NL8104888A - SULPHATE AND / OR SULFONATE BASED EMULGATORS WITH BETTER WATER EMULSIBILITY. - Google Patents

Description

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Sulphate and / or sulphonate based emulsifiers with better water emulsification avoided.

The present invention relates to sulfate and / or sulfonate based emulsifiers having better water emulsifying capacity in water-in-oil emulsions, the emulsifiers containing small amounts of certain acidic, anionic, dissociable compounds either as such and / or in salt form and have a pH value of k95-8.0. Particular preference is given to those dissociable compounds, which in the salt form have a first dissociation constant of at least 1 x 1 × 1. The emulsifiers are preferably used in dry cleaning and for solvent filling (dry filling).

For the treatment of flat materials, especially of textile material in an organic, water-insoluble solvent, it is essential that an amount of water is emulsified in the organic environment. In the chemical cleaning process, that water mainly effects the removal of water-soluble impurities. Dry filling is only successful if substantial amounts of water have been emulsified in the solvent, because only then can a sufficient full effect be achieved. When treating from an organic solvent, e.g. when dyeing, as a rule, the treatment agent, i.e. the dye, dissolved in water and this solution is emulsified. A uniform dyeing is therefore only possible if the aqueous solution is homogeneously distributed.

As emulsifiers for the applications described above, surfactants such as alkyl sulfonates, alkyl aryl sulfonates and alkyl sulfates, usually used alone or in admixture with surfactant, nonionic compounds, e.g. are formed by condensation of alkylene oxides with aliphatic alcohols, alkyl phenols, amines and arnides. The other ingredients of the emulsifiers, e.g. solvents, solution-promoting agents * and control agents are also known.

The said compounds resp. mixtures have the advantage that they are favorable in price. However, the major drawback of the known emulsifiers consists in their low water-emulsifying capacity, so that these emulsifiers can only be used to a limited extent. For dry rolling e.g. the water-emulsifying capacity is generally not sufficient to obtain resistant emulsions and therefore uniform effects cannot be achieved with the known products. Also, when the known emulsifiers are used in the chemical cleaning, the removal of the water-soluble dirt is only incomplete, so that a considerable part of the cleaned wardrobe has to be cleaned again.

U.S. Pat. No. 3-378,996 describes dry cleaning reinforcements which would overcome the known drawbacks. These known dry cleaners are predominantly nonionic surfactants and approximately equal parts anionic sulfonate and sulfate surfactants and ethoxylated phosphoric acid esters. The water-emulsifying ability has been somewhat improved with these dry cleaning reinforcements, but it is still far from sufficient for the above requirements.

The object of the invention is therefore to provide advantageous emulsifiers for the treatment of materials which have been made and those which have not been made up in organic water-insoluble solvents, which are distinguished by a high somewhat emulsifying capacity.

According to the invention, this object is achieved in that the conventional anionic emulsifiers contain small amounts of certain acidic, anionic, dissociable compounds as such and / or in salt form and are adjusted to a specific pH value.

The object of the invention is therefore sulphate and / or sulphonate-based emulsifiers with improved water-emulsifying capacity in water / oil emulsions, which are characterized in that they contain 0.5-6 wt.%, Based on the total emulsifier, of an anionic, dissociable compound from the class of the acidic sulfur and / or phosphorus compounds with at least one alkyl radical of 1 to 6 carbon atoms, which do not contain an alkyl radical and an alkyl chain, of the saturated and / or unsaturated, optionally substituted carboxylic acids with 1 to 6 carbon atoms, of the saturated and / or unsaturated, optionally substituted polycarboxylic acids with 2 to 8 carbon atoms and / or acid esters thereof with 1 to 6 carbon atoms in the alkyl radical, as such and / or in salt form, and have a pH value of 0.5-8.0, in particular of 5.5-7.0.

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Particularly suitable anionic, dissociable compounds can be mentioned which have in the acid form a first dissociation constant of at least 1 x 10, in particular 1.3 x 10 4.

In addition, protection is envisaged for the use of the emulsifiers in dry cleaning and for the filling with solvent.

Sulfate and / or sulfonate-based anionic compounds, as commonly used in the emulsifiers for the aforementioned purposes as active wax constituents, are the alkali and ammonium salts of sulfating products of unsaturated fatty acids, esters and amides thereof, and of fatty alcohols such as sulfonation products of aliphatic, aromatic and / or araliphatic hydrocarbons.

Optionally ethoxylated alkylphosphoric acid esters are also suitable.

The alkyl radicals of these compounds generally have at least 8, especially 10-20 and more, carbon atoms. As examples may be mentioned: alkyl sulfates, alkyl, alkyl aryl and mineral olis sulfonates, as well as dialkyl sulfosuccinates.

These anionic emulsifiers can be used as such. Preferably, however, they are used in the form of a mixture with non-ionic surfactants. Such compounds are obtained by condensation of alkylene oxides (usually ethylene oxide and / or propylene oxide) with compounds that have reactive hydrogen atoms. As examples for such compounds, primary, secondary and tertiary alcohols, primary and secondary amines, aliphatic amides, aliphatic fatty acids and alkyl phenols can be mentioned. The non-ionic compounds are generally added to the anionic substances in amounts of up to 50% by weight, based on the active detergent, i.e. the active substance.

The known emulsifiers, however, do not meet the requirements with regard to the water-emulsifying capacity. According to the invention, therefore, 0.5-6 wt.%, Preferably 1.5 - wt. 5, is based on the total emulsifier, of an anionic, dissociable compound, as will be further described below, are added thereto. The emulsifiers obtained thereby are capable of dissolving water-insoluble 8104883 at a level of about 0 wt.% Of active detergent.

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i: '4 means to six times the weight of their own weight in water. emulsify. When the emulsifiers are prepared in concentrated form, for example, with 80% by weight of active detergent, it is readily possible to emulsify up to twelve times the amount of water, based on the emulsifier's own weight.

As particularly suitable compounds to be used, acidic phosphorus compounds with at least one alkyl radical with 1-6, in particular with 1-4 carbon atoms and / or salts thereof, can be mentioned. Acidic phosphorus compounds should generally be understood to mean those compounds which have at least one P-O bond. to sit.

The alkyl radical of the acidic phosphorus compounds can be directly bound to phosphorus, i.e. according to the invention, phosphonic acids are suitable as such. In addition, however, the acid esters of the phosphonic acids can also be used, however, for the esterification only alcohols with 1 to 6, in particular with 1 to 4, carbon atoms, which are optionally alkoxylated with at most 8 alkylene oxide groups, may again be used, can be used. Examples of such compounds in the acid form are butylphosphonic acid, ethylphosphonic acid mono-butyl ester and the monoester of butylphosphonic acid with ethoxylated hexanol- (1) (average 1 ethoxy group per alcohol residue).

In addition, other acidic phosphorus compounds can also be used with at least one alkyl radical of 1-6, especially 1-4 carbon or atoms. As examples may be mentioned the acid esters of phosphorous acid and alkylphosphonic acids per se or monoesters thereof with alcohols having 1-6 carbon atoms. These compounds are also preferably used in salt form.

Particularly preferred dissociable compounds because of their good emulsifying power are the compounds of the formula shown in the formula sheet.

In that formula, Z has the meaning of M or a radical of the formula V-OC ^ R ') -, an alkyl radical having 1 to 6 carbon atoms, R' signify hydrogen or a methyl radical, M a sodium, potassium, ammonium or optionally hydrogen atom, and x and y an integer from 0 to 8, with the proviso that the sum of x and y does not exceed 8. Of those phosphoric acid esters, these are particularly well suited, wherein the - 8104333 5 alkyl residue 1 - U has carbon atoms and x and y represent a number from 0 - 2, because these compounds improve the emulsifying capacity of the vessel in particular. .

The acidic sulfur compounds, which analogous to the acidic phosphorus compounds contain at least one S-O bond, which are present in the present emulsifiers, are primarily acidic sulfuric acid esters, e.g. methyl sulfate. These compounds are generally used in salt form.

A further, although somewhat less suitable group of acidic sulfur compounds are the alkyl sulfonic acids with 1-6, especially with 1-h carbon atoms in the alkyl residue, as well as the salts of these compounds. Compounds of this kind are generally known and need no further explanation.

Regarding the length of the alkyl residue, the same applies here as with the P-compounds. The compounds with the short chain alkyl radicals generally have a high dissociation constant and thereby improve the case-emulsifying ability to a greater extent.

It is furthermore advantageous to use saturated and / or unsaturated, optionally substituted carboxylic acids with 1 - 6, in particular with 1 - k, carbon atoms and their salts. Among the preferred acids in the acid form may be mentioned formic acid, acetic acid, acrylic acid, methacrylic acid, glycolic acid and lactic acid. However, isovaleric acid and n-caproic acid are also eligible. Among the acids which are preferably used, the substituted and the unsaturated as well as the saturated with 1 and 2 carbon atoms are again very particularly suitable.

Finally, as a particularly suitable group of compounds, mention should be made of the saturated and / or unsaturated, optionally substituted polycarboxylic acids with 2 - 8, in particular with 2 - 6, carbon atoms and / or acid esters thereof with 1 - 6, in especially with 1 - k carbon atoms in the alkyl residue as such and / or in salt form. As examples of acids, oxalic acid, maleic acid, succinic acid, itaconic acid, malic acid, tartaric acid, citric acid and glutaric acid and exemplified acid esters are fumaric acid monohexyl ester and malic acid monoethyl ester.

According to a very particular preference, the present emulsifiers contain such anionic, dissociable compounds, which in the zmr form have a first dissociation constant of -5 -5 at least 1 x 10, in particular of 1.3 x 10 and preferably of 1.75 x ΙΟ'5, because with increasing dissociation constant an ever increasing favorable influence of the water-emulsifying capacity is observed.

In principle it can be said that the said compounds are used at least predominantly in the form of bun salts. However, it is preferable to use the acids or 10 acids which form the basis of these salts. to use acidic compounds directly, more care must be taken that the pH value of the emulsifiers obtained does not fall below a value of U, 5, in particular of 5.5

At a lower value, it is readily possible to neutralize, or at least partially neutralize, image with aqueous alkali metal hydroxide solutions or ammonia solution, etc. In addition, although less well, amines or alkanolamines are suitable on a case-by-case basis for adjusting a pH value of U, 5 - 8.0, in particular of 5.5 - 7.0 * The present emulsifiers are very suitable for bet-dry because of their strong water-emulsifying capacity: cleaning tex-20 textile materials of all kinds, sheets and pelts and for bet dry full and wool-containing articles. The chemical cleaning and filling with solvent are carried out in a known manner. In addition to the aforementioned U.S. Pat. No. 3,378,196, reference may also be made in this connection to, inter alia, British Pat. Nos. 1,392,102 and 1,1) -12,598. The latter also extensively discusses the fulling with solvents.

In addition, the present emulsifiers can also be used for treating flat textile materials and textile-like materials from organic solvents. The present emulsifiers can in particular be used in dyeing. A known method of this kind is described in British patent specification 1.52¼. 1 * 86.

The water-insoluble solvents used for the stated purpose are known. Halogenated hydrocarbons, such as tetrachlorethylene, trichlorethylene, trifluorotrichloroethane and monofluorotrichloroethane, are particularly suitable. Preferably, the chlorinated hydrocarbons are used. In addition, high-boiling gasolines are also used as a solvent.

The invention is further illustrated in the examples below. In these examples, the parts indicated are 5 parts by weight unless otherwise stated.

In order to test the water-emulsifying capacity, each time k g of the emulsifier was diluted with the appropriate amount of water and added to 1 l of tetrachloroethene. At the indicated water-emulsifying capacity (weight ratio of emulsifier to emulsified water), a resistant emulsion was just obtained.

Example I

To prepare a conventional anionic emulsifier, 60 parts of 65% petroleum sulfonate, 20 parts of water, 15 11a mineral oil, 10 parts of isopropanol and 5 parts of butyl diglycol were mixed. The pH-15 value of the emulsifier (about 35% active detergent) was about 6.0 (emulsifier A).

To this emulsifier A, wt.%, Based on the finished emulsifier mixture, of various dissociable compounds was added: Snuffer 3: addition of technical formic acid.

Sneggator C: addition of technical monobutyl sodium maleinate.

Emulsifier D: addition of a technical mixture of mono and dibutyl phosphoric acid ester (approx. 1: 1).

Accelerator E: addition of a technical mixture of mono- and diphosphoric acid ester of ethoxylated hexanol- (1) (average 1 ethoxy group / alcohol residue, mixing ratio 1: 1).

If acidic compounds are added, feed. the pH value is then adjusted again to about 6.0 with 50% sodium hydroxide solution. Accelerator F: For comparison, the dry cleaning booster was prepared in accordance with Example 1 of U.S. Pat. No. 3,378,196 and diluted with water to 35 wt% active detergent content.

The water emulsifying power of the obtained emulsifiers A - F is shown in Table A below.

8104888 • 8 «*

TABLE · A

Water Emulsion Capability 1: 1 B) 1: 5 C) According to the Invention 1: 5 D) 1: 1 E: 1: 3 F. prior art 1: 1.3

The emulsifiers B - E are particularly well suited as cleaning enhancers, because light stains (water-soluble impurities) are also largely removed due to the good water-emulsifying capacity.

Example II

An anionic emulsifier had the following composition: + 0 parts of C-] 2 -18 allyl ionate> 26 parts of tetrachloroethene, 31 parts of water and 15 parts of isopropanol (pH value 5-5.5). This emulsifier A is a commercially available cleaning enhancer.

To the emulsifier A, wt.%, Based on the finished emulsifier mixture, was added each time of concentrated acetic acid (emulsifier B), acrylic acid (emulsifier C) and of a technical mixture of a mono- and dimethyl phosphoric acid ester 1: 1 (emulsifier D) . If necessary, the pH value was adjusted to 5.5-6.0 after addition of the dissociable compound with k5% potassium hydroxide.

The water emulsifying power of the obtained emulsifiers A - D is shown in table B below.

TABLE · B

Emulsifier Water emulsifying power A state of the art 1: 1 B) 1: 5

C) according to the invention 1: T

D) 1: 6 30 The emulsifiers B-D are particularly good cleaning enhancers because of their high emulsifying capacity for water.

8104888. ** „Λ 9

Example. Ill

A commercially available emulsifier preparation (20% by weight dodecyl benzene sulfonate, 8% by weight nonylphenol polyglycol ether with 5 ethylene oxide per mole of nonylphenol, 2% by weight nonylphenol polyglycol ether 5 with 9 ethylene oxide per mole of nonylphenol, 32% by weight mineral oil, residual organic solvents) contained increasing amounts of the phosphorus ester (i) mentioned in Example I, emulsifier D. The pH value was adjusted to 5.5-6.0 with commercial potassium hydroxide as necessary.

10 The water-emulsifying capacity was improved as follows:

TABLE C

_Skulgator_Fater emulsifying power_ A (no addition) state of the art 1: 0.5 B (1% by weight) 1: 2.5 15 C (2% by weight I)) according to 1: 3 D (e.g. % I)) invention 1: k E (6. gβv.% I)) 1: 5

As the added amount of dissociable compound increases further, no significant improvement in the water-emulsifying ability could be observed.

The emulsifiers B-E, in particular C-E, resulted in good removal of water-soluble dirt when used as a cleaning enhancer, but are also well suited for dyeing from organic solvent.

Example IV

A commercially available surfactant composition (10% mineral oil, 28% mineral oil / petroleum sulfonate, 7% dodecylbenzene sulfonate, 11% nonylphenol polyglycol ether with 10 ethylene oxide per mole nonylphenol, 6% isopropanol, balance organic solvents and water (adjusted to pH 6.0 with caustic potash) were mixed with glycolic acid, malic acid and the phosphoric ester indicated in example II according to the data in example II. The water-emulsifying ability of the obtained emulsifiers was improved in approximately the same manner as indicated in Example II.

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Example V

Conventional sulphate and sulphonate-based anionic emulsifiers are hardly suitable as a full aid. According to the invention, however, it is possible to also use such emulsifiers for the aforementioned purpose.

The following ingredients were mixed together: HO parts di (2-ethylhexyl) sulfosuccinate T0%, 20 parts petroleum sulfonate 65% 10 parts nonylphenol polyglycol ether with 5 ethylene oxide per mole nonylphenol, 10 15 parts mineral oil sulfonate 30% 5 parts butyldiglycol and 10 parts oil.

H wt. %, based on the total mixture, of an acidic phosphoric acid ester (see example II, emulsifier D) 15 and the pi value was adjusted to 6.0-6.5 with concentrated caustic potash.

Part of this emulsifier is able to bind 10-11 parts of water, so that it can be used as a full aid.

Example VI

The use of the emulsifier prepared in example V as a full aid is illustrated in the following example:

In a cleaning machine with a nominal load of 50 kg, 35 hg of finely knotted lambswool was applied. A tetrachlorethylene bath containing 5% of the emulsifier and 20% water, each based on the weight, was added to the drum with rotation in a ratio of 6: 1 (volume by weight to weight) and pre-heated for 1 minute. Subsequently, with the drum standing still, but with the small pump circulation switched on, the swelling of the wool was effected and the mixture was then rotated for 3 minutes. The residual bath remaining after filling was subjected to distillation, just like the pendulum bath obtained after swinging (2 minutes). The final drying took place at T0 ° C for 15 minutes. The goods were finally cooled by blowing in cold air.

The commodity showed an even full effect. She was soft with a fleecy grip and no color shifts could be observed.

Example VII

The use of the emulsifier D according to example III as cleaning reinforcing agent is illustrated in the following example:

In a cleaning machine (nominal load 12 kg per load) 9 hg mixed wardrobe (wool component approx. 25 $) was placed. The product was then pretreated in the machine as follows: a built-in steam nozzle with an opening of 0.8 mm injected a total of about 2% water vapor, based on the weight, into 2 minutes in 2 minutes. Simultaneously, through a second nozzle (1.5 mm diameter), 4.5 L of tetrachloroethene containing 45 g / l of the above-mentioned emulsifier was injected into the cleaning drum with rotation over 3 minutes. This was followed by a 3 minute rinse with a short bath of 25 l of pure tetrachloroethene. The rinsing bath and the parts thereof released during the swinging were fed for distillation.

Thereafter, over filter with a bath containing 4.5 g / l of the said cleaning enhancer was cleaned at a bath ratio of 6: 1 (bath volume to weight) in 5 minutes, in order to remove residual dirt and bind residual moisture. . The bath and the subsequent flung-off part were taken to the work tahk. The commodity was dried in the drum at about 0 ° C and then cooled to 30 ° C with cold air.

The cleaning effect of the treated goods was very good, so that only a small part had to be treated afterwards.

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Claims (6)

Sulphate and / or sulphonate-based emulsifiers with improved water-emulsifying capacity and water / oil emulsions, characterized in that the emulsifiers are 0.5-6% by weight, based on the total emulsifier, of an anionic, dissociable compound of the class of the 5 acidic sulfur and / or phosphorus compounds with at least one alkyl radical with 1-6 carbon atoms, which do not contain longer chain alkyl radicals, of the saturated and / or unsaturated, optionally substituted carboxylic acids with 1- 6 carbon atoms, of the saturated and / or unsaturated optionally substituted polycarboxylic acids with 2-8 carbon atoms and / or 10 of acid esters thereof with 1 - 6 carbon atoms in the alkyl radical, as such and / or in salt form and have a pH value of U, 5-8.0, in particular of 5.5-7.0 2. Emulsifiers according to claim 1, characterized in that the dissociable compounds in the acid form have a first dissociation constant of at least 1 x 10 4. Emulsifiers according to claim 1 or 2, characterized in that they contain 1.5 - wt.% Of the dissociable compound. k. Emulsifiers according to claims 1-3, characterized in that as dissociable compounds are present compounds of the general formula shown on the formula sheet, wherein Z has the meaning of M or of the moiety (-OCgH ^ R. ') -, R ^ an alkyl radical with 1 - 6, in particular with 1 - k carbon atoms, R 'hydrogen or a methyl radical, M a sodium, potassium, ammonium or optionally hydrogen atom, and x and y an integer from 0 - 8 , in particular from 0-2 mean, with the proviso that the sum of x and y does not exceed the value of 8. Emulsifiers according to claims 1-3, characterized in that as dissociable compounds substituted, saturated and / or optionally substituted unsaturated carboxylic acids with 1 - carbon atoms and / or mono-C 1 -alkyl esters of C 2 -dicarboxylic acids are present as such and / or in salt form. Use of the emulsifiers according to claims 1 to 5 as cleaning reinforcing agent in chemical cleaning. Use of the emulsifiers according to claims 1-5 as an aid for the solvent filling. 8104888