DE2743607A1 - Aqueous cleaning agent solutions - Google Patents

Description

CHEMISCHE WERKE HÜLS AG - RSP PATENTS -

■ i-

4370 Marl, 26.O9.77

Our sign; O.Z. 2990 Aqueous detergent solutions

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7 drawings

3 - OZ 2990

09/26/77

Aqueous solutions of cleaning agents containing electrolytes are used on a large scale in industry and other commercial operations. Such aqueous solutions are usually added to solubility-improving substances, so-called hydrotropes. The task of the hydrotropic substances is to increase the solubility of the surfactants in the presence of the electrolytes, so that comparatively more highly concentrated solutions can be prepared which maintain homogeneity during storage (approximately between 0 and 0 ° C.). The production of more concentrated solutions is recommended, on the one hand, to avoid large volumes during transport and, on the other hand, to provide agents with an optimal cleaning effect.

From US-PS 2 $ 81,677 it is already known, aqueous solutions containing electrolytes detergent short-chain alkyl benzene, such as cumene, add as hydrotropes.

However, the hydrotropic effect of cumene sulfonate is with application relatively high electrolyte concentrations unsatisfactory, so that no storable electrolyte-containing cleaning agents can be produced.

In addition, aqueous solutions of cleaning agents containing electrolytes are often used in machine cleaning processes. They then usually contain ethylene oxide-propylene oxide adducts as surfactants, since other nonionic and especially anionic adducts foam too much. Are ethylene oxide-propylene oxide adducts however, not always sufficiently biodegradable.

It has now been found that the disadvantages of the prior art are overcome by containing aqueous cleaning agent solutions Customary electrolytes, which are characterized by a content of alkyl glycol sulfates of the formula

RO _{- CH 2} - CH ₂ - 0 - SO ₀ M, "in the

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R is a saturated alkyl radical having 3 to 7 carbon atoms and M means Na or K.

The aqueous cleaning agent solutions expediently contain additionally conventional surfactants in concentrations of 0.1 to 70 percent by weight.

In a further preferred embodiment of the invention is the electrolyte content of the detergent solution at least 10 percent by weight. The content of alkyl glycol sulfate is in particular 5 to 20 percent by weight.

The electrolyte content of the cleaning agent solutions can be up to 30 percent by weight.

A very high electrolyte content will be assigned a surfactant content in the lower and middle specified range, while one in the case of very high surfactant contents, the electrolyte contents can be left in the lower and middle specified range.

Alkyl glycol sulfates to be used according to the invention are suitable n- and iso-compounds, such as n-propyl glycol sulfate, n-butyl glycol sulfate, n-pentyl glycol sulfate, n-hexyl glycol sulfate, n-heptyl glycol sulfate, iso-propyl glycol sulfate, iso-butyl glycol sulfate , iso-pentyl glycol sulfate, iso-hexyl glycol sulfate, iso-heptyl glycol sulfate, but preferably n-butyl glycol sulfate and n-hexyl glycol sulfate at.

The following surfactants that can usually be used in cleaning agent solutions are: alkylarylsulfonates, olefin sulfonates, alkyl sulfates, Alkyl ether sulfates, as well as nonionic surfactants such as oxethylates of fatty acids, fatty acid amides, fatty alcohols or alkyl phenols, also oxypropylene-oxyethylene addition products, alkanesulfonates, Alkyl phosphates, alkyl ether phosphates, amine oxides. As electrolytes can be used in aqueous cleaning agent solutions

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common compounds such as NaOH, KOH, complex phosphates, silicates, gluconates, NTA, EdTA, poly (hydroxicarboxylates), organophosphonic acids, Alkali salts of polycarboxylic acids.

The technical progress achievable with the present invention Compared to the relevant prior art, there is on the one hand that cleaning agent solutions for use in machine Cleaning processes can be made available which foam extremely weakly and which are also readily biodegradable Contains surfactants.

The alkyl glycol sulfates to be used according to the invention take over in aqueous solution containing electrolytes, namely, the role of ten- sids by preventing the wetting of hard surfaces (contact angle measurement) improve the solution considerably. The alkyl glycol sulfates are also readily biodegradable due to their constitution.

Another technical advance achieved according to the invention is the ability to produce detergent solutions with higher concentrations of electrolytes and common surfactants, than is possible when adding prior art hydrotropic substances (such as cumene sulfate). It is therefore possible according to the invention Surprisingly, storable aqueous cleaning agent solutions with high concentrations of electrolytes and To provide surfactants.

Typical basic formulations, which can be produced according to the invention and can be stored between temperatures from 0 ° to h0 ° C., are listed below:

a) 0.1 to 5 percent by weight of alkyl benzene sulfonate

< ^C 11 - S ₃ )

10 to 18 weight percent NaOH

5 to 20 percent by weight butyl glycol sulfate The remainder is 100 percent by weight water

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These recipes are clearly homogeneous down to 0 C. Will the butyl glycol sulfate by cumene sulfonate or homologues exchanged, the approaches are cloudy inhomogeneous; Use: industrial cleaner.

b) 0.1 to 5 percent by weight of fatty alcohol ether sulfate 13 to 23 weight percent NaOH

5 to 20 percent by weight butyl glycol sulfate The remainder to 10O percent by weight water

This recipe is clearly homogeneous down to 0 ° C. Is the butyl glycol sulfate replaced by cumene sulfonate or homologues exchanged, the approaches are cloudy inhomogeneous; Use: foam-active alkaline cleaners.

c) 0.1 to 3 »0 percent by weight fatty amine oxyethylate 15 to 20 percent by weight NaOH

3 to 20 percent by weight butyl glycol sulfate The remainder is 100 percent by weight water

This recipe is clearly homogeneous down to 0 ° C. Is the butyl glycol sulfate replaced by cumene sulfonate or homologues replaced, the approaches are cloudy inhomogeneous; Use: alkaline industrial cleaners.

d) 0.1 to 5 »0 percent by weight of alkylbenzenesulfonate

< ^C 11 - ^C 13 ^} 0.1 to 2.0 percent by weight nonylphenol oxyethylate

(9 EO)

20 percent by weight NaOH 20 percent by weight butyl glycol sulfate 100 percent by weight water

This recipe is clearly homogeneous down to 0 ° C. Is the butyl glycol sulfate replaced by cumene sulfonate or homologues replaced, the approaches are cloudy inhomogeneous; Use: alkaline industrial cleaner.

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12th until 5 until rest to

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e) 0.1 to 5.0 weight percent alkyl benzene sulfonate

< ^C 11 - ^C 1 ₃ )

0.1 to 2.0 percent by weight nonylphenol oxyethylate

(9 EO) 20 to 30 percent by weight tetrapotassium pyrophosphate

phat

5 to 20 percent by weight butyl glycol sulfate The remainder is 100 percent by weight water

This recipe is clearly homogeneous down to 0 ° C. Is the butyl glycol sulfate replaced by cumene sulfonate or homologues replaced, the approaches are cloudy inhomogeneous; Use: alkaline industrial cleaner.

f) 0.1 to 50 percent by weight of propylene oxide

len adduct

7.5 to 15 percent by weight NaOH 3 to 15 percent by weight hexyl glycol sulfate The remainder is 100 percent by weight water

This recipe is clearly homogeneous from 0 to ^ O C. If the hexyl glycol sulfate is replaced by cumene sulfonate or Replaced homologues, the approaches are cloudy inhomogeneous; Use: low-foaming alkaline industrial cleaner.

g) 0.1 to 5 »0 percent by weight of fatty alcohol ethoxylate

(10 EO) 10 to 20 weight percent NaOH

3 to 15 weight percent hexyl glycol sulfate Remainder to 100 percent by weight water. This recipe is clearly homogeneous from 0 to ^ O ° C. If the hexyl glycol sulfate is replaced by cumene sulfonate or Replaced homologues, the approaches are cloudy inhomogeneous; Use: alkaline industrial cleaner.

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The examples and figures given below serve to further explain the invention and what can be achieved with it technical progress.

Examples 1 to 7

1 Table I. * - - - - - Alkyl benzene sulfonate - - 0.8 - - - - Fatty alcohol ether sulfate - 1.4 - - - - - 2-ethylhexanol sulfate - - - 2.5 - 1 - Nonylphenol oxyethylate - - 7.5 - 3 - 1 Fatty amine oxyethylate 7th - 20th 7.5 7.5 5 5 Butyl glycol sulfate 20th , 5 7.5 - 20th 20th 20th 20th Sodium hydroxide - 20th - - H H Nitrilotriacetate - Remainder to 100 Vi water

The cleaning agents listed can be stored clearly and homogeneously at temperatures up to 5 C.

If cumene sulfonate and homologues are used, the corresponding Approaches cloudy inhomogeneous.

Figure 1 contains the clear melting points depending on the addition of tetrapotassium pyrophosphate and hydrotropes for the following recipe:

2.5 percent by weight Na-alkylbenzenesulfonate

< ^c ii - ⁰ I ₃ )

0.5 percent by weight nonylphenol oxyethylate (9 EO) 5 to 30 percent by weight tetrapotassium pyrophosphate χ percent by weight hydrotropic

The remainder is 100 percent by weight water

As can be seen, the preparation to 10 ⁰ C a homogeneous, highly concentrated solutions of tetrapotassium with cumene sulfonate is not possible, however, achieved with the addition of 10 percent by weight of butylglycol.

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Figure 2 contains the clear melting points depending on the addition of NaOH and hydrotropes for the following recipe:

2.5 percent by weight Na-alkylbenzenesulfonate

< ^C 11 - ^C 13 ⁾

0.5 percent by weight nonylphenol oxyethylate (9 E0)

0 to 20 weight percent NaOH

χ Weight percent hydrotropic

The remainder is 100 percent by weight water

As can be seen from Figure 2, up to 20 C homogeneous, Do not prepare highly concentrated solutions with cumene sulfonate on NaOH; However, this succeeds when using butyl glycol sulfate.

Figure 3 contains the clear melting points depending on the addition of hydrotropes for the following recipes:

1: 2.5 percent by weight Na-alkylbenzenesulfonate

< ^C 11 - ^C 13 ⁾ 0.5 percent by weight nonylphenol oxyethylate

(9 EO) 15 weight percent NaOH

χ Weight percent hydrotropes

The remainder is 100 percent by weight water

2; 2.5 percent by weight Na-alkylbenzenesulfonate

(C ₁₁ - C ₁₃ )

0.5 percent by weight nonylphenol oxyethylate

(9 EO) 30.0 weight percent tetrapotassium pyrophosphate

χ Weight percent hydrotropes

The remainder is 100 percent by weight water

A comparison of curves 1 (for formulation 1) shows that at the high NaOH concentration of 15 percent by weight cumene sulfonate is salted out. With butyl and hexyl glycol sulfate, however, it is possible to produce clear solutions even below room temperature obtain.

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If you compare curves 2 (recipe 2) with one another, the result is that at the high concentration of 30 percent by weight Tetrapotassium pyrophosphate with cumene sulfonate at room temperature no clear solutions are obtained. With 5 to 10 percent by weight Butyl glycol sulfate is also formed below room temperature clear solutions.

Figure k shows the homogeneous phase between the cloud and clear melting points depending on the addition of NaOH for the following recipe:

5.0 percent by weight polypropylene oxide poly

ethylene oxide (block polym.) 5.0 percent by weight hydrotropes χ Weight percent NaOH

The remainder is 100 percent by weight water

As can be seen, in formulations with nonionic surfactants, the presence of hexyl glycol sulfate causes a homogeneous phase between 0 and
weight percent.

between 0 and ^ OC even with NaOH concentrations above 5 Ge Figure 5 shows the homogeneous phase between the cloud and clear melting points depending on the addition of NaOH for the following recipe:

5.0 percent by weight fatty alcohol polyglycol ether

(C ₁₂ _ _{ilt -fatty} alcohol, 10 E0) 5 »0 percent by weight hydrotropes χ percent by weight NaOH

The remainder is 100 percent by weight water

It is found that in this formulation with nonionic surfactants, too, the presence of hexyl glycol sulfate in the important temperature ranges from 0 to k0 C, even at NaOH concentrations of over 10 percent by weight, causes a homogeneous phase, while cumene sulfonate fails at such concentrations.

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FIG. 6 shows the cloud points as a function of the addition of NaOH and Na metasilicate for the following recipe:

50 percent by weight fatty alcohol ether sulfate

(C ₁₂ _ _iZr alcohol)

5 »0 percent by weight hydrotropes χ percent by weight electrolytes

The remainder is 100 percent by weight water

As can be seen, the hydrotropic effect of butyl glycol sulfate is far superior to that of cumene sulfonate.

FIG. 7 shows the lowering of the contact angle in aqueous solutions of NaOH and butyl glycol sulfate. The contact angle measurements are a measure of the wettability of hard surfaces (glass, porcelain, metal, etc.). High values mean good wettability. It should be noted here that contact angle reductions above 70 # can no longer be measured. It can be seen from this diagram that at a NaOH concentration of only h ⁰ Jo a Butylglykolsulf at concentration as low as $ 5 already contact angle decreases of from about 60 ° / t> result. Even solutions with 1.5 ^ NaOH and k <$ butylglycol sulfate still show good wetting. The butyl glycol sulfate is therefore able to take on the role of the surfactant in electrolyte solutions itself, so that conventional surfactants do not need to be added or only in small amounts.

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Claims (2)

O.Z. 2990 9/26/77 claims 1. Aqueous cleaning agent solutions containing conventional electrolytes in concentrations of at least 5 percent by weight, characterized by a content of alkyl glycol sulfates of the formula RO _{- CH 2} - CH - 0 - SO M, in the R is a saturated alkyl radical with 3 to 7 carbon atoms and
M means Na or K. 2. Aqueous detergent solutions according to claim 1, characterized in that they additionally contain conventional surfactants in concentrations of 0.1 to 7> 0 percent by weight. 3 · Aqueous cleaning agent solutions according to claims 1 and 2, characterized in that the electrolyte content is at least 10 percent by weight. k. Aqueous cleaning agent solutions according to Claims 1 to 3, characterized in that the content of alkyl glycol sulfates is 5 to 20 percent by weight. 9098U / 0339 ORIGINAL INSPECTED