Improved laundering method

Description

Technical field

[0001] The area of technology pertaining to this invention is that of laundering fabrics, particularly in the context of commercial or industrial laundries which handle very heavy soil loads. The field of compositions useful for laundering fabrics to remove oily soil is also dealt with herein.

Background art

[0002] The prior art teaches that laundering processes may be conducted at a washing temperature roughly equal to the cloud point temperature of the washing liquor, but does not appear to suggest that washing should be carried out substantially above the cloud point temperature, yet below the phase coalescence temperature. For example, U.S. Patent No. 3,707,506, issued to Lozo on December 26, 1972, suggests at Col. 1, lines 44-54, that there is some error in the prior art belief that maximum efficiency in removing dirt with a nonionic washing liquor is obtained at temperatures below the detergent cloud point. The Lozo reference does not provide any positive teaching, however, as to what washing temperature may be selected to improve washing results. An article by Cook entitled "Versatility of Nonionic Detergents" published by Soap and Chemical Specialities, May 1975, pages 47-49, indicates that a nonionic detergent works best if its surface active agent is not completely dissolved, but rather is partially in a colloidal state which promotes micelle formation. U.S. Patent No. 3,925,224, issued to Winston on December 9, 1975, similarly teaches that a cloudy solution of a surfactant is optimal for laundering fabrics. It is believed that the Cook and Winston references essentially describe washing at the cloud point temperature of the washing liquor rather than at a temperature substantially above the cloud point temperature.

[0003] Two references have been found which provide teachings contrary to the present development, indicating that it is undesirable to wash at or above the cloud point temperature. These references are: U.S. Patent No. 3,890,238, issued to Boehmer on June 17,1975; and Colwell et al., "Considerations in the Use of Nonionics Surface Active Agents", American Dye Stuff Reporter, Vol. 39, Sept. 4, 1961, page 679.

[0004] British Patent Specification No. 1,518,676, naming Mould et al. as inventors and published July 19, 1978, teaches washing substantially above the phase coalscence temperature of the washing liquor, but not within the temperature range between the cloud point and phase coalescence temperatures.

[0005] The prior art teaches that it is known to add a strong electrolyte to an aqueous solution containing a nonionic surfactant in order to lower the cloud point of the solution. For example, see Schick, Nonionic Surfactants, Marcel Dekker, Inc. (NY, 1966), Library of Congress Cat. Card No. 66-22492, especially pages 572-573.

[0006] Numerous prior art references can be found which generally indicate that a nonionic detergent may be combined with a builder, a strong electrolyte, or mixtures thereof to form washing compositions. However, no such disclosures are known which reveal compositions having the relatively narrow ranges of proportions of strong electrolytes and builders which are necessary to realize the present improvement at specific temperatures which are typical in the field of commercial laundering.

Summary of the invention

[0007] According to the invention there is provided a process for laundering oily soil from a fabric by contacting the fabric with an aqueous washing liquor containing a nonionic surfactant wherein the process comprises

a) treating said fabric with a wash liquor having a total surfactant hydrophilic lipophilic balance (HLB) index of from 9.5 to 13, said liquor containing 1400-20,000 ppm of a nonionic surfactant component having a CMC of <50 ppm at 25°C in distilled water, 500-10,000 ppm of a sequestering builder selected from sodium potassium and lithium tripolyphosphate, pyrophosphate, orthophosphate, nitrilo triacetate, ethylene diamine tetra acetate nitrilo trimethylene phosphonate ethylene diamine tetra methylene phosphonate and mixtures thereof and 700-20,000 ppm of a strong electrolyte; and

b) maintaining said washing liquor at a temperature in the range 0.30 (B-A)+A--T<B wherein T is the wash liquor temperature, B is the phase coalescence temperature of the wash liquor and A is the cloud point temperature of the wash liquor.

[0008] The nonionic surfactant used to practice the invention is preferably selected from alkyl phenol ethoxylates, ethylene oxide/propylene oxide block copolymers, and aliphatic ethoxylated alcohols. The condensation products of fatty alcohols having 12 to 15 carton atoms with an average of 5 to 8 ethoxylate moieties per molecule of surfactant are especially preferred, and more preferred is the condensate of a primary fatty alcohol having 14 or 15 carbon atoms with an average of 7 ethoxylate moieties per molecule of surfactant.

[0009] A preferred temperature range for practice of the present invention is given by the expression:

and an especially preferred temperature for practice of the present invention is given by the expression:

The process of the present invention also includes as the preferred embodiments, the use of wash liquors formed of specified compositions, one such composition comprising by weight:

a) 20%-51 % by weight of a C_12-C₁₅ fatty alcohol condensed with 5-8 moles of ethylene oxide per mole of alcohol, preferably 29%-35% of a C₁₄―C₁₅ fatty alcohol condensed with an average of seven moles of ethylene oxide per mole of alcohol;

b) 20%-40% preferably 34%-35% of an alkali metal carbonate and

(c) 20%-51% preferably 30%-36% of an alkali metal pyrophosphate or tripolyphosphate.

Such compositions may be dissolved in water to form a solution which contains from 1000 ppm to 40,000 ppm (0.10% to 4.0%) of the composition.

[0010] The following compositions contain preferred proportions of specific ingredients. They may be diluted in the proportions noted above to form washing liquors which may be used to practice the method disclosed herein.

[0011] These compositions are specifically formulated for optimal washing when a wash temperature of 140°F (60° Celsius) is selected:

(a) 36% sodium tripolyphosphate;

(b) 35% sodium carbonate; and

(c) 29% of the condensate of a primary fatty alcohol having 14 to 15 carbon atoms with an average of 7 ethylene oxide moieties per molecule of surfactant; or

(a) 31% tetrasodium pyrophosphate;

(b) 34.6% sodium carbonate; and

(c) 34.4% of the condensate of a primary fatty alcohol having 14 to 15 carbon atoms with an average of 7 ethylene oxide moieties per molecule of surfactant.

[0012] A further preferred composition used in the process of the invention and incorporating a mixed surfactant system comprises

(a) 10%-40% preferably 15%-35% of a mixture of a C₁₂-G₁₅ fatty alcohol condensed with an average of 6-7 moles of ethylene oxide per mole of alcohol and a C_12-C₁₅ primary alcohol condensed with an average of three moles of ethylene oxide per mole of alcohol.

(b) 50%-70% preferably 55% to 65% of a strong electrolyte selected from sodium carbonate, sodium metasilicate and mixtures thereof.

(c) 10%-25% preferably 12%-15% of sodium tripolyphosphate and

(d) from 0.5% to 5% of an anionic surfactant selected from sodium C₁₂ alkyl benzene sulphonate, sodium dodecyl hexa ethoxy sulphate sodium tallow alkyl sulphate and mixtures thereof. These lower pH compositions and washing liquors are gentler to fabrics than the typical compositions used in industrial laundries, which provide a pH in the wash liquor greater than 11.5.

Brief description of the drawings

[0013] 

Figure 1 is a graph showing the relation of the cleaning performance of a washing liquor of the present invention to washing temperature, for a surfactant system with a cloud point temperature of 36°C and a phase coalescence temperature of 71°C.

Figure 2 is a graph showing the cloud point temperature (C) and phase coalescence temperature (B) of a 3000 ppm solution of the condensate of a primary fatty alcohol having 14 to 15 carbon atoms with an average of 7 ethylene oxide moieties per molecule of surfactant as a function of electrolyte (sodium sulfate) concentration. Superimposed is a plot (A) of cleaning performance at 60°C of the solution as a function of electrolyte concentration.

Figure 3 is a graph of cleaning performance versus time for a washing liquor (D) which contains a strong electrolyte, as opposed to a washing liquor (E) which does not.

Figure 4 is a graph of soil removal versus wash time for three nonionic surfactants (F, G, and H) with different hydrophilic/lipophilic balance indices but similar characteristics in other respects.

Figure 5 is a graph of cleaning performance versus time under prior art washing conditions for a surfactant having a high critical micelle concentration (K) versus a surfactant having a low critical micelle concentration (J).

Detailed description of the invention

Definitions

[0014] In the course of describing this invention it will be useful to define the following terms:

By "nonionic surfactant" is meant a surfactant comprising a lipophilic moiety and a hydrophilic moiety, which does not ionize in aqueous solution.

[0015] By "hydrophilic/lipophilic balance index", or "HLB", is meant a numerical index for a given surfactant structure, indicating its balance of hydrophilic and lipophilic properties. A surfactant with a high HLB is more hydrophilic and less lipophilic in character than a surfactant with a low HLB.

[0016] By "critical micelle concentation", or "CMC", is meant the concentration of a surfactant in aqueous solution at which the concentration of monomeric surfactant molecules (as opposed to micelles) is maximized. At concentrations of a surfactant exceeding its CMC, monomer concentration remains essentially constant.

[0017] By "cloud point temperature" is meant the minimum temperature at which the first traces of cloudiness are observed in an aqueous surfactant solution as it is heated. The existence of a cloud point is one of the indicia of nonionic surfactants which are useful to practice the present invention.

[0018] By "phase coalescence temperature" is meant the minimum temperature at which a solution comprising a nonionic surfactant and water separates into two bulk phases, as distinguished from the cloud point temperature at which a single, colloidal bulk phase is observed. (The two bulk phases above the phase coalescence temperature are a largely dehydrated surfactant phase and a phase which is largely water). The presence of a specific phase coalescence temperature in aqueous solution is another characteristic of nonionic surfactants which is a key to the practice of the present invention.

[0019] By "strong electrolyte" is meant a compound which completely ionizes in aqueous solution at moderate concentrations (such as a concentration of 700 ppm to 20,000 ppm).

[0020] By "sequestering builder" is meant a detergent additive which sequesters water hardness to assist a surfactant in performing its intended function. Sequestering builders are electrolytes, but typically are not strong electrolytes as defined herein.

[0021] By "adjuvant" is meant a detergent ingredient which provides a function, such as brightening, bleaching, or the like, other than the functions performed by surface active agents and sequestering builders.

Theory of the invention

[0022] While no limit on the scope of the invention is intended by setting forth the theory of its operation which follows, it is believed that the following theory of operation explains the present invention and distinguishes it from the prior art.

[0023] Molecules of a surface active agent, in particular nonionic surfactants, consist of a lipophilic portion, commonly referred to as a "tail", and a hydrophilic portion, commonly known as a "head". The head, being hydrophilic, prefers an orientation of the surfactant molecule which allows it to be in contact with the water of an aqueous solution. The tail of the surfactant molecule, being lipophilic, prefers an orientation of the surfactant molecule which allows it to be in contact with oily species or tails of other surfactant molecules. The contrasting properties of the head and tail portions of the surfactant molecule, particularly in the case of nonionic surfactants useful in the present invention, dictate the orientation of the surfactant in aqueous solution. The orientation of surfactant molecules in an aqueous system is not constant, but varies in relation to solution temperature, surfactant identity and concentration, the presence of other species in solution, and so forth.

[0024] At a temperature below its cloud point temperature and at a concentration below its critical micelle concentration, surfactant molecules in aqueous solution exist in the form of monomers. In effect, the individual molecules are largely independent of each other, and each surfactant molecule is surrounded by water molecules.

[0025] If the concentration of surfactant in the foregoing solution of monomers is allowed to exceed the critical micelle concentration (CMC) of the surfactant, individual molecules of surfactant begin to orient themselves into micelles, which are structures wherein several surfactant molecules arrange themselves with their oleophilic tails together and their hydrophilic heads presented outward, so that water molecules are isolated from the surfactant tails by an exterior surface of surfactant heads. At surfactant concentrations exceeding the CMC, the concentration of monomers remains more or less equal to the critical micelle concentration, so that the surfactant species present in excess of the CMC exist as micelles.

[0026] If the temperature of the surfactant solution is now increased to exceed the cloud point temperature of the aqueous solution (or if agents are added to the solution to lower its cloud point temperature to below the solution temperature, as further explained hereinafter), the micelles will each become sufficiently large that the solution will scatter light, rendering it cloudy in appearance.

[0027] If the solution temperature is further raised (or its cloud point temperature is further lowered) so that the solution is somewhat warmer than its cloud point temperature, the surfactant species begin to dehydrate. This means that the surfactant species progressively lose their solution-like attraction to water molecules.

[0028] Ultimately, if the temperature of the solution is raised to its phase coalescence temperature (or if the solution's phase coalescence temperature is lowered below its actual temperature by adding agents similar to those added to lower the cloud point temperature), the surfactant species will dehydrate to such an extent that much of the surfactant will separate as a second, surfactant rich, bulk phase.

[0029] Now consider the effects of these potential conditions of a surfactant solution on its ability to function as a washing liquor, particularly in the context of laundering oily soils from fabrics in a washing machine. In this context, cleaning must be both thorough and rapid if a product is to be effective.

[0030] Solutions containing a large proportion of monomeric surfactant species have long been selected by workers in the art for use in washing because they act much faster (under prior art conditions) than highly micellized solutions. This is graphically illustrated in Figure 5, in which plot A illustrates the performance of a surfactant with a CMC of 5 ppm (Neodol 45-7, which is described more fully below), and in which plot B illustrates the performance of a surfactant with a CMC of 200 ppm (Neodol 91-6, as further defined below). The concentration of each surfactant is equal, each surfactant has an HLB of 11.5, and in each case the surfactant concentration is many times greater than the surfactant CMC. The test is conducted below the cloud point temperature of each washing liquor. Under these conditions each solution has a monomer concentration which is roughly the same as its CMC. As will be noted from Figure 5, the high CMC surfactant, with its high concentration of monomers, outperforms the low CMC surfactant for more than 15 minutes, which is a typical maximum length for the washing cycle of a commercial laundering machine. Thus, the need for efficient laundering has led the prior art to the choice of high CMC surfactants.

[0031] It is known in the art that a low CMC surfactant should exhibit better ultimate cleaning than a high CMC surfactant because the former surfactants are superior to the latter ones for reducing the interfacial tension between oil and water in a two-phase system. This means that low CMC surfactants should more efficiently solubilize or emulsify fatty soils. And as Figure 5 suggests, a low CMC surfactant does clean to a better end result, even under prior art conditions, if given enough time. Thus, what has been needed in a way to improve the rate of cleaning of low CMC surfactants while retaining their thoroughness of cleaning.

[0032] The inventors have found that by using low CMC surfactants in a washing liquor maintained at a temperature substantially exceeding its cloud point temperature, so that the surfactant species coexist in a single bulk phase with water but are largely dehydrated, the rate of cleaning of low CMC surfactants is sufficiently increased that they clean better than high CMC surfactants. This surprising result is explained as follows.

[0033] Under prior art conditions the micelles which predominate in solutions of low CMC surfactants migrate to sites of oily soil very slowly and/or do not quickly reorient themselves from their water-stable form, in which their hydrophilic heads are presented outward, to a form in which their lipophilic tails are able to contact droplets of oily soils and solubilize or emulsify them. Under these prior art conditions a high CMC surfactant can clean more quickly because its high concentration of monomers travels quickly through solution to sites of oily soil. These monomers also do not need to reorient themselves into a less stable state to attach themselves to soils, for their lipophilic tails are constantly exposed.

[0034] However, when washing is conducted at a temperature substantially in excess of the cloud point temperature (or, conversely, if the cloud point temperature of the solution is made lower than the washing temperature selected), the disadvantages of micelles as cleaning species are largely eliminated. This effect is believed to result because at a temperature somewhat above the cloud point temperature the surfactant species have just enough affinity for water to remain in a single bulk phase, and this largely dehydrated surfactant species has little difficulty in solubilizing or emulsifying oily soils since the surfactant molecules apparently are more randomly oriented. Moreover, this surfactant species is believed to be transported by bulk transport to the sites of oily soils more rapidly than oridinary micelles, in contrast to prior art conditions which allow only monomeric species to participate in rapid cleaning, thus limiting the concentration of species available for cleaning to CMC, which is low for the preferred (low CMC) surfactants.

[0035] The inventors have also ascertained an upper limit to washing temperatures which may be used if the benefits of the present invention are to be obtained. It has been found that the present invention should be practiced at a washing temperature which does not exceed the phase coalescence temperature of the washing liquor. (Or, to put it another way, the phase coalescence temperature must not be lowered to below the washing temperature selected). This upper limit is probably observed because, while the surfactant will be delivered and mixed with oily soils more rapidly, it will not be removed at all because it is dehydrated and too hydrophobic to be a good solubilizing or emulsifying agent under these conditions. Methods not forming a part of the present invention must be employed to effectively clean fabrics with the two-phase surfactant/water system which exists when the washing temperature exceeds the phase coalescence temperature of the surfactant system in a washing liquor.

Selection of washing conditions

[0036] In practicing the present invention washing is conducted at a temperature within a range given by the following expression:

wherein A is the cloud point temperature of the washing liquor, B is the phase coalescence temperature of the washing liquor and T is the washing temperature. Preferred and especially preferred temperature ranges for practice of the present method are given by the following expressions, respectively:

[0037] The following hypothetical example will illustrate the use of the above expressions to select washing temperatures for washing liquors having particular cloud point and phase coalescence temperatures. Consider a washing liquor of the present invention with a cloud point temperature (A) of 40°C and a phase coalescence temperature (B) of 80°C. (These values would be determined for an actual washing liquor according to the procedure taught below, using a photo gonio diffusometer). The broadest range of washing temperatures is calculated thus:

[0038] The same numbers may be substituted into the expression for preferred washing temperatures as follows:

[0039] In like fashion, the especially preferred temperature for use of the indicated washing liquor is calculated as follows:







Using the above calculations for the hypothetical washing liquor, the broad, preferred, and especially preferred washing temperatures for this washing liquor are found to be 52°C to just less than 80°C, 60°C to just less than 80°C and 68°C to just less than 80°C.

[0040] Figures 1 and 2 illustrate the important of choosing a washing liquor with certain cloud point and phase coalescence temperatures in relation to the washing temperature in order to produce an optimum cleaning result.

[0041] Figure 1 is a plot of cleaning performance (Hunter whiteness) versus temperature for a washing liquor with a cloud point of 36°C and a phase coalescence temperature of 71°C. As the graph illustrates, cleaning performance continues to increase as the wash temperature is increased above the cloud point until the general area of the phase coalescence temperature is reached. Beyond this point, higher temperatures produce poorer performance.

[0042] In Figure 2, plot A shows the washing performance at 60° Celsius (measured as Hunter whiteness of fabrics washed by a standard method) of Neodol 45-7 (a surfactant comprising a primary fatty alcohol containing 14 to 15 carbon atoms condensed with an average of 7 ethylene oxide moieties per molecule of surfactant commercially available from Shell Chemical Co., Industrial Chemicals Division) as a function of concentration of sodium sulfate-an electrolyte which has no substantial function except to lower the phase coalescence and cloud point temperatures of the system. The area between the dotted lines represents an unstable area because the phase coalescence temperature is near the washing temperature. Accurate experimental data in this area is impossible to obtain. On the same graph are plotted the cloud point and phase coalescence temperatures of the washing liquor (C and B, respectively) versus percentage sodium sulfate in the washing liquor, thus defining a series of systems which have the same surfactant and washing temperature but differing phase coalescence and cloud point temperatures. The cleaning test was run at a single temperature in order to eliminate the difference in cleaning which would be expected due to the choice of differing washing temperatures. Figure 2 is an example of altering the cloud point and phase coalescence temperature of a washing system by electrolyte addition. The maximum performance of the system occurs when the phase coalescence temperature is maintained slightly above the wash temperature (60°C).

Washing liquors

[0043] The washing liquors of the present invention are aqueous dispersions of a nonionic surfactant. The surfactant may be present in concentrations of from 1400 ppm to 20,000 ppm. If it is desirable to raise the cloud point and phase coalescence temperatures of the washing liquor in accordance with the teachings of the present invention, the washing liquor may include up to about 10% of an anionic surfactant. Alternatively, one or more nonionic surfactants having a high cloud point temperature may be added to the washing liquor to raise the net cloud point and phase coalescence temperatures of the system. In accordance with the teachings of the present invention, 700 to 20,000 ppm of a strong electrolyte are also added to the washing liquor and serve to lower the cloud point and phase coalescence temperatures of the washing liquor. The cloud point and phase coalescence temperatures of the washing liquor may alternatively be lowered by adding a surfactant with a low cloud point temperature to the washing liquor to lower the net cloud point and phase coalescence temperatures of the system. Washing liquors of the present invention also includes 500 to 10,000 ppm of a sequestering builder in order to improve their cleaning ability. Finally, many detergency adjuvants and other optional ingredients may be added to compositions within the scope of the present invention. In the text which follows, the selection of each of these ingredients is described in greater detail.

Surfactant

[0044] The major essential ingredient of an aqueous washing liquor designed to practice the present invention is a surfactant (or mixtures of surfactants) which has certain properties. The desired concentration of the surfactant in the washing liquor is from 1400 ppm to 20,000 ppm. It will be noted that this concentration is at least 28 times the critical micelle concentration of the surfactant, which should be less than 50 ppm. Thus it will be apparent that the present invention teaches a very high concentration of surfactant compared to its critical micelle concentration, in contrast to the prior art teaching that washing with surfactant concentrations substantially in excess of the critical micelle concentration of the system does not improve surfactant performance because the concentration of the surfactant in excess of its CMC is tied up in the form of micelles.

[0045] The first consideration in choosing a surfactant or mixture of surfactants for use in the present invention is that the primary surfactant should be a nonionic surfactant. Not only.are nonionic surfactants the main category of surfactants which have HLB's within the range which is useful in the present invention, but in addition only a surfactant system consisting entirely or mostly of nonionic surfactants will exhibit a cloud point temperature and a phase coalescence temperature. Since the existence of these particular phase attributes of the washing liquor is essential to the definition of the present invention, it is important that the surfactant system primarily comprise nonionic surfactants.

[0046] The second consideration in choosing a surfactant is its HLB. The choice of a surfactant with an optimized HLB is demonstrated in the plots of Figure 4, in which three washing systems are compared which differ only in the choice of a surfactants HLB. In this test, three nonionic surfactants were chosen, each of which is a condensate of a fatty alcohol and a chain of ethylene oxide moieties. The surfactant chosen for the HLB 8.2 plot (plot H) was an ethoxylation product of a primary fatty alcohol having 12 or 13 carbon atoms with an average of 3 ethylene oxide moieties per molecule of surfactant. The HLB 15.0 plot (plot G) depicts the performance of a nonionic surfactant comprising a condensate of primary fatty alcohols having 14 or 15 carbon atoms with an average of 15 ethylene oxide moieties per molecule of surfactant. The HLB 11.6 plot (plot F) depicts the performance of a nonionic surfactant comprising 14 to 15 carbon primary alcohols with an average of 7 ethylene oxide moieties per molecule of surfactant. The critical micelle concentrations of the nonionic surfactants were 10 ppm, 5 ppm, and 12 ppm respectively. The performance of each of these surfactants was optimized for the washing temperature used (60° Celsius) by the addition of electrolytes as will be described hereinafter. As shown in Figure 4, which plots cleaning performance (measured as Hunter whiteness of fabrics washed with the respective solutions, which is determined as shown in Example 1 below) versus time in minutes, the surfactant with an HLB of 11.6 demonstrated better cleaning performance for all tested washing times than did the surfactant with an HLB of 15 or the surfactant with an HLB of 8.2. This illustrates that optimum cleaning performance is obtained using a surfactant system with an HLB between 9.5 and 13. It will be noted that individual surfactants which have HLB's outside this range may be combined to form a surfactant system which has an HLB within the indicated range without departing from the present invention. Hereinafter the phrase "total surfactant hydrophilic/lipophilic balance index" is used to denote that net HLB of all surfactants in a system. Preferably the total surfactants hydrophilic/lipophilic balance index lies in the range 9.75-12.5, most preferably in the range 10-12.

[0047] The third consideration in choosing a surfactant or mixture of surfactants for use in the present invention is that the surfactant should have a CMC which is below 50 ppm. As is explained above, selection of a surfactant with a CMC which is much less than its in-use concentration, using the particular washing temperatures of the present invention, improves the cleaning action of the surfactant. Example 2 below also demonstrates that a low CMC surfactant displays superior cleaning when used in accordance with the teachings of the present invention.

[0048] When a mixture of surfactants is selected as the surfactant component of a washing liquor which is to be used to practice the present invention, cloud point temperature and phase coalescence temperature values specified herein refer to properties of the washing liquor. The HLB and CMC of the surfactant system are essentially independent of the other components in the wash liquor. Consequently, HLB values for specific surfactants can be determined by methods known to those skilled in the art and CMC values can be measured in distilled water. The values of these parameters for a mixture of surfactants are determined as follows.

[0049] The HLB of a mixture of surfactants is determined using the following formula:

wherein the parameters are the HLB's of the respective surfactants and the coefficients indicate the fraction of total surfactant weight contributed by each surfactant.

[0050] The CMC of a mixture of surfactants is determined using the following equation:

wherein the numerators are the mole fractions of the respective components (compared to total moles of surfactants) and the denominators are the CMC's of the respective surfactants.

[0051] There is no simple relationship between the cloud point and phase coalescence temperatures of individual surfactants and of mixtures of surfactants. However, addition of a high cloud point surfactant to a surfactant solution with a lower cloud point will raise the cloud point of the solution, while addition of a low cloud point surfactant to a similar solution will lower its cloud point. An analogous relation also holds true when the phase coalescence temperature of the system is to be adjusted. Thus, it will be a simple matter for a person skilled in the art to formulate a mixture of surfactants with the desired cloud point and phase coalescence temperatures.

[0052] In the event that an anionic surfactant is to be included in the nonionic surfactant system to raise its cloud point and phase coalescence temperatures, an additional problem in formulation is raised because anionic detergents do not typically have a cloud point or phase coalescence temperature in aqueous solutions. This is the case because the temperature at which such a surfactant dispersion would exhibit these properties is greater than the boiling point of the aqueous dispersion at atmospheric pressure. A person skilled in the art of formulating detergents can resolve this difficulty by obtaining cloud point and phase coalescence temperatures of aqueous surfactant solutions which are subjected to a pressure exceeding their vapor pressure. This will then aid the formulator's initial estimate of the amount of the anionic surfactant which must be added in orderto obtain the desired adjustment in the phase properties of the system.

[0053] Following is a detailed description of specific nonionic surfactants which may be used to formulate surfactant systems when practicing the present invention.

[0054] A first category of nonionic surfactants which are useful in the practice of the present invention are most broadly defined as ethoxylated aliphatic alcohols. These surfactants are the condensation products of a fatty alcohol with an ethoxylate chain comprising at least one ethoxylate moiety per molecule of surfactant, especially between 1 and 12 moles of ethoxylate moieties per molecule of surfactant for purposes of the present invention. Commercially available ethoxylated fatty alcohols generally contain between 8 and 22 carbon atoms in their alcohol moiety, preferably 12 to 15 carbon atoms for the purpose of the present invention. Typical surfactants of this type have a broad distribution of degrees of ethoxylation, since species having various ethoxylate chain lengths are difficult to separate, or even to identify, in the commercially available materials. Preferred ethoxylated alcohol surfactants for use in the present invention have an average of 5 to 8 moieties of ethylene oxide per molecule of surfactant, preferably an average of 7 moieties. When a degree of ethoxylation is specified hereinafter, it will be understood that this refers to the average number of ethoxylate moieties per molecule of surfactant.

[0055] One commercial source of alcohol ethoxylates useful in the practice of the present invention is the series of surfactants, which are available from Shell Chemical Company, under the Trade Name 'Neodol'. The Neodol surfactants are characterized by a low degree of branching in the alcohol chain; typically less than 20% of the surfactant molecules are branched. Neodols are primary alcohol ethoxylates which each have a narrow and precisely indicated range of alcohol chain lengths, but a large variation in the degree of ethoxylation in a given molecule; the average number of ethoxylate groups per molecule is provided for the surfactants. An example of how Neodols are named is Neodol 45-7, which is a condensate of a 14 or 15 carbon fatty alcohol with an average of 7 ethylene oxide moieties per molecule of surfactant. Another example is Neodol 91-6, which comprises the condensate of a 9 to 11 carbon fatty alcohol with an average of 6 ethylene oxide moieties per molecule of surfactant.

[0056] Specific examples of Neodol surfactants which are useful in practicing the present invention are as follows: Neodol 45-7, 45-15, 23-6.5, or 25-7; a mixture of 75% Neodol 25-5 and 25% Neodol 45-7; a mixture of 50% Neodol 25-7 and 50% Neodol 45-7; and a mixture of 50% Neodol 91-6 and 50% Neodol 45-7.

[0057] Another commercial source of ethoxylated fatty alcohols is the series of surfactants which are commercially available from Uniion Carbide Corporation under the Trade Name 'Tergitol'. Tergitols are alcohol ethoxylates, and may be divided into S Tergitols and L Tergitols. The former are relatively unbranched secondary alcohols, while the latter are primary alcohols having a high numerical percentage of branched species. (40% of the alcohol moieties of L Tergitols are branched, while a lower percentage of the alcohol moieties of S Tergitols are branched). In commercially supplied Tergitols, the range of ethoxylation for a given surfactant is somewhat narrower than is observed in the Neodols. The Tergitols are named in a manner analogous to the naming of Neodols, except that the name contains an upper case "S" or "L" interposed between the numerals indicating alcohol chain length and the numeral indicating degree of ethoxylation. Specific examples of Tergitol surfactants which are useful in the practice of the present invention are Tergitols 15-S-3, 15-S-5, 15-S-7, 15-S-9, 25-L-3, 25-L-5, 25-L-7, or 25-L-9. Some of these surfactants must be combined with other ingredients as disclosed herein in order to be useful in the practice of the present invention).

[0058] A second major category of nonionic surfactants which are useful in the practice of the present invention is that of the alkyl phenol ethoxylates. The structure of these surfactants is that of benzene with two substituents in para relationship. The first substituent is an alkyl moiety with a chain length of 7 to 12 carbon atoms, preferably 8 or 9 carbon atoms for purposes of the present invention. The second substituent is an ethoxylation chain. The alkyl phenol ethoxylates have an ethylene oxide substitution level which varies widely for a given surfactant. The degree of ethoxylation in such surfactants is essentially from 1 to 12 ethylene oxide moieties per molecule of surfactant; an average of 7 ethylene oxide moieties per molecule of surfactant is preferred for use in this invention.

[0059] Specific alkyl phenol ethoxylates which are useful in the practice of the present invention are manufactured by General Aniline and Film Corporation under the Trade Name 'Igepal'. The Igepal surfactants are designated by two upper case letters followed by a numeral or series of numerals; the lettered prefix "CA" indicates an octyl radical as the alkyl moiety of the surfactant, while the lettered prefix "CO" indicates a nonyl radical as the alkyl moiety. The inventors are not aware of any connection between the numerals designating species of this class of surfactants and the structures thereof. A specific example of an Igepal surfactant useful in the practice of the present invention is Igepal CO-610.

[0060] A third broad class of nonionic surfactants which are useful in the practice of the present invention are the condensation products of a chain of ethylene oxide moieties with a hydrophobic base formed by the condensation of a chain of propylene oxide moieties with propylene glycol, known hereinafter as ethylene oxide/propylene oxide block copolymers.

[0061] One commercially available series of ethylene oxide/propylene oxide block copolymers is the Pluronic (Series marketed by BASF Wyandotte Corporation. The Pluronics are named using a letter prefix (L for a liquid, P for a paste, and F for a flaked or solid composition) and a two to three digit suffix, the first digit or two defining a molecular weight range and the final digit defining the percent of ethylene oxide in the surfactant, divided by 10. The molecular weight corresponding to the first digits in the surfactant name is indicated in Table I which follows:

[0062] A specific example F A Pluronic surfactant which is useful in the present invention is Pluronic L-43, which is a liquid composition with a hydrophobic portion molecular weight of 1200 and 30% by composition weight of ethylene oxide.

[0063] While certain nonionic surfactants have been indicated as preferred, the invention may be practiced using any of a broad selection of nonionic surfactants, several additional examples of which follow. One additional example of such a surfactant is a polyoxyethylene ester of a fatty acid which is marketed by the Monsanto Company under the Trade Name Stearox CD. Alkyl phenol-based nonionic surfactants include those marketed by Rohm and Haas Company under the Trade Name Triton and the nonyl phenol ethoxylates marketed by Jefferson Chemical Co. Inc. under the Trade Name Surfonic N.

[0064] Other nonionics which are useful in the present invention are the polyoxyethylene mercaptan analogs of the alcohol ethoxylates, and polyoxyethylene adducts of alkyl amines.

[0065] Polyoxyethylene alkyl amides may also be used in the practice of this invention. Another category of nonionic surfactants is the sorbitan esters, such as sorbitan monolaurate.

[0066] This list of nonionic surfactants is not exhaustive, and it is contemplated that routine experimentation will result in the location of other surfactants which may be used to practice the present method invention.

[0067] Table II below contains HLB, CMC, cloud point, and phase coalescence temperature data for a variety of aqueous solutions of pure commercial surfactants. With the aid of this table, a person skilled in the art may formulate a wide variety of washing liquors which are useful for laundering fabrics. (In the table which follows, TAE₁₁ is a primary fatty alcohol ethoxylate surfactant having a predominance of alcohol chain lengths of 14 to 18 carbon atoms and an average of 11 ethoxylate moieties per molecule of surfactant TAE₉ is a similar surfactant, but is substituted with an average of 9 ethoxylate moieties per molecule of surfactant; STP is sodium tripolyphosphate; LAS is a linear alkylate sulfonate surfactant comprising benzene substituted by a sulfonate group and a C₁₂ alkylate group in para orientation; and Na₂C0₃ is sodium carbonate).

[0068] The cloud point temperatures and phase coalescence temperatures of Table II were measured on a photo gonio diffusometer made by Sofica (Model 42.000). The index vat of the above apparatus contained Dow Corning 702 Silicone fluid and the temperature range of the instrument was 30°C to 100°C. The photo detection unit of the instrument was positioned at an angle of 90° with respect to the incoming light beam. Samples of each surfactant were prepared at a concentration of 3,000 ppm using laboratory distilled water. No other special treatment was used to reduce interfering impurity particles. A green instrument filter and no polarizing filter were used, and the instrument's variable slit was adjusted for appropriate base intensity starting light scattering measurements. To obtain the cloud point and phase coalescence temperatures, the samples were heated at the rate of approximately 1/2° Celsius per minute using a variable voltage transformer. The cloud point temperature was determined as the initial temperature at which the light scatter reading deviated from the base light scatter, indicating a sharp increase in light scattering due to the formation of nuclei of sufficient size of scatter light. The phase coalescence temperature was interpreted to be the temperature at which the light scattering returned to the base line scatter after having increased to the maximum. This represents a temperature at which the solution separates into two bulk phases, each of which is much less cloudy than the mixture before separation of aqueous and surfactant phases. The CMC's of Table II were determined in distilled water at 25°C.

Cloud point/phase coalescence temperature adjustment

[0069] Given that the optimum washing conditions for a given surfactant are confined to a narrow temperature range, it is highly desirable to enable the practitioner to vary the cloud point and phase coalescence temperatures of a given surfactant system in order to formulate a composition containing a desired nonionic surfactant to be used at a selected washing temperature. This is highly desirable because certain washing temperatures are highly preferred in the art for washing certain types of fabrics and for removing particular soils.

[0070] In the event that a nonionic surfactant has relatively low cloud point and phase coalescence temperatures, so that the temperature for washing in accordance with the teaching of the invention is lower than the desired washing temperature for given fabric and soil conditions, small amounts of an anionic detergent may be incorporated into a surfactant system which contains a major amount of the nonionic surfactant in order to substantially raise the cloud point and phase coalescence temperatures of the system. It will be noted, however, that the percentage of total surfactant content supplied by an anionic surfactant should not exceed about 10% of the surfactant system to avoid creating a surfactant system which does not have a cloud point or phase coalescence temperature. In such systems the anionic surfactant preferably comprises 0.5% to 5% of the composition.

[0071] One typical anionic surfactant which may be used to raise the cloud point and phase coalescence temperatures of the washing liquors is a linear alkylate sulfonate (LAS), which is benzene substituted with an alkyl moiety and a sulfonate moiety in para relation. An especially preferred LAS has a dodecyl group as its alkyl moiety and is typically referred to in the art as C₁₂ LAS. Another type of anionic surfactant which may'be used for this purpose is an alkylate ethoxylate sulfate (AES) comprising an alkyl moiety, to which is attached an ethoxylate chain, to which in turn is attached a sulfate moiety. One typical AES surfactant has a dodecyl group as its alkyl moiety and a six-unit ethoxylate chain. A third type of anionic surfactant which may be used to raise the cloud point and phase coalescence temperatures of a nonionic surfactant system is a tallow alkyl sulfate (TAS) surfactant. This surfactant contains alkyl moieties having a range of carbon chain lengths, predominantly alkyl moieties having from 14 to 18 carbon atoms.

[0072] For the nonionic surfactants described above which have been found to be most useful for washing, it is typically necessary to lower the phase coalescence temperature and cloud point temperature of the surfactant system in order to produce a composition which is useful for washing at temperatures which are preferred in the art. This is especially true given the recent tendency in the art to prefer lower washing temperatures in order to save energy in the laundering process. A highly preferred way to lower the optimum washing temperature of a washing liquor to a preferred value is to add to the surfactant system any of a wide variety of strong electrolytes.

[0073] It will be appreciated by those skilled in the art of formulating nonionic surfactant compositions that the addition of nearly any strong electrolyte to a system containing a nonionic surfactant will lower the cloud point of the surfactant system, as well as the phase coalescence temperature. Just a very few examples of appropriate electrolytes are the water-soluble chemical compounds of an anion selected from chloride, bromide, silicate, orthosilicate, metasilicate, orthophosphate, sulfate, carbonate, nitrate, fluoride, acetate, hydroxide and citrate, and a cation selected from sodium, potassium, lithium, calcium, magnesium and hydrogen. This list is by no means exhaustive, and those skilled in the art will easily select any of a wide variety of strong electrolytes, depending on the availability of particular salts and other factors. Preferred electrolytes are those which supply some alkalinity to the washing medium, although a high degree of alkalinity is not necessary to the practice of the present invention. Of the electrolytes noted above, the sodium salts are highly preferred as strong electrolytes because they are highly soluble and inexpensive, and of those sodium salts sodium carbonate and sodium metasilicate are the most preferred strong electrolytes in the practice of the present invention. Typically the amount of a strong electrolyte which must be added to the washing liquor to optimize the cloud point and micelle inversion temperatures will lie between 700 ppm and 20,000 ppm.

[0074] Figure 3 is a plot of cleaning performance (Hunter whiteness) versus wash time for two washing liquors. Plot "D" is for a washing liquor containing Neodol 45-7 and a strong electrolyte (sodium sulfate) to optimize its performance at the washing temperature used. Plot E is for the same washing liquor and washing temperature, but excluding the electrolyte. As indicated in Figure 3, for any of the wash times tested the washing liquor containing an electrolyte produces superior washing results. The result is obtained because the washing liquor which did not contain a strong electrolyte had cloud point and phase coalescence temperatures which placed the washing composition and conditions outside the scope of the present invention, while the washing liquor containing a strong electrolyte had lowered phase coalescence and cloud point temperatures which placed the identical washing composition and conditiions within the scope of the present invention.

Sequestering builders

[0075] While washing liquors containing a nonionic surfactant and having particular cloud point and phase coalescence temperatures are useful in themselves for laundering fabrics, their effect is improved by adding thereto 500 ppm to 10,000 ppm of a sequestering builder.

[0076] A wide variety of sequestering detergency builders is known in the art. A number of these are conveniently described as compounds of a cation selected from sodium, potassium, lithium, or hydrogen, and an anion selected from tripolyphosphate, pyrophosphate, orthophosphate, nitrilotriacetate, ethylene diamine tetraacetate, nitrilotrimethylenephosphonate, and ethylene diamine tetramethylenephosphonate. It will also be noted that some ingredients which act as strong electrolytes may also be useful as sequestering detergency builders, for example, orthophosphates. However, the best sequestering builders are only modestly electrolytic at the concentration typically used in a detergent. Especially preferred sequestering builder salts for incorporation in washing liquors of the present invention are any of the polyphosphate builders known to the art, particularly alkali metal tripolyphosphates and pyrophosphates such as sodium tripolyphosphate or tetrasodium pyrophosphate.

[0077] These sequestering builders are widely recognized in the art as important additives for laundry detergents. These builders have traditionally been thought to be primarily useful to prevent water hardness cations from interacting with soaps or anionic detergents to form an insoluble precipitate or soap scum. However, such sequestering builders are also known to provide cleaning benefits to washing liquors containing only nonionic surfactants, which do not interact with water harness ions. The sequestering builders prevent water hardness ions such as calcium and magnesium from interacting with fatty soils to form insoluble precipitates. The sequestering builders also sequester other metal ions such as copper and iron ions which can interfere with the action of the bleaching agents which are frequently used in conjunction with laundry detergents. Several of the sequestering builders also peptize clay soils by replacing various cations in the insoluble clays with sodium cations or the like, rendering the clays somewhat soluble in the washing liquor. Finally, these builders have utility as soil suspending agents.

Commercial detergent compositions

[0078] Commercially useful detergent compositions for laundering fabrics are typically sold as concentrated formulas which are diluted in water by the user in order to produce the desired aqueous washing liquor. What follows is a specific description of washing compositions which may be diluted in water to form washing liquors within the definition of the present method invention.

[0079] The following ingredients may be combined in the indicated proportions to produce compositions which may be diluted in water to produce washing liquors useful to practice the present invention:

(a) from 10% to 78% of a nonionic surfactant;

(b) from 4% to 70% of an electrolyte; and

(c) from 3% to 55% of a detergency builder salt.

such compositions may be dissolved in water to form a solution which contains from 1000 to 40,000 ppm (0.10% to 4.0%) of the composition.

[0080] The following compositions contain preferred proportions of specific ingredients. They may be diluted in the proportions noted above to form washing liquors:

(a) 20% to 51% of an alkali metal tripolyphosphate;

(b) 24% to 40% of an alkali metal carbonate; and

(c) 20% to 51 % of the condensate of a fatty alcohol having 12 to 15 carbon atoms with an average of 5 to 8 ethoxylate moieties per molecule or surfactant; or;

(a) 20% to 40% of an alkali metal pyrophosphate;

(b) 25% to 40% of an alkali metal carbonate; and

(c) 20% to 55% of the condensate of a fatty alcohol having 12 to 15 carbon atoms with an average of 5 to 8 ethoxylate moieties per molecule of surfactant.

[0081] In addition, the following compositions are specifically formulated for optimal washing in the concentrations specified above at a temperature of about 140°F (60° Celsius):

(a) 36% sodium tripolyphosphate;

(b) 35% sodium carbonate; and

(c) 29% of the condensate of a primary fatty alcohol having 14 to 15 carbon atoms with an average of 7 ethylene oxide moieties per molecule (Neodol 45-7); or

(a) 31% tetrasodium pyrophosphate;

(b) 34.6% sodium carbonate; and

(c) 34.4% of the condensate of a primary fatty alcohol having 14 to 15 carbon atoms with an average of 7 ethylene oxide moieties per molecule of surfactant (Neodol 45-7).

[0082] Finally a composition designed to employ a mixed surfactant system comprises:

(a) 10%-40% preferably 15%-35% of a mixture of a C_12-C₁₅ fatty alcohol condensed with an average of 6-7 moles of ethylene oxide per mole of alcohol and a C₁₂-C₁₅ primary alcohol condensed with an average of three moles of ethylene oxide per mole of alcohol.

(b) 50%-70% preferably 55% to 65% of a strong electrolyte selected from sodium carbonate sodium metasilicate and mixtures thereof.

(c) 10%-25% preferably 12%-15% of sodium tripolyphosphate and

(d) from 0.5% to 5% of an anionic surfactant selected from sodium C₁₂ alkyl benzene sulphonate sodium dodecyl hexaethoxy sulphate, sodium tallowalkyl sulphate and mixtures thereof.

[0083] In addition to the cleaning benefits of formulations which may be used to practice the present invention, they may be used to wash effectively at a relatively low pH. Typical washing liquors used in industrial laundries arts are highly alkaline, having an pH substantially in excess of 11.5. Such pH's are essential in conventional industrial laundry detergents in order to saponify oily soils and thus increase their solubility in the washing liquor.

[0084] A number of preferred compositions are desirably formulated to have a pH of 11 or less, particularly from 7 to 11. This is possible because the cleaning ability of the compositions disclosed herein has been found to be relatively insensitive to pH. While a high pH cleaning composition may easily be formulated which provides a washing liquor pH greater than 11.5 no substantial cleaning benefit is found to result from the selection of a high pH. The wash liquors of the present invention are able to solubilize or emulsify oil quite effectively without lying on saponification.

[0085] The compositions may be assembled in any of the ways known to the art to form commercial preparations which are suitable for sale.

Examples

[0086] The following examples do not limit the scope of the present invention, which is defined by the claims concluding this specification. Rather, these examples illustrate the practice of the invention under controlled conditions. In these examples "Na₂C03" is sodium carbonate, "Na₂S04" is sodium sulfate, "STP" is sodium tripolyphosphate, "TSPP" is tetrasodium pyrophosphate, the Neodol surfactants are certain primary fatty alcohol ethoxylates, as characterized above and "TAE_G" is a primary fatty alcohol ethoxylate having a predominance of alcohol chain lengths in the range of from 14 to 18 carbon atoms and an average of 9 ethoxylate moieties per molecule of surfactant. Where dextrin is present it functions as a binder and does not substantially affect the performance of compositions containing it.

Example 1

Removal of oily soil by surfactants of differing HLB

[0087] A series of 65% polyester/35% cotton swatches with a permanent press finish were soiled with used motor oil obtained from automobile crankcases. These swatches were washed for 20 minutes in a Tergotometer, Model 7243, at 60°C in soft water with the compositions listed below. Octadecane at a level of300 ppm was added to the wash solution to simulate extra soil in the system. The temperature of each washing liquor was within the range of the present invention. The washed swatches were rinsed for 10 seconds in cold water and dried, and Hunter whiteness measurements were made using a Hunter Laboratories ColorlDifference Meter (Model D25D2). (This instrument provides a direct readout of Hunter whiteness).

[0088] ^*The Na₂C0₃ level was optimized to give maximum performance for each system.

[0089] The HLB ranges of Compositions B and C were outside the temperature range required for the present invention, while Composition A had an HLB range within the invention and demonstrated superior performance.

Example 2

Removal of oily soil by surfactants of differing CMC

[0090] A series of stains were cut from discarded, naturally soiled industrial uniforms. These stains were split into equally soiled parts; each part was washed with one of the compositions listed below. The stains were washed in a 35 lb. Milnor washer/extractor with 18.5 lbs. of industrial uniform shirts soiled with 1.5 lb. of used motor oil. A wash temperature of 60°C was used. After washing, the stained parts were placed back together and graded visually in a paired comparison manner by a panel of 3 judges using a 0-4 scale. A grade of "0" indicated no difference between the paired swatches; a grade of "1" indicated a perceived difference between the swatches; a grade of "2" indicated a clear difference between the swatches; a grade of "3" indicated a large difference between the swatches; and a grade of "4" indicated a very large difference between the swatches. These grades were statistically combined to produce Paired Comparison Grades, which represent the difference in cleaning performance for a given composition (positive for an improvement) with respect to the inferior composition.

[0091] The CMC of Comparison B was outside the range required by the present invention. The process used with Composition A was within the scope of the present invention and demonstrated superior performance.

Example 3

Removal of oily soil under differing phase conditions

[0092] The procedure described in Example 1 was used.

[0093] The process using Composition B was outside the claims of this invention, for the wash temperature (60°C) exceeded the phase coalescence temperature of the washing liquor. The process used with Composition A is within the claims and produces superior performance.

Example 4

Removal of oily soil by a prior art process vs. the claimed process

[0094] The procedure described in Example 2 was used.

[0095] The process using Composition B is outside the claims of this invention because the wash temperature used was below the cloud point temperature of Composition B. The process used with Composition A was within the claims of this invention and produced superior performance, even though Composition A was substantially more dilute and had a much lower pH than Composition B.

Example 5

Removal of oily soil by products of varying composition

[0096] The procedure of Example 2 was used. The compositions were added to the wash water to produce washing liquors having the indicated concentrations.

[0097] Composition B is outside the more preferred composition range employed in this invention due to its high Na₂C0₃ level. Composition A is near the center of the range and produces superior performance. The 60°C wash temperature was within the temperature range of the present invention for each composition.

Example 6

Removal of oily soil by products of varying composition

[0098] The procedure described in Example 5 was used.

[0099] Composition B is outside the more preferred composition range employed in this invention due to its lower Na₂C0₃ level. Composition A is near the center of the range and produces superior performance. Again, the 60°C washing temperature for each composition was within the temperature range of the present invention.

Claims

1. A process for laundering oily soil from a fabric by contacting the fabric with an aqueous washing liquor containing a nonionic surfactant characterised in that it comprises:

(a) treating said fabric with a wash liquor having a total surfactant hydrophilic-lipophilic balance (HLB) index of from 9.5 to 13, said liquor containing 1400-20,000 ppm of a nonionic surfactant component having a CMC of <50 ppm at 25°C in distilled water, 500-10,000 ppm of a sequestering builder selected from sodium potassium and lithium tripolyphosphate, pyrophosphate, orthophosphate nitrilotriacetate, ethylene diamine tetraacetate nitrilo trimethylene phosphonate, ethylene diamine tetramethylene phosphonate and mixtures thereof and 700-20,000 ppm of a strong electrolyte; and

(b) maintaining said washing liquor at a temperature in the range 0.30(B-A)+A≤T<B

wherein T is the wash liquor temperature, B is the phase coalescence temperature of the wash liquor and A is the cloud point temperature of the wash liquor.

2. A process according to Claim 1 characterised in that the wash liquor temperature is maintained within the temperature range 0.50 (B-A)+A≤T<B preferably within the range 0.70 (B-A)+A≤T<B.

3. A process according to either one of Claims 1 and 2 wherein the nonionic surfactant is selected from alkyl phenol ethoxylates, ethylene oxide-propylene oxide block copolymers and aliphatic ethoxylated alcohols, preferably C_12-C₁₅ primary fatty alcohols containing 5-8 moles of ethylene oxide per mole of alcohol.

4. A process according to any one of Claims 1-3 characterised in that the nonionic surfactant component has a CMC<25 ppm preferably <10 ppm.

5. A process according to any one of Claims 1-4 characterised in that the wash liquor has a total surfactant HLB of 9.75-12.5 preferably 10-12.

6. A process according to any one of Claims 1-5 characterised in that the strong electrolyte is selected from sodium carbonate and sodium silicate.

7. A process according to any one of Claims 1-6 characterised in that the wash liquor is a solution of a composition comprising (in the dry state)

(a) 20%―51% by weight of a C₁₂―C₁₅ fatty alcohol condensed with 5―8 moles ethylene oxide per mole alcohol, preferably 29%-35% of a C14-C15 fatty alcohol condensed with an average of seven moles ethylene oxide per mole alcohol;

(b) 20%-40% preferably 34%-35% sodium carbonate and

(c) 20%-51 % preferably 30%-36% of sodium pyrophosphate or sodium tripolyphosphate.

8. A process according to any one of Claims 1-6 characterised in that the wash liquor is a solution of a composition comprising (in the dry state)

(a) 10%-40% preferably 15%-35% of a mixture of a C_14-C₁₅ fatty alcohol condensed with an average of seven moles of ethylene oxide per mole of alcohol and a C₁₂-C₁₅ primary alcohol condensed with an average of three moles of ethylene oxide per mole of alcohol,

(b) 50%-70% preferably 55% to 65% of a strong electrolyte selected from sodium carbonate, sodium metasilicate, and mixtures thereof,

(c) 10%-25% preferably 12%-15% of sodium tripolyphosphate and

(d) from 0.5% to 5% of an anionic surfactant selected from sodium C₁₂ alkyl benzene sulphonate, sodium dodecyl hexaethoxy sulphate, sodium tallowalkyl sulphate and mixtures thereof.

Revendications

1. Un procédé pour laver une salissure huileuse d'une étoffe, par mise en contact de l'étoffe avec une solution aqueuse de lavage contentant un tensio-actif non ionique, procédé caractérisé en ce qu'il comprend:

(a) le traitement de ladite étoffe par une solution de lavage présentant un indice d'équilibre hydrophile lipophile de tensio-actif total de 9,5 à 13, ladite solution contenant 1400 à 20 000 ppm d'un tensio-actif non ionique ayant une concentration critique de micelles inférieure à 50 ppm à 25°C dans de l'eau distillée, 500 à 10 000 ppm d'un additif à rôle de séquestration, choisi parim du tripolyphosphate, du pyrophosphate, de l'ortho-phosphate, du nitrilotriacétate, de l'éthylène diamine tétraacétate, du nitrilo triméthylène phosphonate, de l'éthylène diamine tétraméthylène phosphonate de sodium, de potassium et de lithium et leurs mélanges, et 700 à 20 000 ppm d'un électrolyte fort; et

(b) le maintien de ladite solution de lavage à une température comprise dans l'intervalle 0,30 (B-A)+A≤T<B, où T est la température de la solution de lavage, B est la température de coalescence de phase de la solution de lavage et A est la température de point de trouble de la solution de lavage.

2. Un procédé selon la revendication 1, caractérisé en ce qu'on maintient la température de la solution de lavage dans l'intervalle de températures 0,50 (B-A)+A%T<B, de préférence dans l'intervalle 0,70(B-A)+A≤T<B.

3. Un procédé selon l'une des revendications 1 et 2, dans lequel le tensio-actif non ionique est choisi parmi des éthoxylates d'alkyl phénols, des copolymères séquencés d'oxyde d'éthylène/oxyde de propylène et des alcools aliphatiques éthoxylés, de préférence des alcools gras primaires en C₁₂ à C₁₅ contenant 5 à 8 moles d'oxyde d'éthylène par mole de l'alcool.

4. Un procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le tensio-actif non ionique a une concentration critique de micelles inférieure à 25 ppm, de préférence inférieure à 100 ppm.

5. Un procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la solution de lavage présente un indice d'équilibre hydrophile lipophile de tensio-actif total de 9,75 à 12,5, de préférence de 10 à 12.

6. Un procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'on choisit l'électrolyte fort parmi du carbonate de sodium et du silicate de sodium.

7. Un procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la solution de lavage est une solution d'une composition comprenant (à l'état sec):

(a) 20 à 51 % en poids d'un alcool gras en C₁₂ à C₁₅, condensé avec 5 à 8 moles d'oxyde d'éthylène par mole d'alcool, de préférence 29% à 35% d'un alcool gras en C,4-C,5 condensé avec, en moyenne, sept moles d'oxyde d'éthylène par mole d'alcool;

(b) 20% à 40% de préférence 34%-35%, de carbonate de sodium, et

(c) 20% à 51%, de préférence 30% à 36% de pyrophosphate de sodium ou de tripolyphosphate de sodium.

8. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la solution de lavage est une solution d'une composition comprenant (à l'état sec):

(a) 10% à 40%, de préférence 15% à 35%, d'un mélange d'un alcool gras en C₁₄―C₁₅ condensé avec en moyenne 7 moles d'oxyde d'éthylène par mole d'alcool et d'un alcool primaire en C12-C15 condensé avec en moyenne 3 moles d'oxyde d'éthylène par mole d'alcool,

(b) 50% à 70%, de préférence 55% à 65%, d'un électrolyte fort choisi parmi le carbonate de sodium, le métasilicate de sodium et leurs mélanges,

(c) 10% à 25%, de préférence 12% à 15%, de tripolyphosphate de sodium, et

(d) de 0,5% à 5% d'un tensio-actif anionique choisi parmi un alkyl benzène sulfonate de sodium en C₁₂, du dodécyl hexaéthoxy sulfate de sodium, de l'(alkyl de suif) sulfate de sodium et leurs mélanges.

Ansprüche

1. Verfahren zum Waschen von öligem Schmutz aus einem Textilgewebe durch Inkontaktbringen des Textilgewebes mit einer wäßrigen Waschflotte, enthaltend ein nichtionisches Tensid, dadurch gekennzeichnet, daß man

(a) dieses Textilgewebe mit einer Waschflotte behandelt, die einen Gesamt-Tensidhydrophilenllipophilen-Gleichgewichtsindex von 9,5 bis 13 aufweist, wobei die Flotte 1 400 bis 20 000 ppm einer nichtionischen Tensid-komponente mit einer kritischen Mycellenkonzentration von <50 ppm bei 25°C in destilliertem Wasser, 500 bis 10 000 ppm eines komplexbildenden Gerüststoffs, ausgewählt aus Natrium-, Kalium- und Lithiumtripolyphosphat, Pyrophosphat, Orthophosphat, Nitrilotriacetat, Ethylendiamintetra-acetat, Nitrilotrimethylenphosphonat, Ethylendiamintetramethylenphosphat und Gemische davon und 700 bis 20 000 ppm eines starken Elektrolyten enthält und

(b) die Waschflotte bei einer Temperatur im Bereich von 0,30(B-A)+A≤T<B hält,

worin T die Waschflottentemperatur, B die Phasencoaleszentemperatur der Waschflotte und A die Trübungspunkttemperatur der Waschflotte bedeuten.

2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Waschflottentemperatur innerhalb des Temperaturbereichs 0,50(B-A)+A≤T<B, vorzugsweise innerhalb des Bereichs 4,70(B-A)+A≤T<B gehalten wird.

3. Verfahren nach einem der Ansprüche 1 und 2, worin das nichtionische Tensid ausgewählt ist aus Aklylphenolethoxylaten, Ethylenoxid-Propylenoxid-Blockcopolymeren und aliphatischen ethoxylierten Alkoholen, vorzugsweise C₁₂―C₁₅-primären Fettalkoholen, enthaltend 5 bis 8 Mol Ethylenoxid je Mol Alkohol.

4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die nichtionische Tensidkomponente eine kritische Mycellenkonzentration <25 ppm, vorzugsweise <10 ppm aufweist.

5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Waschflotte einen Gesamt-Tensid-HLB von 9,75 bis 12,5, vorzugsweise 10 bis 12 aufweist.

6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der starke Elektrolyt ausgewählt ist aus Natriumcarbonat und Natriumsilikat.

7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Waschflotte eine Lösung einer Zusammensetzung ist, enthaltend (im trockenen Zustand)

(a) 20 bis 51 Gew.-% eines C₁₂―C₁₅-Fettaikohois kondensiert mit 5 bis 8 Molen Ethylenoxid je Mol Alkohol, vorzugsweise 29 bis 35% eines C₁₄―C₁₅-Fettalkohols kondensiert mit durchschnittlich 7 Mol Ethylenoxid je Mol Alkohol;

(b) 20 bis 40%, vorzugsweise 34 bis 35%, Natriumcarbonat und

(c) 20 bis 51%, vorzugsweise 30 bis 36%, Natriumpyrophosphat oder Natriumtripolyphosphat.

8. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Waschflotte eine Lösung einer Zusammensetzung ist, enthaltend (im trockenen Zustand)

(a) 10 bis 40%, vorzugsweise 15 bis 35%, eines Gemischs aus einem C14-C15-Fettalkohol kondensiert mit durchschnittlich 7 Mol Ethylenoxid je Mol Alkohol und C₁₂―C₁₅-primärem Alkohol kondensiert mit durchschnittlich 3 Molen Ethylenoxid je Mol Alkohol,

(b) 50 bis 70%, vorzugsweise 55 bis 65% eines starken Elektrolyten, ausgewählt aus Natriumcarbonat, Natriummetasilikat und Gemischen davon,

(c) 10 bis 25%, vorzugsweise 12 bis 15%, Natriumtripolyphosphat und

(d) 0,5 bis 5% eines anionischen Tensids ausgewählt aus Natrium-C₁₂-alkylbenzolsulfonat, Natriumdodecylhexaethoxysulfat, Natriumtalgalkylsulfat und Gemischen davon.

Drawing