JP2017503090A - Wool refining method - Google Patents

Abstract

A method for refining wool is provided. The present invention refines wool by contacting the wool with an aqueous composition comprising alcohol alkoxylate, water, and optional additives such as hydrotropes that act as stabilizers and / or dispersants. Provide a way to do it. The composition was found to exhibit both high detergency in wool refining and high stability when stored at room temperature or lower temperatures, while maintaining a high level of lanolin recovery. [Selection] Figure 1

Description

  The present invention relates to a method for scouring wool, and more particularly to a method for refining wool using a composition comprising an alcohol alkoxylate.

  Known as “greasy wool” or “wool in the grease”, the raw wool from sheep is high levels of lanolin, as well as dirt, dead skin, sweat Contains residues, pesticides, and plant matter. Before it can be used for commercial purposes, wool needs to be refined through the process of washing greedy wool. Scouring can be as simple as a hot water bath or as complex as an industrial process using detergents and alkalis and specialized equipment.

  Lanolin removed from wool is useful and widely used in cosmetics such as hand cream. Lanolins typically wash wool with hot water using a special wool scouring detergent to remove dirt, wool grease (crude lanolin), swints (sweat salinity), and other deposits on the wool Is extracted. Wool grease is continuously removed by a centrifuge during this washing process, which centrifuges the wool grease into a waxy material that melts at about 36-42 ° C (96-108 ° F). Concentrate.

  Like many natural products, the composition of lanolin is complex and variable. For example, typical high purity lanolin consists mostly of long chain waxy esters (about 97% by weight) with the remainder being lanolin alcohol, lanolinic acid, and lanolin hydrocarbon. In lanolin, it is estimated that there are 8,000 to 20,000 different lanolin esters resulting from combinations between as many as 200 different lanolinic acids identified to date and as many as 100 different lanolin alcohols. Due to the complex composition of lanolin, long-chain esters, hydroxy esters, diesters, lanolin alcohol, and lanolin acid, there is always a need to develop detergents that can efficiently and quickly remove lanolin and impurities from wool. I came.

  In general, there are two main criteria for evaluating detergents used in wool refining. 1) Degreasing efficiency, usually characterized by the whiteness of the wool after washing and the grease remaining on the wool, and 2) the efficiency of lanolin recovery from wastewater. For newly developed detergents, both standards should be equivalent to or better than the traditional detergents used in the wool smelting industry, so that the amount and quality of lanolin and no foreign matter is present Preferably both are optimized and the economic benefits are maximized. In addition, the environmental aspects of the proposed detergent will need to be taken into account. Therefore, it is preferable to have a highly efficient detergent, so that a small amount of detergent can be used, and it is further preferred that the detergent is easily biodegraded.

WO 94/00508 discloses that compounds derived from alkenyl succinic anhydrides, especially having a C ₁₄ -C ₂₂ alk (en) yl group and / or functional substituents in other parts of the molecule, It has been disclosed to provide materials having surprisingly different properties. Especially in aqueous systems, they work well as nonionic surfactants with unexpected cloud point properties that exhibit good performance, especially at high temperatures, and have good behavior in alkaline conditions. The surfactant has good biodegradability. The end use of the above surfactants, including wool refining, has also been disclosed. The above surfactant is a very effective surfactant for wool refining, and can maintain good activity even when used for refining fine fiber wool even after multiple refining cycles. Was mentioned. Although the above references have disclosed specific surfactants with good performance in wool refining, compositions containing such surfactants and such specific combinations are used as detergents for the wool refining process. I didn't focus on that.

  WO 99/16942 disclosed a method of refining fibers such as wool with a modified refining machine and chemically treating them to produce refining fibers that are significantly improved with respect to several important quality parameters. In general, the method includes a series of stepwise processes to obtain fibers such as wool that have been acid extracted, bleached, chemically reduced, and treated with detergents and dispersants, in which nonionic Detergents are used for fiber refining, low foam nonionic detergents are used with dispersants and optional reducing agents to further refine the fibers, and EDTA is sulfuric acid and optional to extract iron from the fibers. Used with reducing agent. The above method is a complex process combining different processing steps, and different chemical substances are used in different processing steps.

[Patent Document 1] International Publication No. 94/00508
[Patent Document 2] International Publication No. 99/16942

  The present invention provides a method for refining wool using a composition comprising an alcohol alkoxylate. The composition can degrease wool at relatively low doses and more quickly remove lanolin or grease from the wool. Moreover, the composition has excellent storage stability and overcomes some of the storage problems observed with conventional detergents.

The present invention has developed a series of wool scouring detergents based on an aqueous composition comprising an alcohol alkoxylate, water, and optional additives. The additive includes a quaternary ammonium compound that acts as a hydrotrope, a polymer dispersant that suspends soil particles and prevents soil redeposition, a chelating agent that chelates metal ions such as Ca ²⁺ , Mg ²⁺ , and Including, but not limited to, fillers that improve the antifreeze stability of the formulation and modify the rheology of the product. It has been found that the composition according to the present invention exhibits both high detergency in wool refining and high stability over a wide temperature range, with improved lanolin recovery efficiency and purity.

According to the present invention, the alcohol alkoxylate used as the surfactant is represented by the following general formula (I):
RO (AO) _n -H (I)
An alcohol alkoxy wherein R represents a linear or branched hydrocarbyl group having 4 to 22 carbon atoms, preferably 6 to 13 carbon atoms, more preferably 9 to 11 carbon atoms. It is in the form of a rate mixture.

In the above formula (I), AO represents a C _{2 to} C ₆ alkyleneoxy unit, and n is 1 to 20, preferably 2 to 9, and more preferably 4 to 7. “N” means the number of moles of alkyleneoxy units added per mole of surfactant of formula (I), which is an average value.

  The solubility of the detergent and the ability to emulsify lanolin is related to the HLB value of the alcohol alkoxylate used in the composition. Unless indicated otherwise in the present invention, HLB values are calculated according to the Davis scale (0-40) for both cationic and nonionic surfactants referred to in the present invention. In general, the length of both the hydrophobic alkyl chain and the hydrophilic alkyloxy chain of the alcohol alkoxylate determines the HLB value of the resulting alcohol alkoxylate. Preferably, the alcohol alkoxylate used in the present invention has an HLB of 10.0-15.0. In addition, by including an alcohol alkoxylate with an alkyloxy chain as defined above, the alcohol alkoxylate remains stable during the wool refining process, but the lanolin recovery temperature is increased to or below the lanolin recovery temperature. The cloud point of the resulting wool refining composition is kept in a predetermined range so that it becomes cloudy or phase separates when the temperature is raised beyond. This is because alcohol alkoxylate does not exhibit an effective emulsifier behavior at a temperature higher than the cloud point. As a result, it was found that easy demulsification of lanolin was achieved in the lanolin recovery process. Furthermore, the alcohol alkoxylates having a relatively short hydrophilic alkyloxy chain according to the present invention have improved biodegradability compared to those having a long hydrophilic alkyloxy chain, and are therefore more environmentally friendly. I found it small.

  Surprisingly, it has also been found that the alkyleneoxy unit distribution in alcohol alkoxylates has a significant impact on the detergency and recovery of lanolin. Specifically, when an alcohol alkoxylate with a narrow range of alkyleneoxy unit distribution is used as a surfactant in the detergent composition of the present invention, compared to that observed for a wide distribution range of alkyleneoxy units, It was observed to provide more effective detergency and more complete separation of lanolin.

  The alcohol alkoxylate used according to the present invention is a mixture essentially comprising an unreacted alcohol residue, an alcohol alkoxylate with little addition of alkyleneoxy units, and an alcohol alkoxylate with excess addition of alkyleneoxy units. Without being bound by existing theory, alcohol alkoxylates with low unreacted alcohol residues and low addition of alkyleneoxy units may result in an undesirable odor of defatted wool, with excess alkyleneoxy units. It has been found that the alcohol alkoxylate added to may increase the cloud point of the mixed alcohol alkoxylate, for example, above the recovery temperature of lanolin and adversely affect the recovery efficiency of lanolin.

  As used herein, the term “narrow range” means that the alcohol alkoxylate used in the composition has a narrower mole of alkylene oxyaddition than a normal alcohol alkoxylate, ie, a “wide range” alcohol alkoxylate. Means having a distribution of numbers. Specifically, the narrow range of alcohol alkoxylates used in the present invention has a distribution of moles of alkyleneoxy unit additions of 20 or less, preferably 9 or less, more preferably 7 or less, while alkyleneoxy units. The number of moles of is preferably 2 or more, more preferably 4 or more. As will be appreciated by those skilled in the art, due to the process of preparing the alcohol alkoxylate, the final product is actually an alcohol alkoxylate having a different number of moles of alkyleneoxy unit addition, and a low content of unreacted alcohol. It is in the form of a mixture of raw materials. In the usual process for producing alcohol alkoxylates using KOH, NaOH or the like as an alkoxylation catalyst, the distribution of the number of moles of alkyleneoxy unit addition is wide, and for example, filed on November 24, 1997 by AKZO NOBEL NV In certain processes, such as the process according to EP 0 845 449 B1, a narrower distribution of the number of moles of alkyleneoxy unit addition was achieved than obtained in the normal process.

  According to the present invention, a narrow range mixture of alcohol alkoxylates is 40 wt% or more, preferably 60 wt% or more, more preferably 70 wt% or more of alcohol alkoxylate, 20 or less, preferably 9 or less, more preferably 7 It has the following distribution of the number of moles of alkyleneoxy unit addition, while the number of moles of alkyleneoxy unit addition is preferably 2 or more, more preferably 4 or more.

  The alcohol alkoxylate used in the composition according to the invention has the advantage that it is provided as an aqueous solution. As described above, the cloud point of the composition according to the present invention is relatively low, and is actually kept near room temperature. Thus, at temperatures above room temperature normally applied in either the wool refining process or the lanolin recovery process, the composition of the present invention may become cloudy or even alcohol depending on the characteristics of the different alcohol alkoxylates used in the composition. It is easy to separate into two phases of alkoxylate and water. To stabilize the formulation at high temperatures such as the wool refining temperature of 65-70 ° C., additional hydrotrope is added to the composition, otherwise insoluble nonionic surfactants dissolve in the solution and wettability. Therefore, it is necessary to solubilize the nonionic surfactant to enhance the wettability of the composition. Several hydrotropes for nonionic surfactants are described in various publications. Generally, it is desirable that a hydrotrope suitable for use in the detergent composition of the present invention efficiently solubilizes the nonionic surfactant according to the above formula (I).

In accordance with the present invention, the hydrotrope is further selected to minimize or eliminate adverse effects that the hydrotrope has on the formulation, such as excess foaming, reduced lanolin recovery, and the like. Examples of such hydrotropes include, but are not limited to, bis (ethoxylated) monoalkyl quaternary ammonium compounds of the following formula (II):
Wherein R is C ₆ -C ₂₂ hydrocarbyl, preferably C ₆ -C ₂₂ alkyl or alkenyl, more preferably C ₈ -C ₂₀ alkyl or alkenyl, most preferably C ₁₀ -C ₁₈ alkyl or alkenyl; R ¹ is C ₁ -C ₄ alkyl, preferably methyl or ethyl, most preferably methyl; x is a number from 1 to 40; y is a number from 1 to 40, where x + y is at least 8, Preferably it is at least 9, most preferably at least 10, and at most 25, preferably at most 20, most preferably at most 17; A ⁻ is an anion, such as a halide ion or a methyl sulfate ion. The individual values of x and y are not important, but the sum is important because it affects the HLB of these compounds. Preferably, the ammonium compounds useful in the present invention have a HLB of 25.0-31.0 and are very highly efficient hydrotropes of nonionic surfactants, and therefore these compounds Helps the cleaning performance of compositions in which these compounds are present with nonionic surfactants.

  When used in the composition of the present invention, the weight ratio between the alcohol alkoxylate and the bis (ethoxylated) monoalkyl quaternary ammonium compound is 99: 1 to 60:40, preferably 90:10 to 70: 30.

  The composition according to the invention is designed to be diluted in an aqueous system. Since the wool grease level and contaminant composition vary, the concentration of detergent in the final solution used can be adjusted accordingly. Specifically, the total amount of alcohol alkoxylate of formula (I) and hydrotrope of formula (II), if present, in the aqueous system is more than 10 ppm and less than 1000 ppm, preferably more than 100 ppm and less than 1000 ppm It is.

  In one aspect of the invention, a method for refining wool is provided. The method includes contacting wool with a composition comprising an alcohol alkoxylate of general formula (I).

  According to one embodiment of the present invention, the alcohol alkoxylate used in the composition of the present invention has a narrow range of alkyleneoxy unit distribution and is 40 wt% or more, preferably 60 wt% or more of the alcohol alkoxylate. More preferably 70 wt% or more has a distribution of alkyleneoxy unit additions of 20 or less, preferably 9 or less, more preferably 7 or less, while the addition of alkyleneoxy units is preferably 2 or more, more preferably 4 or more.

  According to one embodiment of the present invention, the alcohol alkoxylate of general formula (I) is selected from alcohol ethoxylate, alcohol propoxylate or a combination thereof, wherein AO is an ethyleneoxy unit, a propyleneoxy unit Or a combination thereof, wherein R and n are as defined above. In the case of a combination of alcohol ethoxylate and alcohol propoxylate, the addition of ethylene oxide units is on average in the range of 2-9, and the addition of propylene oxide units is on average in the range of 0-5.

  According to one embodiment of the present invention, the hydrotrope selected from bis (ethoxylated) monoalkyl quaternary ammonium compounds of formula (II) is an alcohol alkoxylate of formula (I) and formula (II) The weight ratio of bis (ethoxylated) monoalkyl quaternary ammonium compounds is 99: 1 to 60:40, preferably 90:10 to 70:30.

  According to one embodiment of the present invention, the composition according to the present invention comprises the total amount of alcohol alkoxylate of formula (I) and hydrotrope of formula (II), if present, in the aqueous system. Is designed to be diluted in an aqueous system to a concentration greater than 10 ppm and less than 1000 ppm, preferably greater than 100 ppm and less than 1000 ppm.

  In addition to the components described above, the composition may also contain other optional additives such as alkyl glucosides, alkyl sulfates, alkyl ether sulfates, and the like. In addition, the composition may also contain polymeric dispersants, chelating agents, enzymes, pH adjusters, bactericides, fragrances, colorants, and rheology modifiers, as well as other ingredients commonly found in concentrated detergents. .

  In yet another aspect of the invention, use of the composition according to the invention is provided. In general, the compositions according to the invention may be used as detergents in the wool refining process and / or lanolin recovery, but this is not intended to limit the invention to a particular scope.

  The advantages achieved by the composition of the present invention are as follows.

  1) By using an alcohol alkoxylate with a low number of alkylene oxide units per molecule, the composition of the present invention exhibits superior cleaning efficiency compared to conventional detergents used in wool refining.

  2) The composition of the present invention can provide better lanolin recovery. As mentioned above, alcohol alkoxylates with a low number of alkylene oxide units per molecule form stable emulsions with lanolin under the refining process, but in recovery processes where temperatures above the cloud point are usually applied. Lanolin cannot be emulsified. Thus, the emulsion is broken and the alcohol alkoxylate can release much more lanolin compared to one with a higher number of alkylene oxide units.

  3) The composition of the present invention exhibits excellent product stability. Even in the winter of those cold regions, it can be stored for a long time without becoming cloudy or phase separation.

  The above and other objects, features, and advantages of the present invention will become more apparent to those skilled in the art when described in the embodiments with reference to the accompanying drawings.

Figure 2 is a photograph showing the whiteness of wool after rinsing and drying with different detergent formulations. FIG. 6 is a photograph showing the results of a lanolin recovery efficiency test at different times with different detergent formulations. It is a photograph which shows the result of the separation test in a different detergent formulation.

[Experiment]
The following examples are given for illustration and do not limit the claimed invention. Unless otherwise noted, all percentages are percentages by weight.

  A detergent formulation having the composition described in Table 1 was prepared. A quaternary ammonium compound was added as a hydrotrope to stabilize the formulation at high temperatures and to aid in cleaning.

  In order to evaluate the cleaning efficiency of the formulations in Table 1, the following wool refining test was used. Three 800 g heat baths (65-70 ° C.) were prepared, only the second heat bath contained the detergent mixture (0.01%), and the remaining two were tap water only. Subsequently, the dirty raw hair (20 g) was washed (5 minutes in each hot bath), squeezed and dried, and transferred to the hot bath one after another. This process mimics the simplified wool refining process, with the first heat bath used for the deposition of the swint, the second heat bath used primarily for washing the wool, and the third heat bath used for rinsing. Designed.

  Detergent efficiency was evaluated based on the whiteness of the wool after rinsing and drying and is summarized in Table 1.

  Comparing the detergency results with # 1, # 2, # 3, and # 4, it is clear that increasing the hydrotrope concentration improves the whiteness of the washed wool. When the mixture consists of 30% hydrotrope, the whiteness of the washed wool corresponds to the whiteness of the wool washed with NP-9. Since the detergency efficiency of nonionic surfactants is constrained by the cloud point of the surfactant, which correlates with the concentration of hydrotrope, this series of refinements results in achieving optimum detergency efficiency Demonstrates that hydrotrope concentration is important.

[Hydrotrope test]
In this example, formulations were made using multiple hydrotropes listed in Table 2 and compared for hydrotrope efficiency. The lower the amount of hydrotrope that must be added to make the formulation clear at room temperature, the more effective it is as a solubilizer. The numerical values in Table 2 are expressed in wt% units, and water is added to make the total 100%.

[Lanoline recovery efficiency test]
To compare lanolin recovery efficiencies, a series of formulations with 1.00 g detergent, 8.00 g H ₂ O, and 0.50 g lanolin were mixed well and photographed to obtain a solution at 70 ° C. The characteristics of the emulsification process were clarified.

  As shown in FIGS. 2 and 3, from left to right, C9-11 alcohol + 4EO (narrow range ethoxylate), C9-11 alcohol + 5.5EO (narrow range ethoxylate) C9-11 alcohol + 6EO (normal range ethoxylates), C9-11 alcohol + 8EO (normal range ethoxylates), and nonylphenol + 9EO detergents. Lanolin was concentrated in a nonionic surfactant layer that appeared light amber. The results show that C9-11 alcohol + 4EO (narrow range ethoxylate) started demulsification within 5 minutes, but the others did not start demulsification until 30 minutes. C9-11 alcohol + 4EO and C9-11 alcohol + 5.5EO (both in a narrow range of ethoxylates) show more complete separation than others. These results clearly demonstrate that a narrow range of alcohol ethoxylates with a low number of EO additions have advantages over the normal range in lanolin recovery. In contrast, nonylphenol + 9EO, if any, shows a slightly higher layer of lanolin, and instead all lanolin is well solubilized in the aqueous layer.

[Low temperature stability test]
Since detergents are usually pumped into a wash tank, it is important to study the stability of the detergent under low temperature conditions. A series of detergent mixtures were mixed with the composition shown in Table 3, and the phase behavior was observed after the mixture was stored at 2 ° C. and −22 ° C. overnight.

  All five mixtures appeared as clear single phase liquids at room temperature. The mixture became a cloudy translucent liquid when left overnight at 2 ° C. No phase separation was observed in any of the mixtures. The mixture became a white solid without phase separation after overnight at −22 ° C. Gelling or precipitation does not occur in these mixtures at low temperatures (2 and -22 ° C), and when removed from low temperatures, all samples are clear when left at room temperature without shaking or mixing. It is worth noting that it was possible to return to a single-phase liquid. This study demonstrates that these detergent mixtures exhibit excellent stability at low temperatures. These mixtures are therefore suitable for use in winter in their cold regions.

Claims (11)

A method for refining wool, the following general formula (I):
RO (AO) _n -H (I)
Wherein R represents a linear or branched hydrocarbyl group having 4 to 22 carbon atoms, AO represents an alkyleneoxy unit having 2 to 6 carbon atoms, and n is in the range of 1 to 20. And wherein the wool comprises contacting the wool with an aqueous composition comprising an alcohol alkoxylate of 40 wt% or more of the alcohol alkoxylate having a distribution of alcohol alkyleneoxy unit addition in the range of 2-20.   The method of claim 1, wherein 40 wt% or more of the alcohol alkoxylate has a distribution of the alcohol alkyleneoxy unit addition in the range of 4-9.   The method of claim 1, wherein 40 wt% or more of the alcohol alkoxylate has a distribution of the alcohol alkyleneoxy unit addition in the range of 4-7.   The method of claim 1, wherein AO is selected from ethylene oxide units, propylene oxide units, or combinations thereof.   The AO is selected from the combination of ethylene oxide units and propylene oxide units, the ethylene oxide unit addition is in the range of 2-9, and the propylene oxide unit addition is in the range of 0-5. the method of.   The process according to claim 1, wherein R represents a linear or branched hydrocarbyl group having 4 to 22 carbon atoms.   The process according to claim 1, wherein R represents a linear or branched hydrocarbyl group having 6 to 13 carbon atoms.   The process according to claim 1, wherein R represents a linear or branched hydrocarbyl group having 9 to 11 carbon atoms. The composition comprises a bis (ethoxylated) monoalkyl quaternary ammonium compound having the following formula (II)
In which R is C ₆ -C ₂₂ hydrocarbyl, preferably C ₆ -C ₂₂ alkyl or alkenyl, more preferably C ₈ -C ₂₀ alkyl or alkenyl, most preferably C ₁₀ -C ₁₈ alkyl or alkenyl; R ¹ is C ₁ -C ₄ alkyl, preferably methyl or ethyl, most preferably methyl; x is a number from 1 to 40; y is from 1 to 40, where the sum of x + y ranges from 8 to 25 The method of claim 1, further comprising a hydrotrope selected from: wherein A ⁻ is an anion.   The process according to claim 9, wherein the weight ratio of the alcohol alkoxylate of formula (I) to the hydrotrope of formula (II) is 99: 1 to 60:40.   11. The total amount of the alcohol alkoxylate of formula (I) and the hydrotrope of formula (II), if present, in the composition is 10 to 1000 ppm. The method according to item.