occur and with which an excellent washing effect is achieved, which is characterized by the fact that it consists of:

a) I - 40 parts by weight, preferably 4-8 parts by weight of citric acid or their salts

b) 1 part by weight of at least one nonionic surfactant consists.

Such a combination according to the invention of citrate and nonionic surfactant (= called Grundstoffansätζ) is surprising due to the interaction of its constituents as a detergent base, the conventional surfactant-triphosphate combinations with 3-5 parts of anionic surfactants, 1 part of nonionic surfactant and 1 part of soap for washing performance think.

As mentioned in the literature, citrate has a lower washing effect than phosphate when used in detergents and cleaning agents. This is particularly evident when there is a deficit of build-up salt, that is to say with amounts which are far below the ^{concentrations customary for V, T} a schmitt el. A clear fundamental

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additional improvement of the citrate in combination with one Nonionic versus phosphate was not expected. Phosphates are also produced when the conventional surfactant mixers are replaced an improved effectiveness against nonionic surfactants. However, unexpectedly, citrates are just as good as phosphates no longer inferior or even better. This is particularly evident when reducing the build-up salt concentration, which is desirable for eutrophication and price considerations:

While a reduction of the citrate by up to 50 % of its original amount used with the nonionic concentration remaining the same almost preserves the washing effect, it drops significantly as the amount of phosphate decreases, which is generally to be expected. The combination according to the invention, citrate + nonionic, is also less sensitive to higher water hardness and provides the same or lower incrustation values than comparable phosphate versions. It is therefore particularly suitable to be used as an additive to increase washing power under extreme water ratios.

The good effect with the nonionic surfactant used according to the invention is also obtained if 1-15% of the citric acid or its salts are replaced by alkali or ammonium salts of triphosphoric acid, saturated or unsaturated aliphatic or aromatic aminopolycarboxylic acids, polycarboxylic acids or phosphonic acids.

309883/1209

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Suitable nonionic surfactants are preferably those made from saturated or unsaturated ethoxylated fatty alcohols with a carbon chain of 10 to 20 carbon atoms and 3 to 25 moles of ethylene oxide per mole of fatty alcohol, like for example:

- C ₁ gC ₁ gn-alcohol with 10-25 mol of ethylene oxide, preferably

11-15 moles of ethylene oxide

- Combinations 1: 1
C ₁ gC ₁ gn-alcohol + 25 ethylene oxide Q ₁₂ -C ₁ gn-alcohol + 8 ethylene oxide

- Combinations 1: 1
Isotridecyl alcohol + 15 moles of ethylene oxide

+ 8 moles of ethylene oxide

+ 9-15 moles of ethylene oxide, preferably
10-12 moles of ethylene oxide

+ 9 moles of ethylene oxide alcohol + 9 moles of ethylene oxide

90 % C ₁₆ -C ₁₈ n-alcohol + 11 moles of ethylene oxide

10 % copolymer of propylene oxide 90 % + 10 % ethylene oxide

90 % C ₁₂ -C ₁₅ sec alcohol + 9 moles of ethylene oxide

10 % copolymer of propylene oxide 90 % + 10 % ethylene oxide

309883/1209

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The basic material formulation according to the invention can be used together with the usual constituents present in detergents and cleaning agents. So the basic material rate according to the Invention, used together with oxygen-releasing agents or active chlorine-containing bleaches such as alkali perborates, alkali hypochlorites or chlorinated cyanuric acid or their Salts, with other builders and fillers such as silicates, carbonates and other neutral salts, with enzymes, optical Brighteners, bactericides and foam inhibitors.

The addition of foam inhibitors in connection with the erfindurigsgeraässer Base material approach is often not necessary because the nonionic surfactants used according to the invention have little foam development. This is particularly advantageous for detergents and cleaning agents that are included in Drum washing machines and dishwashers can be used, with excessive display development being undesirable.

Other additives are graying inhibitors, e.g. carboxymethyl cellulose as well as the water-soluble alkali salts of synthetic polymers with free carboxyl groups.

In laundry detergents can rub the base material approach according to the invention To improve the grip, lipid-replenishing compounds can be added, e.g. the tallow fatty acid amide of ethanolamine or the copolymer of coconut fatty acid amide and ethylene or Propylene oxide.

Detergents and cleaning agents from the basic approach according to the invention can be solid, for example powdery, granulated or lumpy, especially spray-dried

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or in liquid or pasty form. For the purpose of better solubility, liquid preparations can contain solvents which are miscible with water, in particular ethanol and isopropanol and solubilizers such as the alkali metal salts of benzene, toluene, xylene or Contain ethylbenzenesulfonic acid.

In the manufacture of detergents from the invention Grundstoffansätζ can be done in such a way that you add a salt to the Citric acid, preferably trisodium citrate, directly as such with the nonionic surfactants and the other detergent ingredients or the aqueous paste-like !! Detergent mixture mixed or that one of these mixtures adds free citric acid, the mixture being the one for the Neutralization required excess of alkaline compounds, for example sodium hydroxide, contain have to. In this case the salt is formed during the manufacture or use of the agent.

The composition of detergents and cleaning agents from the The basic approach according to the invention corresponds approximately to the following Lineup for the type of one

a) solid detergents and cleaning agents:

1 - ¹ IO part by weight Building salt according to the invention 1 part by weight nonionic surfactant

0 - 6 parts by weight water-free or containing water of crystallization

Sodium perborate

0.5 - 2 parts by weight Sodium silicate (Na ₃ O: SiO ₂ = 1: 2)

0.1-10 parts by weight Other ^ (enzymes, brighteners, graying agents

inhibitor, stabilizer. Perfume, neutral salt, bactericide, dye, show inhibitor, Water)

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Such a solid detergent and cleaning agent can, for example consist of:

example 1

% Sodium citrate

% nonionic surfactant
% Perborate (tetrahydrate)

% Sodium silicate (Na ₃ O: SiO ₃ = 1: 2.0.) % Water

% Sodium sulfate

5 % other

b) liquid detergents and cleaning agents:

1 - ^ O parts by weight building salt according to the invention

1 wt . nonionic surfactant of the combination according to the invention

0.5 - 5 parts by weight Solubilizer (hydrotropes) 'Ό - 0.5 part by weight Others (brightener, graying inhibitor,

Stabilizer, perfume, dye, bactericide, foam inhibitor)

3-8 parts by weight water

Such a liquid detergent and cleaning agent can, for example, consist of:

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309883/1209

Wireframe ft R * »ni: i>: ■ 'L j. · ·.

Example 2

12 lbs sodium citrate '

12 % nonionic surfactant

8 % solution agent

1 % other
δ? % Water

c) Machine dishwashing detergent:

1 - ¹ JO part by weight Building salt according to the invention 1 part by weight non-technical surfactant of the erf inc \ ^ :, _Ο 3 according to

combination

1-30 parts by weight Natriuranetasilicate v / water-free (SiO ₂ : Na ₂ O = 1: 1) 0-12 parts by weight sodium
0 - H parts by weight Other "(neutral salt, chlorine carrier)

Such a machine dishwashing agent can beir.j.ielsweice consist of:

Example 3

60 % liatric citrate

3 2 nonionic surfactant of the invention. ^ E: r, external combination 30 % sodium rietasilicate

5 % sodium carbonate

2 % other

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Wire address Banck'S'-T LiKi.vijshafenrhDiii

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Containing the cleaning power of detergents and cleaning agents the basic material approach according to the invention and for comparison the usual polyphosphate-based detergent formulations, was carried out on standardized textile samples made of cotton, which were treated with a mixture of kaolin, carbon black, iron oxide and Wool fat (skin fat) had been soiled in a laboratory washing machine (Linitest) checked.

The experimental ash media had the following general additional features (given in %):

Table ι

I II III

non-chemical surfactant 8 8 δ

Build-up calc kO . 30 20

Sodium silicate
(Na ₂ O: SiO ₂ ■ - 1: 2)

Carboxymethyl cellulose * l, 0 *), 0 * ί, 0

Ethylenediamine tetra- _n , - _no

acetic acid ^{u> t?} ">> ^J?;>

Perborate

(Tetrahydrate) ^ OO

Sodium sulphate 16 26 36

I - III identify detergents with different concentration of salt. As a standard used was a V'aschfiiittelzusanunensetzung according to Table I, however, notwithstanding this, a content of 15; "a surfactant mixture (! 9 i> linear alky benzene sulfonate LAS = + 3% + 3% non-ionic surfactant soap).

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No brightener was added in order not to influence the results of the white value determination. The detergent concentration was 5 g / l, the weight ratio of textiles to washing liquor 1: HO and the washing time of 30 minutes was made up of 15 minutes heating time and 15 minutes residence time at 90.degree. The tap water had a hardness of 19 ° DH. The whiteness of the fabrics, rinsed three times and then dried, was measured photometrically with the Elrepho whiteness measuring device from Zeiss.

The results of the washing tests are summarized in Table II. The values given (average of 3 tests) are calculated using the following equation:

% WK = % WG - % WG,

where mean:

% WK = % whitening power

£ WG = % whiteness of the washed fabric % WG. = % Whiteness of the unwashed fabric

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AUPBAUSALZ

Example surfactant trisodium cltrate tripolyphosphate

No. I. II III I II III

40 % 30 $ 20 $ no % 30 % 20 %

Standard 9 % LAS (100 %)

3 % Cig-CjS-n-alcohol 20 15 15 22 18

+ 11 ethylene oxide 3 % Na tallow soap

+ 11 ethylene oxide

1 % copolymer of 28 26 25 26 22 90 % propylene oxide + 10 % ethylene oxide

Ca) I ' '"

^ f ^ ₊ ¹ J <, * P ^ .. n ^ ^ 30 28 28 26 23

co, _-

QQ V, 'Jl Qf CS j,

JJ " ⁺ 25 ethylene oxide

__> 4% C ₁ 2-C ₁ 6-n-alcohol

■ ro ⁺ 8 ethylene oxide

ο

co M 8% C-, ο

CO

CO

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As Table 2 shows, is the combined one according to the invention Grundstoffansätζ in its cleaning effect the cleaning effect of an agent based on sodium nitripolyphosphate clearly superior. Dj it is especially true towards one typical conventional detergent mixture (standard) with a large proportion of anionic surfactants representing the state of the art.

The test results clearly show the sharp drop the whiteness values with reduced phosphate concentrates; in contrast to this is the consistently good reflectivity with a strong reduction in the citrate content.

This very desirable effect makes it possible in particular to use those produced with the basic material formulation according to the invention Detergents and cleaning agents in hard water, which uses part of the citrate to mask hardness, but always sufficient amounts of citrate to form a die Has a washing effect promoting effect available. In addition, such a washing and washing machine according to the invention is thereby achieved From a cost-performance standpoint, detergents are even more important in combating Preserve the eutrophication of our lakes.

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Claims (2)

. ". Remote call (0G21) -T.gc- ι *} O Q Γ | / CO - 668 - Telegraph 04 G4P72 Z t O U 4 D O Wire address B'-r \ cK: rer Ludvyigshafcnrhein - 15 - Claims (l) Basic set of detergents and cleaning agents, consisting of from citric acid or its salts and surfactants, characterized in that it consists of a) 1 - JJO parts by weight, preferably 4-8 parts by weight Citric acid or its salts b) 1 part by weight of at least one non-ionic surfactant consists. 2. Grundstoffansätζ according to claim 1, characterized in that 1-15% of the citric acid or its salts is replaced by alkali or ammonium salts of triphosphoric acid, saturated or unsaturated aliphatic or aromatic aminopolycarboxylic acids, polycarboxylic acids or phosphonic acids. 3 basic material approach according to claim 1 and 2, characterized in that that the surfactant from a saturated or unsaturated ethoxylated fatty alcohol -with a carbon chain of 10 up to 20 carbon atoms and 3 to 25 moles of ethylene oxide per mole of petalcohol or of mixtures of such fatty alcohols. 309833/1209