EP0924291B1 - Aqueous softener with improved softness - Google Patents

Description

The present invention relates to fabric softener in the form of aqueous emulsions or dispersions.

When washing textiles are known to be in the last wash so-called fabric softener used. This will harden the tissue, caused by drying is reduced. The handle of the so treated Textiles such as hand and bath towels as well as body and bed linen is pleasantly influenced.

Cationic compounds are usually used as fabric softener, for example quaternary ammonium compounds, which are in addition to long-chain Alkyl radicals can also contain ester or amide groups, for example as in U.S. Patent 3,349,033, 3,644,203, 3,946,115, 3,997,453, 4,073,735, 4,119,545. These components are used alone or in Mixtures with other cationic or neutral substances in Form of aqueous dispersions added to the rinsing bath.

Ammonium compounds containing ester bonds are frequently used as for example in EP-A-0 239 910, US-PS 3 915 867, US-PS 4 137 180, U.S. Patent 4,830,771.

WO-A-94/20597 relates to concentrated fabric softeners containing quaternary ammonium compounds, in which the long-chain fatty acid residues contain 11 to 21 carbon atoms and have iodine numbers in the range from 5 to 100.

US-A-5,637,743 discloses the provision of a fabric softener containing quaternary ammonium salts, wherein the Fatty acids contain 5 to 23 carbon atoms ratio of fatty acid: amine is 1.85 to 1.40 and Iodine numbers range from 10 to 33.

Ester compounds based on triethanolamine such as N-methyl-N, N-bis (beta-C _14-18 -acyloxyethyl), N-beta-hydroxyethyl ammonium methosulfate, which are sold under trade names such as TETRANYL® AT 75 (trademark of KAO Corp.), STEPANTEX® VRH 90 (trademark of Stepan Corp.) or REWOQUAT® WE 18 (trademark of Witco Surfactants GmbH).

Although these cationic compounds are effective plasticizers in the Represent use in the last rinse, they always indicate use certain disadvantages.

One of the disadvantages of such means is that the required high level of at the same time good rewetting ability and soft feel of those treated with them Textiles are not yet satisfactory.

The absorption of moisture is generally considered to be a rewetting ability understood by the fiber. Inadequate back network assets have an effect but detrimental from where larger amounts of moisture from the skin surface should be included. z. B. with hand or bath towels and at Body or bed linen.

Using processes known per se (batch or continuous processes) can produce stable fabric softener dispersions with these products become.

The object of the invention was to make the above-mentioned disadvantages more conventional To overcome fabric softener formulations and to provide fabric softener, which, in addition to good biodegradability, is significantly improved Level of good soft feel while maintaining good rewetting ability exhibit.

The object was achieved by using quaternary fatty acid amino alcohol esters from triethanolamine in relation to partially hydrogenated fatty acids from 1: 1.6 to 1: 2 in alcohols or glycols.

worin R der Rest einer Fettsäure mit 14 bis 18 Kohlenstoffatomen und Jodzahlen im Bereich von 15-25 ist und a = 1, 2, 3 sein kann. The invention therefore relates to aqueous fabric softeners containing at least one of the compounds of the general formula (I)

wherein R is the residue of a fatty acid with 14 to 18 carbon atoms and iodine numbers in the range of 15-25 and a can be 1, 2, 3.

The quaternary compounds of general use which are also used according to the invention Formula I are made according to those well known in the art Process by esterification of triethanolamine with fatty acid and subsequent Quaternization manufactured.

As fat components for the esterification or transesterification are the known and customary monobasic fatty acids based in this field natural vegetable and animal oils with in particular 14-18 Carbon atoms used, such as tallow fatty acids and palm fatty acids or their methyl or ethyl esters.

The content of these fatty acids or fatty acid esters in unsaturated portions, - as far as this is necessary - by the known catalytic Hydrogenation process set to iodine numbers between 15-25, or by Mixing of fully hydrogenated with unhydrogenated fat components achieved.

The iodine number, as a measure of the average degree of saturation of a Fatty acid, is the amount of iodine, which is from 100 g of the compound for saturation of the double bonds.

Partially hydrogenated tallow fatty acids and palm fatty acids are preferred according to the invention with iodine numbers between 15-25. They are commercial products and are offered by various companies under their respective trade names.

The esterification or transesterification is carried out according to known methods. Here, the triethanolamine with the desired degree of esterification appropriate amount of fatty acid or fatty acid ester, if appropriate in the presence of a catalyst, e.g. B. methanesulfonic acid, under nitrogen 160-240 ° C implemented and the water of reaction or the Alcohol was continuously distilled off, thereby completing the reaction if necessary, the pressure can be reduced.

The subsequent quaternization is also carried out using known methods. According to the invention is preferably carried out so that the ester, if appropriate using a solvent, preferably with in particular Isopropanol, ethanol, 1,2-propylene glycol and / or dipropylene glycol, at 60-90 ° C with equimolar amounts of the quaternizing agent with stirring, possibly under pressure, and the completion of the Reaction is monitored by checking the total number of amines.

Examples of the quaternizing agents used are short-chain dialkyl phosphates and sulfates such as diethyl sulfate, dimethyl phosphate, diethyl phosphate, short chain halogenated hydrocarbons; in particular is according to the invention Dimethyl sulfate used.

Triethanolamine was used to produce the quaternary ammonium compounds (TEA) and fatty acids implemented according to the usual procedures and quaternized.

The following were also used as fatty acids: Fatty acid I: Tallow fatty acid with an acid number of 200-210, an iodine number of 15-25 and a carbon chain distribution of <C ^- 16 approx. 2% C ^- 16 approx. 26% C ^- 16 ' approx. 2% C ^- 17 approx. 3% C ^- 18 approx. 48% C ^- 18 ' approx. 15% C ^- 18 " <1% Fatty acid II Palm fatty acid with an acid number of 205-215, an iodine number of 15-25 and a C chain distribution of <C ^- 16 approx. 3% C ^- 16 approx. 47% C ^- 16 ' - C ^- 17 - C ^- 18 approx. 28% C ^- 18 ' approx. 17% C ^- 18 " approx. 2% > C-18 approx. 2% Fatty acid III Tallow fatty acid with an acid number of 200-210, an iodine number of 45-55 and a carbon chain distribution of <C ^- 16 approx. 4% C ^- 16 approx. 26% C ^- 16 ' approx. 2% C ^- 17 approx. 3% C ^- 18 approx. 17% C ^- 18 ' approx. 41% C ^- 18 " <4% > C-18 approx. 2%

It was quaternized with dimethyl sulfate. Component A: TEA: fatty acid I 1: 2 Component B: TEA: fatty acid I 1: 1.6 Component C: TEA: fatty acid II 1: 2 Component D: TEA: fatty acid II 1: 1.6 Component E: TEA: fatty acid III 1: 2 Component F: TEA: fatty acid III 1: 1.6

The fabric softener is produced by emulsifying or dispersing of the individual components in water. This can be done on this Conventional procedures are applied.

Usually one proceeds in such a way that the down to approx. 10 ° C The melting point of the plasticizer is preheated water, with good stirring first the dye solution, then the required one Antifoam emulsion and finally the clear melt of the individual Plasticizer is dispersed one after the other. After adding a subset Perfume oil is added to an electrolyte solution, followed by the remaining amount Electrolyte solution, and then allowed to cool to room temperature with stirring. The fabric softeners according to the invention can be the specified ones Contain components within the usual limits in this area, such as 15-22% by weight of the compounds of the general formula (I); 2-5% by weight of a solvent, such as in particular isopropanol, Ethanol, propylene glycol, dipropylene glycol; 0.5-1.5% by weight of an alkali and / or alkaline earth metal salt; 0.5-1.5% by weight of perfume oil and the rest of 100 % By weight (ad 100) water.

Like the fabric softeners belonging to the known prior art the fabric softener according to the invention following the actual Washing process added in the last rinse. The application concentration after dilution with water lies in the range depending on the application 0.1-10 g of fabric softener per liter of treatment liquor.

Determination of the net assets

Based on DIN 53924, the test fabric (approx. 3 kg cotton twill, 100% cotton; Supplier: WFK-Testgewebe GmbH, Krefeld) washed twice with 100 g test detergent and then without detergent (each 95 ° C program with prewash). The test fabric will hung up to dry for one day at room temperature. After drying test strips about 25 cm long and 1.5 cm wide are cut. It is important to ensure that all test strips in a test series are the same Have thread course.

The test strips are marked with a ballpoint pen. At both ends holes are punched into the test strip; there should be a 5 cm thick fabric edge remain.

The corresponding amount of demineralized water is in the beakers submitted and 0.025%, based on the solids content, of the test Product stirred. A blind test is carried out by demineralizing Water is presented in the immersion bath.

10 test strips are placed in each of these fleets, 5 minutes at approx. 50 rpm stirred with a magnetic stirrer and then 5 min without stirring leave in it. The test strips are then left for 24 hours at room temperature hanging dried. After this time, use a water-soluble marker pen on the smooth side of each strip, a line parallel to the long one Outer edges drawn.

The test strips treated in this way (blank value + test product (s)) are now on attached to the immersion device. It should be noted that there is no stretching the streak occurs. The immersion device with the strips is in the a height of 8 cm filled with demineralized water (corresponds to about 10 l) Put the tub and leave it there for 5 min. 10 min after removing the Immersion device from the tub will increase the height of the water that is at the running felt pen color can be seen, determined in mm It is on it to ensure that the lower edge of the hole with the upper side directly on the (Suspended) hook is present to avoid reading errors. The demineralized Water must be replaced after every attempt.

evaluation

Experience has shown that slight scatter can occur with this method to be taken into account in the calculation by specifying the standard deviation are.

BW:

Steighöhe des Wassers (Farbstoffes) in mm der Blindproben im arithmetischen Mittel

A:

Steighöhe des Wassers (Farbstoffes) in mm der Proben eines Weichspülers im arithmetischen Mittel

Calculation: Network assets (%) = Rise height A in mm x 100% Rise height BW in mm

BW:

Rise height of the water (dye) in mm of the blank samples in the arithmetic mean

A:

Rise height of the water (dye) in mm of the samples of a fabric softener in the arithmetic mean

Execution of the fingering test

3 kg of the test fabric ("Duosoft" fabric, 100% cotton; supplier: Fa. Vossen) twice with 100 g of test detergent and then twice washed without detergent (each 95 ° C program with prewash, Duration approx. 2 h); Spin speed: 1200 rpm.

Due to a fixed rotting size of 15 (Miele W 719) a liquor ratio of 1: 5. After washing, the test fabric becomes a Hung up to dry at room temperature and then until Processing stored at room temperature.

To immerse the tissue, calculate the calculated amount in the beaker Amounts of fabric softener at 15-20 ° C and tap water from approx. 9 ° dH and 15-20 ° C to 2 l. Then on the Magnetic stirrer stirred until homogeneous dispersions or solutions is present.

A blind test is carried out using pure tap water in the immersion bath is presented. 1 piece of test fabric is dipped in each rinse bath. After 10 min the tissue is removed from the rinsing bath, slightly wrung out, three times gently shaken and dried hanging in one layer at room temperature for 48 h.

The test fabric treated in this way is cut into 10 pieces of the same size (approx. 16x25 cm) cut. Each test person receives a new test piece for assessment. It must be prevented that the test pieces after a few attempts are "softly gripped".

The test fabrics treated with different fabric softeners are now compared in pairs. The test subjects can use whole points as an evaluation distribute between 0 and 5, with 0 points bad (hard) and 5 points good (soft) mean.

evaluation

The differences between the individual pairs are each in the second Column (difference points) entered.

Then the difference has to be allocated to the better rated product. The more The difference points a product contains, the better its softness.

Examples

According to this process (batch process) the components mentioned Dispersions made:

Example 1:

22.0 g Component A 0.60 g Dye (1% solution SANDOLAN® Walkblau NBL 150 from Sandoz) 0.20 g Defoaming agent (SAG 220 from OSI) 0.80 g Perfume oil Fragrance® (D 60515 W from Haarmann und Reimer GmbH) 0.20 g CaCl ₂ ad 100 Water, 9 ° dH

Example 2:

19.2 g Component B 0.60 g Dye (1% solution SANDOLAN® Walkblau NBL 150 from Sandoz) 0.20 g Defoaming agent (SAG 220 from OSI) 0.80 g Perfume oil Fragrance® (D 60515 W from Haarmann und Reimer GmbH) 0.20 g CaCl ₂ ad 100 Water, 9 ° dH

Example 3:

22.0 g Component C 0.60 g Dye (1% solution SANDOLAN® Walkblau NBL 150 from Sandoz) 0.20 g Defoaming agent (SAG 220 from OSI) 0.80 g Perfume oil Fragrance® (D 60515 W from Haarmann and Reimer 0.20 g CaCl ₂ ad 100 Water, 9 ° dH

Example 4:

19.2 g Component D 0.60 g Dye (1% solution SANDOLAN® Walkblau NBL 150 from Sandoz) 0.20 g Defoaming agent (SAG 220 from OSI) 0.80 g Perfume oil Fragrance® (D 60515 W from Haarmann und Reimer GmbH) 0.20 g CaCl ₂ ad 100 Water, 9 ° dH

Comparative Examples Example 5:

22.0 g Component E 0.60 g Dye (1% solution SANDOLAN® Walkblau NBL 150 from Sandoz) 0.20 g Defoaming agent (SAG 220 from OSI) 0.80 g Perfume oil Fragrance® (D 60515 W from Haarmann und Reimer GmbH) 0.20 g CaCl ₂ ad 100 Water, 9 ° dH

Example 6:

19.2 g Component F 0.60 g Dye (1% solution SANDOLAN® Walkblau NBL 150 from Sandoz) 0.20 g Defoaming agent (SAG 220 from OSI) 0.80 g Perfume oil Fragrance® (D 60515 W from Haarmann und Reimer GmbH) 0.20 g CaCl ₂ ad 100 Water, 9 ° dH

Results

Soft grip [points] Network assets [%] Component A 42 56 Component B 40 58 Component C 40 61 Component D 38 63 Component E 32 62 Component F 29 65 Soft grip [difference points] Component A: Component B 6: 4 Component A: Component C 6: 4 Component A: Component D 5: 1 Component A: Component E 10: 0 Component A: Component F 13: 0 Component B: Component C 6: 6 Component B: Component D 5: 3 Component B: Component E 9: 1 Component B: Component F 11-0 Component C: Component D 6: 4 Component C: Component E 10: 2 Component C: Component F 11-0 Component D: Component E 8: 2 Component D: Component F 10: 1 Component E: Component F 6: 3

Claims (3)

1. An aqueous fabric softener comprising at least one of the compounds of the general formula (I)

   

   in which R is the radical of a fatty acid having from 14 to 18 carbon atoms and iodine numbers in the range 15-25 and
   a = 1, 2 or 3.
2. The aqueous fabric softener as claimed in claim 1 in which the ratio of triethanolamine : fatty acid = 1 : 1.6 to 1 : 2.
3. The aqueous fabric softener as claimed in claim 1 in which R is the radical of a tallow fatty acid or palm fatty acid having iodine numbers from 15 to 5.