DE4215689A1 - Nitrogen-free active ingredient in fabric softener formulations - Google Patents

Description

The invention relates to alkoxylated natural oils and fats as sticks Substance-free active ingredient component in fabric softener formulations and their use for it. The alkoxylated natural oils and fats can both alone and in admixture with conventional nitrogenous ones cationic active ingredient components with and without the addition of dispersants, Emulsifiers and / or solubilizers are used. But you can even in a mixture only with dispersants, emulsifiers and / or Solvent mediators are used.

It is known to use nitrogen-containing cationic compounds as allei to use few active ingredient components in fabric softener formulations. The active ingredient M, N-Di used in fabric softeners for many years stearyl-N, M-dimethylammonium chloride (DSDMAC) is because of its un favorable aquatoxic behavior more and more by substitutes, such as e.g. B. Imidazoline derivatives (see, inter alia, US Pat. No. 4,762,685, EP-A 0 199 383), qua ternated fatty acid esters of triethanolamine (so-called esterquats, see u.a. U.S. Patent 4,830,771) or 2,3-dihydroxypropyl-1-trimethyl-ammonium salt deri vate (DE-OS 27 28 841) replaced.

In the medium and long term, it can be expected that nitrogen-containing water softener active ingredient components u. a. because of the possibility of Nitrosamine formation through largely nitrogen-free alternatives or must be replaced completely. These alternatives should go through a high softening potential, antistatic and rewetting egg properties and an advantageous ecotoxicological behavior be drawn. DE-OS 34 16 669 describes the use of kristal Linen sheet silicates or their alkali salts as softening agents fe in detergents. The same is true in DE-OS 23 34 899 and DE-OS 33 12 774 described the use of saponites, hectorites and montmorilloni claimed as softening agents in detergents. The soft The effect of these substances is obviously based on their function as a cation exchanger and thus as a water softener. In soft water So these substances are ineffective.  

The invention is therefore based on the object, nitrogen-free action Finding fabric components as an alternative to sole use of nitrogen-containing fabric softener active components or in com combination with these if necessary after appropriate emulsification or Dispersion and / or addition of solubilizers can be used nen. They should not only be miscible and compatible with them, son they also work synergistically if possible, or also soften them alone have appropriate properties.

The object is achieved by the use of alkoxylated natural oils and fats as a nitrogen-free active ingredient solves. The fats which can be used according to the invention as starting material basically include all triglycerides and their mixtures with free ones Fatty acids, mono- and / or diglycerides. The alkoxylation can be OS 36 17 657 and DE-OS 38 26 179 take place.

The invention therefore relates to a nitrogen-free active ingredient composition nente for fabric softener formulations consisting of alkoxylated natural fats, oils and their mixtures with free fatty acids, Mo no- and / or diglycerides.

Another object of the invention is the use of alkoxylated natural fats or oils and their mixtures with free fatty acids, Mono- and / or diglycerides alone or in mixtures with nitrogen containing cationic active fabric softener components and counter if necessary, dispersants, emulsifiers and / or solubilizers as sticks fabric-free fabric softener ingredient.

The proportion of alkoxylated natural fats, oils and their mixtures with free fatty acids, mono- and / or diglycerides as fabric softener Active ingredient component is 1 to 100%, preferably 20 to 80%, of the ge entire amount of fabric softener active ingredient.

Mixtures of various alkoxylated natural fats, Oils and their mixtures with free fatty acids and / or mono- and / or Diglycerides are used.  

Furthermore, the mixture of different natural fats, oils and de Ren mixtures with free fatty acids mono- and / or diglycerides also before the alkoxylation.

The following usable Ep called oxides:

Ethylene oxide, propylene oxide, butylene oxide, 2-methyl-2-butene oxide, 3,3-dimethyl-1-butene oxide, C ₆ -C ₂₄ epoxides, styrene oxide, 1,2-epoxy butadiene, 1,2-epoxy cyclohexene, and also glycide esters and -ether. If more than one epoxy is used, these can be reacted with the fatty substances either in succession or simultaneously.

The proportion of the cationic nitrogen-containing fabric softener is effective fabrics and their mixtures with one another as an active ingredient in fabric softeners component is 0 to 99%, preferably 20 to 80%, based on the total amount of fabric softener active ingredient.

Examples are laundry softeners containing cationic nitrogen Active ingredient components called: N, N-distearyl-N, N-dimethylammonium salts, Imidazoline derivatives (quaternized or protonated), quaternized fatty acid reester of triethanolamine and 2,3-dihydroxypropyl-1-trimethylammonium salt derivatives as fabric softener active components. Both the alk oxylated natural oils and fats alone as well as their blends with the cationic nitrogen-containing fabric softener active ingredient nents can use Disper to further increase the effectiveness gators, emulsifiers and / or solubilizers are used.

The ratio of dispersants, emulsifiers and / or solubilizers or mixtures thereof to said fabric softener active ingredient component is 0 to 10: 1.

In addition to the fabric softener active ingredients and possibly dis emulsifiers, emulsifiers and / or solubilizers or mixtures of them ben can add additives such. B. fragrances, dyes, viscose regulator and water are added.  

It has been found that 0.3 to 0.4 g of the alkoxylated oils are effective and fats per liter of washing liquor used are a significant softener compared to non-fabric-treated terry towels. Are the recommended additions for fabric softener observed and on converted the amount of water required for a washing machine rinse, So if you know the active ingredient of the fabric softener, you get one Amount of approx. 0.3 g active substance per liter of washing liquor.

Become marketable nitrogen fabric softener active components or softener formulations with the alkoxylated oils and fats stretched, it turns out that in some cases up to a mixing ratio of 4: 1 with a constant total concentration of 0.35 g / l softening effect compared to pure nitrogen-containing laundry active fabric softener components or fabric softener formulations remains the same or even improves. These mixtures have the advantage part, with the same performance profile a much smaller stick to have substance content. Even smaller shares of the marketable ones Fabric softener active ingredients or fabric softener formulations NEN are used when conventional emulsifiers, dispersants and / or Solubilizers are added. The preservation of the plasticizing effect perfect necessary share of the commercially available nitrogenous laundry softener Detergent active components or fabric softener formulations can do so can be reduced to 0%.

Usual emulsifiers, dispersants and solubilizers as they fiction can be used according to z. B. those described in "Encyclopedia of Emulsion Technology "Vol: 1-3, 1983, New York and all their mixtures. Examples include:

• (1) from the group of anionic surfactants:
  Sulfates, sulfonates, alkoxylated sulfates, alkoxylated sulfonates, carboxylates, alkoxylated carboxylates, phosphates and alkoxylated phosphates.
• (2) from the group of nonionic surfactants:
  Fatty alcohol alkoxylates, aryl alkoxylates, alkoxylated oils and fats, amines, amides, alkoxylated amines, alkoxylated amides and amine oxides.
• (3) from the group of cationic surfactants:
  Cetylpyridinium chloride and bromide and the nitrogen-containing fabric softener active components already mentioned.
• (4) from the group of solubilizers:
  Isopropanol, ethanol, ethylene glycols, propylene glycols, butyl glycols.
• (5) Ampholytes and betaines.
• (6) metal soaps

as well as additional alkyl polyglycosiles and the alkoxylated oils and fats self.

Description of the test method of the softening effect (triangular test)

The softening effect of alkoxylated fats, oils or their Ge mix with free fatty acids and / or mono- and / or diglycerides or their blends with commercially available fabric softener active components was determined as follows: A batch of 72 terry towels (44 cm × 30 cm, approx. 60 g, from WFK-Testgewebe GmbH), even if not all 72 wipes were used (for reasons of even wear tongue), once with 100 g of a commercially available heavy-duty detergent (Persil) machine washed at 95 ° C, rinsed and spun. Subsequently followed by a wash cycle at 95 ° C without detergent including rinse cycle and brief spin-on, so that clean, moist, about 2.5 times yours Wipes containing dry weight of water for manual fabric softener could be removed.

For a test plan analogous to Table A, 9 wipes were used in 9 Rinse liquors with the standard (= S) and 9 wipes in 9 rinse liquors with the Test substance (= T) rinsed soft. For this purpose, each was in plastic bowls  2 liters of tap water and 0.00 or 0.35 g / l standard (active substance ge calculates) or predisperses a freely selectable amount of the test substance and the wet wipes for 10 min. leave in it. After 5 min. were the Towels once turned. The rinsed cloths were washed individually 30 sec hurled and dried on the drying rack in still air net.

Table A

Experimental plan for the sensory soft grip test with 6 examiners

The test subjects were each given 3 wipes in encrypted form after the Test plan according to table A (so-called triangular test) submitted. The task for the examiner was to apply the cloth treated differently to senso to find out by means of an expert assessment.

If this was possible, the examiner noted whether the different cloth was white felt harder or harder. At least 5 of the 6 examiners accepted this softened cloth (T for examiners 1 to 3, S for examiners 4 to 6), exists according to DIN 10 951 with a probability of greater than 95% between the test substance and the standard a significant Difference. The result is expressed using 3 numbers: the 1st Number indicates the number of reviewers who treated those with the standard Wipes felt softer or those with the test substance harder. The second number indicates the number of examiners who will be assigned the standard felt cloths as harder or those with the test substance as softer. The 3rd number finally indicates the number of examiners who are on due to the slight sensory differences with the test substance  or the cloth treated in the standard, the cloth treated differently could determine or did not give the correct answer.

example 1

With 0.2-0.5 g of the product from the conversion of skin fat with 10% by weight Treated ethylene oxide and 10 wt .-% propylene oxide per liter of washing liquor Wipes were tested against wipes that weren't with one Fabric softener were treated. The result is summarized in Table 1 sums up.

Table 1

From a concentration of 0.4 g of the test substance per liter of wash liquor is therefore a significant difference in softness in favor of wipes treated with the test substance compared to untreated Cloths.

Example 2

With 0.2-0.5 g of the product from the conversion of skin fat with 15% by weight Towels treated with propylene oxide per liter of rinse liquor were compared checked with cloths that had not been treated with a fabric softener. The The result is summarized in Table 2.  

Table 2

From a concentration of 0.4 g of the test substance per liter of wash liquor is therefore a significant difference in softness in favor of wipes treated with the test substance compared to untreated Cloths.

Example 3

With 0.2-0.5 g of the product from the conversion of palm oil with 15% by weight Towels treated with propylene oxide per liter of rinse liquor were compared checked with cloths that had not been treated with a fabric softener. The The result is summarized in Table 3.

Table 3

From a concentration of 0.3 g / l of the test substance, a signi fierce difference in softness in favor of that with the test substance treated wipes compared to untreated wipes.

Example 4

With blends of the product from the conversion of Lard oil with 15 wt .-% Propylene oxide with a commercially available quaternized fatty acid ester of Triethanolamins (Esterquat, Stepantex VR 85, Stepan) differentiated composition (constant total concentration: 0.35 g per liter  Rinsing liquor) treated wipes were tested in comparison with wipes, which were only treated with the commercially available ester quat (constant con concentration: also 0.35 g per liter of washing liquor). The result is in Table 4 summarized.

Table 4

It is therefore possible to reduce the amount of ester without sacrificing the soft feel quats to 30 wt .-% and the missing amount with the test add substance (see Sample No. 17).

Example 5

Mixtures of the product from the conversion of skin fat with 15% by weight Propylene oxide with a commercially available ester quat of different composites composition (constant total concentration: 0.35 g per liter of washing liquor) Treated wipes were tested against wipes that only treated with the marketable ester quat (constant concentration: also 0.35 g per liter of washing solution). The result is in Table 5 summarized.  

Table 5

The result is similar to that from Example 4 (see Sample No. 21).

Example 6

Mixtures of the product from the conversion of skin fat with 15% by weight Propylene oxide with a ditallow fatty acid ester of 2,3-dihydroxypropyl Marketable fabric softener containing 1-trimethylammonium chloride 1 un Different composition (constant total concentration: 0.35 g wipes treated per liter) were compared to wipes tested that were only treated with the commercial fabric softener 1 (constant concentration: also 0.35 g per liter of washing liquor). The The result is summarized in Table 6.

Table 6

With the help of the test substance it is even possible to use the softening egg properties to improve significantly if the standard fabric softener 1 40 to 60% by weight of the test substance can be added (see Sample No. 25  and 26). If a test substance / 1 - (4: 1) mixture is used, then the softening properties are the same as those of pure 1 (see sample no. 27).

Example 7

Mixtures of the product from the conversion of palm oil with 15% by weight Propylene oxide with a ditallow fatty acid ester of 2,3-dihydroxypropyl Marketable fabric softener containing 1-trimethylammonium chloride 1 un Different composition (constant total concentration: 0.35 g wipes treated per liter) were compared to wipes tested that were only treated with the commercial fabric softener 1 (constant concentration: also 0.35 g per liter of washing liquor). The The result is summarized in Table 7.

Table 7

The result is similar to that from Example 4 (see Sample No. 32).

Example 8

Mixtures of the product from the conversion of skin fat with 15% by weight Propylene oxide with 1-methyl-2-alkyl-3-alkylamido-ethylimidazolinium metho sulfate 2 of different composition (constant total concentration tion: 0.35 g per liter of wash liquor) treated wipes were compared checked with cloths that were only treated with the marketable 2 (constant concentration: 0.35 g per liter of washing liquor). The result is summarized in Table 8.  

Table 8

The test substance can be mixed with 2 abmi in all the mixtures examined the soft feel of the treated wipes does not deteriorate is even partially improved (see sample no. 34-36).

Example 9

Mixtures of the product from the conversion of skin fat with 15% by weight Propylene oxide with a protonated 2-alkyl-3-oxoacylalkyl-ethylimida zolin salt of the marketable soft containing acetic or lactic acid dishwasher 3 of different composition (constant overall concentration tion: 0.35 g per liter of wash liquor) treated wipes were compared checked with cloths that only work with the standard fabric softener 3 delt were (constant concentration: also 0.35 g per liter of washing liquid te). The result is summarized in Table 9.

Table 9

The test substance can be used in all examined ratios with the containing the protonated 2-alkyl-3-oxoacylalkyl-ethylimidazoline salt mix commercially available fabric softener 3, taking the soft handle of the treated Cloths stays the same.

Example 10

Mixtures of the product from the conversion of palm oil with 15% by weight Propylene oxide with the same fabric softener 3 as in Example 9 below different composition (constant total concentration: 0.35 g per Liters of washing liquor) treated wipes were compared to wipes checks that were only treated with the standard fabric softener (con constant concentration: also 0.35 g per liter of washing liquor). The result Table 10 summarizes:

Table 10

So it is possible, without sacrificing softness, the amount of that pro toned market containing 2-alkyl-3-oxoacylalkyl-ethylimidazoline salt restrict common fabric softener 3 to 30 wt .-% and the missing Add the quantity with the test substance (see sample no.47).

Examination of the rewetting property

In accordance with DIN 53 924 (climbing height method) were simplified Form rewetting tests carried out on terry cloth. To this Towels were used according to the in Chap. "Description of the test me method of softening effect "method described with the to te constant substances treated. After drying, strips (in cross  direction) of 30 cm in length and 8 cm in width and cut vertically into a beaker filled with 500 ml demineralized water. The immersion depth of the fabric was 1 cm.

0.5 g K ₂ CrO _{4 was} added to the water to better indicate the height of the climb. The immersion time was 5 minutes each. The water was then removed and the height of climb reached was measured. The rising height without further water supply was measured after 65 min.

Table 11 shows the determined heights of climb with samples 1-47 from the examples 1-10 treated terry cloth. It han are mean values from duplicate determinations.

Table 11

Rising heights found of the terry cloth treated with samples 1-47 from examples 1-10

Explanation of the climbing height results

In order to better classify the test results, the found heights of the D-sample (terry cloth, only with the standard General detergent (Persil) treated after 5 min .: 10.2 cm, after 65 min .: 18.5 cm) with those of the sample no. 13 or 18 (with pure ester quat treated, after 5 min: 6.9 cm, after 65 min: 12.2 cm), 23 or 28 (with treated with pure 1, after 5 min .: 4.8 cm, after 65 min. 8.6 cm), 33 (with pure 2 treated, after 5 min: 6.0 cm, after 65 min: 10.0 cm) and 38 or 43 (treated with pure 3, after 5 min .: 3.9 cm, after 65 min .:  5.3 cm) can be compared. It is clear to see that everyone under were looking for cationic nitrogen-containing fabric softener agents components or their finished formulations significantly lower climbing heights hen compared to the D-sample cause what a greatly reduced Wetting capacity equals. The alkoxylated natural fet te, oils and their mixtures with free fatty acids, mono- and / or diglyce Riders do this with a similar application concentration of 0.3 or 0.4 g per liter of washing liquor only to a very small extent or even at all not how the sample no. 2, 3, 6, 7, 10 and 11. With alkoxylated natural fats, oils and their mixtures with free Terry cloth treated with fatty acids, mono- and / or diglycerides shows thus an excellent rewetting ability. Become the alkoxylator ten natural fats, oils and their mixtures with free fatty acids, Mo no- and / or diglycerides mixed with the above. cation active stick fabric-containing fabric softener active components or their finished form formulations used, this becomes apparent when taking the climbing heights into account after 5 and 65 min. the following: None of those recommended in Examples 1-10 This mixture results in comparison to the corresponding cations active substances a reduction in the heights. Often even one occurs substantial enlargement.

Claims (12)

1. Nitrogen-free active ingredient component for fabric softener formulation gene consisting of alkoxylated natural fats, oils and their Mixtures with free fatty acids, mono- and / or diglycerides. 2. Nitrogen-free active ingredient component according to claim 1, characterized, that for the alkoxylation of natural fats, oils and their Mi or with free fatty acids, mono- and / or diglycerides several alkoxylating agents are used and their addition takes place simultaneously or in succession. 3. nitrogen-free active ingredient component according to claim 1, characterized, that mixtures of various alkoxylated natural fats, oils and their mixtures with free fatty acids, mono- and / or diglycerides be used. 4. nitrogen-free active ingredient component according to claim 1, characterized, that the mixture of different natural fats, oils and their Mixtures with free fatty acids, mono- and / or diglycerides before Alkoxylation takes place. 5. Use of alkoxylated natural fats, oils and their Mi mixtures with free fatty acids, mono- and / or diglycerides according to An Proverb 1 alone as a nitrogen-free fabric softener active ingredient nente or in mixtures with nitrogen-containing cation-active Active ingredient of fabric softener and optionally dispersato ren, emulsifiers and / or solubilizers. 6. Use according to claim 5, characterized, that the proportion of alkoxylated natural fats, oils and their Mixtures with free fatty acids, mono- and / or diglycerides 1 to  100%, preferably 20 to 80%, of the total fabric softener amount of substance. 7. Use according to claim 5, characterized, that as a cation-active nitrogen-containing fabric softening agent component N, N-distearyl-N, N-dimethyl-ammonium salts, quaternized or protonated imidazolines, quaternized fatty acid esters of tri ethanolamines and 2,3-dihydroxypropyl-1-trimethylammonium salt deri vate or mixtures thereof are used. 8. Use according to claim 5, characterized, that the proportion of cationic nitrogenous laundry softened active ingredients and their mixtures with each other 0 to 99%, be preferably 20 to 80% of the total amount of fabric softener active ingredient is. 9. Use according to claim 5, characterized, that as dispersants, emulsifiers and / or solubilizers ionic surfactants, nonionic surfactants, cationic surfactants, solvents medium, ampholytes, betaines, metal soaps or mixtures thereof be set. 10. Use according to claims 5 and 9, characterized, that as dispersants, emulsifiers and / or solubilizers alkyl poly glycosides, alkoxylated natural fats, oils and their mixtures be used with free fatty acids, mono- and / or diglycerides. 11. Use according to claims 5, 9 and 10, characterized, that mixtures of the dispersants, emulsifiers and / or solubilizers be used.   12. Use according to claim 5, characterized, that the ratio of dispersants, emulsifiers and / or dissolvers average to the total amount of fabric softener active ingredient 0 to 10: 1 is.