AU766557B2

AU766557B2 - Method for washing raw wool

Info

Publication number: AU766557B2
Application number: AU49149/00A
Authority: AU
Inventors: Wolfgang Becker; Christa Hartschen; Bernd Wahle
Original assignee: Cognis Deutschland GmbH and Co KG
Current assignee: Cognis IP Management GmbH
Priority date: 1999-05-08
Filing date: 2000-04-29
Publication date: 2003-10-16
Anticipated expiration: 2020-04-29
Also published as: WO2000068492A1; EP1177341B1; DE19921330A1; EP1177341A1; DE50014369D1; AU4914900A

Description

Method for Washing Raw Wool This invention relates to a process for washing wool, more particularly raw wool, and to the use of certain fatty alcohol ethoxylates for washing wool.

In the processing of wool, the raw material first has to be freed from the adhering wool wax and suint and from sand, dirt and other impurities. In the industrial washing of wool, surfactants based on nonylphenol ethoxylates are used for this purpose. Unfortunately, these surfactants are toxicologically unsafe. However, they do show favourable price/performance behaviour so that they have not yet been universally replaced by ecologically safe substances.

The problem addressed by the present invention was to find an ecologically safe alternative to the toxicologically unsafe surfactants for example based on nonylphenol hitherto used to wash wool, more particularly on an industrial scale, which would represent an acceptable alternative to the industry both in terms of washing performance and in terms of price.

It has been found that certain fatty alcohol derivatives exhibit the required properties.

In a first aspect of this invention, there is provided a use of branched fatty alcohol ethoxylates containing 8 to 22 carbon atoms in admixture with aminodicarboxylic acids or their salts, oligomers or polymers thereof and/or together with aspartic acid and/or glutamic acid or their salts, oligomers or polymers thereof and/or alkyl phosphonic acids or derivatives thereof as surfactants for washing raw wool.

The invention also provides a surfactant for washing raw wool comprising one or more branched fatty alcohol ethoxylates containing 8 to 22 carbon atoms in admixture with one or more aminodicarboxylic acids or their salts, oligomers or polymers thereof and/or together with aspartic acid and/or glutamic acid or their salts, oligomers or polymers thereof and/or alkyl phosphonic acids or derivatives thereof.

SThe invention further provides a process for washing wool, wherein the wool is contacted at 25 least once with an aqueous liquor containing branched fatty alcohol ethoxylates containing 8 to 22 carbon atoms, in admixture with dicarboxylic acids or derivatives thereof and/or alkyl phosphonic acids or derivatives thereof, the liquor having a temperature of 25 to 80°C, and the wool is then dried in known manner.

In another aspect, the invention provides a process for washing raw wool, wherein the raw wool is contacted at least once with an aqueous liquor containing fatty alcohol ethoxylates containing 8 to 22 carbon atoms in admixture with aminodicarboxylic acids or their salts, oligomers or polymers thereof and/or together with aspartic acid and/or glutamic acid or their salts, oligomers or polymers thereof and/or alkyl phosphonic acids or derivates thereof, the liquor having a temperature of 25 to 80 0 C, and the raw wool is then dried in known manner.

35 According to DIN 60001 T1 (October 1990), wool is understood to be both the ca. 5 to 30 cm ong hairs of various domestic sheep breeds and the hair of South American lamas, camels, rabbits and goats. However, most industrially processed wool comes from sheep. Wool is a protein fibre which consists mainly of keratin, one of the scleroproteins. The raw wool UbC/Cognis/571446response WO 00/68492 PCT/EP00/03892 obtained from sheep by shearing is soiled with sand, dust, etc. and contains large amounts of suint, a mixture of potassium salts of fatty acids, hydroxy, amino and other organic acids formed by the drying of animal perspiration. In addition, raw wool contains wool fat which is formed in the sebaceous gland of sheep and which consists mainly of lanolin, a mixture of various fatty acid esters. Wool from Australian Merino sheep, for example, contains ca. 49% by weight of wool fibers, ca. 19% by weight of dirt, ca. 16% by weight of fat, ca. 10% by weight of water and ca. 6% by weight of suint. Further particulars can be found in Ullmann's Encyclopedia of Industrial Chemistry, Volume 28 A, Fifth Edition, 1996, pages 395 to 421.

According to the invention, fatty alcohol ethoxylates are used in the washing of wool. These are ethoxylated fatty alcohols which correspond to general formula

R

1 OH (I) in which R' is a branched alkyl group containing 8 to 22 carbon atoms and 0 to 3 double bonds. However, saturated alcohols corresponding to formula are preferably used, fatty alcohol ethoxylates based on branched fatty alcohols containing 8 to 15 carbon atoms being particularly preferred. Fatty alcohols such as these can be synthesized by known methods, the branched products of the oxo synthesis being particularly suitable. Another source of branched fatty alcohols suitable for the purposes of the invention is the so-called Guerbet reaction. In the Guerbet reaction, linear primary fatty alcohols are condensed under high pressure at 2000C in the presence of copper or sodium via the intermediate stage of the aldehydes and subsequent aldol reaction to form branched fatty alcohols. Due to the management of the reaction, 2-alkylalkanols are obtained by Guerbet synthesis. Accordingly, the Guerbet alcohols WO 00/68492 PCT/EP00/03892 correspond to general formula (II):

R

2 CH CH 2 OH (II)

R

3 where R and R' independently of one another represent an alkyl group containing 1 to 12 carbon atoms. According to the invention, particularly suitable branched fatty alcohols are 2-ethyl hexanol, isooctanol, isononanol, isodecanol, isoundecanol, isododecanol and branched alcohols containing 13 and 15 carbon atoms. Depending on the particular synthesis route, technical mixtures of various isomers are obtained.

Besides the single-branch fatty alcohols, multiple-branch fatty alcohols, for example 2,6-dimethyl-4-heptanol, 3,5,5-trimethyl-l-hexanol or trimethylheptanol, are also suitable. In principle, mixtures of ethoxylates of the above-mentioned branched fatty alcohols are used. The branched fatty alcohols are ethoxylated in known manner under pressure and at high temperatures in the presence of acidic or basic catalysts, alkoxylated compounds reacted with 4 to 12 mol and preferably 5 to 10 mol of ethylene oxide per mole of fatty alcohol preferably being used.

The fatty alcohol ethoxylates are used for washing wool, preferably raw wool, and to this end are dissolved as a surfactant component in the wash liquor. The ethoxylates are used in quantities of 0.1 to 10 g/l, preferably in quantities of 0.5 to 5 g/l and more particularly in quantities of to 2.5 g/l (active substance) for this purpose.

It has proved to be of advantage to use other auxiliaries selected from the group of dicarboxylic acids or derivatives thereof and/or alkyl phosphonic acids or derivatives thereof in addition to the fatty alcohol ethoxylates. Accordingly, the use of such auxiliaries is particularly preferred for the purposes of the present technical teaching.

WO 00/68492 PCT/EP00/03892 Dicarboxylic acids correspond to general formula (III):

HOOC-(CH

2 )n-COOH (111) in which n is zero or an integer of 1 to 8. Besides the dicarboxylic acids, their derivatives, especially their nitrogen-containing derivatives, are preferred auxiliaries in the context of the present technical teaching.

Aminodicarboxylic acids, such as aspartic and glutamic acid, their salts and the oligomers and polymers of these compounds are preferably used. The use of polyaspartic acid and sodium or potassium salts thereof is most particularly preferred. The molecular weight of the polyaspartic acid is preferably in the range from 2,000 to 4,000 and more particularly in the range from 2,000 to 3,000. The products are distinguished in particular by good biodegradability. Another preferred embodiment is characterized by the use of succinic acid or derivatives thereof, more particularly iminodisuccinates, especially the corresponding sodium or potassium disalts.

Alkyl phosphonic acid derivatives are also suitable auxiliaries for washing wool. Hydroxyethane diphosphonic acid is particularly preferred and is preferably used in combination with aminotrismethylene phosphonic acid. Where such auxiliaries are used, their concentration in the wash liquor is in the range from 0.01 to 1.0 g/l (active substance). The auxiliaries are present in the liquor in quantities of typically 0.1 to 0.8 g/l. Mixtures are also suitable, in which case the total concentration of auxiliaries is at most 1.5 g/l wash liquor. Particularly preferred mixtures are combinations of branched C10-12 fatty alcohols with 5 to 8 parts EO and polyaspartic acid or salts thereof.

Surprisingly, the presence of the above-mentioned auxiliaries leads to a distinct improvement in washing performance, i.e. the percentage of residual fat in the wool is again distinctly reduced. Typical residual fat WO 00/68492 PCT/EP00/03892 levels are in the range from 0.1 to 5% by weight. In addition, the washed wool shows better reflectance values. The fatty alcohol ethoxylates according to the invention are also toxicologically safe and readily biodegradable.

In another embodiment, the present invention relates to a process for washing wool in which the wool is contacted at least once with an aqueous liquor containing branched fatty alcohol ethoxylates containing 8 to 22 carbon atoms, optionally in admixture with dicarboxylic acids or derivatives thereof and/or alkyl phosphonic acids or derivatives thereof, and is then dried in known manner. The temperature of the wash liquor is in the range from 25 to 800C. Washing temperatures of 40 to 700C are preferred, values in the range from about 45 to 650C being particularly preferred. The pH of the wash liquor is preferably between 7 and 9.

The following method is used for the laboratory testing of detergents.

In order to differentiate the effectiveness of various washing systems, the spent wash liquor is made up after each wash to its original volume with (small amounts of) fresh liquor so that this regenerated liquor can be used.

The size of the increase in the residual fat content and of the reduction in whiteness correlates with the effectiveness of the system. In general, the wool is contacted with the liquor between 1 and 15 times.

On an industrial scale, this is done is special washing baths, the wash liquor being exchanged between the individual baths in dependence upon the degree of soiling. The industrial processes are generally carried out continuously, the wool passing successively through the individual baths and being freed from the wash liquor after each bath by squeezing out. The residual fat content of the wool after undergoing the washing process is preferably in the range from 0.1 to 2% by weight and more particularly in the range from 0.2 to 1% by weight, based on the weight of the raw wool. After the wool has been contacted with the wash liquor, the washed raw wool is dried in known manner, i.e. by hot air, and may then be WO 00/68492 PCT/EP00/03892 further processed.

Examples The following products were tested: Table I: ethoxylated fatty alcohols No. Compound Biodegradability Eliminatability in Test No.* 1 Isodecyl alcohol 5 EO Readily degradable ca. 90% 301 E 2 Isodecyl alcohol 6 EO Readily degradable ca. 90% 301 E 3 Undecyl alcohol 5 EO Readily degradable ca. 80% 301 E 4 Undecyl alcohol 6 EO Readily degradable ca. 80% 301 E Undecyl alcohol 7 EO Readily degradable ca. 80% 301 E 6 Isododecanol 6.5 EO Readily degradable ca. 70% 301 E 7 Isododecanol 7.4 EO Readily degradable ca. 70% 301 E 8 Isododecanol 6 EO Readily degradable ca. 70% 301 E 9 Isododecanol 8 EO Readily degradable ca. 70% 301 E Table II: additives No. Compound Biodegradability Eliminatability in Test No.* Polyaspartic acid, Na salt Readily 68% 301 B (38% by weight, Bayer AG) degradable Iminodisuccinate, Na salt Very readily 79% 301 E by weight, Bayer AG) degradable Hydroxyethane Eliminatable ca. 50% 302 B diphosphonic acid/aminotrismethylene phosphonic acid mixture (29% by weight AS, Henkel KGaA) OECD Test WO 00/68492 PCT/EP00/03892 Procedure Raw wool with various fat contents up to ca. 20% by weight was placed in an aqueous solution of the detergent and gently agitated. The pH value was neutral or was adjusted with soda to ca. 8.5. The raw wool sample weighed 50 g. The concentration of the fatty alcohol ethoxylate (Table I) in the wash liquor was 1.0 g/l. Additives (Table II) were optionally used in quantities of 0.10, 0.25 and 0.5 g/l. The temperature of the wash liquor was 64°C and 54°C. The washing time was 6 minutes.

The wool samples were then removed from the liquor and centrifuged for 20 seconds (Miele WZ 5942). This washing process was repeated up to 15 times. The washed and centrifuged wool samples were then dried at 700C. In order to be able better to differentiate the behavior of the individual compounds, several wash cycles were carried out with a regenerated liquor in the described laboratory tests. To this end, the liquor was made up with fresh liquor after each wash and the regenerated liquor was used for the next wash. In this way, the amount of fat and dirt in the liquor naturally increases continuously. However, the fat and dirt suspending capacity of the tested surfactants is particularly clear at high fat and dirt levels.

The washed wool samples were tested for: reflectance at 460 nm (Datacolor Spektraflash) washing performance based on the residual fat content (extraction of the wool sample with acetone for 2.5 h in a Soxhlet in accordance with DIN 54278) sedimentation of the wash liquor: 2 liters of the wash liquor were poured into a measuring cylinder up to the calibration mark and sedimentation was determined after 24 and 48 hours and expressed in ml.

fat separation of the wash liquor: 2 liters of the wash liquor were

L

WO 00/68492 PCT/EP00/03892 poured into a measuring cylinder up to the calibration mark and the fat creaming of the wash liquor was determined after 24 and 48 hours and expressed in ml.

The results are set out in Tables III to VIII. The results of a commercially available product based on a C9/11 isopolyglycol ether and the results of a nonylphenol polyglycol ether are set out for comparison in Tables IX and X, respectively. It can be seen that some of the products according to the invention are more efficient than the known products.

Unlike the comparison products, especially the nonylphenol derivative, the products according to the invention are toxicologically safe and biodegradable.

Table III Raw wool: fat content ca. 20% by weight, neutral, 64°C Residual fat content Whiteness Product Wash cycle 460 nm 1 1 0.4 60.3 1.5 46.2 1.5 45.2 3.8 35.6 2 1 0.5 59.7 0.6 47.9 1.6 46.5 2.3 38.4 WO 00/68492 PCT/EP00/03892 Table IV Raw wool: fat content ca. 20% by weight, neutral, 64°C RF~Sid~lRl fat content Whiteness Product Wash cycle 460 nm 3 1 0.6 57.9 1.3 42.9 1.8 38 2.3 33.6 4 1 0.3 61.3 2.6 36 3.5 31.5 4.2 32.7 1 0.4 56.1 0.8 51.8 1.5 41.1 2.4 37.9 Table Va Raw wool: fat content ca. 20% by weight, neutral, 64°C Residual fat content Whiteness Product Wash cycle 460 nm 9 0.9 0.9 54.9 1.1 49.4 1.4 45.2 2 41.1 9+A 0.5 g/l 1 0.5 60.2 1.2 49.7 1.8 46.5 1.8 43.2 i WO 00/68492 PCT/EP00/03892 Table Vb Raw wool: fat content ca. 12% by weight, neutral, 64°C Residual fat content Whiteness Product Wash cycle 460 nm 8 1 0.9 59.5 1.6 57.4 2.4 52.6 3.5 49.8 8+A 0.5g/I 1 1.0 61.4 1.8 55.2 2.3 53.0 2.2 50.8 8+B 0.5 g/I 1 0.6 1.5 55.0 1.8 52.7 2.5 51.2 Table VI Raw wool: fat content 20% by weight, neutral, 64°C Residual fat content Whiteness Product Wash cycle 460 nm 6 1 0.5 59.9 1.2 47.8 2.5 36.6 2.7 34.3 7 1 0.4 57.8 1.5 44.9 4.6 33.9 5.9 28.3 8 1 1 57.1 4.6 42.5 8.2 31 10 31.5 WO 00/68492 PCT/EP00/03892 Table VII Raw wool: fat content ca. 20% by weight, neutral, 64°C Residual fat content Whiteness Product Wash cycle 460 nm 7+C 0.5 g/I 1 0.2 58 1.1 51.4 2.9 40.1 9.5 27.8 7+A 0.5 g/1 1 0.8 56.1 2.3 43.9 2.8 38.9 6.3 32.9 Table VIII: Raw wool: fat content ca. 20% by weight, alkaline, 54°C Product Wash cycle Residual fat Whiteness 9 1 0.5 57.3 0.8 52.1 1.1 45.3 1.1 44.1 9+A 0.5 gl 1 0.4 58.2 0.9 52.5 1.5 44.6 1.7 42.2 9+A 0.25 g/l 1 0.5 58.1 1.0 49.8 0.8 46.3 0.9 42.7 9+A 0.1 glI 1 0.5 61.3 1.1 54.3 1.3 51.7 1.5 49.9 WO 00/68492 WO 0068492PCT/EPOO/03892 Table IX (comparison), neutral, 6400 Whiteness Product Wash cycle 460 nmn Comparison X 1 0.6 60.4 Raw wool old Fat content ca. 12% by weight 1.1 56.3 2.0 51.6 2.2 49.8 Comparison X 1 0.7 58.8 Raw wool Fat content ca. 20% by weight .5.4 37.5 9.5 33.1 19.8 25.4 Comparison X 0.5 gI 1 0.8 62.8 Raw wool Fat content ca. 12% by weight 5 0.8 55.4 10 1.6 53.4 15 2.1 50.2 Comparison su rfactant X: iso-C 9 11 -polyglycol ether Table X: fat content ca. 20% by weight, alkaline, 54*C Product Wash cycle Residual fat Whiteness 400 nmn 9+A 0.1 g/l 1 0.5 60.6 5 0.8 53.2 10 1.0 44.0 15 1.2 45.9 Comparison Y 1 0.4 61.8 0.7 54.9 0.8 51.6 _15 1.2 49.2 Comparison surfactant Y: nonyiphenol polyglycol ether

Claims

1. A surfactant for washing raw wool comprising one or more branched fatty alcohol ethoxylates containing 8 to 22 carbon atoms in admixture with one or more aminodicarboxylic acids or their salts, oligomers or polymers thereof and/or together with aspartic acid and/or glutamic acid or their salts, oligomers or polymers thereof and/or alkyl phosphonic acids or derivatives thereof.

2. The surfactant claimed in claim 1, wherein the branched fatty alcohol ethoxylates contain 4 to 12ml ethylene oxide per mol of fatty alcohol.

3. The surfactant claimed in claim 1 or claim 2, wherein the branched fatty alcohol ethyoxylates contain 8 to 15 carbon atoms.

4. The surfactant claimed in any one of claims 1 to 3, wherein the branched fatty alcohol ethoxylates are used together with polyaspartic acid or salts thereof. The surfactant claimed in any one of claims 1 to 4, wherein the branched fatty alcohol ethoxylates are used together with iminodisuccinates.

6. The surfactant claimed in any one of claims 1 to 5, wherein the branched fatty alcohol ethyoxylates are used in the form of an aqueous solution.

7. The surfactant claimed in claim 6, wherein the aqueous solution contains the branched fatty alcohol ethoxylates in quantities of 0.1 to 10g/L (active substance).

8. The surfactant claimed in claim 7, wherein the aqueous solution contains the branched fatty alcohol ethoxylates in quantities of 0.5 to 5g/L (active substance).

9. The surfactant claimed in claim 7 or claim 8, wherein the aqueous solution contains the branched fatty alcohol ethoxylates in quantities of 0.5 to 2.5g/L (active substance). The surfactant claimed in any one of claims 6 to 9, wherein the aqueous liquor contains the dicarboxylic acids or their derivatives and/or alkyl phosphonic acids or their derivatives in quantities of 0.01 to 1.Og/L (active substance).

13. A surfactant for washing raw wool said surfactant being substantially as hereinbefore described with reference to any one of the examples but excluding the comparative examples.

14. The use of branched fatty alcohol ethoxylates containing 8 to 22 carbon atoms in admixture with aminodicarboxylic acids or their salts, oligomers or polymers thereof and/or together with aspartic acid and/or glutamic acid or their salts, oligomers or polymers thereof and/or alkyl phosphonic acids or derivatives thereof as surfactants for washing raw wool. The use claimed in claim 14, wherein the branched fatty alcohol ethoxylates contain 4 to 12mol ethylene oxide per mol of fatty alcohol.

16. The use claimed in claim 14 or claim 15, wherein the branched fatty alcohol ethyoxylates contain 8 to 15 carbon atoms. 35 17. The use claimed in any one of claims 14 to 16, wherein the branched fatty alcohol ethoxylates are used together with polyaspartic acid or salts thereof.

18. The use claimed in any one of claims 13 to 17, wherein the branched fatty alcohol ethoxylates are used together with iminodisuccinates.

19. The use claimed in any one of claims 13 to 18, wherein the branched fatty alcohol ethyoxylates are used in the form of an aqueous solution. LibC/Cognis/571446response 14 The use claimed in claim 19, wherein the aqueous solution contains the branched fatty alcohol ethoxylates in quantities of 0.1 to 10g/L (active substance).

21. The use claimed in claim 20, wherein the aqueous solution contains the branched fatty alcohol ethoxylates in quantities of 0.5 to 5g/L (active substance).

22. The use claimed in claim 20 or claim 21, wherein the aqueous solution contains the branched fatty alcohol ethoxylates in quantities of 0.5 to 2.5g/L (active substance).

23. The use claimed in any one of claims 19 to 22, wherein the aqueous liquor contains the dicarboxylic acids or their derivatives and/or alkyl phosphonic acids or their derivatives in quantities of 0.01 to 1.Og/L (active substance).

24. The use of branched fatty alcohol ethoxylates containing 8 to 22 carbon atoms for washing raw wool, said use being substantially as hereinbefore described with reference to any one of the examples but excluding the comparative examples. A process for washing wool, wherein the wool is contacted at least once with an aqueous liquor containing branched fatty alcohol ethoxylates containing 8 to 22 carbon atoms, in admixture with dicarboxylic acids or derivatives thereof and/or alkyl phosphonic acids or derivatives thereof, the liquor having a temperature of 25 to 80 0 C, and the wool is then dried in known manner.

26. The process claimed in claim 25, wherein the branched fatty alcohol ethoxylates contain 4 to 12mol ethylene oxide per mol of fatty alcohol.

27. The process claimed in claim 25 or claim 26, wherein the branched fatty alcohol ethyoxylates contain 8 to 15 carbon atoms.

28. The process claimed in any one of claims 25 to 27, wherein the branched fatty alcohol ethoxylates are used together with polyaspartic acid or salts thereof.

29. The process claimed in any one of claims 25 to 28, wherein the branched fatty alcohol ethoxylates are used together with iminodisuccinates. 25 30. The process claimed in any one of claims 25 to 29, wherein the branched fatty alcohol ethyoxylates are used in the form of an aqueous solution.

31. The process claimed in claim 30, wherein the aqueous solution contains the branched fatty alcohol ethoxylates in quantities of 0.1 to 10g/L (active substance).

32. The process claimed in claim 31, wherein the aqueous solution contains the branched fatty alcohol ethoxylates in quantities of 0.5 to 5g/L (active substance).

33. The process claimed in claim 31 or claim 32, wherein the aqueous solution contains the branched fatty alcohol ethoxylates in quantities of 0.5 to 2.5g/L (active substance).

34. The process claimed in any one of claims 25 to 33, wherein the aqueous liquor contains the dicarboxylic acids or their derivatives and/or alkyl phosphonic acids or their derivatives in 35 quantities of 0.01 to 1.Og/L (active substance). A process for washing raw wool, wherein the raw wool is contacted at least once with an S aqueous liquor containing fatty alcohol ethoxylates containing 8 to 22 carbon atoms in admixture with aminodicarboxylic acids or their salts, oligomers or polymers thereof and/or together with aspartic acid and/or glutamic acid or their salts, oligomers or polymers thereof and/or alkyl phosphonic acids or UbC/Cognis/57l446response I derivates thereof, the liquor having a temperature of 25 to 80 0 C, and the raw wool is then dried in known manner.

36. The surfactant claimed in claim 35, wherein the aqueous liquor contains the dicarboxylic acids or their derivatives and/or alkyl phosphonic acids or their derivatives in quantities of 0.01 to 1.Og/L (active substance).

37. A process for washing wool comprising the steps substantially as hereinbefore described with reference to any one of the examples but excluding the comparative examples.

38. Washed wool produced by the process of any one of claims 25 to 37. Dated 13 August 2003 COGNIS DEUTSCHLAND GMBH CO. KG Patent Attorneys for the Applicant/Nominated Person SPRUSON&FERGUSON g* S *:see .oo o** 0 0 *l o *o *00 O* *be• LibC/Cognis/571446response