DE1034307B - cleaning supplies - Google Patents

Description

It has been found that detergents containing an ion detergent and an acyclic alkyl monoamine, which has one, and only one, alkyl group having more than 6 carbon atoms are excellent Possess properties.

In the course of fundamental research into the nature of the washing process, it was found that it there are certain acyclic, aliphatic amines which are not detergents in the sense that they by themselves, if alone used by themselves, will show any significant cleaning effect, but if they are in the solutions ion detergents (i.e. anion or cation detergents) are capable of The cleansing effect of the latter can be increased considerably. Apparently these amines are able to to form molecular complexes with the detergents and to increase their effectiveness in any way.

It is possible to determine the formation of the molecular complexes by observing the behavior of surface films of the amine on the surface of an aqueous solution into which the detergent had been injected demonstrate. As the results of surface investigations show, it appears that molecular complexes are involved in the Interface between air and liquid between one or more molecules of detergent and one or more molecules of the amine, depending on the circumstances in certain molecular proportions. The exact nature of these molecular complexes has not yet been fully elucidated, but they can be both with Soap as well as synthetic ion detergents can be made, especially eye-dropping ones Effects can be achieved. In some cases, the washing effect can be increased several times in this way will.

Possible acyclic alkyl monoamines are primary, secondary or tertiary amines, their alkyl group consists of a straight or branched chain with more than 6 carbon atoms, in particular amines whose alkyl group contains 7 to 12 carbon atoms are suitable. You get good results with primary n-alkylamines, such as. B. n-hepthylamine, n-octylamine, n-decylamine and n-dodecylamine, as well but also with dimethyl-n-decylamine. During examinations with the surface balance it was found that such amines have a marked tendency to form of molecular complexes with both anion and cation detergents of various types.

In most cases it is expedient to incorporate the amine into the detergent solution, for example by dissolving (this is sometimes possible even if the amine is more or is less insoluble), but it is not exactly necessary and it is even possible to add the amine to the one to be washed cleaning supplies

Applicant:
Monsanto Chemicals Limited, London

Representative: Dr. M. Eule, patent attorney,
Munich 13, Kurfürstenplatz 2

Claimed priority:
Great Britain 19 February 1953 and 22 January 1954

Mageret Anne Anderson Wilson, Leven, Fife

(Great Britain),
has been named as the inventor

Apply material and then add the detergent solution.

In the context of the invention, both soap and synthetic ionic detergents can be used as ion detergents in question, although the invention is of particular value in the use of synthetic anion detergents is, such as B. in the case of alkyl aryl sulfonates and the primary alkyl sulfates. As a cation detergent can, for example, a quaternary ammonium salt, such as. B. cetyltrimethylammonium bromide or cetylpyridinium bromide, be used.

If the amine is easily soluble in water or in the detergent solution, then the preparation of the preparation is necessary a simple thing. Otherwise it may be appropriate to use the amine in the form of a soluble derivative which it is then made free to introduce. So z. B. are the long-chain alkylamines, such as. B. that n-decylamine and n-dodecylamine, not very soluble in water or detergent solutions; but they can in the form of their easily soluble salts, especially the hydrochlorides, introduced and from these by means of alkalis, such as B. sodium carbonate, can easily be made free. If you first add the hydrochloride in the detergent solution and then dissolves the alkali, the amine is released in as highly dispersed a state as when it was introduced of the amine as a free base.

As already indicated above, it is also possible to add the amine to the material to be cleaned before it is introduced of the ion detergent, in which case the amine, for example, in the form of an aqueous solution or in the form of the aqueous solution of a water-soluble derivative, which is subsequently in a manner converted into the free base similar to the one described above

809 577/411

is migrated, comes to use. It is even a perforated plunger in the beaker one % possible to move the amine to the material to be cleaned up and down for a period of 3 minutes ψ _{: together} with a contaminating substance, which and with 60 strokes per minute. The washed material was then washed out of the detergent solution by means of a Buchner filter, such as the one when processing 5 filters, and rinsed by placing it in 300 cm ^{3 of} wool Here the amine can be added directly to the oil of distilled water at 40 ° C, also in a beaker, so that when washing with glass of 500 cm ³ , introduced and the perforated immersion *

Using a suitable ion detergent solution, the active flasks in this beaker were moved up and down the detergent in the manner according to the invention for 1 minute. The material was then recently filtered off ΐ is increased. Obviously, there are also various io and in a second batch of 300 cm ³ of distilled water, other methods in which the amine either in a beaker of 500 cm ³ (this time at 3O ⁰ C) such or in the form of a derivative of which is introduced, the plunger being subsequently freed in t amine for 1 minute; Operation was. The material was then filtered off, and "!""Provided that the detergent and the amine currency for 30 minutes at 70 ⁰ C dried. Was allowed to Prorend the washing process are brought together 15 domestic product, that is, the washed and rinsed material, wherein" If you achieve the improved cleaning room humidity you get damp again and weighed it. '"'""J effect. It was then placed in a small glass extraction column. ■;«;:;

The required amount of amine in proportion to that packed and carefully ^{extracted with 10 cm 3 of} ether. "

The amount of ion detergent used depends on the The eluate was evaporated and the residue was weighed,! turned away substances; as a rule, a good 20 is obtained, which means that the amount of

Results when much less amine was received as a detergent remaining polluting substance. ''

is present. If the amine of the detergent solution is used directly in the following examples

incorporated, good results will be achieved with an amine content. of 10% based on the weight of the detergent, notice similar circumstances. These differences are '

and achieved with a little less. If necessary, however, on the order of the experimental the proportion of amine can also be considerably lower, and deviations, as is the case with experiments of this type down to 2% or less. In general it is to be expected, especially when different woolen Proportion of 3 to 20% suitable, but this pattern can be treated also be more than 20%. Will the amine too

Remove the cleaning material before the ion detergent

then it is possible to use a lot less amine. A sample of

because the amine on the surface of the wool material is concentrated at 3.43% by weight. In this case, an amount of 'liquid paraffin is soiled and with a 0.1% strength about ^x / ₄ up to about 1%, based on the weight of the washing aqueous solution of sodium cetyl sulfate, as previously referred to, is often sufficient. 35 described, washed. That on the material after the

It is often convenient if the amine and laundry detergent residual contaminants totaled up medium to a ready-to-use mixture still combined to 81.9% of the original amount. Of the be, for example in solid form. The experiment was made with a sample of the same material

The present invention is of particular value using the same detergent solution that for washing wool and other protein-containing 40 to which 0.1% sodium carbonate was added, Textiles, also for washing synthetic, repeated; the remaining contaminant then amounted to Nitrogen-containing textiles, such as. B. polyamide to 70.2% of the original amount, fibers. The washing attempt was then carried out with another

The special advantages are due to the pattern from the same lot of the soiled wool standing Examples of the details explained; this additional material was repeated using a games describe the washing of a woolen material, 0.1% aqueous solution of sodium cetyl sulfate, in which for experimental purposes with liquid paraffin which first 0.01% n-decylamine hydrochloride and has been polluted. The efficiency of the washing before then 0.1% sodium carbonate had been dissolved ganges was determined by its use. This time the remaining dirt was only the detergent in the presence and in the absence of the 50-24.8% of the original amount, amines according to the invention.

The wool material for use in washing Beismel 2 ^:

try was prepared in the following way:. ΐ

A woolen fabric was made at an angle of 45 °.

cut into strips to form a chain, in a Schnitzel 55 material, which is 3.36%, based on its weight, machine was chopped up into lengths of about 0.2 mm and liquid paraffin was stained, like 'ΐ

then stirred into hot water until it turns into the previously described with a 0.1% aqueous solution individual fibers had dissolved. These were then added by sodium cetyl sulfate, which also contained 0.1% sodium carbonate '

first with ether and then extracted with alcohol to get the contained washed. That after washing on the; ·

in these solvents soluble contaminants to 60 material remaining residual contaminants amounted to ί

remove. The remaining fiber mass made up 70.2% of the original amount. "

The wool material used in the experiments, which was then repeated with the washing experiment, with

about 3 ¹ Z ₂ ⁰ Zo. ^au f are by weight liquid paraffin wear of n-decylamine hydrochloride to the spotted J "

in ethereal solution (the ether subsequently became material. - ΐ

evaporated) has been artificially soiled. 65 As a result, another pattern was made out of the same _; «|

The wool material was then taken to a standard washer batch of the soiled material and placed in ';^{; Si}

such was subjected in the following manner: An amount of 150 cm ^{3 of} a 0.02% solution of n-decylamine hydrog of the material was placed in 300 cm ^{3 of} chloride detergent solution at 60 ° C. This solution was introduced 1 minute at a temperature of 60 ° C. in a beaker by means of the 500 cm ³ content used in the washing experiment. An electric motor gave 70 perforated plungers stirred. The plunger was

1 Liquid paraffin n-decylamine Remaining liquid 2 in spotted in liquid Paraffin after 3 material paraffin To wash 4th Weight percent % % test 3.22 67.7 test 3.45 2 37.5 test 3.43 3 41.6 test 3.38 5 40.6

Example 4

A sample of paraffin prepared in the above manner and at 3.45% by weight liquid paraffin Soiled wool material was treated with a 0.25% aqueous solution of a commercially available detergent mass from 40 percent by weight sodium dodecylbenzenesulfonate and 60% sodium sulfate using the described procedure washed. The experiment was carried out with a sample from the same batch of material using the same detergent solution to which 0.1% sodium carbonate had been added.

Then the washing test was carried out with other swatches from the same lot of the soiled wool material repeatedly, using a 0.25% aqueous solution of the same commercially available detergent, which various additives had been incorporated, namely:

Test 1: 0.01% n-decylamine,

Test 2: 0.01% n-decylamine and 0.1% sodium carbonate,

Test 3: 0.01% n-decylamine hydrochloride and 0.1%
Sodium carbonate,

Test 4: 0.01% n-dodecylamine hydrochloride and 0.1% Sodium carbonate.

IO

then stopped, and 150 cm ³ of a 0.2 ° / ₀ aqueous solution of sodium cetyl sulfate, which also contained 0.2% sodium carbonate added (also at 60 ° C) to give 300 cm ³ of a detergent solution of the same Detergent concentration as obtained in the initial standard experiment. The standard washing test was then carried out using this 300 cm ³ detergent solution. This time the contaminant residue was only 15.4 per _{cent of} the original amount.

The weight ratio of n-decylamine hydrochloride the detergent used is 1:10.

Example 3

In this example the n-decylamine became the contaminant itself incorporated, so that the former during the washing process with the detergent was united.

A sample of wool material prepared in the above manner and soiled with liquid paraffin alone was washed in the manner described with a 0.1% strength aqueous solution of sodium cetyl sulfate. Other soiled patterns were made in a similar manner (made from the same wool) using liquid Paraffins with a content of n-decylamine of 2 or 3 and 5%, based on the weight, produced and in washed the same way. The amine used in the washing tests and the ionic detergent used were in the ratio of 1: 222 and 1: 150 and 1: 93 by weight.

The following results were obtained:

The following results were obtained:

Remaining liquid

Paraffin after

To wash

0 / / 0

Without additives 85

With 0.1% sodium carbonate 67.8

Test 1 10.5

Test 2 "6.4

Test 3 13.6

Test 4 36.8

Example 5

A sample of paraffin prepared in the above manner and 3.58% by weight liquid paraffin Soiled wool material was washed using the procedure described, with a 0.25% aqueous solution of a commercial detergent made from 40 percent by weight sodium dodecylbenzenesulfonate and 60% sodium sulfate to which 0.1% sodium carbonate had been added.

The washing test was then carried out with other swatches from the same lot of the soiled wool material repeatedly, using a 0.25% aqueous solution of the same commercially available detergent, 0.1% sodium carbonate and 0.01% hydrochloric acid n-octylamine or n-decylamine or n-dodecylamine had incorporated.

The following results were obtained:

Remaining liquid

Paraffin after

To wash

Without amine 39.0

With n-octylamine 2.0

With n-decylamine 3.8

With n-dodecylamine 27.6

The results of another, similar experiment also showed the superiority of n-octylamine versus n-decylamine and n-dodecylamine.

Example 6

A sample of paraffin prepared in the above manner and 3.54% by weight liquid paraffin Soiled wool material was washed using the procedure described, with a 0.25% solution of a commercial detergent made from 40 percent by weight sodium dodecylbenzenesulfonate and 60% sodium sulfate to which 0.1% sodium carbonate had been added.

The wash test was then carried out with a different swatch from the same lot of the soiled wool material repeatedly using a 0.25% aqueous solution of the same commercially available Detergent to which 0.1% sodium carbonate and 0.01% n-heptylamine had been incorporated.

The amount left on the material after washing

residual dirt was 50.7% of the original amount if n-heptylamine was not used compared to only 7.1% when using the amine.

Example 7

Further washing tests were carried out using exactly the same procedure as in Example 6, except that 0.01% dimethyl-n-decylamine was used in place of the n-heptylamine and that the The wool material used was soiled with 3.37%, based on weight, of liquid paraffin.

The liquid paraffin remaining on the material after washing was 51.9% of the original Amount if no dimethyl-n-decylamine was used. When using the tertiary amine, on the other hand, only 19.9% of the original amount of liquid remains Paraffins.

A sample of prepared in the manner described above and containing 3.36% by weight liquid paraffin soiled wool material was washed with a 0.25% aqueous Solution of the commercial detergent mentioned in Example 4 using the normal procedure.

A second experiment in which 0.1% sodium carbonate was incorporated into the detergent solution, was also carried out.

The washing test was then repeated with another swatch after applying n-Decylamine hydrochloride on the soiled material, using exactly that described in Example 2 Method in which the detergent solution this time contained 0.1% sodium carbonate dissolved in order to free the amine do.

Another attempt was similarly soiled with another swatch from the same batch Materials executed, this time using n-dodecylamine hydrochloride instead of n-decylamine hydrochloride was used (again as described in Example 2, as a 0.02% aqueous solution).

The washing test was then carried out with two more swatches from the same batch of soiled wool material repeated. The first of these tests used the same detergent solution that used 0.1% sodium carbonate had added, in the second test, the same detergent solution, which was 0.01% n-decylamine hydrochloride and added 0.1% sodium carbonate was used.

The following results were obtained:

Remaining liquid

Paraffin after

To wash

Vo

Initial attempt 83.7

With 0.1% sodium carbonate 81.0

With 0.01% n-decylamine hydrochloride and 0.1% sodium carbonate 25.1

Example 11

A sample of prepared in the manner described and at 3.54% by weight, liquid Paraffin-soiled wool material was washed in the manner described, with a 0.1% strength aqueous solution of cetylpyridinium bromide to which 0.1% sodium carbonate had been incorporated.

The washing test was carried out with another sample from the same batch of soiled wool material

Repeatedly using a similar detergent These tests gave the following results: 30 solution containing both 0.01% n-decylamine hydrochloride

as well as the sodium carbonate had added.

The liquid paraffin remaining on the material after washing was 67.6% of the original Amount if no n-decylamine hydrochloride was used. When using the amine hydrochloride

Remaining liquid

Paraffin after

To wash

Initial attempt:

a) Without sodium carbonate

b) With 0.1% sodium carbonate. With n-decylamine hydrochloride ... With n-dodecylamine hydrochloride.

Example 9

84.2 67.8 10.3 14.7

40

A sample of prepared in the manner described and liquid at 3.43% by weight Paraffin soiled wool material was washed using the standard procedure with a 0, l% aqueous solution of ordinary soap, which one 0.1% sodium carbonate had been incorporated.

The washing test was carried out with another sample from the same batch of soiled wool material repeatedly, using a similar detergent solution, which is 0.01% n-decylamine hydrochloride had also incorporated.

The residual liquid paraffin remaining on the material after washing was 92.7% of the original Amount if no n-decylamine hydrochloride was used. When using the amine hydrochloride only 8.9% of the liquid paraffin remained.

Example 10

A sample of what has been prepared in the manner described and wool material stained with 3.43% by weight liquid paraffin was disclosed in US Pat Way washed with a 0.1% aqueous solution of cetyltrimethylammonium bromide. That residual soil residue on the material after washing was 83.7% of the original Lot.

60

65

70 only 43.7% of the liquid paraffin remains on the material.

Claims (7)

Patent claims: 1. Cleaning agent, characterized in that the same is an ion detergent and an acyclic Alkyhnonoamin, which has one, and only one alkyl group with more than 6 carbon atoms, contains. 2. Cleaning agent according to claim 1, characterized in that the acyclic alkyl monoamine is a Contains an alkyl group of 7 to 12 carbon atoms. 3. Cleaning agent according to claim 1 or 2, characterized in that the acyclic alkyl monoamine is a primary n-alkylamine, preferably n-heptylamine, n-octylamine, n-decylamine or n-dodecylamine. 4. Cleaning agent according to claim 1 or 2, characterized in that the acyclic alkyl monoamine Is dimethyl-n-decylamine. 5. Cleaning agent according to one of claims 1 to 4, characterized in that the ionic detergent Ordinary soap, the sodium salt of a primary alkyl hydrogen sulfate, sodium cetyl sulfate, an alkylarylsulfonate, the sodium salt of a dodecylbenzenesulfonate or a cation detergent of the quaternary ammonium salt type, e.g. B. Cetyltrimethylammonium bromide or cetylpyridinium bromide. 6. Cleaning agent according to one of the preceding 'claims, characterized in that the proportion of the acyclic alkyl monoamine is 3 to 20% based on the weight of the ionic detergent, amounts to. 9 10 7. Cleaning agent according to one of the previously considered publications: going claims, characterized in that Swiss Patent No. 193 628, the same ionic detergent and acyclic alkyl US Pat. No. 2,471,645; monoamine in the form of an aqueous solution of the same Lüttgen, »organic and inorganic detergents, includes. 5 Bleaches and Cleaning Agents «, pp. 93 and 149. © 809 577/411 7.58